Paint binders

Ancient paint binders come from trees, plants, animal protein and minerals. Tree resin was used in ancient ceremonies honoring death and birth, transformation, emptiness and abundance. It is also one of the earliest paint binders found in ancient Buddhist cave paintings, Japanese calligraphy, Greek and Middle Eastern paintings and scriptures. Trees have provided some of the earliest paint binders through sap, gum and resin since humans first made marks. 

Tree sap wants to be smelled, it’s resin smokes with fire and saturates shrines, temples, cathedrals and ancient places where people are transformed in spiritual and mental states by chemical olfactory sensations. This resin is the blood of the tree and carries with it the essence of these trees, released through alchemy and altering human experience in rituals as old as we are.

Theo’s unique research into ancient paint binders is reflected in her work. “I have collected tree saps and resins from the Pacific Northwest and worldwide to reduce tree resin into paint mediums. I use the mediums in my painting and printmaking by incorporate the essence of these ancient record keepers. The trees I traveled to visit captivated me and left me with their impressions, resins and stories.”

Excerpts from “Worldwide Ethnographic Paint Binders”…..

The name Elemi comes from an Arabic saying meaning “above and below,” and refers to its function as a spiritual and emotional reference and in ceremonies documented worldwide (Mantel 1950). In ancient Roman times, animi or enhaemon were terms used for Elemi (Gooch 2002).

Pliny said elemi contained tears extracted from the olive tree of Arabia (Gooch 2002).

Mediterranean civilizations mixed carbon with cedar resin for making paint (Gooch 2002).

Birch bark pitch was found to be used by ancient native people to produce a glue used to make a hardening glue between the stone head and wooden shaft of the tool (Oblaender 2023). A 50,000 year old artifact was found in a German mine in 1963, revealing the finger print of a Neanderthal person who made the tool (Oblaender 2023).

Copaiba is obtained from the trunk of several South American leguminous trees (gebus Copaifera). It exudes a thick, transparent oleoresin which can vary in color from dark brown to light gold (Mantel 1950).

Leguminous trees, such as gebus Copaifera, are medicinally important trees as a result of their anti-fungal, anti-bacterial, and anti-microbial properties which is due to either flavonoids, terpenoids, quinones or xanthones being present in the saps of the tree (Khan 2017)

Benzoin is a balsam resin extracted from the bark of a tree from the genus Styrax (Mantel 1950). Growing in forests of Sumatra and Indonesia, it makes an aromatic incense used in Orthodox Christian churches and Hindu and Japanese temples.

Sandarac, a gum or resin from the cypress, or alerce tree, was often combined in recipes with linseed oil, as Cennino Cennini describes (Rene de la Rie 1989). Sandarac was also used in inks to write European and African 15th century treaties (Gooch 2002).

Northwest Coast Tribes have used fish oil mainly in food preservation and in some cases as binders. Steelhead oil was used as a preservative and binder in paint by the Yakima tribe (Beaverton 2017). Fish from the ocean was thought to have a high oil content (Beaverton 2017). Although herring eggs and salmon egg are found to be plentiful to coastal tribes, fish eggs were used specifically, knowing that it would darken the paint (Ancheta 2019). In some cases, red and black paints were mixed with salmon eggs in Northwest Coast painting (McLennan and Duffek 2000).

“On the westfork of the Kitlobe river, the river that flows into Gardners Canal from near Kimsquit river, is a clearing about five acres in area where the Indians long ago burned rock to make paint, the trees having been burned in the process. The paint was mixed with salmon eggs. -Harlan I. Smith's notes on conversation with Bert Robson, Nuxalk, 22 July 1921 (McLennan and Duffek 2000).”

Drying oils containing fish oil binders were known to be used in the late 1800’s, often times mixed with linseed oil (McLennan and Duffek 2000). Some Northwest Coast tribes used a traditional mineral-based paint consisting of gypsum, quartz, silicate, calcite and kaolin fillers oil (McLennan and Duffek 2000). These were ground with stone mortars and pestles and added to pigments. Paints which are mixed with a fatty lipid binder are made denser, non-translucent and rendering a shinier surface than water based binders (Ancheta 2019; Taft and Mayer 2000).

Menhaden (Brevoortia sp.) fish oil was used by east coast natives close to the Atlantic sea and reportedly instructed the pilgrims to put it on their crops as fertilizer (Franklin 2007). In 18th and 19th century paintings, Menhaden fish oil was found in historic paintings by Franz Kline and Barnett Newman (La Nasa et al. 2021). Referenced in an 1823 encyclopedia, a paint recipe with Menhaden fish oil combines with a 1:60, one part linseed oil to sixty parts menhaden oil ratio (La Nasa et al. 2021). Fish oils often times are mixed with a small amount of vegetable oil to avoid tackiness where the surface of the paint film remains tacky after the initial drying time (La Nasa et al. 2021).

 
  • Written and researched by Theodora Jonsson-Macrae

    1. Introduction

    Across the world and through centuries, different paint mediums have been developed that serve as the invisible components holding the pigments in paints, dyes, inks and varnishes.

    Ancient paint mediums, although critical to application and preservation of paint, have not been studied to the same degree as the pigments within the paint. A paint medium is comprised of a binder and a carrier, which directly affect the application and preservation of the paint. They are the primary focus of this paper, however, some pigments, dyes, varnishes, thinners, and inks are mentioned when they help explain the history, function, or chemistry of the medium. Binders and carriers in the medium are closely related and sometimes overlap. (See Table 7. List of Binders and Carriers found in Historic Paints).

    This paper and associated literature review will address the following questions:

    1. What ingredients have been used to create long lasting and vibrant paints by artists living in literate societies, ancient to the present?

    2. How do these ingredients function in the paint?

    3. Which ingredients are found in nature and which are industrially produced or human-made?

    Since ancient times, paints were highly valued and important to the cultural identity of the people who used them (Barnett et al. 2006). Communication, adornment and decoration have led to the evolution of paint recipes throughout history (Barnett et al. 2006).

    Ancient paints were produced using binders such as egg, milk, glue or plant saps which were combined with mineral pigments, ashes, charcoal, and other substances to create different colors of paint (Gooch 2002). In a dynamic process, artists and their apprentices made paint according to recorded mixtures and recipes, but also altered them to their artistic preferences and what materials were available. Paint was made by hand prior to the invention of disposable paint tubes in 1884 (Barnett et al. 2006).

    Binders in paintings originated as naturally occurring adhesives from animal skin found in Egyptian, Chinese, and Japanese paintings (Newman 2013). Varieties of paint media used in binders and carriers affect how the paint behaves, flows, dries, and how thick or thin it is (Taft and Mayer 2000). Knowledge of paint media is essential in understanding ancient painting and material technologies.

    Later oil-based paints and plant gums were popular for illuminators and painters in Renaissance Europe, providing a greater optical effect than egg tempera (Kroustallis 2011). Traditional egg tempera combines pigments with water (the dilutant) and adds egg yolk or egg white as a binder (Levy et al. 2018). During the 15th century and Renaissance period, tempera grassa and other oil and egg recipes were introduced, as well as the use of siccative oils in binders to accelerate the drying time of paint (Levy et al. 2018).

    In the field of art and historic manuscript conservation, scientists have developed analytical tools to determine how to preserve or restore ancient and historic painted works of art. These analysis techniques were initially developed through the science of medicine or industry and have been successfully used for the analysis of paint ingredients (Osada et al. 2001). Determining the ingredients in paints, dyes and inks through various analysis techniques has been important in the conservation of works of art. This research often looks at stratigraphic layers and the micro-topography of painted and scripted artworks found in wall frescoes, painted ceramics and manuscripts from South America, Europe, the Middle East, Japan, China and India.

    The use and application of these technologies in art history has evolved over the years leading to greater clarity in determining the manufacturing process and structure of specific paintings, while bringing insights into the perishability of artwork due to different ingredients and binders.

    Another important purpose is separating the work of the original artist from subsequent repainting activities (Gent et al. 2015; Rene de la Rie 1989). Scientific analysis is critical to differentiate between original ingredients, undocumented restorations, and known historic changes in paint technologies (for example, the transition from egg tempura to oil paint during the Renaissance) (Casadio et al. 2001; Ioele et al. 2017; Magrini 2013).

    I briefly describe some of the analytical tools used to identify different types of binders in paints in the third portion of this paper, and the analyses I found during my literature review. This section is broken down into the following classifications: (1) hyperspectral Imaging, (2) spectral imaging, (3) mass spectrometry and gas chromatography, (4) immune response analysis (5) chemical tests, (6) nuclear analyses, and (7) genetic analyses.

    I reviewed over seventy publications, looking at worldwide cultural uses of organic materials as binders and carriers in recipes for paints. The published binders and carriers include materials derived from lipids (including animal and deer fat), lichen (Roquero 2008), honey, tree gum, plant gum (Granzotto et al. 2019), gums from the fruits of trees (Taft and Mayer 2000), resin, turpentine, beeswax, casein (including egg, milk, and cheese), urine (Kriss et al. 2018), animal skin, animal hooves, fish glue (Yu 2019), and insects such as aphids (Nabil 2018), beetles and the Kermes insect (Nabil 2018; Tripković et al. 2012; Vandenabeele et al. 1999).

    At the conclusion of this paper is a table that lists over 100 specific ingredients found in the literature review, including binders and additives used in various regions of the world, and how they function in paints, dyes and inks, textiles, and history. The information is based on the writings of literate peoples in ancient societies, including Maya, Aztec, Inca, Japanese, Persian, Indian, and European cultures. Research reveals a wide range of binders and carriers and how they function in diverse recipes throughout history, as well as how complex the correspondence was between cultural processes and technologies involving ceremonies, food, textiles, and painting, all of which are part of the evolution of complicated pigment binding techniques (Mandana 2016).

    1.1 Components of Paint

    Paint is comprised of three basic components: the pigment, binder and carrier (Newman 2013). The pigment is made from an organic or inorganic powder and is spread out in a liquid, the binder and/or carrier, which causes the powdered particles to cling to each other and to the surface of the painting (Newman 2013). The pigment contains the color and must be ground evenly to be dispersed homogeneously throughout the paint carrier (Barnett et al. 2006).

    The second component, the binder, can be made of natural ingredients such as egg, gum, resin, glue, or a synthetic such as an alkyd resin, acrylic polymer or vinyl (Taft and Mayer 2000). Binders are a substance which hold elements of the paint mixture together as a consistent, cohesive compound. Binders can be classified by three major categories of origin: plant, animal and mineral. This paper explains some important historic examples within each of the major categories.

    A third element which is sometimes necessary is a carrier or dilutant which is competent with the binder (Gooch 2002). For instance, turpentine dilutes oils, and water dissipates gum, egg and acrylic (Gooch 2002). Carriers can be interchangeable with binders and both be made of gum turpentine, diluted resin, oils, and synthetic alkyd or acrylic polymer.

    Carriers and binders are “invisible” liquid components of paint. Binders are responsible for the quality, temperament and nature of the paint, but typically not the color (Taft and Mayer 2000). Water, oil, turpentine, varnish and lacquer are all different carriers which affect the fluidity of a paint mixture. Carriers dissipate and transport the pigment and the binder. Carriers, sometimes referred to as “vehicles” are not always necessary; some paint recipes are made up solely of pigment and binder.

    Carriers must be discussed with binders because the two work in tandem and sometimes interchangeably depending on other ingredients, concentrations and processing. For example, a larger amount of turpentine might turn a gum from a binder into a carrier. The carrier determines whether a paint mixture moves fast or slow, is fluid or stiff, waxy or glossy, fast drying or slow drying, lasting or fading (Taft and Mayer 2000).

    1.2 Historic Relationship between Paints, Dyes, and Inks

    Civilizations made synthetic paint since ancient times. In the eighth century CE., Theophilus wrote about the earliest syntheses of artificial pigments and the preparation process (Gooch 2002). The first man-made polymers made into lacquers became available as paint binders in the middle of the 19th c. (Gooch 2002). Prior to this, recipes of sumac sap and shellac in ethanol were used for centuries (Gooch 2002).

    Over centuries, paint mediums evolved alongside dye and textile recipes as artisans, and artisan guilds from the far East Indies, Middle East and Africa migrated for the purposes of trade and commerce in the textile industry (Hanna 2015). It was this mass relocation of artisans along trade routes which was responsible for making available the resources which led textile commerce during the industrial revolution of the 1900’s (Hanna 2015).

    Dyes are responsible for the coloring of textiles, fabrics, paper, leather, and many trade goods. Traditional dyes are made from plants and minerals found in nature. Dyes and inks have been important throughout history as processes that involve extracting pigments and binders from nature and creating human-made substitutions which have influenced the evolution and uses of one another over time and culture (Barnett 2005).

    Black iron gall ink, the most significant ink to Western history, was used in Roman times as well as the Middle Ages (Hahn et all 2004). Iron gall ink was used extensively by early European and Middle Eastern scribes making illuminated manuscripts, and used the same binders as paint, i.e. glue and egg, as a binder (Darzi 2021).

    Today, there are many modern synthetic, cheaper substitutes in binders and paint.

    Oleoresin paints were produced in large scale in colonial North America (Gooch 2002). Linseed oil made up ninety percent of the market in 1900 (Gooch 2002). Linseed oil accounted for fifty percent of the drying oil binder/carrier found in paints, printmaking ink and industry until the 1950’s and is increasingly substituted for fish oil, tung oil, soybean oil, dehydrated castor oil, and oiticica oil (Gooch 2002). Oleoresins were the main binder/carrier until the 1920’s when synthetic polymers replaced many of their functions (Gooch 2002).

    2. Paint Mediums: Past to Present

    (See Table 7. List of Binders and Carriers found in Historic Paints)

    2.1 Plant Based Mediums

    Binders extracted or made from plants come from a variety of organic substances including gum, resin, sap, lacquer, lignin, mastic, starch paste, wax, and oils (Gooch 2002).

    A better understanding of the difference between gums and resins informs various binders. Resin and some gums come mainly from pine or evergreen trees in the Pinaceae family (Dietemann et al 2019). Gums also come from many varieties of other plants (Newman 2013). Resins, gums and saps have seemingly similar characteristics, but when looked at more closely reveal their differences in function and property (Sadowski 2020). Generally, resins are expelled from the bark of a tree, and are soluble in ethers, alcohol and other solvents and insoluble in water (Sadowski 2020).

    Gums are usually expelled from the stems or branches of a tree or plant and are soluble in water (Taft and Mayer 2000). Paint mixtures made with gums are often resistant to mold and fungal growth over time due to the properties of gum as a fungal inhibitor (Sadowski 2020).

    Distinctions can also be made between gum-resin, sap and resinoids. Gum-resins, such as frankincense and myrrh, have been obtained for millennia by tapping into particular trees to express combinations of gum and resin (Sadowski 2020).

    2.1.1 Gum

    Gums are formed by the decomposition of tissues inside a plant. They are polysaccharides which can swell in water to form a gel (Osada 2001). Gums may exude from stems or branches, bringing an anti-fungal ingredient to a damaged part of the plant’s extremities (Sadowski 2020; Vandenabeele et al. 1999).

    Gums include gum acacia, gum tragacanth, milkvetch and Indian tragacanth (Sadowski 2020). Gum arabic, gum tragacanth and cherry gum are most commonly used in painting (Osada 2001; Vandenabeele et al. 1999). Tragacanth gum cannot be dissolved in water but can be mixed with a small amount of water, where it becomes a viscous gel which can be painted on fabrics or made into pastel crayons (Kroustallis 2011). Commonly found gums in the archaeological field include: gum arabic, cherry gum, locust bean and tragacanth gum (Granzotto 2019).

    Typically used in the food industry as an emulsifier and thickener, gum arabic has also been used as a binder for watercolor paints since the 18th century (Taft and Mayer 2000). It is found in ancient Egypt in the 3rd millennium BCE (Taft and Mayer 2000).

    Fruit gums come from the fruit-bearing trees of species such as pear, peach, plum, apricot, and almond (Taft and Mayer 2000). Fruit gums were used as binders for watercolor paints for a thousand years or more and were also added to milk (casein) and egg recipes to increase glossiness (Vandenabeele et al. 1999).

    Gum of ramie was thought to have been employed as a binder to hold pigment particles together in Chinese painting and in mummy painting in Egypt during 5000-3000 BCE (Jin et al. 2012). Ramie is a flowering plant related to the nettle which served as a main fiber crop for many centuries in Chinese Qin (230-563 BCE) and Han (202-220 CE) Dynasties (Jin et al. 2012). The manufacturing of ramie gum poses an interesting problem as ramie fibers contain 20-30% gum containing pectin and hemicellulose. As described in Chinese literature, a waterlogging technique was implemented possibly as one of the first degumming methods used. (Jin et al. 2012).

    In the original sketch of Raphael’s School of Athena, tragacanth gum (from the astragalus plant), was found, along with fatty soaps (Ioele et al. 2016). It is speculated that the white drawing was made with a white oil stick or crayon composed of tragacanth gum, lead white, and fixed with a fatty ingredient such as wax (Ioele et al. 2016).

    Sandarac, a gum or resin from the cypress, or alerce tree, was often combined in recipes with linseed oil, as Cennino Cennini describes (Rene de la Rie 1989). Sandarac was also used in inks to write European and African 15th century treaties (Gooch 2002).

    2.1.2 Resin

    Resin is a tacky liquid excretion caused by the oxidation of oil extruded by tree bark, primarily from the Pinaceae family, and is soluble in solvents like alcohol or ethers largely because it is made up by a large amount of natural solvents (Taft and Mayer 2000). Resin resides in the resin ducts of tree bark and protects the tree from insects, microbial pathogens and damage (Sadowski 2020). Similar to making charcoal, the early process for expelling oleoresin was to heat wood in a stone furnace and let the heat of the wood expel the pitch (Gooch 2002).

    Resins create a glossy sheen on the surface of the paint, increasing the reflectivity of light which enhances the colors, making the paint appear deeper and more intense (Taft and Mayer 2000). It is for this reason that resins are used as carriers in glazes, a thin, often translucent layer of paint, built up to create an illusion of depth within the paint. Types of resins include oleoresins, gum resins and hard resins (Sadowski 2020; Taft and Mayer 2000).

    Oleoresins are part liquid, part solid, extracts of resin and essential oils and most are obtained by distilling spices from seeds. Oleoresins include turpentine, balsam, elemi, copaiba, and benzoin (Sadowski 2020).

    Copaiba is obtained from the trunk of several South American leguminous trees (gebus Copaifera). It exudes a thick, transparent oleoresin which can vary in color from dark brown to light gold (Mantel 1950).

    Benzoin is a balsam resin extracted from the bark of a tree from the genus Styrax (Mantel 1950). Growing in forests of Sumatra and Indonesia, it makes an aromatic incense used in Orthodox Christian churches and Hindu and Japanese temples.

    Benzoin is referred to both as a gum and a resin in binding recipes for varnish (Sadowski 2020).

    Resinoids are made by expelling resin from a resinous plant using a solvent. This has been practiced for thousands of years (Gooch 2012). In Egyptian era, Chios turpentine and pine resin were the commonly used resin in waterproof glues and varnishes in paintings (Taft and Mayer 2000).

    Copal refers to a large group of resins classified by their hardness and melting temperature (Mantel 1950). Copals are found in East and West Africa, South American tropics and Mexico (Mantel 1950). Originally named after a region of Mexico, it refers to a type of hard resin which is combined with drying oils and considered an oil varnish or amber resin (Mantel 1950). In the nineteenth century, copals, mastic and damar varnishes became popular (Taft and Mayer 2000).

    Subfossil copal, which is found three to nine feet below living copal trees, and also can be found from roots of trees that lived thousands of years earlier (Gigliarelli 2015).

    Copal is a resinous substances in a middle stage of polymerization and hardening between gum resin and amber (Gigliarelli 2015).

    Mediterranean civilizations mixed carbon with cedar resin for making paint (Gooch 2002).

    Birch bark pitch was found to be used by ancient native people to produce a glue used to make a hardening glue between the stone head and wooden shaft of the tool (Oblaender 2023). A 50,000 year old artifact was found in a German mine in 1963, revealing the finger print of a Neanderthal person who made the tool (Oblaender 2023). Chemical analysis showed that the glue was something made, not a natural substance such as pure pitch.

    The process of making such a glue is complicated and reflects the intelligence behind these prehistoric people’s techniques. The recipe involves heating birch bark to 750 degrees fahrenheit in order for the pitch to be released from the bark, which is complicated as birch bark ignites at far lower temperatures and burns up (Oblaender 2023). Oblaender interviews two scientists who attempted to replicate the process used by these ancient peoples. They used two large bird eggs with cracked openings in the top. The egg with a much larger opening is buried in the dirt below to collect the pitch that will eventually drain into it. The egg with the smaller opening, containing the birch bark, is placed on top of the bottom egg and mud is used to seal the two containers together so that oxygen cannot ignite the bark from within (Oblaender 2023). Hot coals are put around the sealed eggs and after 30 minutes an oily pitch is produced.

    2.1.3 Turpentine

    Turpentine is distilled from the exudates of pine and other species of conifer trees and is referred to as gum turpentine, spirits, or turps, coming from the Greek word for resin.

    Two primary types of turps are Venice and Strasbourg turpentine.

    Venice turpentine, derived from European larch trees, is commonly used as a paint varnish because of its resinous acids and terpenes (naturally occurring plant compounds) and, unfortunately, it causes the painting to darken with age (Taft and Mayer 2000). Sandarac, amber, and Venice turpentine, used in early Middle Ages treatises, were commonplace in that era of painting (Taft and Mayer 2000).

    Strasbourg turpentine comes specifically from a conifer, which grows in The Vosges Mountains, in France, and was used since the 16th century as a varnish, in oil and tempera paint (Vandenabeele et al. 1999).

    2.1.4 Balsam

    Balsam is a resinous sap or exudate from particular trees and shrubs (Van der Werf et al. 2000). Named after the gum of the balsam tree from Biblical times, balsam is comprised of a solution of plant resin in plant solvents, including essential oils, and can include resin esters and alcohols (Vandenabeele et al. 1999).

    Throughout different eras of antiquity, and during medieval and Egyptian time in Europe and the Middle East, balsam was derived from a specific Egyptian plant (Vandenabeele et al. 1999; Van der Werf et al. 2000).

    In the early 1700’s, balsam was used in a variety of varnish recipes, mainly for glazes, by British painter Sir Joshua Reynolds (Van der Werf et al. 2000). Balsam paint media was common in the beginning of the 19th century in Germany and according to literature, was often mixed in recipes with wax (Van der Werf et al. Et al. 2000).

    2.1.5 Elemi / Frankincense

    Elemi refers to a variety of resins, which came from different species of the Burseraceae family of trees, especially Boswellia, a tree, which also produces frankincense (Gooch 2002).

    Elemi was used worldwide, in cultures from Ancient Rome to Brazil as a spirit varnish, in addition to various resins like copal. Manila elemi is the most well-known and was originally from the Philippines (Mantel 1950). During the 17th and 18th centuries, elemi came from the resin from trees of the Icica family in Brazil (Gooch 2002).

    Frankincense, extracted from the yegaar tree, originated in Somalia where it is called Maydi, meaning king of all frankincense (Mantel 1950; Gooch 2002).

    The name Elemi comes from an Arabic saying meaning “above and below,” and refers to its function as a spiritual and emotional reference and in ceremonies documented worldwide (Mantel 1950). In ancient Roman times, animi or enhaemon were terms used for Elemi (Gooch 2002).

    Pliny said elemi contained tears extracted from the olive tree of Arabia (Gooch 2002).

    2.1.6 Copaiba

    Copaiba is a balsam extracted from various species of Copaifera trees, which grow in South America and Africa (Mantel 1950). It was a common additive in European paint recipes from the beginning of the 19th century (Van der Werf et al. 2000).

    Copaiba was a popular paint binder used by artists circa 1884-85 (Van der Werf et al. 2000). Copaiba balsam was used as a medium in paint in order to extend drying time and to obtain a wide range of results (Van der Werf et al. 2000). Examples include Van Gogh’s paintings where this binder was used to achieve an impasto affect with more saturation and deepening of colors, but without cracks or wrinkling from drying (Van der Werf et al. 2000).

    Sir Joshua Reynolds (1723-92) made medium and varnish recipes for glazes from copaiba balsam (Van der Werf et al. 2000). It was also a predominant ingredient in a German paint company's Roberson’s zinc white recipe, as well as a painter’s medium of linseed oil mixed with copaiba balsam sold by the Dutch company Talens (Vandenabeele et al. 1999).

    2.1.7 Sap (also see lacquer)

    Saps extracted from plants and trees contain starches and sugars (Sadowski 2020). Lacquer from Asia contains saps of a variety of trees containing alcohol and polysaccharides and glycoproteins (Newman 2013). It is important to note that gum and resin are not the same as sap. Sap provides water and nutrients by the process of transpiration as it passes through the veins, or phloem, of a tree (Sadowski 2020).

    Saps from trees can be used for many purposes in paint mixtures as well as in sealing wood and other materials (Gooch 2002). Sap increases the tackiness of paint mixtures, affecting drying times (Gooch 2002).

    2.1.8 Varnish

    Natural resins are the material primarily used for varnishing (Vandenabeele et al 1999). Varnishes can be classified in two groups: oil resin varnishes, which contain a mixture of resin combined with a drying mixture and secondly, spirit varnishes, also known as essential oil varnishes (Vandenabeele et al 1999).

    Spirit varnishes were introduced in 16th century Italy, replacing oil varnishes (Rene 1989). They were solutions of a natural resin mixed with a volatile solvent such as oil of turpentine (Rene 1989).

    Beginning in the 11th century in Europe, oil varnish was prepared by boiling linseed oil and dissolved resin together (Rene 1989). By the 13th century in France, a common carrier for varnishes and paints was the oleoresin from conifers (Gooch 2002). Throughout the Renaissance, artists Rembrandt (1606-1669) and Leonardo da Vinci (1452-1519) created their own paints by combining pigments with binders such as resin, sandarac and linseed oil (Gooch 2002).

    There are 500 species of conifers that express oleoresin, also termed gum (Gooch 2002). This type of oleoresin dries by oxidizing in a moist environment (Gooch 2002). Throughout the Ming Dynasty, 1362-1644 CE, high gloss paints and varnishes were made with this resin by combining it with pigment and applying as many as 250 layers of resin (Gooch 2002).

    Japanese varnish recipes combined benzoin with sandarac, mastic, copal, rosin and Venice turpentine (Ballardie 2000). The varnish was combined with isinglass fish glue to make white sizing, a material applied to prepare a paint canvas, in the 16th and 17th century (Ballardie 2000).

    The Maya carbonized resin from a tree called the chacak tree. They also combined resin with juice from the chichebe plant mixed with lime juice to create a white paint, red paint from shavings of heartwood, blue pigments from aniline materials, and yellow from achiote fruit (Gooch 2002).

    Amber is a fossil resin produced from specific trees (Gooch 2002). Over millions of years, pressure and temperature transform the resin through fossilization (Gooch 2002). Amber varnish, made from amber resin, has been used since ancient times (Drzewicz 2016).

    2.1.9 Lacquer

    Lacquer was produced from both plants and insects, also discussed below under animal binders.

    Lacquer was developed in ancient India and Asia as a high gloss, very hard finish varnish (Ballardie 2000). Lacquer was made from a variety of plant origins (Ballardie 2000). The sap from the Chinese lacquer tree, Japanese sumac (the Varnish Tree) was treated and dyed to seal many different types of artisan objects, including wood, shell, and metal (Ballardie 2000).

    A variety of lacquers were common in Japan, China and Egypt (Newman 2013). Lacquer made of sap from the sumac or conifer tree originated as early as 3000 years ago, during the Zhou Dynasty period in China (Newman 2013). Paints and lacquers from this sap are expected to last thousands of years (Gooch 2002).

    The Japanese sumac, or Japanese wax tree, from the poison ivy family, contains urushiol, a toxic oil, referred to as urushi in Japanese, which is also the name for the traditional method for making lacquerware from this specific Asian tree (Ballardie 2000; Gooch 2002). The process was referred to as "Japanning" in paint recipes (Ballardie 2000).

    Ancient Chinese lacquer was also added to black carbon to make the paint primarily used for writing on bamboo strips during the 2nd century BCE (Gooch 2002). By the 2nd century, it was also used on pottery, on buildings and musical instruments (Gooch 2002).

    2.1.10 Mastic

    Mastic, a resin from the Mediterranean tree-bush Pistacia lentiscus was known in Greece as the tears of Chios and has been harvested for approximately 2,500 years (Paraschos et al. 2012).

    Since the 16th c., mastic has primarily been used as a varnish (Vandenabeele et al. 2000). It was also mixed in small amounts as a binding additive in paint recipes like tempera. Mastic can be used to make a drying varnish when mixed with drying oils and a solvent, or a spirit varnish when mixed with volatile solvents without an oil (Vandenabeele et al. 2000). In the Book of Art by Cennino Cennini, a French recipe combines mastic, saponified wax and fish glue to make the paint especially glossy (Herringham 2018). In Midieval Europe, Cennini describes mastic varnish as providing a nice gloss but not a lot of durability (Herringham 2018).

    Oil varnishes using mastic were gradually phased out by spirit varnishes in 16th c. Italian painting, employing resins dissolved in spirits, usually in a turpentine solution (Rene de la Rie 1989). Today, mastic is less commmonly used due to its tendency to yellow (Rene de la Rie 1989).

    2.1.11 Plant based oil

    Major plant oils used in a variety of paint media include coconut butter, safflower, sunflower, walnut, and poppyseed oils (Taft and Mayer 2000).

    The most commonly used drying oils in painting have been linseed, walnut, poppyseed and flax seed oil (Taft and Mayer 2000). These oils dry at different speeds. Linseed oil and flaxseed oil are both cold-pressed from the flax plant (Vandenabeele et al. 2000).

    According to Gooch 2002, drying oils react with oxygen in the air to create a solid gel, which also creates an oxidizing film on the surface of the paint (Gooch 2002). These include: soybean, castor, safflower, and tung (china wood) oils, fish oils, and tall oil (from pine trees) (Gooch 2002).

    Drying oils, when combined with resins to make varnish, are considered fast drying oils (Vandenabeele et al. 2000).

    Since medieval Europe, oils such as linseed were used in paint mixtures, introducing a new form of paint, which, during the Renaissance, took precedence over the prior egg tempera (Taft and Mayer 2000). Oil painting was popularized in the Netherlands in the early 15th c. (Taft and Mayer 2000).

    In the 16th century varnishes and driers were introduced to paint mixtures (Gooch 2002). “Driers” is a term for faster drying oils and resins, which were used to increase or decrease the curing time of paint (Vandenabeele 1999). These had been known and documented in the 2nd century but not used widely until much later, and by the mid 17th century, driers were used in many paint mixtures (Gooch 2002). Common drying oils include linseed, walnut, sunflower and poppyseed (Vandenabeele 1999). The most commonly used drying oil medium was linseed oil, originating from the flax seed, it tends to yellow over time but dries faster than the other oils (Vandenabeele 1999). Walnut oil, one of my favorite oil carriers to mix my paint mediums, dries more slowly than linseed oil and allows more duration when working on a painting.

    In the 11th c., Theophilus described making oil varnishes by boiling natural resins such as gum mastic, sandarac, or rosin with drying oils such as walnut or linseed oil (Rene de la Rie 1989). In Il Libro dell' Arte, from 1390, Cennini often mentioned the “vernice liquida” (liquid paint), in, which recipes are described with mixtures of sandarac and linseed oil (Rene de la Rie 1989).

    Evidence also shows that oil painting medium was in use as early as the 12th c. (Taft and Mayer 2000). The use of resins and drying oils as varnish were known as far back as the 8th c. (Vandenabeele et al. 1999).

    Walnut oil comes from the English walnut and is comprised of acids including stearic and linolenic acids (Vandenabeele et al. 2000). Walnut oil was used in combination with resins for varnish in the 5th c. (Vandenabeele et al. 2000). Much later, during the Renaissance, walnut oil was favored by Leonardo da Vinci as a binder in light paint pigments (Vandenabeele et al. 2000).

    Poppyseed oil, from the opium poppy, is a slow drying oil, which has been used since the 7th c. and is considered a high-quality oil medium in painting although it tends to yellow (Vandenabeele et al. 2000).

    In the end of the 18th c., a recipe leading to commercial paint recipes combined heated gum elemi and poppy oil as the binding medium (Ballardie 2000).

    Since the twentieth century, sunflower oil has been used as another slow drying medium in painting. It comes from the macerated seeds of the sunflower plant and is a common additive in oil varnish used with resins (Taft and Mayer 2000; Vandenabeele 1999).

    2.1.12 Starch paste

    Starch is harvested from a variety of plants such as potato, corn and rice. Each plant produces starch with different characteristics (Taft and Mayer 2000).

    In Asia, starch was predominantly used historically as a glue or binder for paint pigments applied to large wall paintings (Yu 2019).

    Starch paste was traditionally made from wheat, dating back to the 15th and 16th centuries in Japan (Taft and Mayer 2000). Japanese woodblocks, known as ukiyo-e prints, were created during the 18th to 19th centuries (Biron et al. 2020). Ukiyo-e were made with traditional pigments and binders made from water and rice starch glue (Biron et al. 2020).

    It was the “gluten makers” or “Fuya” who made dumplings to sell for food who additionally made starch paste for artists in Kyoto, Japan (Willis 2013).

    Pre-Hispanic books, referred to as The Codices, are intact books documenting the culture and paint materials used by the native people (Miliani et al. 2012). After the Spanish genocidal takeover of the native people, the natives were forced to make detailed narratives about the events and their own culture (Miliani et al. 2012). Discovered in paintings made within these codices, starch was found as evidence of a corn or maize based binder (Miliani et al. 2012).

    2.1.13 Carbohydrate binders

    Carbohydrates in plants, known as simple sugars, were used in paint binders and found in sugars, orchid and flower juices, and plant gums (Taft and Mayer 2000). Cellulose, the basic building block, is the primary molecule in plants. Carbohydrates are the primary component in corn and wheat-based starch binders. (Taft and Mayer 2000).

    Soluble in water, simple sugars create a very sticky solution, which binds easily with pigments and has been used since antiquity as a paint binder, although it is not long lasting (Taft and Mayer 2000).

    Mixteca-Puebla artistic iconographic style and codices were prevalent in Mesoamerican regions of central Mexico (Garcia 2017). It is consistently mentioned that an orchid gum binder was used for the carrier in many of these paints (Garcia 2017). The results reveal the sophistication required in gesso, paint and binder recipes by the artists in making multi layers of the painting to achieve such color saturation and intensity (Garcia 2017). Tzacuhtli, a glue binder made from a variety of orchid plants, and often seen in glue recipes, can be combined with ground maize (Miliani et al. 2011).

    2.1.14 Lignin

    Lignin is a material found in the tissues of most plants (Song et al. 2020). Lignin forms in the plant cell walls similarly to carbohydrates but is not the same (Song et al. 2020). Chemically it is an organic polymer and is considered to be an eco-friendly binder in commercial paint materials (Song et al. 2020). It is comprised of the secondary cellular walls of plants, wood and bark, and is a biopolymer accountable for the mechanical properties and strength of these tissues (Song et al. 2020). Currently, lignin is being incorporated as a carrier into modern paints, inks, and varnishes in order to affect viscosity (Naceur Belgacem et al. 2003).

    2.2 Animal Based Binders

    Binding mediums in paint made from animal-based materials were most frequently used in tempera painting (Gooch 2002). Examples include albumin, casein, and animal glues (Young Lee et al. 2015).

    Tempera has been used in combination with other paint media due to its lack of fluidity yet durable, brittle surface (Taft and Mayer 2000). Large scale fresco paintings perfected by the Cretan and Etruscan peoples (A.D 40-90) of Ancient Greece utilized glues and albumin as binders in tempera painting (Gooch 2002). Paint bound by glue, gum, or egg binders dry through the evaporation of water, in which they are dissolved (Taft and Mayer 2000).

    2.2.1 Fats (lipids)

    Lipids can come from plant or animal origins (Taft and Mayer 2000). (see plant lipids above).

    From an analytical viewpoint, fats and oils fall into the lipid category (Meriam-Webster’s Dictionary 2021). They are generally very slow drying and create a solid over time, when exposed to air (Taft and Mayer 2000).

    Major oils used as binders from animals include animal fat, collagen (animal bone and skin), glue, fish oil, casein (milk), bone marrow and albumin (egg) (Gooch 2002). Albumin is a water-soluable protein found in egg and blood (Meriam-Webster’s Dictionary 2021).

    Protein binders in paint, exhibiting an array of durability, consisted of egg yolk and white, milk in quark cheese and casein powder, different collagens from rabbit, bovine, porcine and sturgeon (Tripkovic et al. 2013). Bovine bone glue, hide glue, rabbit skin glue, isinglass from fish bladders, and gelatin from pig skin were all used in paint recipes (Tripkovic et al. 2013).

    Protein binders were the most common type of painting medium before siccative oils became the primary paint medium in the fifteenth century (Tripkovic et al. 2013). Oil binders in paint replaced water based egg tempera paint as the primary medium in art during the 15th c.. Protein binders remained the primary binders utilized in panel painting and illuminated manuscripts in the Byzantine world of South East Europe and are still used in Russian and Greek Orthodox iconic paintings (Tripkovic et al. 2013).

    13th c. altar paintings in Norway are very early examples of the use of oil paint as they were painted with drying oil such as linseed oil and egg yolk (Taft and Mayer 2000).

    2.2.2 Egg and Fish Oil

    Egg has been a predominant binder in paint medium since ancient times. Egg glair, produced from egg whites which are allowed to sit overnight, is used in a type of tempera painting, which requires transparent glazing (Tripkovic et al. 2013). Albumin is the white, water-soluable protein found in egg and is the binding element in egg-based paints (Tripkovic et al. 2013; Meriam-Webster’s Dictionary 2021).

    Throughout the Middle Ages, glair and gum arabic were the primary binders for inks and paint used by Early European and Middle East scribes making illuminated manuscripts (Kroustallis 2011; Newman 2013). Later, oil-based paints and plant gums were popular for scribes known as “illuminators” and painters in Renaissance Europe because they provided a greater optical affect than egg tempera (Newman 2013).

    Northwest coast and eastern tribes have used fish oil mainly in food preservation and in some cases as binders. Steelhead oil was used as a preservative and binder in paint by the Yakima tribe (Beaverton 2017). Fish from the ocean was thought to have a high oil content (Beaverton 2017). Although herring eggs and salmon egg are found to be plentiful to coastal tribes, fish eggs were used specifically, knowing that it would darken the paint (Ancheta 2019). In some cases, red and black paints were mixed with salmon eggs in Northwest Coast painting (McLennan and Duffek 2000).

    “On the westfork of the Kitlobe river, the river that flows into Gardners Canal from near Kimsquit river, is a clearing about five acres in area where the Indians long ago burned rock to make paint, the trees having been burned in the process. The paint was mixed with salmon eggs. -Harlan I. Smith's notes on conversation with Bert Robson, Nuxalk, 22 July 1921 (McLennan and Duffek 2000).”

    Whale, walrus and seal oil known to be a long-lasting preservative for food and it is thought that it may have been used as a paint extender along with bear or deer fat possibly by Northwest Coastal communities (Miller 2000: La Nasa 2021).

    Drying oils containing fish oil binders were known to be used in the late 1800’s, often times mixed with linseed oil (McLennan and Duffek 2000). Paints which are mixed with a fatty lipid binder are made denser, non-translucent and rendering a shinier surface than water based binders (Ancheta 2019; Taft and Mayer 2000).

    Menhaden (Brevoortia sp.) fish oil was used by east coast natives close to the Atlantic sea and reportedly instructed the pilgrims to put it on their crops as fertilizer (Franklin 2007). In 18th and 19th century paintings, Menhaden fish oil was found in historic paintings by Franz Kline and Barnett Newman (La Nasa et al. 2021). Referenced in an 1823 encyclopedia, a paint recipe with Menhaden fish oil combines with a 1:60, one part linseed oil to sixty parts menhaden oil ratio (La Nasa et al. 2021). Fish oils often times are mixed with a small amount of vegetable oil to avoid tackiness where the surface of the paint film remains tacky after the initial drying time (La Nasa et al. 2021).

    Northwest coast and eastern tribes have used fish oil mainly in food preservation and in some cases as binders. Steelhead oil was used as a preservative and binder in paint by the Yakima tribe (Beaverton 2017). Fish from the ocean was thought to have a high oil content (Beaverton 2017). Although herring eggs and salmon egg are found to be plentiful to coastal tribes, fish eggs were used specifically, knowing that it would darken the paint (Ancheta 2019). In some cases, red and black paints were mixed with salmon eggs in Northwest Coast painting (McLennan and Duffek 2000).

    “On the westfork of the Kitlobe river, the river that flows into Gardners Canal from near Kimsquit river, is a clearing about five acres in area where the Indians long ago burned rock to make paint, the trees having been burned in the process. The paint was mixed with salmon eggs. -Harlan I. Smith's notes on conversation with Bert Robson, Nuxalk, 22 July 1921 (McLennan and Duffek 2000).”

    Drying oils containing fish oil binders were known to be used in the late 1800’s, often times mixed with linseed oil (McLennan and Duffek 2000). Some Northwest Coast tribes used a traditional mineral-based paint consisting of gypsum, quartz, silicate, calcite and kaolin fillers oil (McLennan and Duffek 2000). These were ground with stone mortars and pestles and added to pigments. Paints which are mixed with a fatty lipid binder are made denser, non-translucent and rendering a shinier surface than water based binders (Ancheta 2019; Taft and Mayer 2000).

    Menhaden (Brevoortia sp.) fish oil was used by east coast natives close to the Atlantic sea and reportedly instructed the pilgrims to put it on their crops as fertilizer (Franklin 2007). In 18th and 19th century paintings, Menhaden fish oil was found in historic paintings by Franz Kline and Barnett Newman (La Nasa et al. 2021). Referenced in an 1823 encyclopedia, a paint recipe with Menhaden fish oil combines with a 1:60, one part linseed oil to sixty parts menhaden oil ratio (La Nasa et al. 2021). Fish oils often times are mixed with a small amount of vegetable oil to avoid tackiness where the surface of the paint film remains tacky after the initial drying time (La Nasa et al. 2021).

    2.2.3 Urine

    Recipes found in several Medieval treaties include human urine in the making of paint binders with ivy gum (Nabil 2018). As described in recipes dating from the 9th to late 12th century in the Mappae Clavicula manuscripts, “In the month of March, when all types of plants receive sap from the earth, pierce ivy shoots slightly with an awl or pin, and a gum liquor will emerge, which is called ‘ivy gum’, this is cooked with ..the urine of man.. and will be a sanguine colour which is called ‘lacha’ or ‘sinopel (Nabil 2018;4).

    Indian yellow is made from cows, which were fed only mangoes (Harvard Art Museum 2016).

    In 1884, a resin coating made from condensed uric acid and formaldehyde was patented (Gooch 2002).

    2.2.4 Casein (Milk)

    Casein is considered a phosphoprotein, a major ingredient in milk (Vandenabeele et al. 1999). It is heated, filtered and acidified, creating a powder, which can be made into a binding medium when dissolved in a water solution (Vandenabeele et al. 1999).

    Guache and casein are a paint media similar to tempera (Taft and Mayer 2000). Guache is made with gum Arabic mixed with casein as binders, producing a fast drying, yet brittle watercolor paint (Taft and Mayer 2000).

    Casein, functioning only as a binder, shares traits with guache and tempera but differs in that the binder made from a milk solid is very strong and not soluble in water after it dries (Taft and Mayer 2000). Artists are able to apply many layers of color and rework the painting with the final coat providing more sheen (Taft and Mayer 2000).

    Milk based binders are found in 3rd to 5th century Korean traditional Dancheong paintings dating to the Joseon dynasty. They are also found in 4th to 8th century Chinese paintings and paintings in Buddhist Grottoes (Hu 2015).

    In Europe, casein from milk binders were also found in paintings during the medieval and Renaissance periods (Calvano 2020). In sixteenth century Italy, casein along with other protein binders, was used on the angel statue and painted altarpiece of the work of art “Assumption of the Virgin” in Apulia, Italy (Calvano 2020).

    2.2.5 Animal Glue

    Traditionally glues and adhesives were created from animal gelatin or collagen by rendering or boiling down animal skin, hooves or cartlidge (Taft and Mayer 2000). Collagen is a protein molecule, which comes from the connective tissues of animals (Taft and Mayer 2000). This animal gelatin, or collagen, was then used for a variety of functions (Taft and Mayer 2000). It was used as a sealer, glue, binder and adhesive in paper and leather making and in paint recipes (Taft and Mayer 2000).

    Glues are made from skin, hooves, bone, fish and isinglass (flotation sacs of fish) (Vandenabeele et al. 1999).

    2.2.6 Lacquer from animals

    Lacquer was produced from both plants and animals, also discussed above under plant binders.

    Scale insects secrete lac, used for centuries as a source of binders and pigments (Gooch 2002). Insects used in lac include those from the genus Kermes, the cochineal insect, and various types of lac insects (Gooch 2002). Lac insects have been used for thousands of years as the source of lacquer, shellac and many varnishes used worldwide (Gooch 2002).

    Pliny, in 23-79 CE, described an early shellac recipe, which he called Indian amber (Gooch 2002). Made from lac insects, this rare resin is secreted by a coccid insect (Laccifer lacca), found in lac trees in India and Thailand. According to Pliny, “the resin was used in making lac sticks to coat rotating objects on a lathe over 3000 years ago” (Gooch 2002).

    Shellac is in fact the resin secreted by the female lac insect of Thailand and India (Nabil 2019). It is dissolved in a solvent such as alcohol and then applied as a sealer or varnish (Gooch 2002). It functions like a natural plastic (Gooch 2002). Shellac is produced in a wide variety of colors from light yellow to dark brown and orange or scarlet red (Vieira 2019).

    Colorants have been made from aphids as an alternative to scaly insects. 80 species of insects have been analyzed for their colorant properties. The ivy aphid, wormwood aphid and giant willow aphid have been the only species used successfully in place of the lac insect for making resin (Nabil 2019).

    A recipes for “Jappaning,” a Japanese lacquer, from 1688 by Stalker and Parker used isinglass, collagen from fish bladders, as the binding medium (Ballardie 2000).

    2.2.7 Beeswax

    Beeswax was most commonly used for wall paintings as a paint extender and a natural damage inhibitor because it contains natural pesticides, which inhibit insects and rodent damage (Sadowski 2020). Bees collect resin and plant sap which they bring back to the hive to make beeswax and propolis (Morrison and Vilaubi 2017). Propolis, made from beeswax, is an antibacterial adhesive made from beeswax which is a building component used in the strongest, longest lasting part of the hive’s honeycomb (Morrison and Vilaubi 2017).

    Throughout antiquity, and in Egyptian times, beeswax was combined with hot water and pigment as a binder to make paint (Gooch 2002; Taft and Mayer 2000).

    Beeswax was preferred in part because of its solubility in all types of solvents, weak and strong. The mixture produced a strong, enduring coating, which made it popular for thousands of years (Taft and Mayer 2000).

    “Encaustic” painting, meaning “burned in” in Latin, was popular during Greek and Roman eras (Newman 2000). Wax and pigment are melted together for application and could be reheated for reworking and layered applications (Newman 2000). However, heat is not essential for reworking a paint made with beeswax. The paint film remains flexible and reworkable with a variety of applications (Taft and Mayer 2000).

    During the Joseon dynasty, in the traditional Dancheong paintings from several Korean 17th century temples, it is known that the Dancheong paint binder included a variety of organic materials including beeswax (Yu 2019).

    2.2.8 Honey

    Honey was used as a binder for paint more commonly in antiquity than it is now. One example was its use as a binder in medieval illuminated manuscripts (Vetter et al. 2019). Fructose, a common sugar found in honey, is easily redissolved in water and therefore makes a binder, which can break down if exposed to wet environmental conditions (Taft and Mayer 2000).

    In European Medieval manuscripts, solutions containing fish glue, honey or gum were also used in mixtures with pigment (Taft and Mayer 2000; Vetter et al. 2019).

    The Egyptian, Roman and Chinese civilizations discovered how to make refined human-made colors, deriving them from organic and inorganic (not living) pigments found in nature (Bouherour 2001). The pigments were generally mixed with chalk or a honey binder (Gooch 2002). Other binders used at the time included egg whites, mixed with combinations of honey, gum arabic and other plant gums (Rene de la Rie 1989).

    2.3 Synthetic Binders

    2.3.1 Acrylic binders

    Acrylic medium, a polymer emulsion, has been employed since the 1930’s (Taft and Mayer 2000). Its ability to be used as a water-based binder and extender with fast drying properties has made it popular with artists and commercial paint companies (Taft and Mayer 2000). This new, synthetic medium created an explosion of experiments and possibilities (Taft and Mayer 2000). It can be built up thickly with a palette knife, or diluted and applied with a brush like watercolor (Taft and Mayer 2000).

    Beginning in the 1950s, mural painters found the acrylic medium a versatile addition to making workable paint for large scale projects (Taft and Mayer 2000).

    2.3.2 Alkyds

    Alkyd mediums, from esther oils, became an important part of the commercial paint market in 1927 (Gooch 2002). Paint technology in Oloeresins led to the development of air curing resins such as alkyd (Gooch 2002). Alkyd is an oil-modified polyester resin, which is named for its reactants, alcohol and acid (Gooch 2002). Alkyd resins can be mixed with many varieties of paint mediums, oils and resins (Gooch 2002). In my experience as a painter, alkyd mediums create hard varnishes that have high gloss, are toxic to breathe and dry incredibly fast. Alkyds are currently widely available in many oil paints and mediums.

    2.4 Mineral Binders

    2.4.1. Lime-paint

    Lime has been used since antiquity as a binder in paint recipes and glazes. Lime-paint was a technique used in antiquity to make frescoes on walls (Gooch 2000). The process involves mixing a lime-water solution called “slaked lime” with pigment, which is applied to dry plaster (Piovesan et al. 2012).

    To make slaked lime, the lime is added to water, and the resulting chemical reaction produces calcium hydroxide, which is responsible for the carbonization of paint. Water and lime create a chemical reaction as the paint dries, which results in the pigment being surrounded and protected by lime crystals (CaCO3)). (Botticelli 1992; Piovesan et al. 2012).

    Lime-paint was used to paint Egyptian mummy coffins sealed with varnish (Gooch 2002).

    2.4.2 Gypsum

    Gypsum has been used since ancient Egyptian and Biblical times as a base in paint both as a ground and as an additive in paint (Gooch 2002; Levy et al. 2018). The Pictorical Museum and Optic Scale by Antonio Palomino mentions combining animal “glues with gypsum for artistic purposes.” Producing “cola de tejadas by boiling bones, nerves and feet from goats and cows (Levy et al. 2018).”

    Beeswax, gelatin, gum arabic, egg, white and yolk were added to gypsum, along with lime plaster and plaster of Paris to create a binding agent with the pigment (Huntley et al. 2015; Gooch 2012).

    2.4.3 Quartz / Feldspar / Whewellite

    Some Northwest Coast tribes used a traditional mineral-based paint consisting of gypsum, quartz, silicate, calcite and kaolin fillers oil (McLennan and Duffek 2000). These were ground with stone mortars and pestles and added to pigments (Ancheta 2019).

    The Egyptian, Roman and Chinese civilizations created synthetic paints including Egyptian Blue, Chinese blue, and Chinese purple. The colors were identified from the 6th Dynasty through to the Roman era in eleven original specimens. Quartz and mica were found to be frequently used as a common paint additive in Egyptian Blue and Chinese Blue and Purple synthetic paint mixtures (Stodulski 1984). Egyptian samples from tombs revealed that the starting components for Egyptian Blue were normally calcite, quartz and copper containing substances (Stodulski 1984). These could include minerals such as malachite, copper metal or azurite in combination with a flux to purify and prevent oxidation of the metals. cuprorivaite and wollastonite and libethenite as synthetic ingredients in a paint mixture for a greenish-blue hue of Egyptian Blue (Bouherour 2001; Stodulski 1984).

    Some of these man-made paints were used in the form of paint sticks as found in the specimens from the Chinese Terracottoa army. Paint sticks also contained synthetic additives of barium-lead and a barium-copper-silicate mixture in the synthetic ancient Chinese paint mixtures use on the Terracotta Army figures (Bouherour 2001).

    Analysis of rock art from ancient sites in Australia has described the use of minerals as binders in pictographs. Analysis of this “mulberry ocher paint,” apparently demonstrated that minerals such as quartz, anorthite (feldspar), hematite and others were used both as pigments and binding materials in the paint (Huntley et al. 2015).

    Naturally occurring mulberry hematite paint mixtures are mostly made up of inorganic jarosite minerology, red paints with hematite, a blood binder and an organic base, possibly tree sap. The minerology was detected to be gypsum, quartz, anorthite (feldspar), hematite and the colorant was thought to be hematite. Mineral silica accretions were investigated to contain salts, phosphate salts, clays, and oxalates such as whewellite. In reading this article, there is some skepticism as to where whewellite was intentionally mixed into a paint recipe and where it occurred naturally as a crystalline material developing from environmental conditions (Huntley et al. 2015).

  • There are as many binder and paint medium recipes as geologically diverse cultures and artists. Recipes have evolved and been adapted since humans first made paint. The binder, can be made of natural ingredients such as egg, gum, resin, or glue. Binders are sourced from plants, animals and minerals.

    The medium, or liquid carrier, is competent with the binder. For instance, turpentine dilutes oils, and water dissipates gum, egg and acrylic (Gooch 2002). Binders are responsible for the quality, temperament and nature of the paint.

    Favorite Paint Binder/Medium Recipes

    These mediums can be mixed with dry pigments. First, make a water paste with the pigments and then add to the medium in small amounts, mixing as you go. A knowledge of basic paint making is helpful.

    Concerning egg tempera, draining the egg yolk from the sack, for wax and oil emulsions, heating is done while thoroughly mixing the solution. Dry powdered ingredients such as lime, starch, hide glue crystals, should be made soluble first in water….resin crystals in turpentine. Have fun, these mediums all have a variety of characteristics, adding thick and thin, glazing, shiny and coarse affects to the paint.

    1-Plant starch medium, made from wheat, rice or potato flour can be used as a fast-drying paint and sealer for paper.

    Starch 1 part

    Cold Water 3 parts

    Hot Water 3 parts

    2-Starch and Oil Medium

    Starch (dissolved in water) 4 parts

    Oil or Resin 1 part

    Combine flour to cold water and stir until smooth, then pour into boiling water while stirring.

    2-Egg and lime medium

    Egg yolk 1 part

    Lime water 1 part

    3- Egg Tempera

    Egg Yolk 1 part

    Water 1 part

    4- Egg, Resin, Oil medium

    Egg Yolk 1 part

    Oil (Linseed, Walnut, Sunflower, or Varnish) 1 part

    Water 1 part

    5- Egg and Damar Varnish Medium

    Whole Egg 4 parts

    Damar Varnish 1 part

    Water 12 parts

    6- Animal Hide Glue (Rabbit) and Oil Medium

    Hide Glue (dissolved in water) 2 parts

    Oil or Resin 1 part

    7- Damar and Beeswax Medium

    Damar Varnish or Mastic 1 part

    Beeswax 1 part

    8- Canadian Basalm and Linseed Oil

    Canadian Basalm 4 parts

    Linseed oil 1 part

    Turpentine 2 parts

    9-Beeswax and Elemi Resin Medium

    Elemi Resin 1 part

    Beeswax 1 part

    Pine Turpentine 2 parts

    10-Plant Gum Medium (acacia gum, gum tragacanth, cherry gum

    Gum Arabic, Orchid Gum)

    Gum 1 part

    Water 2 parts

    11-Gum, Stand Oil, Damar Resin Medium

    Gum solution 5 parts

    Stand Oil 1 part

    Damar Varnish 1 part

  • Bibliography

    Ancheta, Melanie

    2019 Revealing Blue on the Northwest Coast. American Indian Culture and Research Journal. 43 (1): 1-30. https://doi-org.proxy.lib.sfu.ca/10.17953/aicrj.43.1.ancheta

    Andreu-Coll, Luc´ıa , Luis Noguera-Artiaga , Angel A. Carbonell-Barrachina, Pilar Legua , and Francisca Hernandez

    2020 Volatile composition of prickly pear fruit pulp from six Spanish cultivars. Journal of Food Science Vol. 85, Iss. 2.

    Agresti, Georgia, Pietro Baraldi, Claudia Pelosi, and Ulderico Santamaria.

    2015 Yellow Pigments Based on Lead, Tin, and Antimony: Ancient Recipes, Synthesis, Characterization, and Hue Choice in Artworks. Department of Cultural Heritage Sciences, University of Tuscia, Largo Dell’University, Viterbo Italy. Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, Italy.

    Albertini, Emidio, Lorenzo Raggi, Manuela Vagnini, Alessandro Sassolini, Alessandro Achilli, Gianpiero Marconi, Laura Cartechini, Fabio Veronesi, Mario Falcinelli, Brunetto Giovanni Brunetti, and Costanza Miliani.

    2010 Tracing the biological origin of animal glues used in paintings through mitochondrial DNA analysis. Analytical and BioAnalytic al Chemistry. Vol. 399. Pp. 2987-2995. https://doi-org.proxy.lib.sfu.ca/10.1007/s00216-010-4287-2

    Aral, Siji and K. B. Rameshkumar

    2016 Gamboge- The bark exudate from Garcinia species. Diversity of Garcinia species in the Western Ghats: Phytochemical Perspective. p174-181.

    Araujo, Rita, Paula Nabais, Isabel Pombo Cardoso, Conceicao Casanova, Ana Lemos, and Maria J. Melo.

    2018. Silver paints in Midieval Manuscripts: A First Molecular Survey into their degradation. Heriyage Science. 6: Article 8

    Arocena, J. M., Hall, K., and Meiklejohn, I.

    2008 Minerals provide tints and possible binder/extender in pigments in San rock paintings (South Africa), Geoarchaeology: An International Journal, 23(2), 293–304.

    Balas, Costas, George Epitropou, Athanasios Tsapras, Nicos Hadjinicolaou

    2018 Hyperspectral imaging and spectral classification for pigment identification and mapping in paintings by El Greco and his workshop. Multimed Tools. Vol. 77 Pp. 9737–9751 https://doi.org/10.1007/s11042-017-5564-2

    Ballardie, Margaret J.

    2000 Jappaning in Seventeenth and Eighteenth Century Europe: A brief discussion of some materials and methods; Painted Wood: History and Conservation. Published by The Getty Institute.

    Barkeshli, Mandana

    2016 Historical Persian Recipes for Paper Dyes. Journal Restaurator. International Journal for the Preservation of Library and Archival Material. Published by De Gruyter. Feb 16, 2016

    https://doi.org/10.1515/res-2015-0012

    Barnett, J.R., Sarah Miller, Emma Pearce

    2006 Colour and art: A brief history of pigments. Optics and Laser Technology. Vol. 38, Issues 4-6. Pp. 445-453.

    Baser, K.H.C., B. Demirci, Aman Dekebo, Ermias Dagne.

    2003 Essential oils of some Boswellia spp., Myrrh and Opopanax. Flavor and Fragrance Journal. Vol.18, No. 2, Pp 153-156.

    Bates, Lennon N., Amanda M. Castaneda, Carolyn E. Boyd, and Karen L. Steelman. 2015. A black Deer at Black Cave. Journal of Texas Archaeology and History. Vol 2:45-57.

    Beaverton, Virginia R.

    2017 The Gift of Knowledge/Ttnuwit Atawish Nch’inch’imami: Reflections on Sahaptin Ways. Edited by Janne L. Underriner. University of Washington Press, Seattle.

    Bennett, Hayley

    2014 Dibromoindigo. Chemistry World. April 1, 2014. Online journal. https://www.chemistryworld.com/podcasts/dibromoindigo/7237.article

    Bertrand, Loïc , Claire Gervais, Admir Masic, and Robbiola.

    2018. Paleo-inspired Systems: Durability, Sustainability, and Remarkable Properties. Angewandte Chemie International Edition 2018, 57 (25) , 7288-7295. https://doi.org/10.1002/anie.201709303

    Biron, Carole, Aurelie Mounier, Gwenaelle Le Bourdon, Laurent Servant, Remy Chapoulie, and Floreal Daniel.

    2020 Revealing the Colours of Ukiyo-e Prints by Short Wave Infrared Range Hyperspectral Imaging (SWIR). MicroChemical Journal. Elsevier. 27 February 2020

    Black, Stephen L.

    2008 BonfireShelter. Webpage, https://www.texasbeyondhistory.net/bonfire/index.html, accessed March 10, 2022.

    Boas, F.

    1995 A wealth of thought: Franz Boas on Native American art. University of Washington Press.

    Boyd, Carolyn

    2003 Rock Art of the Lower Pecos. Texas A&M University Press. College Station, Texas.

    Boyd, C. E., & Dering, J. P.

    2013 Rediscovering ingredients in paintings of the Pecos River–style. Painters in Prehistory: Archaeology and Art of the Lower Pecos Canyonlands, Pp.180-181.

    Bonaduce I, Colombini MP, Degano I, Di Girolamo F, Nasa J, Modugno F, and et al.

    2013. Mass spectrometric techniques for characterizing low-molecular-weight resins used as paint varnishes. Anal Bioanal Chem. 2013;405:1047–65. DOI: 10.1007/s00216-012-6502-9.23151653

    Botticelli, G.

    1992 Metodologie di restauro delle pitture murali, Centro Di, Firenze. ISBN:

    8870382281(pbk.); 887038229X

    Bouherour, Soraya, Heinz Berke, Hans Georg Weildemann

    2001 Ancient Man-made Copper Silicate Pigments Studied by Raman Microscopy. Art and Chemical Sciences. Vol. 55, No. 11. Pp. 942-951

    Boyd, Caroline E. and J. Phil Daring

    1996 Medicinal and hallucinogenic plants identified in the sediments and pictographs of the Lower Pecos, TexasvArchaic. Antiquity, 1996-06, Vol.70 (268), Pp.256-275.

    Boyd, Caroline E. and J. Phil Daring

    2013 Rediscovering Ingredients in Paintings of the Pecos River Style. In Painters in Prehistory: Archaeology of the Lower Pecos Canyonlands. Edited by Harry J. Shafer. Trinity University Press, San Antonio Texas.

    Brolis, M. B. Gabetta N. Fuzzati, R. Pace, F. Panzeri, F. Peterlongo

    1998 Identification by high-performance liquid chromatography–diode array detection–mass spectrometry and quantification by high-performance liquid chromatography–UV absorbance detection of active constituents of Hypericum perforatum. Journal of Chromatography A. Vol. 825, Iss. 1, Pp. 9-16.

    Brons, Cecile, Kaare Lund Rasmussen, Marta Melchiorre Di Crescenzo, Rebecca Stacey and Anna Lluveras-Tenorio

    2018 Painting the Palace of Apries I: Ancient Binding Media and Coatings of the Releifs from the Palace of Apries, lower Egypt. Heritage Science. Vol. 6 .Pp. 6. https://doi.org/10.1186/s40494-018-0170-9

    Brook, George A. Nora V. Franco, Alexander Cherkinsky, Agustin Acevedo, Dánae Fiored , Timothy R. Popee , Richard D. Weimar IIIe , Gregory Nehere , Hayden A. Evanse , Tina T. Salguero.

    2018 Pigments, binders, and ages of rock art at Viuda Quenzana, Santa Cruz, Patagonia (Argentina). Journal of Archaeological Science. Report 21, p.47-63.

    Bu, K., J. V. Cizdziel, J. Russ

    2013 The Source of Iron-Oxide Pigments Used in Pecos River Style Rock Paints. Archaeometry. Published January 16, 2013.

    https://doi-org.proxy.lib.sfu.ca/10.1111/arcm.12011

    Buckley M, Collins M, Thomas-Oates J, Wilson JC.

    2009 Species identification by analysis of bone collagen using matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry. Rapid Commun Mass Spectrom. 2009;23:3843–54. DOI: 10.1002/rcm.4316.19899187 Search in Google Scholar

    Buckmeier, David L.

    2008 Life History and Status of Alligator Gar Atractosteus spatula, with recommendations for Management. Heart of the Hills Fisheries Science Center, Texas Parks and Wildlife Dept, Mountain Home, Texas.

    Burgio, Lucia, and Robin J.H. Clark

    2001 Library of FT-Raman spectra of pigments, minerals, pigment media and varnishes, and supplement to existing library of Raman spectra of pigments with visible excitation. Spectrochimica Acta Part A 57. P. 1491–152.

    Buxbaum, Gunter

    1998 Industrial Inorganic Pigments. Weinheim; New York, Chichester, Brisbane, Singapore, Toronto.

    Calvano, Cosima D., Elena C.L. Rigante, Tommaso R.I. Cataldi, Luigia Sabbatini.

    2020. In Situ Hydrogel Extraction with Dual-Enzyme Digestion of Proteinaceous Binders: the Key for Reliable Mass Spectrometry Investigations of Artworks. Analytical Chemistry , 92 (15) , 10257-10261.

    https://doi.org/10.1021/acs.analchem.0c01898

    Calvano, Cosima Damiana , Inez Dorothé van der Werf, Francesco Palmisano, Luigia Sabbatini.

    2016. Revealing the composition of organic materials in polychrome works of art: the role of mass spectrometry-based techniques. Analytical and Bioanalytical Chemistry 2016, 408 (25) , 6957-6981.

    https://doi.org/10.1007/s00216-016-9862-8

    Calvano, C.D., E. Rigante, R.A. Picca, T.R.I. Cataldi, L. Sabbatini.

    2020. An easily transferable protocol for in-situ quasi-non-invasive analysis of protein binders in works of art. Talanta 2020, 215 , 120882.

    https://doi.org/10.1016/j.talanta.2020.120882

    Campana, Michael G. Mim A. Bower, Melamie J., Bailey, Frauke Stock, Tamsin C. O’Connell, Ceiridwen J. Edwards, Caroline Checkley-Scottf , Barry Knight, Matthew Spencer , Christopher J. Howe.

    2010 A flock of sheep, goats and cattle: ancient DNA analysis reveals complexities of historical parchment manufacture. Journal of Archaeological Science. Vol 37. Pp 1317-1325.

    Cardon, Dominique (translator, editor)

    2016 The Dyer’s Handbook: Memoirs of an 18th-Century Master Colorist. Ancient Textiles Series. Vol 26, Ch. 1

    Casadio, Francesca, and Lucia Toniolo.

    2001. The analysis of polychrome works of art: 40 years of infrared spectroscopic investigations. The Journal of Cultural Heritage. Vol 2:issue 1, 71-78

    Casini, A, M. Bacci, C. Cucci, F. Lotti S. Porcinai, M. Picollo, B. Radicati, M. Poggesi, L. Stefani.

    2005 Fiber optic reflectance spectroscopy and hyper-spectral image spectroscopy- two integrated techniques for the study of the Madonna dei Fusi. Optical Methods for Arts and Archaeology, 58570M. doi: 10.1117/12.611500

    Catalin, Schiopu Emil

    2020 Vegetable Products Used for the Extraction of Natural Dyes. Annals of the Constantin Brancusi. University of Targu Jiu, Romania. Engineering Series, No. 4.2020.

    Castaneda, Amanda M.

    2015 The Hole Story: Understanding Ground Stone Bedrock Feature Variation in the Lower Pecos Canyonlands. MA Thesis to Graduate Council of Texas State University.

    Cattò, Cristina , Michela Gambino, Francesca Cappitelli, Celia Duce, Ilaria Bonaduce, Fabio Forlani.

    2017. Sidestepping the challenge of casein quantification in ancient paintings by dot-blot immunoassay. Microchemical Journal 2017, 134 , 362-369.

    https://doi.org/10.1016/j.microc.2017.07.004

    Chang, Chein-I

    2013 Hyperspectral Imaging: Techniques for Spectral Detection and Classification. New York, NY: Springer 2013

    Chaturvedi U.K., U. Steiner, O. Zak, G. Krausch, G. Schatz, and J. Klein

    1990 Structure at polymer interfaces determined by high‐resolution nuclear reaction analysis. Applied Physics Letters. Vol 56. Issue 13.

    Chavannes, Edouard

    1906 Chinese Books Before the Invention of Paper. The Open Court: Vol. 1906. Iss. 10, Article 6

    Chiari, G., P Sarrazin and M. Gailhanou

    2016 C-8: Portable XRD/XRF Instrumentation for the Study of Works of Art. Cambridge University Press. Cambridge, UK.

    Christensen, D. D., Dickey, J., & Freers, S. M.

    2013 Rock Art of the Grand Canyon Region. Sunbelt Publications, Incorporated.

    Cicatiello, Paola, Georgia Ntasi, Manuela Rossi, Gennaro Marino, Paola Giardina and Leila Birolo.

    2018. Minimally Invasive and Portable Method for the Identification of Proteins in Ancient Paintings. Analytical Chemistry , 90 (17) 10128-10133.

    https://doi.org/10.1021/acs.analchem.8b01718

    Cizdziel, James, Kaixuan Bu

    2013 The source of Iron-Oxide Pigments Used in Pecos River Style Rock Paints. Archaeometry. December 2013

    Clarke, Mattew L., Francesca Gabrieli, Kathryn L. Rowberg, Andrew Hare, Jiro Ueda, Blythe McCarthy and John K. Delaney.

    2021 Imaging spectroscopies to characterize a 13th century Japanese handscroll, The Miraculous Interventions of Jizō Bosatsu. Heritage Science.. 9:20

    Colombini, Maria Perla and Francesca Modugno.

    2009. Organic Mass Spectrometry in Art and Archaeology: Organic Materials in Art and Archeology…binders, resins, proteins. Universita di Pisa.

    Cooksey, Christopher

    2001 Tyrian Purple: 6,6’-Dibromoindigo and Related Compounds. Molecules. Sept; 6(9): 736-769. Published online 2001 Aug 31. doi: 10.3390/60900736

    Covey, Thomas R., Edgar D. Lee, Andries P. Bruin s and Jack D. Henlon

    1986 Liquid Chromatography Mass Spectrometry. Analytical Chemistry. Vol. 58. No. 14. Pp. 1451-1461.

    Cruz, Antontio, Erica Eires, Luis Dias, Teresa Desterro and Calra Rego

    2018 Identification of vivianite, an unusual blue pigment, in a sixteenth century painting and its implications. Color Research and Application. Vol. 43. Issue 2. Pp. 177-183.

    Daher, Celine, Ludovic Bellot-Gurlet, Anne-Solenn Le Ho, Celine Paris, and Martine Regert.2013. Advanced discriminating criteria for natural organic substances of Cultural Heritage interest: Spectral decomposition and multivariate analyses of FT-Raman and FT-IR signatures. Talanta, Volume 115, 2013, pp. 540-547

    Dallongeville, Sophie, Nicolas Garnier, Christian Rolando, and Caroline Tokarski .

    2016. Proteins in Art, Archaeology, and Paleontology: From Detection to Identification. Chemical Reviews 2016, 116 (1) , 2-79.

    https://doi.org/10.1021/acs.chemrev.5b00037

    Dallongeville, Sophie, Monika Koperska, Nicolas Garnier, Genevieve Reille-Taillefert, Christian Rolando, and Caroline Tokarski.

    2011 Identification of Animal Glue Species in Artworks Using Proteomics: Application to a 18th Century Gilt Sample. Analytical Chemistry. Vol. 83. Pp. 9431-9437.

    Daniel, F., Mounier, A., Pérez-Arantegui, J., Pardos, C., Prieto-Taboada, N., Fdez-Ortiz de Vallejuelo, S., and Castro, K.

    2016. Hyperspectral imaging applied to the analysis of Goya paintings in the Museum of Zaragoza (Spain). 2016. MicroChemical Journal. 126: 113-120

    Darzi, Maedeh, Benjamin Stern, Howell G.M. Edwards, Alex Surtees, Mohammad Lamehi Rachti.

    2021 A study of colorant uses in illuminated Islamic manuscripts from the Qajar period (1789-1925 C.E.), early modern Iran. Journal of Archaeological Science: Report 39.

    Delaney, John K., Jason G. Zeibel, Mathieu Thoury, Roy Littleton, Kathryn M. Morales, Michael Palmer, E. Rene de la Rie.

    2009 Visible and infrared reflectance imaging spectroscopy of paintings: pigment mapping and improved infrared reflectography. Optics for Arts, Architecture, and Archaeology II. Vol. 7391, O3A.

    Dering, Phil

    2006 Daily Bread and Healing Balm: A Deep History of Native Plant Use in the Trans-Pecos of Texas. The Sabal. Vol: 23, No. 1.

    Dering, Phil

    1999 Earth-Oven Plant Processing in Archaic Period Economies: An Example from a SemiArid Savannah in South-Central North America. American Antiquity, Vol. 64, No. 4 (, pp. 659-674. Published by: Cambridge University Press Stable URL: https://www.jstor.org/stable/2694211

    Dering, Phil

    2008 Late Prehistoric Subsistence Economy on the Edwards Plateau. Plains Anthropologist. Vol. 53:205, 59-77.

    Diaz, Gisele and Alan Rodgers

    1993 The Codex Borgia. Dover Publications. Left Coast Press, Walnut Creek, CA.

    Dibble, D. S. and D. Lorrain

    1968 Bonfire Shelter: A Stratified Bison Kill Site, Val Verde County, Texas. Texas Memorial Museum Miscellaneous Papers 1, The University of Texas at Austin.

    Dietemann, Patrick, Katherine von Miller, Charolette Hopker, and Ursula Baumer

    2019 On the Use and Differentiation of Resins from Pinaceae Spewcies in European Artwork Based on Written Sources, Reconstructions and Analysis. Studies in Conservation. Vol. 64 (1), Pp. 62-73.

    Dillingham, Eric, Ryan Powell, Evelyn Billo, Robert Mark, and Martin Stein.

    N.D. Survey of Rock Art of the Central Guadalupe Mountains, New Mexico.

    Domon, B. and Ruedi Aebersold

    2006 Mass Spectrometry and Protein Analysis. Science. Vol. 312 (5771). DOI: 10.1126/science.1124619

    Dossie, Robert

    1777 The Handmaid to the Arts. Printed for J. Nourse, London.

    Di Gianvincenzo, Fabiana, Clara Granzotto, and Enrico Cappellini.

    2019. Skin, Furs, and Textiles: Mass Spectrometry-based Analysis of Ancient Protein Residues. 2019,,, 304-316. https://doi.org/10.1017/9781108656405.013

    Dmitry Kurouski, Stephanie Zaleski, Francesca Casadio, Richard P. Van Duyne, and Nilam C. Shah . Tip-Enhanced Raman Spectroscopy (TERS) for in Situ Identification of Indigo and Iron Gall Ink on Paper.

    2014 Journal of the American Chemical Society 2014, 136 (24), 86778684. https://doi.org/10.1021/ja5027612

    Dr. Ravit Linn, Dr. Ilaria Bonaduce, Dr. Georgia Ntasi, Prof. Leila Birolo, Prof. Assaf Yasur-Landau, Prof. Eric H. Cline, Dr. Austin Nevin, Dr. Anna Lluveras-Tenorio.

    2018. Evolved Gas Analysis-Mass Spectometry to Identitfy the Earliest Organic Binder in Aegean Style Wall Paintings. Journal of German Chemical Society.

    Du, Jianghao, Zhanyun Zhu, Junchang Yang, Jia Wang, Xiaotong Jiang.

    2021. A comparative study on the extraction effects of common agents on collagen-based binders in mural paintings. Heritage Science , 9 (1)

    https://doi.org/10.1186/s40494-021-00519-y

    Escott, John Boyd

    2011 An investigation, using synchrotron radiation and other techniques, of the composition of San rock art paints and excavated pigments from Maqonqu shelter, and comparative paint data from three other sites in KwaZulu-Natal, South Africa. Doctor of Philosophy. Discipline of Soil Science School of Environmental Sciences. University of KwaZulu-Natal (Pietermaritzburg).

    Estrada-Castillón, Eduardo, Estrada-Castillón, Brianda Elizabeth Soto-Mata, Miriam Garza-López, José Ángel Villarreal-Quintanilla, Javier Jiménez-Pérez, Marisela Pando-Moreno, Jaime Sánchez-Salas, Laura Scott-Morales and Mauricio Cotera-Correa1.

    2012 Medicinal plants in the southern region of the State of Nuevo León, México. Journal of Ethnobiology and Ethnomedicine, Vol.8,Iss. 45.

    Hay, Jeff, and Linda Holler

    2007 Engishik. The Greenhaven Encyclopedia of World Religions. Greenhaven Press, Detroit MI.

    Hore, P.J.

    2015 Nuclear Magnetic Resonance, second edition. Oxford University Press. Great Clarendon Street, Oxford, OX2 6DP, UK.

    Finlay, Victoria

    2004 Color: A natural history of the palette. New York Random House.

    Fitzergerald, Devin

    2015 Between Paper and Wood, or the Manchu Invention of the Dang’an. Harvard University. Volume 13.

    Fitzwilliam Museum

    2021 COLOUR: The Art and Science of Illuminated Manuscripts. University of Cambridge Museums. Online website. https://fitzmuseum.cam.ac.uk/visit-us/exhibitions/colour-the-art-and-science-of-illuminated-manuscripts

    Folkmann, F, C. Gaarde, T. Huus, ans K. Kemp

    1974 Proton Induced X-Ray emission as a Tool for Trace Element Analysis. Nuclear Instruments and Methods. Vol. 116. Iss.3. Pp. 487-499.

    Franklin, Bruce H.

    2007 The Most Important Fish in the Sea: Menhaden and America. Washington : Island Press/Shearwater Books. ISBN/ISSN: 9781597261241 1597261246

    Gallios, N., J. Templier, S. Derenne

    2007 Pyrolysis-gas chromatography–mass spectrometry of the 20 protein amino acids in the presence of TMAH. Journal of Analytical and Applied Pyrolysis. Vol. 80 p. 216-230.

    Garcia, Elodie Dupey

    2017 The Materiality of Color in Pre-Columbian Codices: Insights from Cultural History. Ancient Mesoamerica, 28 (2017), 21-40. Cambridge University Press.

    Garcia-Arce, Zahirid Patricia and Roberto Castro-Munoz

    2021 Exploring the potentialities of the Mexican fermented beverage: Pulque. Journal of Ethnic Foods 8:35. https://doi.org/10.1186/s42779-021-00111-6.

    Gardiner, Derek J. and Pierce R. Graves

    1989 Practical Raman Spectroscopy. Springer, Berlin, Heidelberg

    Garnier, Nicolas, Dario Bernal-Casasola, Cyril Driard, and Inês Vaz Pinto.

    2018. Looking for Ancient Fish Products Through Invisible Biomolecular Residues in the Roman Production Vats from the Atlantic Coast. Journal of Maritime Archaeology 2018, 13 (3) , 285-328.

    Gatenby, Sue and Janet Bridgland

    1993 An identification method for fat and/or oil binding media used on Australian Aboriginal objects. ICOM Committee for Conservation tenth triennial meeting, Washington, DC, 22-27 August 1993

    Gellerstedt, G.

    1992 Gel Permeation Chromatography. Methods in Lignin Chemistry. Springer Series in Wood Science. Springer, Berlin, Heidelberg. https://doi-org.proxy.lib.sfu.ca/10.1007/978-3-642-74065-7_34

    Gent, Alexandra, Rachel Morrison, and Nelly von Aderkas

    2015 ‘1st Olio after Capivi’: Copaiba Balsam In The Paintings Of Sir Joshua Reynolds

    Getty J. Paul Museum

    2016 The Alchemy of Color and Chemical Change in Medieval Manuscripts. #manuscripts #gettymanuscripts #gettymuseum

    https://www.youtube.com/watch?v=REMPiP5Fgmc

    Getty J. Paul Museum

    2014 Making Manuscripts

    #manuscripts #gettymanuscripts #gettymuseum

    https://www.youtube.com/watch?v=nuNfdHNTv9o

    Gigliarelli, Giulia ; Becerra, Judith X ; Curini, Massimo ; Marcotullio, Maria Carla

    2015 Chemical Composition and Biological Activities of Fragrant Mexican Copal (Bursera spp.). Molecules (Basel, Switzerland. Vol.20 (12), Pps.22383-22394

    Giorgi, L. A. Nevin, L. Nodari, D. Comelli, R. Alberti, M. Gironda, S. Mosca, E. Zendri, M. Piccolo, and F.C. Izzo.

    2019. In-situ technical study of modern paintings part 1: The evolution of artistic materials and painting techniques in ten paintings from 1889 to 1940 by Alessandro Milesi (1856–1945). Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2019, 219 , 530-538. https://doi.org/10.1016/j.saa.2019.04.083

    Giuffrida, Maria Gabriella , Roberto Mazzoli, Enrica Pessione. Back to the past: deciphering cultural heritage secrets by protein identification.

    2018. Applied Microbiology and Biotechnology 2018, 102 (13) , 5445-5455.

    https://doi.org/10.1007/s00253-018-8963-z

    Global Times.

    2010. Conservators Struggle to Preserve True Original Colors of China’s Terracotta Warriors. Global Times 19:01:29.

    Gooch, Jan

    2002 Lead Based Paint Handbook. Chapters 2-4. PP 13-100

    Kluwer Academic Publishers, NY

    Gottschaller P, Khandekar N, Lee LF, Kirby DP.

    2012. The evolution of Lucio Fontana’s painting materials. Studies in Conservation, 2012-04-01, Vol.57 (2), p.76-91. Routledge.

    Granzotto, Clara and Julie Arslanoglu, Christian Rolando, and Caroline Tokarski.

    2017. Plant gum identification in historic artworks. Scientific Reports 2017, 7 (1)

    https://doi.org/10.1038/srep44538

    Granzotto C, Sutherland K.

    2017. Matrix assisted laser desorption ionization mass fingerprinting for identification of Acacia gum in microsamples from works of art. Anal Chem. 2017;89:3059–68. DOI: 10.1021/acs.analchem.6b04797.28192977

    Granzotto C, Sutherland K, Arslanoglu J, Ferguson GA.

    2019. Discrimination of Acacia gums by MALDI–TOF MS: applications to micro-samples from works of art. Microchem J. 2019;144:229–41.10.1016/j.microc.2018.08.058 Search in Google Scholar

    Griffiths, Anthony, Susan R. Wessler, Sean B. Carroll, John F. Doebley

    2015 Introduction to Genetic Analysis. W.H. Freeman & Company . New York

    Griffiths, Peter R., and James A. De Haseth

    2007 Fourier Transform Infrared Spectometry, Second Edition. John Wiley & Sons, Inc. Hoboken NJ., and Canada.

    Guasch-Ferre, Nuria, Jose Luis Prada Perez, Ma. Luisa Vazquez de Agredos Pascual, Laura Ostete-Cortina and Maria Teresa Domenech-Carbo.

    2019 Polysaccharide remains in Maya mural paintings: is it an evidence of the use of plant gums as binding medium of pigments and additive in the mortar? STAR: Science and Technology of Archeological Research. Vol. 5, No. 2, Pp. 200-220.

    Gunther, Detlef and Bodo Hattendorf

    2005 Solid sample analysis using laser ablation inductively coupled plasma mass spectrometry. TrAC Trends in Analytic ChemistryI. Vol. 24, Issue 3. Pp. 255-265.

    Hahn, O., W. Malzer, B. Kanniesser and B. Beckoff

    2004 Characterization of iron-gall inks in historical manuscripts and music compositions using x-ray fluorescence spectrometry. X-Ray Spectrometry. I Vol. 33. Pp. 234-239.

    Hanna, Nelly

    2015 Alternative Ways of Studying Middle East and Asian History before Colonialism; Textiles in the Ottoman, Safavid and Mughal Empires. AFMA Keynote Lecture. Distinguished University Professor, American University in Cairo.

    Harvard Art Museum

    2016 This Man Protects the World's Rarest Colors. https://www.youtube.com/watch?v=F8aVfqDKx1U&t=91s

    Hasan, Mehedhi

    2001 Basic Principles of Textile Coloration. Society of Dyers and Colourists.

    He, Yujie, Ming Wen, Xiao Zhou, Feng Gao, Hongmei Lu.

    2021. Rapid Characterization of Proteinaceous Binders Used in Artwork and Cultural Heritage Materials by Surface-Enhanced Raman Spectroscopy (SERS). Analytical Letters 2021: 1-11

    https://doi.org/10.1080/00032719.2021.1948049

    Heisinger, Bryan

    2019 The Archaeology of Skiles Shelter (41VV165): A Long-Term Plant Rockshelter Baking Facility in the Lower Pecos Canyonlands of Texas. MA Anthropology at Texas State University.

    Hendy, Jessica.

    2021. Ancient protein analysis in archaeology. Science Advances 2021, 7 (3) , eabb9314. https://doi.org/10.1126/sciadv.abb9314

    Hernandez, Hector, Carlos Gómez-Hinostrosa and Barbara Goettschi

    2004 Checklist of Chihuahuan Desert Cactaceae. Harvard Papers in Botany, Vol. 9,No. 1, Pps. 51–68.

    Herringham, Christina J

    (2018) 1899 Explanation of the Tempera-Painting of the ‘Trattato’

    The Book of the Art of Cennino Cennini, 1899, p.194-209. Routledge, London. January 2018. Reprinted.

    Hibbitts, Terry and Troy

    2017 Texas Turtles & Crocodilians: A Field Guide. Texas Natural History Guides. Texas University Press. Austin, Texas

    Hong C, Jiang H, Lü E, Wu Y, Guo L, Xie Y, and et al.

    2012. Identification of milk component in ancient food residue by proteomics. PLoS ONE. 2012;7:e37053. DOI: 10.1371/journal.pone.0037053. Search in Google Scholar

    Howe, Ellen, Emily Kaplan, Richard Newman, James H. Frantz, Ellen Pearlstein, Judith Levinson, and Odile Madden.

    2018 The Occurrence of a Titanium Dioxide/ Silica White Pigment on Wooden Andean Qeros: a Cultural and Chronological Marker. Heritage Science, 6:41

    Hu, W, H Zhang, B Zhang .

    2015. Identification of organic binders in ancient Chinese paintings by immunological techniques. Microscopy and Microanalysis Journal. Cambridge University Press. Vol 21: 5

    Hyman, Marian, Solveig A. Turpin, and Michael E. Zolensky

    1996. Pigment Analysis from Panther Cave, Texas. Rock Art Research 13(2): 93-103. Australian Rock Art Research Association.

    Huntley, J., M. Aubert, J. Ross, H.E.A. Brand, and M.J. Morwood

    2015 One Colour, (At Least) Two Minerals: A Study of Mulberry Rock Art Pigment and a Mulberry Pigment ‘Quarry’ from The Kimberley, Northern Australia. Archaeometry 57, 1 (2015) 77-99.

    Hyman, Marian and Marvin Rowe

    1997 Plasma extraction and AMS 14C dating of rock paintings. Techne (Paris). Vol 5. Published by Laboratoire de recherche des musées de France, Paris

    Hyman, Marian, Solveig A. Turpin and Michael Zolensky

    1996 Pigment Analysis from Panther Cave, Texas. Rock Art Research. Vol. 13, No. 2

    Idjouadiene, Lynda, Toufik A. Mostefaoui, Abdelyamine Naitbouda, Houcine Djermoune , Djamel Eddine Mechehedd, Marco Garganoe, and Letizia Bonizzoni.

    2021 First applications of non-invasive techniques on Algerian heritage manuscripts: the LMUHUB ULAHBIB ancient manuscript collection from Kabylia region. Journal of Cultural Heritage. 49, p289-297.

    Ioele, Marcella , Armida Sodo, Annalaura Casanova Municchia, Maria Antonietta Ricci, and Alfonso Pio Russo.

    2016. Chemical and spectroscopic investigation of the Raphael’s cartoon of the School of Athens from the Pinacoteca Ambrosiana. Applied Physics A 2016, 122 (12)

    https://doi.org/10.1007/s00339-016-0580-z

    Ishii, Yuuko

    1992 Needle crystals of calcium oxalate monohydrate in plant. Electron Microscopy. 41: 53-56 (1992). Department of Home Science, Mukogawa Women's University, 6-46 lkeblraki-cho, Nishinomiya-shi, Hyogo, 663 Japan.

    Janzen, Anneke, Kristine Korzow Richter, Ogeto Mwebi, Samantha Brown, Veronicah Onduso, Filia Gatwiri, Emmanuel Ndiema, Maggie Katongo, Steven T. Goldstein, Katerina Douka, Nicole Boivin

    2021 Distinguishing African bovids using Zooarchaeology by Mass Spectrometry (ZooMS): New peptide markers and insights into Iron Age economies in Zambia. Plos NonProfit, San Francisco. https://doi.org/10.1371/journal.pone.0251061

    Jasiczak J, Zielinski K.

    2006. Effect of protein additive on properties of mortar. Cem Concr Compos. 2006;28:451–7. DOI: 10.1016/j.cemconcomp.2005.12.007. Search in Google Scholar.

    Jin, Pujun, Tinayou Wang, Mingzhi Ma, Xiaogang Yang, Junxiao Zhu, Puheng Nan, and Su Wang.

    2012 Research on the Pigments from Painted Ceramics Excavated from the Yangq Iaopan Tombs of the Late Han Dynasty (48 BC – AD 25) Archaeometry 54, 6, p1040-1059.

    Johnson Rozelle Parker

    1935 Notes on Some Manuscripts of the Mappae Clavicula. Speculum , Jan., 1935, Vol. 10, No. 1 (Jan., 1935), pp. 72-81

    Johnson, Rozelle Parker

    1938 The Manuscripts of the Schedula of Theophilus Presbyter. Speculum , Jan., 1938, Vol. 13, No. 1 (Jan., 1938), pp. 86-103

    Jurasekova, Z., E. del Puerto, G. Bruno, J.V. Garcia-Ramos, S. Sanchez Cortes and C. Domingo.

    2010 Extractionless Non-Hydrolysis Surface-Enhanced Raman Spectroscopic Detection of Historical Mordant Dyes on Textile Fibers. Journal of Raman Spectroscropy. Published online in Wiley Online Library: March 29. wileyonlinelibrary.com DOI 10.1002/jrs.2651

    Jurgens, Christopher J.

    2007 The fish fauna from Arenosa Shelter (41VV99), Lower Pecos region, Texas. Science Direct. Quaternary International 185 (2008) 26–33

    https://pdf.sciencedirectassets.com

    Karlberg, Karlberg and Gil E. Pacey

    1989 Flow Injection Analysis: A Practical Guide. Elsevier Science Publishing Company Inc. New York.

    Khan Aisha Saleem

    2017 Leguminous Tress abd Their Medicinal Properties. Medicinally Important Trees. Springer, Cham. DOI https://doi.org/10.1007/987-3-319-56777-8_9

    Khandekar N, Mancusi-Ungaro C, Cooper H, Rosenberger C, Eremin K, Smith K, and et al.

    2010. A technical analysis of three paintings attributed to Jackson Pollock. Stud Conserv. 2010;55:204–15. DOI: 10.1179/sic.2010.55.3.204.

    Knipe, Penley, Katherine Eremin, Marc Walton, Agnese Babini, and Georgina Rayner.

    2018 Materials and techniques of Islamic manuscripts

    Science Heritage. 6:55

    Klinken, Rieks D. van; Graham, Jodi; Flack, Lloyd K.

    2006 "Population Ecology of Hybrid Mesquite (Prosopis Species) in Western Australia: How Does it Differ from Native Range Invasions and What are the Implications for Impacts and Management?". Biological Invasions. 8 (4): Pp. 727–741.

    Koenig, C.W., A.M. Castaneda, C.E. Boyd, M.W. Rowe and K.L. Steelman.

    2014 Portable X-Ray Flourescence Spectroscopy of Pictographs: A Case Study from the Lower Pecos Canyonlands, Texas. Archaeometry. July 16, 2013.

    Kriss, Dawn , Ellen Howe, Judith Levinson, Adriana Rizzo, Federico Caro, and Lisa DeLeonardis.

    2018 A material and technical study of Paracas painted ceramics. Cambridge University Press. 92:366

    Kroustallis, Stefanos

    2011 Binding Media in Medieval Manuscript Illumination: A Source Research. Revista de Historia da Arte. Serie W. N 1.

    Kučera, Lukáš ,Jaroslav Peška, Pavel Fojtík, Petr Barták, Diana Sokolovská, Jaroslav Pavelka, Veronika Komárková, Jaromír Beneš, Lenka Polcerová, Miroslav Králík, and Petr Bednář.

    2018 Determination of Milk Products in Ceramic Vessels of Corded Ware Culture from a Late Eneolithic Burial. Molecules 2018, 23 (12) , 3247.

    https://doi.org/10.3390/molecules23123247

    Kuckova S, Baumer U, Dietemann P:

    2018 Proteomics distinguishing between whole egg and egg yolk tempera. Paper under preparation (2018). Search in Google Scholar[42]

    Kuckova S, Hamidi-Asl E, Sofer Z, Marvan P, de Wael K, Sanyova J, and et al.

    2018. A simplified protocol for the usage of new immuno-SERS probes for the detection of casein, collagens and ovalbumin in the cross-sections of artworks. Anal Methods. 2018;10:1054–62. DOI: 10.1039/c7ay01864a. Search in Google Scholar

    Kuckova S, Santrucek J, Adamec M, Hynek R, Zeman A.

    2016. Chemical analysis of Gothic mortar from a bridge pier in Roudnice nad Labem (Czech Republic). J Liq Chromatogr Related Technol. 2016;16:739–44. DOI: 10.1080/10826076.2016.1238394. Search in Google Scholar

    La Nasa, J., Joy Mazurek and C. Rogge.

    2021 The identification of fish oils in 20th century paints and paintings. Journal of Cultural Heritage, July 1.

    La Torre, Delores L. and Felipe A.

    1977 Plants Used by the Mexican Kickapoo Indians. Economic Botany, July-Sept. 1977, Vol. 31, No. 3. Pp. 340-357. Published by Springer on behalf of New York Botanical Garden Press. https://www.jstor.org/stable/4253858.

    Levy, Ivana K., Ricardo Neme Tauil, Maria P. Valacco, Silvia Moreno, Gabriela Siracusano, Marta S. Maier.

    2018 Investigation of proteins in samples of a mid-18th century colonial mural painting by MALDI-TOF/MS and LC-ESI/MS (Orbitrap). Microchemical Journal 2018, 143 , 457-466.

    https://doi.org/10.1016/j.microc.2018.07.030

    Lindon, John C., George E. Tranter, and David Koppenaald

    2010 Encyclopedia of Spectroscopy and Spectrometry. Second edition. Academic Press, Elsevier Ltd.. Washington, DC.

    Lluveras-Tenorio, Anna, Roberto Vinciguerra, Eugenio Galano, Catharina Blaensdorf, Erwin Emmerling, Maria Perla Colombini, Leila Birolo,and Ilaria Bonaduce

    2017 GC/MS and proteomics to unravel the painting history of the lost Giant Buddhas of Bāmiyān (Afghanistan). PLOS ONE 2017, 12 (4) , e0172990.

    https://doi.org/10.1371/journal.pone.0172990

    Lofrumento, Cristiana, Marilena Ricci, Luca Bachechi, Denise De Feod and Emilio Mario Castelluccie

    2011 The First Spectroscopic Analysis of Ethiopian Prehistoric Rock Painting. Journal of Raman Spectroscopy. Vol 43. Pp. 809-816.

    Lord, K. J.

    1984 The Zooarchaeology of Hinds Cave (41VV456). Ph.D diss. University of Texas, Austin.

    Lomax SQ, Lomax JF, De Luca-Westrate A.

    2014. The use of Raman microscopy and laser desorption ionization mass spectrometry in the examination of synthetic organic pigments in modern works of art. J Raman Spectrom. 2014;45:448–55. DOI: 10.1002/jrs.4480. Search in Google Scholar

    Lu, HouYuan.

    2017. New methods and progress in research on the origins and evolution of prehistoric agriculture in China. Science China Earth Sciences 2017, 60 (12) , 2141-2159

    https://doi.org/10.1007/s11430-017-9145-2

    Luo, Yanbing, Jiali Chen, Cheng Yang, and Yifan Huang.

    2019 Analyzing ancient Chinese handmade Lajian paper exhibiting an orange-red color. Heritage Science 2019, 7 (1) https://doi.org/10.1186/s40494-019-0306-6

    MacDonald Brandi Lee, David Stalla, Xiaoqing He, Farid Rahemtulla, David Emerson, Paul A. Dube, Matthew R. Maschmann, Catherine E. Klesner, Tommi A. White.

    2019 Hunter-Gatherers Harvested and Heated Microbial Biogenic Iron Oxides to Produce Rock Art Pigment. Scientific Reports; 9 (1) DOI: 10.1038/s41598-019-53564-w

    Macdonald, H.

    2004 Geologic Puzzles: Morrison Formation, Starting Point. Science Education Resource Center at Carleton College. http://serc.carleton.edu/introgeo/interactive/examples/morrisonpuzzle.html

    Macrae, James BH (James B. Harrison III)

    2005 Anthropomorphizing the Landscape: The Pecos River Style Core Motifs. Making Marks: Graduate Studies in Rock Art Research at the New Millenium, edited by Jennifer K.K. Huang and Elisabeth V. Culley, pp. 115-134. Occassional Paper, No. 5, American Rock Art Research Association. Tuscon, Arizona. P 129

    Macrae, James BH (formerly James Burr Harrison III)

    2022 A Theory about the Stylistic Development of Pecos River Pictographs spanning the Middle and Late Archaic Periods. The Bulletin of the Texas Archaeological Society.

    Macrae, James BH (formerly James Burr Harrison III)

    2018 Pecos River Style Rock Art: A Prehistoric Iconography. Texas A&M University Press, College Station, Texas.

    2010 Digging Into the Mind: Methods Used in the Study of “Enigmatic Characters” in Pecos River Style Pictographs. Paper presented at the American Rock Art Research Association 2010 Conference, Del Rio, Texas.

    Macrae, James BH

    2023 Oral account with author and researcher James BH Macrae. Bow, WA

    McLennan, Bill and Duffek, Karen

    2000 The Transforming Image: Painted Arts of Northwest Coast First Nations. UBC Press.

    Magrini, Donata, Susanna Bracci, Irina Crina Anca Dandu

    2013 Fluorescence of organic binders in painting cross-sections. SciVerse ScienceDirect. Procedia Chemistry 8 (2013) p194-201.

    Maier MS, Parera SD, Seldes AM.

    2004. Matrix-assisted laser desorption and electrospray ionization mass spectrometry of carminic acid isolated from cochineal. Int J Mass Spectrom. 2004;232:225–9. DOI: 10.1016/j.ijms.2003.12.008. Search in Google Scholar

    Mamyrin, B.A.

    2001 Time-of-flight mass spectrometry (concepts, achievements, and prospects)

    International Journal of Mass Spectrometry. Vol. 206, Iss. 3, Pp. 251-266.

    Manley, Marena

    2014 Near-infrared spectroscopy and hyperspectral imaging: Non-destructive analysis of biological materials. Royal Society of Chemistry: Chemical Society Reviews. Vol. 43 Pp. 8200-8214.

    Mantel, C.L.

    1950 The natural hard resins-Their Botany, Sources and Utilization. Economic Botany. Vol. 4 Pp. 203-242. July 1950

    Martelli Matteo

    2020 Ancient handbooks and Graeco-Egyptian collections of alchemical recipes. University of Bologne: BJHS Themes (2020), 5, 39–55 doi:10.1017/bjt.2020.4

    Martin, Paul S. and Byron E. Harrell

    1957 The Pleistocene History of Temperate Biotas in Mexico and Eastern United States. Ecology. Vol. 38, No. 3 (Jul., 1957), pp. 468-480. Wiley on behalf of the Ecological Society of America. https://www.jstor.org/stable/1929892

    Massey, Robert

    1967 Formulas for Painters. Watson-Guptill Publications, New York, NY.

    Mastros, Sara

    2021 The Big Book of Magical Inscense. Weiser Books, Newburyport, MA

    Mastrotheodoros, G, K.G.Beltsios, N Zacharias

    2010 Assessment of the Production of Antiquity Pigments Through Experimental Treatment of Ochres and Other Iron Based Precursors. Mediterranean Archaeology and Archaeometry. Vol. 10, No. 1. Pp 37-59.

    Mauran, G ; Lebon, M ; Lapauze, O ; Detroit, F ; Bahain, J.-J ; Pleurdeau, D ; Nankela, A ; LESUR, J Springer Verlag

    2020 Archaeological ochres of the rock art site of Leopard Cave (Erongo, Namibia): looking for Later Stone Age socio-cultural behaviours. The African archaeological review.

    Mawk, E. J., M. Hyman and M. Rowe

    2001 Re-examination of Ancient DNA in Texas Rock Paintings. Journal of Archaeological Science. Vol 29. Pp 301-306.

    Maya Ethnobotanicals

    2021 Online website. https://maya-ethnobotanicals.com/herbs/by-plant-form/dry-extracts

    McCouat, Philip

    2013 The Life and Death of Mummy Brown. Journal of Art in Society

    www.artinsociety.com.

    McNair, Harold M., James M. miller, and Nicolas H. Snow.

    2019 Basic Gas Chromatography. John Wiley and Sons, New Jersey.

    Meade, Pachomius (Matthew J.)

    2020 The Lower Senses in Early Netherlandish Epiphany Altarpieces. Dissertation, Art History and Archaeology, University of Missouri. https://doi.org/10-32469/10355/79507

    Medeghini, Laura, Pier Paolo Lottici, Caterina De Vito, Silvano Mignardi, and Danilo Bersani

    2013 Micro-Raman Spectroscopy and Ancient Ceramics. Journal of Raman Spectography. Vol. 45, Pp. 1244-1250.

    Melo, Maria J., Rita Castro, Paula Nabais and Tatiana Vitorino

    2018 The book on how to make all the colour paints for illuminating books: unravelling a Portuguese Hebrew illuminators’ manual. Heritage Science. 6:44

    México, Facultad de Química Educación química, 2011-01, Vol.22 (3), p.191-197

    Miliani, C., D. Domenici, C. Clementi, F. Presciutti, F. Rosi, D. Buti, A. Roamani, L Laurenich Minelli, A. Sgamellotti

    2011 Colouring materials of pre-Columbian codices: non-invasive in situ spectroscopic analysis of the Codex Cospi. Journal of Archaeological Science. Vol 39, Issue 3, March 2012, p 672-679.

    Miller, David M. and Diane C Shakes

    1995 Chapter 16 Immunofluorescence Microscopy. Methods in Cell Biology. Vol 48. Pp. 365-394. https://doi.org/10.1016/S0091-679X(08)61396-5

    Miller, R. J.

    2000 Exercising Cultural Self-Determination: The Makah Indian Tribe Goes Whaling. American Indian Law Review, 25(2), 165–273. http://www.jstor.org/stable/20070661

    Moritz, C.

    1994 Applications of Mitochondrial DNA analysis in Conservation: A Critical Review. Molecular Ecology. Vol. 3, Iss. 4, Pp. 401-411.

    Morrison, Alethea and Marcelino Vilaubi

    2017 Homegrown Honeybees. Storey Publishing. Massachusetts

    Muhlethaler, Bruno and Jean Thissen

    2014 Smalt. Studies in Conservation. Vol 14. Issue 2.

    Nabil Ali

    2018 Colourants made from aphids and ivy gum. Heritage Science (2018) 6:38 https://doi.org/10.1186/s40494-018-0204-3

    Naceur Belgacem, Mohamed, Anne Blayo, and Alessandro Gandini

    2003 Organosolv lignin as a filler in inks, varnishes and paints. Industrial Crops and Products. Vol 18. Pp. 145-153.

    Neddo, Nick

    2014 The Organic Artist: Make Your Own Paint, Paper, Pigments and Prints frm Nature. Laguna Hills : Quarto Publishing Group USA

    Neelmeijer, C. and M. Mader

    2002 The merits of particle induced X-ray emission in revealing painting techniques. Nuclear Instruments and Methods in Physics Research B 189 (2002) 293–302 .n

    Newman, Richard

    2013 Binders in Paintings. The Science of Art: MRS Bulletin, Volume 21, Issue12, pp. 24-31

    https://doi.org/10.1557/S0883769400032085

    Newman R, Kaplan E, Derrick M.

    2015 Mopa Mopa: Scientifc Analysis and History of an Unusual South American Resin Used by the Inka and Artisans in Pasto, Colombia. J Am Instit Conserv. 2015;54(3):123–48

    Newman, Richard

    2000 Organic binders. In The science of paintings (pp. 26-41). Springer, New York, NY.

    Nevin, A., S. Cather, D. Anglos, and C. Fotakis

    2007 Laser-induced fluorescence analysis of protein-based binding media. In Lasers in the Conservation of Artworks (pp. 399-406). Springer, Berlin, Heidelberg.

    Nibbs, Simone

    2012 Binding Ochre to Theory. Pomona Senior Theses

    Pomona College.

    Ntasi, George, Daniel P. Kirby, Ilaria Stanzione, Andrea Carpentieri, Patrizia Somma, Paola Cicatiello, Gennaro Marino, Paola Giardina, Leila Birolo.

    2021. A versatile and user-friendly approach for the analysis of proteins in ancient and historical objects. Journal of Proteomics 231 104039.

    https://doi.org/10.1016/j.jprot.2020.104039

    Oblaender, Carsten

    2023 Neanderthal apocalypse: a journey from extinction to genetic legacy. C-Tales Entertainment Inc. and Canadian Film, 2DF. Enterprises. Accessed 12/08/2023

    https://www.youtube.com/watch?v=KMiyN4XuPTY

    Olivares, M, Castro, K., Corchón, M. S., Gárate, D., Murelaga, X., Sarmiento, A., and Etxebarria, N.

    2013 Non-invasive portable instrumentation to study Palaeolithic rock paintings: the case of La Peña Cave in San Roman de Candamo (Asturias, Spain), Journal of Archaeological Science, 40, 1354–60.

    Ooi, Salvador, Martins, Pereira, Caldeira, and Ramalho.

    2019 Development of a Simple Method for Labeling and Identification of Protein Binders in Art. Heritage 2019, 2 (3) , 2444-2456.

    https://doi.org/10.3390/heritage2030150

    Ooi Su Yin, João P. Prates Ramalho, António Pereira, Sérgio Martins, Cátia Salvador, A. Teresa Caldeira.

    2019. A simple method for labelling and detection of proteinaceous binders in art using fluorescent coumarin derivatives⋆. The European Physical Journal Plus 2019, 134 (2)

    https://doi.org/10.1140/epjp/i2019-12478-4

    Orna, Mary Virginia

    2011 Chemistry and Art: Ancient textiles and medieval manuscripts examined through chemistry. Universidad Nacional Autónoma de

    Orna, Mary Virginia, Manfred J. D. Low, N. S. Baer,

    1980 Synthetic Blue Pigments: Ninth to Sixteenth Centuries. I. Literature, Studies in Conservation 25, 53-63.

    Orsini, Sibilla, Francesco Zinna, Tarita Biver, Lorenzo Di Bari, and Ilaria Bonaduce.

    2016. Circularly polarized luminescence reveals interaction between commercial stains and protein matrices used in paintings. RSC Advances 2016, 6 (98) , 96176-96181.

    https://doi.org/10.1039/C6RA14795J

    Orsini S, Yadav A, Dilillo M, McDonnell LA, Bonaduce I.

    2018. Characterization of degraded proteins in paintings using bottom-up proteomic approaches: new strategies for protein digestion and analysis of data. Anal Chem. 2018;90:6403–8. DOI: 10.1021/acs.analchem.8b00281.29733588 Search in Google Scholar

    Ortiz-Hidalgo Carlos, MD, and Sergio Pina-Oviedo, MD.

    2019 Hematoxylin: Mesoamerica’s Gift to Histopathology. Palo de Campeche (Logwood Tree), Pirates’ Most Desired Treasure, and Irreplaceable Tissue Stain. International Journal of Surgical Pathology. Vol, 27 (I) 4-14.

    Osada, Yoshihito, Kanji Kajiwara, Hatsuo Ishida (editors)

    2001 Gels Handbook: The Fundamentals. Published by Elsevier, first edition.

    Packard, Jane edited by Gerald North, Jurgen Schmandt and Judith Clarkson

    1995 The Impact of Global Warming on Texas. University of Texas Press, Austin Texas.

    Padden, Nikki A., Vivian Dillon, Philip John John Edmonds, M. David Collins, and Nerea Alvarez.

    1998 Clostridium used in mediaeval dyeing. Nature. 396, 225 (1998) Published: 19 November

    Page, Jason S., Ryan T Kelly, Kegi Tang, and Richard D. Smith

    2007 Ionization and transmission efficiency in an electrospray ionization—mass spectrometry interface. Journal of American Society for Mass Spectometry. Vol 18, Pp. 1582-1590.

    Paraschos, S., Mitakou, S., Skaltsounis, A.

    2012 Chios Gum Mastic: A Review of its Biological Activities. Current Medicinal Chemistry. Vol. 19, No. 14. Pp. 2292-2302.

    Perets, EA, Indrasekara AS, Kurmis A, Atlasevich N, Fabris L, and Arslanoglu J.

    2015. Carboxy-terminated immuno-SERS tags overcome non-specific aggregation for the robust detection and localization of organic media in artworks. Analyst. 2015;140:5971–80. DOI: 10.1039/c5an00817d.26171756

    Perez-Seoane, Matilde Muzquiz,

    1999. Techniques, Individual Artists, and Artistic Concepts in the Painting of Altamira. In The Cave of Altamira. Pedro A. Saura Ramos, editor. Harry N. Abrahms Inc. pp. 59-87

    Perrin, Jean

    2005 Brownian Motion and Molecular Reality.

    Dover, New York, 2005.

    Pascual, de Ágredos, M.L.V., Carbó, M.T.D. and Carbó, A.D.

    2008 Resins and Drying Oils of Precolumbian Painting: A Study from Historical Writings: Equivalences to Those of European Painting. Arché Publicación del Instituto Universitario de Restauración del Patrimonio De La UPV, 3, p.185.

    Piovesan, R., C. Mazzoli, L. Maritan, P. Cornale

    2012 Fresco and Lime-Paint: An experimental study and objective criteria for distinguishing between these painting techniques. Archaeometry. Online publication, Jan 16.

    https://doi-org.proxy.lib.sfu.ca/10.1111/j.1475-4754.2011.00647.x

    Pitthard, V., S. Stanek1 , M. Griesser1 , T. Muxeneder

    2005 Gas Chromatography – Mass Spectrometry of Binding Media from Early 20th Century Paint Samples from Arnold Scho¨nberg’s Palette. Chromotagraphia. Vol. 62, p.175-182.

    Ploeger, Rebecca , and Aaron Shugar.

    2016. Where science meets art. Science 2016, 354 (6314) , 826-828.

    https://doi.org/10.1126/science.aai8387

    Pozzi, Frederica, Julie Arslanoglu, Francesca Galluzzi, Caroline Tokarski, and Reba Snyder.

    2020. Mixing, dipping, and fixing: the experimental drawing techniques of Thomas Gainsborough. Heritage Science 2020, 8 (1)

    https://doi.org/10.1186/s40494-020-00431-x

    Prescuitti, Frederica, Juan Perlo, Federico Casanova, Stefan Glöggler, Costanza Miliani, Bernhard Blümich, Brunetto Giovanni Brunetti, and Antonio Sgamellotti.

    2008 Noninvasive nuclear magnetic resonance profiling of painting layers. Applied Physics Letters. 93, 033505. American Institute of Physics. published online 22 July 2008 . https://doi.org/10.1063/1.2963026

    Pruvost, Sebastien, Pascal Berger, Claire Herold, Philippe Lagrange

    2004 Nuclear microanalysis: An efficient tool to study intercalation compounds containing lithium. Science Direct:Carbon. Vol. 42. Pp. 2049-2056.

    Raun, G.

    1966 A Vertebrate Paleofauna of Amistad Reservoir. In A Preliminary Study of the Paleoecology of the Amistad Reservoir Area, assembled by D.A. Story and V.M. Bryant, Pp. 209-220. Final Report under National Science Foundation.

    Ramos, Pedro A. Saura

    1988 The Cave of Altamira. Lunwerg Publishers, Barcelona.

    Reese, Ronnie Lynn, J.N. Derr, M. Hyman, M.W. Rowe and S. K. Davis

    1996a Ancient DNA in Texas Pictographs. Journal of Archaeological Science 23:269-277.

    Reese, Ronnie Lynn, J.N. Derr, M. Hyman, M.W. Rowe and S. K. Davis

    1996b Ancient DNA from Texas Pictographs. In Archaeological Chemistry V: Organic, Inorganic, and Biochemical Analysis: 378-390, edited by M.V. Orna. Advances in Chemistry Series, American Chemical Society, Washington, D.C.

    Reese, Ronnie Lynn

    1994 DNA Studies of the Ancient Paint Binder/ Vehicles used in Lower Pecos Rock Art Pictographs. Texas A&M PHD Department of Chemistry.

    Reiss, Breanna

    2018 Compositional Analysis and Cross-Cultural Examination of Blue and Blue-Green Post-Fire Colorants on Tolita-Tumaco Ceramics. University of New Mexico Masters Thesis.

    Rene de la Rie, E.

    1989 Old master paintings: a study of the varnish problem. Americal Chemical Society. Vol. 61 No.21, Nov. 1989.

    Ricciardi Paola

    2019 Manuscripts in the Making: Art and Science. Heritage Science (2019) 7:60 https://doi.org/10.1186/s40494-019-0302-x

    Riley, Tim

    2008 Diet and seasonality in the Lower Pecos: evaluating coprolite data sets with cluster analysis. Journal of Archaeological Scienc.e Vol. 35 Pps. 2726-2741.

    Roldán, Clodoaldo, Sonia Murcia-Mascarós, Esther López-Montalvo, Cristina Vilanova, Manuel Porcar.

    2018. Proteomic and metagenomic insights into prehistoric Spanish Levantine Rock Art. Scientific Reports 2018, 8 (1)

    https://doi.org/10.1038/s41598-018-28121-6

    Roquero, Ana

    2008 Identification of Red Dyes in Textiles from the Andean Region (2008). Textile Society of America Symposium Proceedings. 129. https://digitalcommons.unl.edu/tsaconf/129

    Roquero, Ana

    2006 Tintes y Tintoreros de América “Dyes and Dyers from America.”

    Rowe, Marvin W.

    1996 Ancient DNA from Texas Pictographs. Journal of Archaeological Science.

    Rowe, Marvin W.

    2002 Re-examination of Ancient DNA in Texas Rock Paintings. Journal of Archaeological Science.

    Rowe, Marvin W.

    2004 Radiocarbon Dating of Ancient Pictograms with Accelerator Mass Spectometry. Rock Art Research 21:145-153.

    Rudner, Ione

    1983 Paints of the Khoisan Rock Artists. Vol. 4, New Approaches to Southern African Rock Art . pp. 14-20.

    Russ, Jon, Marian Hyman and Marvin Rowe

    1992 Direct Radio-Carbon Dating of Rock Art. Radiocarbon. Vol 34, No 3. Pp. 867-872.

    Russ, J., M. Hyman, H. Shafer and M. Rowe

    1990 Radiocarbon dating of prehistoric rock paintings by selective oxidation of organic carbon. Nature (London). Vol. 348. Pp. 710-711.

    Russ, Jon, Marian Hyman and Marvin Rowe

    1992 Direct Radio-Carbon Dating of Rock Art. Radiocarbon. Vol 34, No 3. Pp. 867-872.

    Sadowski, Kathy

    2020 The Difference between Resins and Gums for Aromatherapy Use. NAHA, National Association for Holistic Aromatherapy. February 10, 2020

    Salem, Nidhal, Myrian Lamine, Bilel Damergi, Fatma Ezahra, Nedia Feres, Selim Jallouli, Majdi Hammami, Saber Khammassi, Sawsen Selmi, Salem Elkahouli, Ferid Limam, Olfa Tabben.

    2020 Natural colourants analysis and biological activities. Association to molecular markers to explore the biodiversity of Opuntia species. Phytochemical Analysis. 2020;31: Pps. 892–904.

    Shafer, Harry J.

    2013 Painters in Prehistory; Archaeology and Art in the Lower Pecos Canyonlands. Trinity University Press, San Antonio Texas.

    Saunders J.W.

    1986 The Economy of Hinds Cave. Ph. D. dissertation. Southern Methodist University, Dallas.

    Schadler, Koo

    20178 History of Egg Tempera Painting. Online Publication at www.kooschadler.com

    Schmitt, Sibylle

    2020 Research on the Pettenkofer method and the historical understanding of paint film swelling and interaction; Conservation of Easel Paintings. Routledge 2nd edition.

    Schochetman, Gerald, Chin-Yin Ou and Wanda K. Jones

    1988 Polymer Chain Reaction. The Journal of Infectious Diseases. Vol. 158, No. 6, Pp. 1154-1157.

    Sciutto,G, LS Dolci, M Guardigli, M Zangheri, S Prati, R Mazzeo, A Roda.

    2013. Single and multiplexed immunoassays for the chemiluminescent imaging detection of animal glues in historical paint cross-sections. Analytical and bioanalytical. link.springer.com

    Seladi-Schulman, Jill, Jenneh Rishe, RN (Medically review)

    2022 What is Bone Marrow and What Does It Do? Healthline, online publication. https://www.healthline.com/health/function-of-bone-marrow

    Shackley. M Steven

    2010 An Introduction to X-Ray Fluorescence (XRF) Analysis in Archaeology. Springer New York.

    Shafer, Harry J (Editor). 2013. Painters in Prehistory: Archaeology and Art of the Lower Pecos Canyonlands. Trinity University and the Witte Museum.

    Shevchenko, Anna , Andrea Schuhmann, Henrik Thomas, Günter Wetzel, . Fine Endmesolithic fish caviar meal discovered by proteomics in foodcrusts from archaeological site Friesack 4 (Brandenburg, Germany). PLOS ONE 2018, 13 (11) , e0206483.

    https://doi.org/10.1371/journal.pone.0206483

    Shortland, Andrew, Lukas Schachner, Ian Freestone, Michael Tite.

    2006 Natron as a flux in the early vitreous materials industry: sources, beginnings and reasons for decline. Journal of Archaeological Science. Vol.33 Issue 4. Pp. 531-530.

    Sibilla Orsini, Sibilla , Emilia Bramanti, and Ilaria Bonaduce.

    2018 Analytical pyrolysis to gain insights into the protein structure. The case of ovalbumin. Journal of Analytical and Applied Pyrolysis 2018, 133 , 59-67

    https://doi.org/10.1016/j.jaap.2018.04.020

    Sibilla, Orsini, Avinash Yadav, Marialaura Dilillo, Liam A. McDonnell and Ilaria Bonaduce.

    2018. Characterization of Degraded Proteins in Paintings Using Bottom-Up Proteomic Approaches: New Strategies for Protein Digestion and Analysis of Data. Analytical Chemistry , 90 (11) , 6403-6408.

    https://doi.org/10.1021/acs.analchem.8b00281

    Song, Yoojung, Jinwoo Park, Chanoong Lim, and Dong Woog Lee

    2020 In-Depth Study of the Interaction Mechanism between the Lignin Nanofilms: Toward a Renewable and Organic Solvent-Free Binder. ACS Sustainable Chemistry and Engineering. Vol 8. Pp. 362-371.

    Spades, S. and J. Russ

    2005 GC-MS Analysis of lipids in Prehistoric Rock Paints and Associated Oxalate Coatings from the Lower Pecos Region, Texas. Archaeometry. Vol 47. Iss. 1. Pp. 115-126.

    Steelman, Karen L., Marvin Rowe, Peter W Veth, Jo McDonald.

    2012 Radiocarbon Dating of Rock Paintings: Incorporating Pictographs into the Archaeological Record. A Companion to Rock Art. John Wiley & Sons, Ltd. Chichester, UK. Pp.563-582

    Steger, Simon , Heike Stege, Simone Bretz, Oliver Hahn.

    2018 Capabilities and limitations of handheld Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) for the analysis of colourants and binders in 20th-century reverse paintings on glass. Acta Part A: Molecular and Biomolecular Spectroscopy 2018, 195 , 103-112.

    https://doi.org/10.1016/j.saa.2018.01.057

    Stijinman, Ad

    2002 Iron-gall ink and ink corrosion. Archivum Lithuanicum. Vol.4, Pp. 171-178.

    Stodulski, L. E. Farrell and R. Newman

    1984 Identification of Ancient Persian Pigments from Persepolis and Pasargadae. Studies in Conservation , Taylor & Francis, Ltd. Aug., 1984, Vol. 29, No. 3 pp. 143-154

    https://www.jstor.org/stable/1506017

    Stuart, B.H., P.S. Thomas

    2017 Pigment characterisation in Australian rock art: a review of modern instrumental methods of analysis. Heritage Science. 5:10

    Scientific Editors: Swami, Sukhdev, Handa Suman, Preet Singh, Khanuja Gennaro, and Longo Dev Dutt Rakesh

    2008 Extraction Technologies for Medicinal and Aromatic Plants. International Centre for Science and High Technology. Trieste, Italy

    Swink, Clint

    2014 Messages. Redtail Press; First Edition. Sacramento, CA.

    Taft, Stanley W. Jr. and James W. Mayer

    2000 The Science of Paintings. Springer-Verlag, New York, Inc.

    Takats, Zoltan, Justin M. Wiseman, Bogdan Gologan and R. Graham Cooks

    2004 Mass Spectrometry Sampling Under Ambient Conditions with Desorption Electrospray ionization. Science. Vol. 306, No. 5695.

    Tamburini, Diego , Joanne Dyer, Ilaria Bonaduce.

    2017 The characterisation of shellac resin by flow injection and liquid chromatography coupled with electrospray ionization and mass spectrometry. Scientific Reports 2017, 7 (1

    https://doi.org/10.1038/s41598-017-14907-7

    Tanasi, Davide, Annamaria Cucina, Vincenzo Cunsolo, Rosaria Saletti, Antonella Di Francesco, Enrico Greco, Salvatore Foti.

    2021 Paleoproteomic profiling of organic residues on prehistoric pottery from Malta. Amino Acids 53 (2) 295-312.

    https://doi.org/10.1007/s00726-021-02946-4

    Texas Parks and Wildlife

    2023 Alligator Gar: Texas’ largest and most misunderstood freshwater fish. Online source July 2,2023. www.tpwd.texas.gov

    Thiemann, Laura, Stefanie Gerzer, Ralf Kilian

    2010 Vitruvius and Antique Techniques for Plaster work and Painting. 2nd Historic Mortars Conference HMC2010 and RILEM TC 203-RHM Final Workshop 22-24 September 2010, Prague, Czech Republic.

    Thompson DV.

    1936 The practice of tempera painting. New Haven: Yale University Press, Reprinted by Dover Publications (1962). Search in Google Scholar

    [37] Sickels LB. Organic additives in mortars. Edinburgh Archit Res. 1981;8:7–20. Search in Google Scholar [38]

    1956 The materials and techniques of medieval paintings. New York: Dover Publications.

    Tripkovic T., C. Charvy, S. Alves, A.D. Lolic, R.M. Baosic, Nikolic-Mandic, and J.C. Tabet

    2013. Identification of protein binders in artworks by MALDI-TOF/TOF tandem mass spectrometry. Talanta, Volume 113, 2013, pp. 49-61

    Trojanowicz, Marek

    2000 Flow Injection Analysis: Instrumentation and applications. World Scientific Publishing, London, NJ, Singapore.

    Tsien, Tsuen-Hsuin.

    1973 Raw Materials for Old Papermaking in China. Journal of the American Oriental Society, vol. 93, no. 4, pp. 510–19. American Oriental Society. https://doi.org/10.2307/600169.

    Turner, Matt Warnock

    2009 Remarkable Plants of Texas : Uncommon Accounts of Our Common Natives. University of Texas Press.

    Turpin, Solveig A.

    2017 Ethnographic Observations of Bison in the Lower Pecos River Region: Implications for Environmental Change.

    Plains Anthropologist. Vol. 32, Iss. 118.

    Turpin, Solveig A.

    1996 Painting on bones and other unusual media in the Lower and Trans-Pecos Region of Texas and Coahuila. Plains Anthropologist: Journal of the Plains Anthropological Society. Vol 41, Iss. 157.

    Turpin, Solveig A.

    1997 Pigment Cakes from the Lower Pecos River Region, Texas. La Tierra Vol 24, No. 4. October 1997.

    Turpin, Solveig A

    1986 Toward a Definition of a Pictograph Style: The Lower Pecos Bold Line Geometric. Lincoln, NE: Routledge. Plains anthropologist, Vol.31 (112), Pp.153-163.

    Tuurnala, T. , A. Hautojärvi and Kirsti Harva

    1985 Non-destructive analysis of paintings by PIXE and PIGE.

    Studies in Conservation , May, 1985, Vol. 30, No. 2 (May, 1985), pp. 93-99

    2019 University of Missouri-Columbia. "Scientists use modern technology to understand how ochre paint was created in pictographs: Ochre, one of Earth's oldest naturally occurring materials, was often seen as a vivid red paint." ScienceDaily. ScienceDaily, 19 November 2019. <www.sciencedaily.com/releases/2019/11/191119132515.htm>.

    Van Dam EP, van Den Berg KJ, Gaibor AN, and van Bommel M.

    2016. Analysis of triglyceride degradation products in drying oils and oil paints using LC–ESI–MS. Int J Mass Spectrom. 2017;413:33–42. DOI: 10.1016/j.ijms.2016.09.004.

    Vandenabeele, P. B. Wehling, L. Moens, H Edwards, M De Reu, G Van Hooydonk.

    2000 Analysis with micro-Raman spectroscopy of natural organic binding media and varnishes used in art. Analytica Chimica Acta. Vol. 407, Issue 1-2, p.261-274.

    Van Den Berg JD, Vermist ND, Carlyle L, Holcapek M, and Boon JJ.

    2004. Effects of traditional processing methods of linseed oil on the composition of its triacylglycerols. J Sep Sci. 2004;27:181–99. DOI: 10.1002/jssc.200301610.15334906 Search in Google Scholar

    Van der Werf, Inez Dorothé , Cosima Damiana Calvano, Giulia Germinario, Tommaso R.I. Cataldi, Luigia Sabbatini.

    2017 Chemical characterization of medieval illuminated parchment scrolls. Microchemical Journal 2017, 134 , 146-153 https://doi.org/10.1016/j.microc.2017.05.018

    Van der Werf, Inez D., Klaas van den Berg, Sibylle Schmitt and Jaap J. Boon.

    2000 Molecular Characterizations of Copaiba Balsam as Used in Painting Techniques and Restoration Procedures. The Journal of the International Institute for Conservation of Historic and Artistic Works. Vol 45, No 1.

    Van Doorn N.L.

    2014 Zooarchaeology by Mass Spectrometry (ZooMS). In: Smith C. (eds) Encyclopedia of Global Archaeology. Springer, New York, NY. https://doi-org.proxy.lib.sfu.ca/10.1007/978-1-4419-0465-2_2418

    Vazquez de Agredos Pascual, Luisa, Teresa Domenech Carbo, and Antonio Domenech Carbo

    2008 Resins and Drying oils of Pre-Colombian paintings: A Study from Historical Writings. Equivalences to Those of European Painting. ARCHÉ. PUBLICACIÓN DEL INSTITUTO UNIVERSITARIO DE RESTAURACIÓN DEL PATRIMONIO DE LA UPV.

    Vetter, Wilfried, Irene Latini and Manfred Schreiner.

    2019 Azurite in medieval illuminated manuscripts: a refelction-FTIR study concerning the characterization of binding media. Heritage Science. 7:21

    Vieira, Márcia, Paula Nabais, Eva Mariasole Angelin, Rita Araújo, João Almeida Lopes, Lourdes Martín, Marta Sameño and Maria J. Melo.

    2019 Organic red colorants in Islamic manuscripts (12th-15th c.) produced in al-Andalus, part 1. Dyes and Pigments 2019, 166 , 451459. https://doi.org/10.1016/j.dyepig.2019.03.061

    Villa, Paola, Luca Pollarolo Ilaria Degano, Leila Birolo, Marco Pasero, Cristian Biagioni, Katerina Douka, Roberto Vinciguerra, Jeannette J Lucejko, Lyn Bicho Wadley, and Nuno.

    2015. A Milk and Ochre Paint Mixture used 49,000 years ago at Sibudu, South Africa. SAN FRANCISCO: PUBLIC LIBRARY SCIENCE

    PloS one, 2015-06-30, Vol.10 (6), p.e0131273-e0131273

    Vinciguerra, Roberto, Anna Illiano, Addolorata De Chiaro, Andrea Carpentieri, Anna Lluveras-Tenorio, Ilaria Bonaduce, Gennaro Marino, Piero Pucci, Angela Amoresano, and Leila Birolo.

    2019 Identification of proteinaceous binders in paintings: A targeted proteomic approach for cultural heritage. Microchemical Journal 2019, 144 , 319-328.

    https://doi.org/10.1016/j.microc.2018.09.021

    Vinciguerra R, Galano E, Vallone F, Greco G, Vergara A, Bonaduce N, et al.

    2015. Deglycosylation step to improve the identification of egg proteins in art samples. Anal Chem. 2015;87:10178–82. DOI: 10.1021/acs.analchem.5b02423.26399393 Search in Google Scholar[34]

    Voss, Gundula

    2006 The analysis of indigoid dyes as leuco forms by NMR spectroscopy.

    Department of Bioorganic Chemistry, University of Bayreuth, D-95440 Bayreuth, Germany

    Accepted: 14 July 2006

    doi: 10.1111/j.1478-4408.2006.00046.x

    Wallquist, Olof and R. Lenz

    2002 20 years of DPP Pigments-Future Perspectives. Macromolecular Symposium. Vol 187. Pp. 617-629.

    Wang, Xin, Gang Zhen, Xinying Hao, Ping Zhou, Zhan Wang, Jia Jia, Yan Gao, Shaohua Dong, and Hua Tong.

    2021. Micro-Raman, XRD and THM-Py-GC/MS Analysis to Characterize the Materials Used in the Eleven-Faced Guanyin of the Du Le Temple of the Liao Dynasty, China. Microchemical Journal 40:106828.

    https://doi.org/10.1016/j.microc.2021.106828

    Watrous, James

    1957 The Craft of Old Master Drawings. The University of Wisconsin Press, Madison Wisconsin, and London.

    Watts, Kristen E, Anthony F Lagalante

    2018 Method development for binding media analysis in painting cross-sections by desorption electrospray ionization spectrometry. England: Wiley Subscription Services, Inc. Rapid communications in mass spectrometry, 2018-08-30, Vol.32 (16), p.1324-1330

    White, Joe L., and Charles B. Roth

    1986 Infrared Spectrometry. Methods of Soil Analysis: Part 1 Physical and Mineralogical Methods, 5.1, Second Edition. Chapter 11. American Society of Agronomy, Inc. Soil Science Society of America, Inc.

    Willis, Paul

    2013 The manufacture and use of Japanese Wheat Paste Adhesives in the Treatment of far Eastern Pictorial Art. Studies in Conservation.

    Online publication. Dec 13, 2013. Pp 123-126.

    Witkowski, Bartłomiej , Anna Duchnowicz, Monika Ganeczko, Agnieszka Laudy, Tomasz Gierczak, and Magdalena Biesaga.

    2018 Identification of proteins, drying oils, waxes and resins in the works of art micro-samples by chromatographic and mass spectrometric techniques. Journal of Separation Science 2018, 41 (3) , 630-638

    https://doi.org/10.1002/jssc.201700937

    Yerushaimi-Rozen, Rachel and Jacob Klein

    1995 Polymer brushes paint a stable picture. Physics World. 8 (8) 30

    Yoshioka, Sachio

    2021 In Search of Forgotten Colours - Sachio Yoshioka and the Art of Natural Dyeing. Online site. https://www.youtube.com/watch?v=7OiG-WjbCQA

    Young, M. Jane

    1988 Sign from the Anscestors: Zuni Cultural Symbolism and Perceptions of Rock Art. University of New Mexico Press.

    Young Lee, Hae, Natalya Atlasevich, Clara Granzotto, Julia Schultz, John Loike and Julie Arslanoglu.

    2015 Devlopment and Application of an ELISA Method for the Analysis of Protein-Based Binding Media of Artworks. Analytical Methods. Vol 7, Pp. 187-196. DOI: 10.1039/C4AY01919A

    Yu, Jia Yong Jae Chung.

    2019. Analysis of Cow Hide Glue Binder in Traditional Dancheong by Enzyme-linked Immunosorbent Assay. August 2019. Journal of Conservation Science. 35(4):363-372

    Xian, Feng, Christopher L. Hendrickson, and Alan G. Marshall

    2012 High Resolution Mass Spectrometry. Analytical Chemistry. Vol. 84 Pp. 708-719.

    Zhang, Yao, Zhenjiang Miao, Yanghua Liu and Wei Zhou

    2012 An ink-diffusion-based rendering method for Chinese ink painting. Proc. SPIE 8334, Fourth International Conference on Digital Inage Processing (ICDIP), 83344L; https://doi-org.proxy.lib.sfu.ca/10.1117/12.976037

    Zilberstein, Gleb, Svetlana Zilberstein, Uriel Maor, Emmanuil Baskin, Alfonsina D'Amato, and Pier Giorgio Righetti.

    2019. De re metallica. Johannes Kepler and alchemy. Talanta 2019, 204 , 82-88.

    https://doi.org/10.1016/j.talanta.2019.05.094

  • Theodora Jonsson-Macrae

    Simon Fraser University 2021

    Cross Cultural Ingredients and Scientific Analysis Techniques for Identifying Archaeological Paint Binders and Carriers

    Introduction

    Across the world, and through centuries, binders and their carriers are the vehicles for pigments in paints, dyes, inks and varnishes. Paint binders and their carriers, compared to the pigments, are less understood, yet essential, in creating long lasting paintings. These binders and carriers function as the mode and body character of the paint and directly affect its application and preservation.

    The following paper and associated literature review will attempt to answer the following questions:

    1. What ingredients have been used to create long lasting and vibrant paints by artists living in literate societies, ancient to the present?

    2. How do these ingredients function in the paint?

    3. How many of the ingredients are found in nature and how many are industrially produced or man-made?

    4. Are there existing scientific methods that can test for the presence of the ingredients in historic and archaeological paintings?

    5. Are these methods destructive or non-destructive?

    6. Are these methods used in situ?

    7. Have the significant methods been used, and if so, what was the result?

    Since prehistoric times, humans used paint for communication, adornment and decoration. Ancient paints were produced using binders such as egg, milk, blood or plant saps which were combined with mineral pigments, ashes, charcoal, and other substances to create different colors of paint (Gooch 2002). Natural ingredients were extracted and hand processed to create paint, inks and dyes.

    Moving forward, in the 8th century A.D., Theophilus wrote about the earliest syntheses of artificial pigments and preparation process. By the 9th century AD, man-made substitutes in pigments were common, for example to produce a more affordable option for blue paint (Gooch 2002; Orna et al. 1980).

    Paint is comprised of three basic components: the pigment, binder and vehicle. The binder can be made of egg, gum, oil or a synthetic such as an alkyd or acrylic polymer (Gooch 2002). The pigment is made from an organic or inorganic powder and is spread out in a liquid which enables it to bind the powdered particles together and to the surface of the painting. The third element which is sometimes necessary is a vehicle or dilutant which is competent with the binder. For instance, turpentine dilutes oils, and water dissipates gum, egg and acrylics.

    Binders and their carriers are “invisible” component of paint which are responsible for the quality, temperament and nature of the paint, but not typically the color. Binders and carriers determine whether a paint mixture moves fast or slow, is fluid or stiff, waxy or glossy, fast drying or slow drying, lasting or fading. Binders can be classified by three major categories of origin: plant, animal and mineral. This paper explains subcategories within each of the major types.

    I briefly describe the analytical tools used to identify different types of binders in paints in the second portion of this paper. This section delves more deeply into the various analytical techniques which are broken down into the following classifications: (1) hyper-spectral Imaging, (2) spectral imaging, (3) mass spectrometry and gas chromatography, (4) immune response analysis (5) chemometrics/chemical testing, (6) nuclear analyses, and (7) DNA analysis.

    I reviewed over seventy publications, looking at worldwide cultural uses of organic materials as binders and carriers in recipes for paints, inks and dyes. The binders and carriers described include materials derived from lipids (including animal and deer fat), lichen (Roquero 2008), honey, tree gum, plant gum and fruit, resin, turpentine, beeswax, casein (including egg, milk, and cheese), mummies (Jin 2012), urine, animal skin, animal hooves, fish glue (Yu 2019), and insects such as Kermes, aphids and beetles (Tripković et al. 2012; Vandenabeele et al. 1999).

    Many research articles I reviewed are somewhat different from the archaeological objective of my research, the identification of paint recipes in prehistoric rock art, but the techniques reviewed in this paper show promise in empirically answering those questions.

    In the conclusion of this paper, I included a table that lists over 261 specific ingredients found in the literature review—binders and additives used in various regions of the world, and how they function in paints, dyes and inks, textiles, and history.

    The information is based on the writings of literate peoples, including ancient societies, including Mayan, Aztec, Incan, Japanese, Persian, Indian, African, and European sources. This research is revealing how diverse the recipes for lacquers, paints, inks, and dyes have been throughout history, as well as how complex the correspondence was between cultural processes and technologies involving ceremonies, food, textiles, and painting, all of which are part of the evolution of complicated pigment binding techniques (Mandana 2016).

    Much of the literature stems from the field of art and historic manuscript conservation, and research to determine how to preserve or restore ancient and historic painted works of art. Determining the ingredients in paints, dyes and inks through various analysis techniques has been important in the conservation of ancient and Old-World works of art. This research often looks at stratigraphic layers and the micro-topography of painted and scripted artworks found in wall frescoes, painted ceramics and illuminated manuscripts from South America, Europe, the Middle East, Japan, China and India.

    The use and application of these technologies in art history has evolved over the years leading to greater clarity in determining the manufacturing process and structure of specific paintings; while bringing insights into the perishability of artwork due to different ingredients and binders; separating the work of the original artist from subsequent repainting activities. Scientific analysis is critical to differentiate between original ingredients, undocumented restorations and known historic changes in paint technologies (for example the transition between egg tempura to oil paint during the Renaissance) (Kriss 2018; Magrini 2013).

    Binders in paintings originated as naturally occurring adhesives from animal skin that are found in Egyptian, Chinese, and Japanese paintings. Varieties of paint media used in binders and carriers affect how the paint behaves, flows, dries, and how thick or thin it is. Knowledge of paint media is essential in understanding ancient painting and material technologies.

    Early European and Middle East illuminated manuscript scribes originally used glue and egg as binders for inks and paint (Darzi 2021). Later oil-based paints and plant gums were popular for illuminators and painters in Renaissance Europe, providing a greater optical affect than egg tempera (Kroustallis 2011). Traditional egg tempera combines pigments with water (the dilutant) and egg yolk or egg white as a binder. During the 15th century and Renaissance period, tempera grassa, and other oil and egg recipes, were introduced, as well as the use of siccative oils in binders to accelerate the drying time of paint (Levy et al. 2018).

    Major Analytical Techniques

    Scientific analytical techniques, many developed for chemistry or medicine, have been fruitfully adapted for the analysis of paint binders and ingredients in studies worldwide.

    In order to simplify a wide range of complex analytic techniques, I utilized the following general categories: (1) hyper-spectral Imaging, (2) spectral imaging, (3) mass spectrometry and gas chromatography, (4) immune response analysis (5) chemometrics/chemical testing, (6) nuclear analyses, and (7) DNA analysis.

    There are various specific analysis techniques and methods under each category summarized in (Tables 1-7) and some are used in combination with others. Some specific techniques with interesting or promising results are described in the text.

    Analysis techniques are more useful with a better understanding of their functions and how they evolved to be used in combination to better identify paint binders. The forms of analysis used in the early 1990’s for paint ingredients give a general classification of all types of material present in paint mixtures.

    Earlier analysis methods include 1-biological staining of cross sections of media to identify a binder; 2- immunoflorescent staining, giving a general classification of all types of compounds; 3- micro-fourier transform infrared (FTIR) analysis, commonly used to determine the chemical structure of a binder, such as determining whether it is made up of a lipid, protein or sugar derivative, carbohydrate or natural resin; and 4- gas chromatography–mass spectrometry (GC–MS) which can identify more closely whether the binder ingredient is composed of milk, egg or glue protein.

    Taking analysis steps further, more specific techniques for identifying binders include: 5- pyrolysis mass spectrometry to give a general and many times specific identification; 6- liquid chromatography, to identify proteins specifically; and 7- gas chromatography, to give specific identification of binders (Newman 1996).

    More recently, developments in analysis techniques have led to additional information in helping to identifying the species origin of a binder. This differentiates whether a protein binder originated from a specific species or sub population within a species (Albertini et al. 2010). DNA analysis takes the investigation process further to identify the exact origin of the binder (as long as the sample is not contaminated as tiny bits of DNA sampling can be easily affected by environmental conditions). The development of mitochondrial DNA, mtDNA, analysis can reveal helpful information about ancient species and differentiation in a lineage of a species (Albertini et al. 2010).

    Hyperspectral Imaging

    Hyperspectral Imaging is a major class of paint binder and pigment analysis techniques found during my literature review. It involves bombarding paint samples with frequencies of electromagnetic radiation above or below those of visible light, such as those in the ultraviolet, infrared, gamma-ray and X-ray frequencies. Each technique requires different equipment according to the method and range of the electromagnetic wavelengths it generates. Since the data they produce are outside the visible spectrum, their data must be linked to a visible spectral imaging method such as spectroscopy or spectrometry which converts hyperspectral data into spectral data.

    Hyperspectral imaging is useful because many more ingredients can be detected by isolating individual frequencies. It is used often in conjunction with additives which cause targeted proteins to fluoresce in the visible spectrum, delineating where the binder is located within a paint mixture as well as its composition.

    Hyperspectral imaging analysis, HSI, has been used by museums for more than a decade for in situ analysis within the visible range of colorants. It is considered to be non-destructive and has had great advantages in identifying ingredients in Japanese woodblock prints.

    Japanese woodblocks, known as ukiyo-e prints, were created generally during the 18th to 19th centuries. Ukiyo-e were made with traditional pigments including red safflower (orpiment), Prussian blue, aniline red, violet and indigo. Color materials were able to be identified, such as gamboge, a partially transparent deep saffron to mustard yellow pigment.

    Gamboge is also the traditional color used to dye Buddhist monks' robes, in combination with verdigris, a bright bluish-green patina formed on copper by atmospheric oxidation and orpiment, and a bright yellow mineral consisting of arsenic trisulfide.

    Minerals such as indigo and gamboge, verdigris and indigo, Prussian blue and orpiment, with dragon’s blood, brazilwood (logwood), cochineal, malachite and azurite, and chrysocolla were also detected using HSI.

    Results indicate that near-infrared analysis is helpful in distinguishing between various pigments.

    The identification of pigments has also been possible using short wave infrared hyperspectral imaging (SWIR) and HSI. These methods determined the location of organic materials and distinguished between inorganic and organic color agents.

    These conclusions were found to be parallel with those obtained with visible hyperspectral imaging.

    Infrared false color imagery is used with a hyperspectral imaging camera to identify pigments. Hyperspectral imaging, HSI, can identify a great number of pigments, however, it remains a weak point of HSI to distinguish between pigments with identical colors (Biron 2020; Taft et al. 2000).

    Infrared reflectography uses the differential reflection of infrared rays to allow us to discern multiple layers of a paint sample, detecting underpainting and substrate layers and illuminating the history of a painting (Taft and Mayer 2000).

    Infrared microscopy and spectrometry are widely used tools for simultaneously assessing information about binders and pigments and require a very small sample to do so.

    Binders which have different proteins and show nearly the same spectra cannot be differentiated, such as in egg, animal glue and casein. In my research I found that in an investigation of a cartoon drawing of the Raphael’s work titled “The School of Athens,” in Pinoteca, Ambrosiana, scanning electron microscopic/energy-dispersive spectrometic (SEM/EDS) was used in combination with Raman and fourier transform-infrared spectroscopy,FTIR, to determine which part of the drawing was original and which was added later at some point as a part of restoration. The analysis was destructive requiring 37 micro-samples from the front and back of the drawing and not in situ. Samples of the paper with a patina were analyzed with SEM/EDS, revealing calcium as well as lead, silicon, sulphur, potassium, iron and aluminium probably from a very thin layer of guache. SEM/EDS was not however, able to detect the ingredients FTIR revealed including a protein animal glue, gypsum and a polysaccharide, most likely gum Arabic. SEM/EDS can however, be used in situ, on fragments by using microscopic analysis (Ioele et al. 2016).

    Fourier transform-infrared spectrometry (FT-IR) uses a multichromatic light and a mathematical transformation of spectral data received to analyze samples. is less helpful in modern painting analysis because in more modern paint mixtures, due to the strong absorption of infrared from high levels of pigment versus binder mixtures, the infrared signal can be overwhelmed and may not be able to identify the binder ingredient. When the pigment and binder does not absorb infrared light to a high degree and more infrared is reflected back, can an identification be made (Watts and Lagalante 2018).

    In my research I came upon an investigation into dark red colors found in the conservation of Islamic manuscripts using microspectrofluorimetry and infrared spectroscopy (microFTIR). The manuscript, Fondo Ka’ti, Timbuktu, Mali, initiated investigation into the organic red colorant applied in five different manuscripts: a Quran from 1198 A.D., a theology treatise (14th c.), a biography of the Prophet from 1468 A.D., a manuscript 19 from 1485 A.D. and a book of poems from Al-Sarishi (15th c.). MicroFTIR, a micro-spectroscopy technique was able to categorize the paint formula by identifying the protein nature of the fillers and binding materials in the paint. Analysis of the Theology treatise revealed the use of a polysaccharide such as mesquite gum and, in other manuscripts, varying proportions of shellac resin and protein binder were found using the infrared spectra of red colorants in Quran, Theology treatise, and the Prophet biography. The infrared spectra of red colorants in the Quran establishes the presence of shellac resin as well as in a lac dye red used to paint the Dove diagram in Lorvão Book of birds. Both medieval paint spectra reflect the use of a shellac resin (Vieira 2019). Fluorimetry is a non-destructive technique and can be performed in situ.

    XRD, X-ray defraction is a rapid analytical technique primarily used for phase identification of a crystalline material. XRD was used in combination with other techniques (Micro-Raman and THM-Py-GC/MS ) to analyze the ingredients in the Eleven-Faced Guanyin of the Du Le Temple in Tianjin, Liao Dynasty, China. Looking at the pigments and binders present, the study revealed that adhesives were used comprised of heat-bodied tung oil in gold areas, adhesives in other areas comprised of glue-protein and mineral pigments black carbon, red cinnabar, orange litharge, blue sadalite, and green atacamaite were determined to be used in the paint. XRD used with micro-Raman spectroscopy was successful in testing samples, using micro-destructive and non-destructive means, not in situ, to determine the specific type and composition of pigments. XRD results showed that their blue pigments were mainly ultramarine blue and blue sodalite (Wang et al. 2021).

    XRF, and MacXRF (macro), X-ray fluorescence is a rapid analytical technique primarily used for phase identification of a crystalline material. It is a non-destructive common tool, used in situ, which can be used from the visible to the near infrared spectral range. XRF was used on the large scale artwork titled “The Miraculous Interventions of Jizō Bosatsu.” To better understand its history and fragile structure, including damage it has undergone, MAXRF uses imaging spectroscopy to better look at specific scenes containing a variety of paint compunds. Original pigments common in Japanese scroll paintings were detected including a chloride lead based white pigment, indigo, organic yellow/brown, vermillion and iron based yellow and red ochres. Due to the scroll’s age and its handling during past use as a teaching tool, it has a number of conservation needs and shows evidence of past repairs. (Clarke et al. 2015).

    Japanese woodblocks, known as ukiyo-e prints, were created generally during the 18th to 19th centuries. Ukiyo-e were made with traditional pigments including red safflower (orpiment), Prussian blue, aniline red and violet and indigo. These bright-colored variety of colors were made from pure colorants in a 40 deposition reference color chart using 28 pigments and dyes in a 1:1 ratio two pigment mixture. Color materials were able to be identified, such as gamboge, a partially transparent deep saffron to mustard yellow pigment. It is the traditional color used to dye Buddhist monks' robes, and Theravada Buddhist monks in particular, verdigris, a bright bluish-green encrustation or patina formed on copper by atmospheric oxidation and orpiment, a bright yellow mineral consisting of arsenic trisulfide. Combinations such as indigo and gamboge, verdigris and indigo, Prussian blue and orpiment, with dragon’s blood, brazilwood, cochineal, malachite and azurite, and chrysocolla were detected.

    Near infrared spectroscopy (NIR), or near hyperspectral imaging Identification of all types of media and general categorization possible. Uses monochromatic light and is not as accurate as FTIR. This technique has been used successfully in museums on paintings to classify and identify pigments and binders used in cross sections or painting layers. However, these studies are concentered on inorganic pigments mixed with different binders (Biron 2020).

    Particle induced X-ray emission (PIXE) and particle-induced gamma-ray emission (PIGE) This technique requires a particle accelerator and are therefore used more rarely but both have the capability of being completely non-destructive. In my research, PIXE and PIGE are highly promising techniques for identifying components in paintings. PIGE has a high sensitivity and can detect lighter elements such as nitrogen, fluorine, sodium, magnesium, aluminium and silicon. The benefits of PIXE and PIGE techniques are: no samples preparation is needed, analysis time is only about five minutes while there is simultaneous analysis of all elements with atomic numbers (Tuurnala et al 1985).

    PIXE and PIGE are non-destructive and is not in situ. These techniques are primarily used for art restoration in determining sequences of applications and layers of paint, binders and substrates. This particular technique is more useful for identifying the characterization of the elements within pigments than binders (Neelmeijer and Mader 2002).

    The Raman spectra is a reference for fingerprinting unknown varnish and binder mediums. The identification of the binder and pigment in a sample of a medieval illuminated manuscript illustrates this technique. In this analysis, a spectra of natural organic binding media and varnish are successfully identified as present in the paint media. According to their chemical, or spectroscopic, properties, these painting mediums can be classified into four major groups: proteinaceous media, polysaccharide media, fatty acid-containing media and resinous media. The spectra in the analysis establishes clear distinctions providing a fast and non-destructive identification of the medium used in a micro-sample taken from the artifacts (paintings, polychrome sculptures, and manuscripts, etc.). One such identification was of a beeswax binder and pigment found in a 15th century illumination in a Book of Hours, originally from western France (Vandenabeele et al. 2000).

    Micro-Raman spectroscopy (MRS), is non-destructive, and can successfully identify different types of proteinaceous binders and varnishes in paintings such as albumin, gelatin, casein, isinglass, fish glue, polysaccharides such as starch, gum arabic, cherry gum and tragacanth, fatty acid (such as beeswax, sunflower oil, poppy-seed oil, linseed oil, walnut oil,) and resin mediums such as sandarac, copal, shellac, amber, mastic, dammar, dragon’s blood, gamboge, Venice turpentine, Strasbourg turpentine, colophony and elemi.

    High resolution mass spectrometry (FTICR) is useful in identifying proteins in glues of animal origin. This technique is able to classify specific species of bovine, rabbit and fish, for example, due to the species-specific peptides found by analyzing the peptides after they are broken down by enzyme hydrolosis. The method specified that three rabbit peptides were found, fifteen bovine species peptides, and in the sturgeon glue, three fish peptides were found specific to the rainbow trout. This method was tested on a very small sample from an 18th century church, St Maximin (Dallongeville et al. 2011).

    Table 1. Hyperspectral Imaging analysis types used in archaeological and historical paint research.

    # Acronym Term Destr-uct?

    In-situ? Reference Function

    1 NIR near infrared spectroscopy

    No Yes Biron 2020

    Identification of all types of media and general categorization possible. Uses monochromatic light and is not as accurate as FTIR.

    2 SEM– EDS

    &

    FESEM-EDS

    Scanning electron microscopy energy dispersive X-ray spectroscopy

    Yes No Ioele et al. 2016; Wang et al. 2021

    Allows for targeted analysis of sample surfaces and is widely used for material surface analyses. SEM provides a visual look at surfaces and EDS gives an elemental and structural analysis of sample

    3 FTIR

    Fourier transform-infrared spectroscopy No Yes Vieira 2019; Watts and Lagalante 2018

    Uses a multichromatic light and a mathematical transformation of spectral data received to analyze samples.

    4 HSI

    Hyperspectral imaging

    No Yes Biron et al. 2020 Takes data which is beyond the wavelength of the visual spectrum (RGB) and re-interprets to RGB spectrum.

    5 IRFC

    InfraRed False Colors imagery

    No Yes Biron et al. 2020 Uses the near infrared, red and green spectral bands mapped to RGB

    6 MAXRF

    macro X-ray fluorescence (MAXRF) imaging spectroscopy and reflectance imaging spectroscopy No Yes Clarke et al. 2021 Essential analytical method for substance identification and spatial mapping. It also provides an understanding of production techniques.

    7 PIGE

    particle-induced gamma-ray emission

    No No Tuurnala et al 1985 Gamma-rays are produced by bombarding the sample with a focused beam of ions. 
 Spectroscopy is used to analyze the rays.

    8 PIXE

    particle-induced X-ray emission

    No No Miliani et al. 2012;

    Neelmeijer and Mader 2002

    Similar to the gamma-ray technique, but using the x-ray spectrum. Both used to determine the elemental composition of a sample.

    9 XRD

    X-ray defraction

    No Yes Wang et al. 2019

    A rapid analytical technique primarily used for phase identification of a crystalline material.

    10 XRF

    And

    MacXRF (macro)

    X-ray fluorescence No Yes Clarke et al. 2021; Huntley et al. 2015 A rapid analytical technique primarily used for phase identification of a crystalline material.

    11 SWIR

    Short Wave Infrared Range Hyperspectral Imaging

    No Yes Biron 2020

    Using short wave infrared false images and principal component analysis to discriminate between organic and inorganic colorants.

    12 VNIR HSI

    Visible-near Infrared hyperspectral imaging No Yes Balas et al. 2018 Similar to SWIR. Note: PRISMS is a portable hyperspectral imaging system designed for high resolution, in situ, remote imaging of paintings at inaccessible heights from the ground level.

    13 X-Rite reflectance spectrophotometer No Yes Agresti et al. 2015 Analyzes reflected light from sample surface as well as internal (diffuse) reflection.

    14 MRS Micro-Raman spectroscopy No No Vandenabeele 2000 A microscope fitted with a microspectrometer, allowing collection of Raman data from microscopic samples

    Spectral Imaging

    Spectral imaging techniques are those that study and break down the visible spectrum of light to better understand paints and binders. These are mostly non-destructive techniques and the majority are not in situ.

    Spectral imaging includes analysis techniques that utilize the visual spectrum of light. Each color or wavelength can be individually separated, which allows for the imaging or recognition of details within the painting as well paint layering. These are important techniques in the analysis of historical paintings. Binders can be differentiated from pigments and other components of paint when they refract light back in different frequencies. Visual light is broken down into its constituent wavelengths which can then be analyzed individually or proportionally. One example utilizes software that is able to identify layers of paint that are barely detectable visually. Fiber optic reflectance spectroscopy (FORS) and Fourier-transform infrared spectroscopy (microFTIR), includes methods which are used with a specific “made-to-measure” database to determine the exact fingerprint of a material (Vieira et al. N.D.).

    IR reflectography and spectrometry are very useful in that the amount of infrared radiation transmitted by a material that can be measured from looking at patterns of the wavelengths produced. It can determine the classification of a binding material such as protein, oil or gum. Due to the cross readings with pigments, identifying different mediums within a paint mixture is not always possible (Taft and Mayer 200). Raman Spectoscropy is a technique that requires that a small sample, which remains undamaged, be analyzed in a lab. A spectrum is then produced, giving the fingerprint description of a material. Unfortunately, pigments can mask information from the infrared radiation, because they make up a majority of the paint sample, making it hard to differentiate the binder. The infrared spectrum may be able to identify oil but not distinguish between oil and wax as described in the analysis of the painting “Detroit Industry,” by Diego Riviera (Taft and Mayer 200).

    Fibre optic reflectance spectroscopy (FORS-VIS) delivers a lazer light through fiber optics to a device which translates the vibration or wavelength of reflected light giving information (from the reflected light reading the sample) into pixels which can be seen to identify the molecule (Casini 2005). During my research, I found that dark red colors found in the conservation of Islamic manuscripts were identified using fibre optic reflectance spectroscopy (FORS-VIS) and FTIR mentioned earlier. In order to investigate the ingredients in the paint recipes, fiber optic reflectance spectroscopy (FORS-VIS) was used to analyze three recipes of lac dye are compared with the Islamic organic red colorants containing natural animal or plant origins such as cochineal and kermes, of which the energy dispersive X-ray fluorescence (EDXRF) and FORS indicates possible colorants. Using FORS, it is possible to differentiate between anthraquinone chromophores produced by parasitic insects, such as carminic, kermesic and laccaic acids, all from anthraquinones of plant origin (Vieira et al. 2019).

    Raman spectoscropy is non-destructive and is able to identify raman spectra of starch, various gum binders as well as resins. This technique is able to differentiate and therefore classify binding media from various classes of binders. These include vegetable (such as starch in potato, rice, corn and gums, which are secretions of a polysaccharide vegetable substance) and animal (such as protein from egg, casein or animal glue). In a comparison I found in research documented in Vandenabeele (2000), that due to the peak intensity of spectra due to the location on the bandwidth, it is possible to distinguish between the spectra of a starch, gum, tragacanth, and cherry gum binders due to the intensity or weakness of the peak on the spectra reading.

    Table 2. Spectral Imaging analysis types used in archaeological and historical paint research.

    # Acronym Term Destr-uct? In-situ? Reference Function

    1 Raman Raman spectroscopy No Both Ioele 2019; Vandenabeele 2000 Raman spectra identify the chemical composition of many different substances, including starch, various gum binders, and resins.

    2 FORS-VIS

    fibre optic reflectance spectroscopy

    No Both Casini 2005; Clarke et al. 2021; Vieira 2019 Identifies organic and inorganic substances in pigments, binders, and applied substrates and distinguishes between the ages of the layers of the sample. Caution: too much light can cause degradation of the sample.

    3 LIBS

    laser-induced breakdown spectroscopy Yes No Online LIBS website Lasers cause the sample to emit atomic particles which are analyzed by spectroscopy to identify the composition of a wide variety of substances, including pigments and binders.

    4 PLM

    polarized light microscopy Yes No Butler 1960 Lasers cause the sample to emit atomic particles which are analyzed by spectroscopy to identify the composition of a wide variety of substances, including pigments and binders.

    5 IR Infrared reflectography No Yes Taft and Mayer 2000 Infrared radiation penetrates the paint layers to reveal underlying versions or changes to a work.

    6 D Stretch decorrelation stretch No Yes D Stretch

    Online website A method of enhancing color separation to improve visual interpretations. Used to identify pictographs that are not visible to the naked eye.

    7

    ENVI

    Spectral Hourglass Wizard tool

    No Yes Clarke et al. 2021

    Working from an image, a method of mapping color spectra created from multiple sources which individually detect various components in a sample, identifying and mapping them individually. The final map shows the interrelation of all the constituent substances.

    Mass Spectrometry (MS) and Gas Chromatography (GC)

    Mass spectrometry and gas chromatography are two different technologies that are commonly used together to determine what an unknown material is made of. Mass spectrometry is used for the identification of all biomolecules in general and has been used specifically for identification of proteins. Mass spectrometry plots the function of the mass-to ratio charge of an ion after it has been chemically broken down into its smallest potential atomic form through processes such as gas chromatography (Domon and Aebersold 2018).

    A gas chromatography machine breaks down any material into a gaseous form which separates it into its constituent atoms and molecules which can then be individually analyzed. This process uses ionized atoms and molecules each of which is recognizable based on its unique atomic weight. Therefore, every substance has a unique fingerprint which can be used to identify what it is including what kind of binders and pigments are used in paints. Mass spectrometry/gas chromatography is extremely useful because you can identify exactly what ingredients and binders are in an unknown paint sample. However, you must have a large enough sample to dissolve, destroying the sample and it must be able to be vaporized and is therefore destructive and not able to be analyzed in situ.

    Different potential binders require different mass spectrometry/gas chromatography analyses to detect. Oil binders are problematic because of the large size of the molecules and cannot be analyzed with gas chromatography unless they are chemically reduced. Natural resins on the other hand contain mainly small molecules that can be identified using standard gas chromatography techniques. Protein binders are formed of constituent amino acids which can be analyzed by all forms of chromatography. Sugar based binders containing monosaccharides, such as plant gums, and are also easily analyzed by all forms of chromatography (Taft and Mayer 2000; Vieira et al. N.D.).

    A chromograph can reveal a lot of information about a paint sample including distinguishing between similar based binders such as drying oil, pine resin and beeswax. Mass spectrometry/gas chromatography can also be helpful in identifying carbohydrate-based media, such as plant gums including simple sugars like monosaccharides as well as distinguish different proteins binders, from amino acid analysis, such as what the painting was painted on, animal glue substrate and egg medium in the paint mixture. Mass spectrometry/gas chromatography is currently the most commonly used analysis used for analyzing paint binders and is destructive and is used both in situ and not in situ.

    Liquid chromatography mass spectrometry

    Liquid chromatography is a related technique that sprays tiny ionized particles containing a single type atom or molecule into a mass spectrometry machine that is able to recognize individual atoms and molecules using an electron stream.

    Liquid chromatography mass spectrometry is a tandem technique, which combines the physical separation of spraying ionized particles into a machine that then analyses the molecule in a mass spectrometer and can identify molecules in binders with high specificity.

    Another form of chromatography deals with liquid analysis and employs diode array detection and mass spectrometry (HPLC-DAD-MS) to identify the unique fingerprint.

    High-performance liquid chromatography (HPLC) is less commonly used than gas chromatography due its cost but is more easily implemented as the sample does not have to be volatile, but it does have to be soluble to achieve small enough particles to analyze. (Taft and Mayer 2000/ Vieira et al. N.D.).

    In Pyrolysis-gas chromatography, the process of pyrolysis uses heat at 600-1000 degrees celcius to break down molecules, in a vaccum, through thermal decomposition. The bonds in large molecules are broken down, allowing them to be small enough to pass through the gas chromatography machine and be analyzed (Gallios et al. 2007).

    Time of flight -SIMS (TOF-SIMS) analyzes molecules, clusters and ions after they are freed. The method relies on a low primary ion current which excites the surface of the sample in order to free the ions (Macdonald 2004).

    Matrix assisted laser desorption ionization-time-of-flight mass spectrometry MALDI-TOF/TOF is a biochemical identifier of binders and is preferred because it produce fast results, is inexpensive and accurate. This technique can be used in situ and is destructive. Hydrophilic gel, is used in combination with MALDI-TOF/TOF to extract protein binders. Hydrophilic gel is highly absorbent, yet it does not dissolve in water, and can be used to identify protein-based binders without leaving a residue. Through MALDI-TOF/TOF, casein along with other protein binders were found to be used on the altar piece and angel statue of the painted altarpiece “Assumption of the Virgin,” XVI century, Apulia, Italy (Calvano 2020).

    Matrix assisted laser desorption ionization-time-of-flight mass spectrometry MALDI-TOF/TOF and LC–MSMS were used to analyze micro-samples from a mural painting in an 18th century church called “Our Lady of Copacabana de Andamarca” in Bolivia. The tests were able to identify ingredients including collagen from animal and egg proteins. The test results, along with the identification of drying oil through GC–MS, concluded that an tempera grassa was used as the pigment binder. Results from the LC-MSMS testing, on micro-samples from the murals, revealed that collagen, egg proteins, muscle proteins and waste from the domesticated camelid were present in the paint and implies that this can be used as evidence of muscle proteins in ancient artworks. In following with the traditional secco painting style, it was also hypothesized from this test that the primer was made from animal glue (Levy et al 2018).

    Desorption electrospray ionization mass spectrometry (DESI-MS) is an atmospheric mass spectrometric analysis technique which begins with a liquid instead of a gas and can ascertain between the presence of a lipid binding material from an acrylic binding material. It has proven to be successful in the analysis of layered paint binders and intact cross-sections. DESI mass spectral imaging has been applied to the study of inks on paper and other tissue thin cross sections in chromatography. In looking at the process and technique in cross section samples taken from The Triumph of David, 17th C baroque painting (1630 AD), it was revealed that lipid containing paint layers were identified using DESI-MS, therefore differentiating original lipid containing paint layers from modern acrylic layers is possible. DESI is unable to distinguish between an ion unique to oil or egg, therefore, areas of oil and egg tempura were hard to distinguish using DESI-MS. In the future, refinements of DESI-MS may be a solution used to identifying cholesterols in paint layers to help distinguish between oil and egg binders (Watts et al. 2018).

    Electro spray ionization-mass spectrometry (ESIMS) uses high voltage to create an aerosol which can identify molecules in binders through mass spectrometry analysis (Page 2007).

    Flow Injection Analysis (FIA) is a part of chemical analysis, by forcing a sample into a flowing liquid (Trojanowicz 2000).

    Gel permeation chromatography (GPC) is used for larger molecules like polymers, it is a size-exclusion chromatography that separates elements using organic solvents (Gellerstedt 1992).

    High performance liquid chromatography with diode array detection and mass spectrometry (HPLC-DAD-MS) is an advanced technique of mass spectrometry able to identify different plant compounds with a high level of accuracy (Vieira et al. 2019).

    Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) is able to test metals and some non-metals in liquid solutions using low concentrations. The method ionizes a sample with inductively coupled plasma which it then atomizes making atomic and polyatomic ions. It is then able to detect the ions that are present (Gunther 2004).

    Zooarchaeology MS (ZooMS)

    Zooarchaeology by mass spectrometry is a method to identify animal origin through peptide fingerprinting. The method relies on the fingerprinting to test for mineralized fiberous proteins found in animal materials (Van Doorn N.L. 2014).

    Table 3. Mass Spectrometry and Gas Chromatography Specific analysis types used in archaeological and historical paint research.

    # Acronym Term Destructive? In-situ? Reference Function

    1 MS mass spectrometry Yes No

    Domon and Aebersold 2018 Determines the identity of unknown substances, including binders, by measuring the substance’s atomic and molecular weight.

    2 ESIMS

    electro spray ionization-mass spectrometry

    Yes No

    Watts and Lagalante n.d.

    Uses high voltage to create an aerosol which can identify moleules in binders through MS.

    3 LC-MS/MS liquid chromatography–tandem mass spectrometry

    Yes No

    Hendy 2021 a tandem technique, which sprays ionized particles into a machine that then analyses the molecule in a mass spectrometer and can identify molecules in binders with high specificity.

    4 DESI-MS Desorption electrospray ionization mass spectrometry Yes No

    Watts and Lagalante n.d.

    atmospheric mass spectrometric analysis that can differentiate a lipid from acrylic binder. It has proven to be successful in the analysis of layered paint binders and intact cross-sections.

    5 FIA Flow Injection Analysis Yes No

    Bonaduce et al. 2012 a part of chemical analysis, by forcing a sample into a flowing liquid.

    6 GPC Gel permeation chromatography Yes No

    Bonaduce et al. 2012 is used for larger molecules like polymers, it is a size-exclusion chromatography that seperates elements using organic solvents.

    7 HPLC-DAD-MS High performance liquid chromatography with diode array detection and mass spectrometry Yes No Vieira et al. n.d.

    is an advanced technique of mass spectrometry able to identify different plant compounds with a high level of accuracy.

    8 LA-ICP-MS Laser Ablation Inductively Coupled Plasma Mass Spectrometry Yes No

    Bu and Cizdziel 2013 test for metals and some non-metals in liquid solutions using low concentrations by ionizing a sample with inductively coupled plasma which it then atomizes making atomic and polyatomic ions which it then detects.

    9 MALDI-TOF MS matrix assisted laser desorption ionization-time-of-flight mass spectrometry Yes No Calvano 2020;

    Perez-Seoane & Matilde Muzquiz 1999;

    Granzotto et al. 2019

    a biochemical identifier of binders and is preferred becase it produce fast results, is inexpensive and accurate.

    10 PY GC-MS pyrolysis gas chromatography–mass spectrometry

    yes Both

    Gallios et al. 2007

    Newman, Kaplan and Derrick 2015;

    General an specific identification of paint binders and ID of some ingredients in the mixture.

    11 TOF-SIMS Time of flight -SIMS Yes No

    Watts and Lagalante n.d.

    analyzes molecules, clusters and ions after they are freed. The method relies on a low primary ion current which excites the surface of the sample in order to free the ions.

    12 ZooMS Zooarchaeology MS Yes No

    Hendy 2021

    Method to identify animal origin through peptide fingerprinting using mineralized fiberous proteins found in animal materials.

    Immune Response Analysis

    Immunoassay Analysis utilizes biological processes of the immune system to determine various ingredients based on the ability of known antigens to cause a reaction and create antibodies. Those antibodies produce enzymes which can be detected chemically to identify ingredients in the sample. Therefore, an ingredient can be identified based upon its reaction or no reaction to to known antibodies. I found in my research that ELISA, enzyme linked immunosorbent assay, was used to identify animal binders in mural paintings dating back to the 3rd and 5th century in Korea. ELISA revealed that pigments celadonite, cinnabarr, white pigment and red ochre were mixed with 1 mg of animal glue as a binder in the paint mixtures. In this case, ELISA was useful in identifying the amount of the binder in the paint mixture as well as the pigments present (Yu 2019).

    Immunoflourescence miscroscopy (IFM) Light microscopy is used to detect the fluorescence produced in a sample when a known antibody with an attached light-emitting chemical binds with specific biomolecules, thereby identifying them. This technique was used to identify binders in paint (Miller 1995). During my research, I found an interesting study where immune response analyses have demonstrated their technical value in identifying binders in 4th to 8th century Chinese paintings across six provinces. The sites where the samples were taken include a royal tomb with terracotta army, Buddhist Grottoes and large murals from tombs in Shanxi Province, 317-420 AD. The techniques applied were IFM, immunoflourescence miscroscopy and ELISA, enzyme-linked immunosorbent assay. Commonly found are protein substances in casein, milk, or egg, chicken ovalbumin and in glues in bovine, dog, pig, and rabbit.

    A study, comparing nine paint samples, all using the combined methods of ELISA and IFM, found that the results cross-validated one another with high specification and needing only micro-samples.

    Methods of cross analysis included using rabbit antibody to ovalbumin, rabbit antibody to collagen I, rabbit antibody to bovine casein, and rabbit antibody to fish collagen. Samples were made with different protein binders from fish glue, mammalian glue, peach glue, bovine milk and whole egg combined with pigments and aged for one year. The model polychrome samples and nine micro-samples from nine ancient paintings were tested using the tandem procedures and confirmed that, although IFM and ELISA have limitations in their unspecialized identification of antigens, they are reliable techniques for determining organic ingredients and concluded that egg and mammalian glue were considerably used as binders in ancient Chinese paintings (Hu 2015).

    Table 4. Immunoassay Analysis types used in archaeological and historical paint research

    # Acronym Term Destr-uct? In-situ? Reference Function

    1 ELISA

    Enzyme-linked immunosorbent assay

    Yes No Yu 2019 Uses known antigens and antibodies to identify the ratio of the binder in the paint mixture as well as the ingredients.

    2 IFM

    immuno-fluorescence microscopy

    Yes No Fluorescence of organic binders in painting cross-sections

    Uses antibodies with fluorescent dyes which highlight molecules within the cell. These molecules are then analyzed and a binder source can be identified

    Nuclear Magnetic Resonance (NMR)

    Nuclear Magnetic Resonance, NMR, identifies various materials based upon the electromagnetic spin which is a unique magnetic field based upon the molecular weight of different materials. Resonance refers to the wavelength at which any particular substance alternates between two polar electromagnetic spin states. The freguency is different for various materials allowing for their identification. A solvent without organic components is used to break down an unknown organic material. At that point an NMR device is used to identify the resonance frequencies which determine what materials are present.

    Presciutti et al. describe how NMR was used to analyze old master paintings while in situ, using non-destructive means. A more recent or original layer of paint can be determined using NMR. By observing tempera binders using NMR, researchers are able to differentiate between the original paint layers and more recent restored layers. In analysis of the “Adorazione dei Magi” by Pietro Vannucci, NMR was able to detect four separate layers within the painting as well as canvas sub-structure and thickness. The layers analyzed were the wood, the canvas, underpainting and painting layers. No varnish layer was detected, however, glue attaching the canvas to the wood was detected. NMR is able to give a stratigraphic, 3D map of a painting’s profile in terms of depth. In my research, I have found it to be a successful tool for determining the nature of binders, such as oil, casein and tempera, as well as the binder pigments. It is also a useful tool in conservation as it is able to determine the aging history of paint binders by observing the mobility of the binder molecules. NMR spectroscopy is a helpful technique for structural analysis and identifying compounds (Presciutti et al. 2008 and Voss 2006).

    Nuclear Reaction Analysis (NRA) Is a method of nuclear spectroscopy where the distribution of certain chemical components can be measured according to concentration and depth. Samples are placed in a magnet device which generates a super magnetic field, causing polymers in the sample to emit radio-frequency waves. A spectrometer and computer interpret the radio waves, identifying and analyzing sample components.

    Some binders are a type of polymer long used in painting carriers, which form a thin layer to create a more even application of paint. To analyze the composition and distribution of polymers using NRA, the sample is labeled with deuterium so it can be detected. The energy produced from the nuclear reaction is analyzed to give a measurement of the exact distribution of the polymer. This analysis has was widely used by researchers at University of Cambridge and Cornell University and was originally considered destructive and not performed in situ (Yerushalmi-Rozen and Klein 1995). More recently, however, NRA has been found to be non-destructive and can be performed in situ (Presciutti et al. 2008). Nuclear reaction analysis is a compositional analysis of materials and can provide a depth profiling of elements (Pruvost et al. 2004).

    Table 5. Nuclear Analysis types used in archaeological and historical paint research.

    # Acronym Term Destr-uct? In-situ? Reference Function

    1 NMR

    Nuclear Magnetic Resonance yes no Presciutti et al. 2008 and Voss 2006 Gives a stratigraphic map pf media and identifies specific compounds and their aging history.

    2 NRA

    Nuclear Reaction Analysis

    no yes Presciutti et al. 2008 Is a method of nuclear spectroscopy where the distribution of certain chemical components can be measured according to concentration and depth.

    Chemometrics / Chemical Test

    Chemical tests include several other chemistry-based reactive techniques that can be used to determine the presence or absence of different ingredients and do not fall into the categories listed above. For instance, specific chemical tests can be employed to identify the presence or absence of certain binders. Chemical tests are limited in that they can tell you what kind of compound is present, such as carbohydrates, lipids or proteins, but cannot specifically differentiate the binder’s origin, such as a protein from a cow or rabbit.

    The Lugol test employs an iodine and potassium iodide solution which can detect starches in organic compounds. In my research, I found that a Lugol test was used in the analysis of Raphael’s “The School of Athens,” to differentiate between a gum arabic, used in the patina, and one in the binder. A Lugol test can reveal whether the polysaccharide bands found in the FTIR spectra were from starch, or gum. In this case, a negative Lugol test for starch concluded that gum arabic was used (Ioele 2016; Newman 1996).

    Biological staining, as described by Taft and Mayer 2000, is a useful technique for identifying different types of binders, , predominantly those that fall into the lipid, oil, or protein category. By using cross sections of a painting sample, different stains can identify oils and lipids, which can be problematic if you are analyzing a solution containing egg, and therefore a protein and a drying oil, or a glue and egg. In this situation, the test does not distinguish between the two. Fluorescent stains identify different classes of binders when placed under an ultraviolet light. Immunofluorescent stains use antibodies to identify specific protein binders. These tests require a sample to be stained and therefore are considered a destructive techniques not performed in situ (Taft and Mayer 2000).

    Table 6. Chemical test analysis types used in archaeological and historical paint research

    # Acronym Term Destr-

    uct? In-situ? Reference Function

    1 N/A Lugol test

    Yes No Ioele 2016 employs an iodine and potassium iodide solution which can detect starches in organic compounds

    2 N/A Biological staining*

    refers to several types of stain Yes No Taft and Mayer 2000 identifying different types of binders, predominantly those that fall into the carbohydrate, lipid, or oil, and protein category

    Genetic DNA Analysis

    Genetic analytical techniques have evolved to provide more specific information about the scientific category of paint ingredients. A variety of DNA analyses exist for identifying specific ingredients in paint including mitochondrial DNA analysis and polymerase chain reaction analysis.

    Mitochondrial DNA analysis (mtDNA) offers a unique ability to analyze ancient samples for a very specific identification of a material and its origin with very little material. Due to the high number of copies of mitochondria DNA in each cell, it is more common and is more available for extraction. It can also give specific information about the taxonomic assignment of DNA in a sample as well as intraspecies classifications. For instance, a study was done in 2010 on samples taken from a polychrome terracotta sculpture “Madonna of Citerna” by Donatello, in attempts to identify the biological origin of the glue which had been mixed with gypsum used in the preparation of the artwork. The test was not only able to confirm that Donatello used animal glue for the preparation of the painted layers of the Madonna, but also specifically identified that the animal glue was from a unique bovine herd animal from a lineage of the European Auroch, which is now extinct but was present in Italian herds of the Renaissance period (Albertini et al. 2010).

    Polymerase Chain Reaction (PCR) is an analytical technique which can take DNA from a work of art or archaeological setting and, by replicating fragments of DNA to get a large enough sample, can identify the origin of a paint ingredient Using an established phylogenetic relationship among related species, the source for an organic binder/vehicle may be identified. (Campana 2010 & Mawk et al. 2001). DNA analysis of ancient rock art binders has been used for some time and was used in a study performed on Lower Pecos River rock art to determine whether a binder/vehicle used in the paint was related to a hoofed bovine. Using PCR analysis, Reese hypothesized that the origin of rock art binder could possibly be from a hoofed mammals similar to deer (Reese 1994). PCR analysis is easily contaminated because it is hard to get a clean sample due to natural and environmental contaminants.

    Table 7. DNA analysis types used in archaeological and historical paint research.

    # Acronym Term Destr-

    uct? In-situ? Reference Function

    1 mtDNA Mitochondrial DNA analysis No no Albertinti 2010 Uses little material sample to identify and classify intraspecies of origin of a binder.

    2 PCR Polymerase Chain Reaction No no Campana 2010;Mawk 2001;Reese

    1994 Used for quantitative nucleic acid analysis to identify a material and the source for an organic binder/vehicle.

    Plant Binders

    Binders extracted or made from plants create a variety of organic substances including gum, resin, sap, lacquer, shellac, lignin, mastic, starch paste, wax, oil, and dye.

    A better understanding of the difference between gums and resins informs various binders . Resin and some gums come mainly from pine or evergreen trees in the Pinaceae family. Gums also come from many varieties of other plants. Resins, gums and saps have seemingly similar characteristics, but when looked at more closely reveal their differences in function and property (Sadowski 2020).

    Generally, resins are expelled from the bark of a tree, and are soluble in ethers, alcohol and other solvents and insoluble in water.

    Gums are usually expelled from the branches or stems of a tree or plant and are soluble in water.

    Distinctions can also be made between gum-resin, sap and resinoids. Gum-resins have been obtained for millennia by tapping into particular trees to express combinations of gum and resin such as frankincense and myrrh for religious and medicinal purposes (Sadowski 2020).

    Gum

    Gums are made by the decomposition of tissues inside a plant and are considered polysaccharides which can swell in water to form a gel. Gums may exude from stems or branches, bringing an anti-fungal ingredient to a damaged part of the plant’s extremities.

    Gums include gum acacia, gum tragacanth, milkvetch and Indian tragacanth. Gum arabic, gum tragacanth and cherry gum are most commonly used in painting (Osada 2001; Sadowski 2020; Vandenabeele et al. 1999).

    Typically used in the food industry as an emulsifier and thickener, gum arabic has also been used as a medium for watercolor paints since the 18th century. It is found in ancient Egypt in the 3rd millennium BCE.

    Commonly found gums in the archaeological field include: gum arabic (A. Senegal), cherry gum, locust bean and tragacanth gum (Granzotto 2019). Tragacanth gum cannot be dissolved in water but can be mixed with a small amount of water, where it becomes a viscous gel which can be painted on fabrics or made into pastel crayons.

    Fruit gums come from the fruit-bearing trees of species such as pear, peach, plum, apricot, and almond. Fruit gums were used as binders for watercolor paints for a thousand years or more and were also added to milk (casein) and egg recipes to increase glossiness (Vandenabeele et al. 1999).

    Scientific analysis has been done to identify gums in binders by using Matrix Assisted Laser Desorption Ionization-Time-of-Fight Mass Spectrometry. MALDI-TOF MS can identify different plant sources for gums by determining the individual mass fingerprint of the polysaccharide structure associated with each gum.

    It has been successful even in complex recipes of inorganic pigment and organic binders such as resin or oil. The technique was reliably used to analyze micro-specimens from a variety of works including artifacts from ancient Egypt to 20th century paintings (including George Braque) in the collections of The Metropolitan Museum of Art, New York and the Art Institute of Chicago (Granzotto 2019).

    In the original sketch of Raphael’s School of Athena, tragacanth gum, which comes from the astragalus plant, was found, along with fatty soaps. It is speculated that the white drawing was made with a white oil stick or crayon composed of tragacanth gum, lead white, and fixed with a fatty ingredient such as wax (Ioele et al. 2016, 2017).

    Sandarac, a gum or resin from the cypress, or alerce tree, was used in Europe and Africa to write 15th century treaties. In the 16th century varnishes and driers were introduced to paint mixtures (Casadio 2001; Vandenabeele 1999).

    In Il Libro dell' Arte, from 1390, Cennini often mentioned the “vernice liquida” (liquid paint), in which recipes are described with mixtures of sandarac in linseed oil. Litharge, or lead monoxide, white lead, or lead carbonate, were included in order to delay drying.

    “Driers” is a term for faster drying oils and resins which were used to increase or decrease the curing time of paint. These had been known and documented in the 2nd century but not used widely until much later, and by the mid 17th century, driers were used in many paint mixtures (Casadio 2001; Vandenabeele 1999).

    Resin

    Resin is a tacky liquid excretion caused by the oxidation of oil extruded by tree bark, primarily from the Pinaceae family, and is soluble in solvents like alcohol or ethers. Resin resides in the resin ducts of tree bark and protects the tree from insects, microbial pathogens and damage (Sadowski 2020).

    Resins create a glossy sheen to the surface of the paint, increasing the reflectivity of light which enhances colors, making them appear deeper and more intense. It is used in glazes for this reason (Taft and Mayer 2000). Types of resins include oleoresins, gum resins and hard resins.

    Oleoresins are part liquid, part solid, extracts of resin and essential oils and most are obtained by distilling spices from seeds. Oleoresins include turpentine, balsam, elemi, copaiba, and benzoin (Sadowski 2020).

    Resinoids are made by expelling resin from a resinous plant using a solvent. This has been practiced for thousands of years (Gooch 2012). Resin has been used since Egyptian times to make waterproof glues and varnishes. It was also used for essential oils and as a fixative in perfume (Taft and Mayer 2000).

    Copal, originally named after a region of Madagascar, refers to a type of hard resin which is combined with drying oils and considered an oil varnish or amber resin.

    Gamboge is extracted from an East Asian tree called Garnicia morella (Vandenabeele et al. 1999). It is a partially transparent deep saffron to mustard yellow pigment and is the traditional color used to dye Theravada Buddhist monks' robes. If it is used in combination with blue pigments it forms a green paint (Aral 2016).

    Turpentine

    Turpentine is distilled from the exudates of pine and other species of conifer trees and is referred to as gum turpentine, spirits, or turps, coming from the Greek word for resin.

    Two primary types of turps are Venice and Strasbourg turpentine.

    Venice turpentine is commonly used for varnish because of its resinous acids and terpenes.

    Strasbourg turpentine comes specifically from a conifer which grows in The Vosges Mountains, in France, and was used since the 16th century as a varnish, in oil and tempera paint (Vandenabeele et al. 1999).

    Balsam

    Balsam is a resinous sap or exudate from particular trees and shrubs. Named after the gum of the balsam tree from Biblical times, balsam is comprised of a solution of plant resins in plant solvents, including essential oils, and can include resin esters and alcohols.

    During antiquity, medieval and Egyptian times in Europe and the Middle East, balsam was derived from a specific Egyptian plant (Vandenabeele et al. 1999; Van der Werf 2000).

    In the early 1700’s, balsam was used in a variety of varnish recipes, mainly for glazes, by British painter Sir Joshua Reynolds.

    Balsam paint media was common in the beginning of the 19th century in Germany and according to literature, was often mixed in recipes with wax (Van der Werf 2000).

    Elemi / Frankincense

    Elemi also refers to a variety of resins which came from different species of the Burseraceae tree family. In earlier eras, elemi referd to resin extracted from Boswellia, a tree which also produces frankincense.

    The Boswellia tree is a member of the family Burseraceae. Elemi was used worldwide, in cultures from Ancient Rome to Brazil as a spirit varnish, in addition to various resins like copal. During the 17th and 18th centuries, elemi came from the resin from trees of the Icica family in Brazil.

    Frankincense, extracted from the yegaar tree, originated in Somalia where it is called Maydi, meaning king of all frankincense (Gooch 2002).

    In ancient Roman times, animi or enhaemon were terms used for Elemi.

    Pliny said it contained tears extracted from the olive tree of Arabia (Gooch 2002).

    Copaiba

    Copaiba is a balsam extracted from various species of Copaifera trees which grow in South America and Africa. It was a common additive in paint recipes from the beginning of the 19th century (Van der Werf 2000).

    Used during an early period of painting restoration, the “Pettenkofer regeneration treatment”, this binder was popular with artists circa 1884-85 (Van der Werf et al. 2000). Copaiba balsam was used as a medium in paint in order to extend drying time and to obtain a wide range of results. Examples include Van Gogh’s paintings where this binder was used to achieve an impasto affect with more saturation and deepening of colors without cracks or wrinkling from drying.

    Sir Joshua Reynolds (1723-92) made medium and varnish recipes for glazes from copaiba balsam. It was also a predominant ingredient in a German paint company's Roberson’s zinc white recipe, as well as a painter’s medium of linseed oil mixed with copaiba balsam sold by the Dutch company Talens (Vandenabeele et al. 1999).

    Sap

    Saps extracted from plants and trees contain starches and sugars. It is important to note that gum and resin is not the same as sap. Sap provides water and nutrients by the process of transpiration as it passes through the veins, or phloem, of a tree (Sadowski 2020).

    Saps from trees can be used for many purposes in paint mixtures as well as in sealing wood and other materials. Sap increases the tackiness of paint mixtures, affecting drying times. Sap, called rosin, can improve the static friction of bows for stringed instruments (Gooch 2002).

    In Lesotho, South Africa, plant sap was found in rock art mixed with other binders and carriers. Sap from the stem of the plant Ascepia gibba, related to the milkweed plant, was used in paint mixtures as a binder, mixed with animal blood. Escott also mentions that plant saps were sometimes used as blood coagulator when blood was present in the mixture (Escott 2011).

    Whewellite, thought to at times to occur from the sap of a plant similar to aloe vera, may have been used in paint as a binder and possibly a whitener or paint extender in rock art found in South Africa and Mexico. Its identification is based on a recognizable rounded crystal morphology (Huntley et al. 2015).

    Benzoin

    Benzoin is a balsam resin extracted from the bark of the Styrax species of tree.

    Growing in int forests of Sumatra and Indonesia it makes an aromatic incense used in Orthodox Christian, Hindu and Japanese temples.

    Benzoin is referred to both as a gum and a resin in binding recipes for varnish (Sadowski 2020).

    Japanese varnish recipes combined benzoin with sandarac, mastic, copal, rosin and Venice turpentine. The varnish was combined with isinglass fish glue to make white sizing, a material applied to prepare a paint canvas, in 16th and 17th century.

    This process was referred as "Japaning" in paint recipes (Ballardie 2000).

    Lacquer / shellac / varnish

    Lacquer was produced from both plants and insects, discussed below under Animal Binders.

    Lacquer was developed in ancient India and Asia as a high gloss, very hard finish varnish. The sap from the Chinese lacquer tree, Japanese sumac (the Varnish Tree) was treated and dyed to seal many different types of objects, including wood, shell, and metal (Ballardie 2000).

    The Japanese sumac, from the poison ivy family, contains urushiol, a toxic oil, referred to as urushi in Japanese, which is also the name for the traditional method for making lacquerware from this specific Asian tree (Gooch 2002).

    Paints and lacquers were common in Japan, China and Egypt. Lacquer from sap from the sumac or conifer tree originated as early as 3000 years ago, during the Zhou Dynasty period in China. Paints and lacquers from this sap are expected to last thousands of years (Gooch 2002).

    There are 500 species of conifers that express oleoresin gum. This type of oleoresin dries by oxidizing in a moist environment. Throughout the Ming Dynasty, 1362-1644 CE, high gloss paints were made with this resin by combining it with pigment and applying as many as 250 layers of resin.

    Ancient Chinese lacquer was also added to black carbon to make the paint primarily used for writing on bamboo strips during the 2nd century BCE. By the 2nd century CE, it was also used on pottery, on buildings and musical instruments (Gooch 2002).

    Mediterranean civilizations mixed carbon with cedar resin for making paint and cedar oil for making ink.

    The Maya carbonized resin from a tree called the chacak tree. They also used juice from the chichebe plant mixed with lime juice to create a white paint, red paint from shavings of the heartwood, blue pigments from aniline materials, and yellow from achiote fruit (Gooch 2002).

    Natural resins are the material primarily used for varnishing. Varnishes can be classified in two groups: oil resin varnishes, which contain a mixture of resin combined with a drying mixture and secondly, spirit-varnishes, also known as essential oil varnishes.

    These were introduced in 16th century Italy, replacing oil varnishes. These spirit varnishes were solutions of a natural resin mixed with a volatile solvent such as oil of turpentine (Rene 1989).

    Amber is a fossil resin produced specific trees. Over millions of years, pressure and temperature transform the resin through fossilization. Amber varnish has been used since ancient times (Drzewicz 2016).

    More recently, oleoresin paints were produced in colonial North America (Gooch 2002).

    Lignin

    Lignin is a material found in the tissues of most plants. Chemically it is an organic polymer, currently being considered as a eco-friendly binder in commercial paint materials.

    It is comprised of the secondary cellular walls of plants, wood and bark, and is a biopolymer accountable for the mechanical properties and strength of these tissues (Song et al. 2020).

    Mastic

    Mastic, a resin from the Mediterranean tree-bush Pistacia lentiscus was known in Greek as the tears of Chios and has been harvested for approximately 2,500 years (Paraschos et al. 2012).

    It is mentioned as “bakha” in the Bible, where ancient Jewish law specifies the chewing of mastic on Shabbat only for medical reasons.

    Mastic is an ingredient in chrism, a holy oil used in Orthodox churches for anointing (Mastros 2021).

    Since the 16th c., mastic has primarily been used as a varnish. It is also known to be mixed in small amounts as a binding additive in paint recipes like tempera. Mastic can be used to make a drying varnish when mixed with drying oils and a solvent, or a spirit varnish when mixed with volatile solvents without an oil.

    Drying varnishes were described in the 11th century by Theophilus as a process of boiling resins like gum mastic, rosin or sandarac with walnut or linseed oil.

    Oil varnishes using mastic were gradually phased out by spirit varnishes employing resins dissolved in spirits, usually a turpentine solution (Rene de la Rie 1989).

    Plant based oil

    Since medieval Europe, oil such as linseed oil was used in paint mixtures, introducing a new form of paint that, during the Renaissance, took precedence over the prior egg tempera. Oil painting was popularized in the Netherlands in the early 15th c.

    From an analytical viewpoint, fats and oils fall into the lipid category. They are basically very slow drying and create a solid when subjected to air.

    13th century altar paintings in Norway are very early examples of oil paint as they were painted with drying oil such as linseed oil and egg yolk (Taft and Mayer 2000).

    Evidence also shows that oil painting medium was in use as early the 12th c. The use of resins and drying oils as varnish were as known as far back as the 8th century (Taft and Mayer 2000; Vandenabeele et al. 1999).

    In painting, the most commonly used oils have been linseed, walnut and flax oil. These oils have also been combined with resins to make varnish.

    Linseed oil and flaxseed oil are both cold-pressed from the flax plant. Flaxseed oil is pure and used in food; linseed oil is processed differently for other uses such as paint.

    Walnut oil comes from the English walnut and is comprised of acids including stearic and linolenic acid. It was used in combination with resins for varnish in the 5th c.

    During the Renaissance, walnut oil was favored by Leonardo da Vinci as a binder in light paint pigments.

    Poppyseed oil, from the opium poppy, is a slow drying oil that has been used since the 17th c. and is considered a high-quality oil medium in painting although it tends to yellow.

    Since the 20th c., sunflower oil has been used as another slow drying medium in painting. It comes from the macerated seeds of the sunflower plant and is a common additive in oil varnish used with resins (Taft and Mayer 2000, Vandenabeele 1999).

    Starch paste

    Starch is harvested from a variety of plants such as potato, corn and rice. Each plant produces starch with different characteristics.

    Historically, in Asia, starch was predominantly used as a glue or a binder for paint pigments applied to large wall paintings (Yu 2019).

    Starch paste was traditionally made from wheat, dating back to the 15th and 16th centuries in Japan.

    It was the “gluten makers” or “Fuya” who made dumplings to sell for food who additionally made starch paste for artists in Kyoto, Japan (Willis 2013).

    Carbohydrate binders

    Carbohydrates in plants, known as simple sugars, were used in paint binders and found in sugars, orchid and flower juices, and plant gums. The primary molecule in plants, cellulose, is the basic building block.

    Soluble in water, simple sugars create a very sticky solution which binds easily with pigments and has been used since antiquity as a paint binder, although not a long lasting one.

    Carbohydrates the primary component in corn and wheat-based starch binders. (Taft and Mayer 2000).

    Charcoal

    Charcoal, used as a drawing and coloring tool, is comprised of carbon left over from burning wood. Found in rock art since pre-historic times, charcoal is thought to have been one of the original basic drawing tools.

    Charcoal was found both in paintings from the Mixteca-Puebla region and in codices from Mesoamerica. Black pigments were made from fine pine soot found in torches, called “ocotlilli”, coming from the ancient Aztec word for torch (Garcia 2017).

    In Cennino Cennini's 1390 book Il Libro dell’ Arte, Cennini describes charcoal made from the bones of cuttlefish, used with sepia as both initial drawing tools and powdered for surface preparations (Herringham 2018).

    In Ancient Rome, and according to author Vitrivius, charcoal was one of the natural color pigments used in wall painting (Gooch 2002). In Europe, charcoal was used more as a drawing tool than an ingredient in paint, due to its thin tinting strength compared to other organic inks. Its preparation was specific and is still used today.

    One of my mentors, Gene Pizzuto was trained in traditional European methods of charcoal and paint making which drove him to gather his materials from nature and prepare them using ancient techniques.

    Bundles of thin strips of wood, bound with wire, and then placed into a container and into the fire. Tightly wrapped, the air flow is restricted for slow burning and baking them into pure charcoal overnight (Watrous 1957).

    I still have a bundle of charcoal he made by wrapping sticks in wire, then baking them in tinfoil on a campfire, like a potato. Willow, or a willow species called sallow, as well as linden, plum, dog-wood, and spindle wood are the preferred woods to use.

    Animal Binders

    Binding mediums made from animal-based materials were most frequently used in tempera painting. Examples include albumin, casein, and animal glues.

    Fats (lipids) and organs

    There are specific references in “Paints of the Khoisan Rock Art” of paint binders that include ostrich fat, eland fat, vegetable fat or oil, bone marrow, and brains (Rudner 1983). Although considered illiterate in the western sense, San rock art shows in two studies that accounts of boiling (eland) fat or brains, and mixing them with the paint pigments was used in the Botswana-Namibia-northern Cape Region of Arica. Blood was applied in five experiments to a rock in a similar cave environment and was found to not last more than four years. It appears unlikely that a blood or bone marrow binder was used in the rock art. Brains show to have been used as the sole media or vehicle in rock art of the Northern Kalahari. A paste was made of boiled brains from antelope and mixed with red ochre which could be reheated to be applied onto the surface of the rock (Escott 2011).

    Egg

    Eggs have been predominant binders in paint medium since ancient times. Egg glair, produced from egg whites which are allowed to sit overnight, is used in a type of tempera painting which requires transparent glazing.

    Throughout the Middle Ages, glair and gum arabic were the primary binders used, mixed with pigments, for painting medieval illuminated manuscripts (Kroustallis 2011).

    Urine

    Snakes produce uric acid in a semi-solid state. Use of snake urine as an ingredient in rock art was documented in “Paints of the Khoisan Rock Art” (Rudner 1983). Indian yellow pigment is made from cow’s which were only fed mangoes (Harvard Art Museum 2016).

    In 1884, a resin coating made from condensed uric acid and formaldehyde was patented (Gooch 2002).

    Milk (casein)

    Casein is considered a phosphoprotein, a major ingredient in milk. It is heated, filtered and acidified, creating a powder which can be made into a binding medium when dissolved in a water solution.

    A liquid mixture made from powdered pigment and milk was found in the analysis of residue from a stone spall 49,000 years old in Sibudu, South Africa. Despite the logical conclusion that binders with milk would be used in pastoral people, whose lives are dependant on dairy animals, here is an example of hunter/gatherers using milk from killing a nursing wild animal. It is the first significant evidence of milk used as a binder before the first introduction of domesticated animals, including cattle to South Africa in the first millennium B.C.E. The ochre / milk-based mixture was neither an adhesive nor a residue from treating animal skins, but rather, a paint medium for surfaces or applied to human skin (Villa et al. 2015; Vandenabeele 2000).

    Milk based binders are found in 3rd to 5th century Korean traditional Dancheong paintings dating to the Joseon dynasty. They are also found in 4th to 8th century Chinese paintings and paintings in Buddhist Grottoes (Hu 2015).

    In Europe, casein from milk binders were also found in paintings during the medieval and Renaissance periods.

    In 16th century Italy, casein along with other protein binders were used on the angel statue and painted altarpiece of the work of art “Assumption of the Virgin” in Apulia, Italy (Calvano 2020).

    Animal glue, hide, hooves

    Gelatin is the common term for animal glues. Glues are made from skin, hooves, bone, fish and isinglass (flotation sacs of fish). Collagen is made from cooking the materials in hot water (Yu 2019).

    Insects, aphids, beetles

    Scale insects secrete lac, used for centuries as a source of binders and pigments. Insects used include those from the genus Kermes, the cochineal insect, and various types of lac insects.

    The colorant from the Kermes insect was extracted with an alkali and then precipitated with alum to create a red dye used by Indian and Arabian cultures for coloring silk. In the 12th century, trade between Bologna and Ferrara was known for this brilliant cloth, and it flourished in the cities of Venice and Florence in the 14th century (Nabil 2019).

    In the old-world, from the 9th to 12th century, red dye was made from a colorant, carminic acid, found in cochineal insects. This dye from newly discovered Mexico was introduced to Europe via Spanish conquests in the early part of the 16th century (Nabil 2019).

    Pliny, in 23-79 CE, described an early shellac recipe which he called Indian amber. Made from lac insects, this rare resin is secreted by a coccid insect (Laccifer lacca), found in lac trees in India and Thailand. According to Pliny, “the resin was used in making lac sticks to coat rotating objects on a lathe over 3000 years ago (Gooch 2002).”

    Lac insects have been used for thousands of years as the source of lacquer, shellac and many varnishes used worldwide.

    Shellac is in fact the resin secreted by the female lac insect of Thailand and India (Nabil 2019). Shellac is dissolved in a solvent such as alcohol and then applied as a sealer or varnish. It functions like a natural plastic.

    Shellac is produced in a wide variety of colors from light yellow to dark brown and orange or scarlet red (Vieira 2019).

    Recently, colorants have been made from aphids as an alternative to scaly insects. 80 species of insects have been analyzed for their colorant properties.

    The ivy aphid, wormwood aphid and giant willow aphid have been the only species used successfully as paint (Nabil 2019).

    Beeswax

    Beeswax was most commonly used for wall paintings as a paint extender and a natural inhibitor to damage because it contains natural pesticides which inhibit insects and rodent damage (Sadowski 2020).

    Throughout antiquity, beeswax was combined with hot water and pigment to make paint. The water evaporated, or sometimes it was mixed with an alkaline solution.

    Beeswax was preferred in part because of its solubility in all types of solvents, weak and strong. The mixture produced a strong, enduring coating which made it popular for thousands of years (Taft and Mayer 2000).

    Wax and pigment are melted together for application and could be reheated for reworking and layered applications. “Encaustic” painting, meaning “burned in” in Latin, was popular during Greek and Roman eras.

    Bees wax and drying oils are fatty acids that can be identified using Infrared spectrometry (Taft and Mayer 2000).

    Honey

    Honey was used as a binder for paint more commonly in antiquity than it is now. One example was its use as a binder in medieval illuminated manuscripts.

    Solutions containing fish glue, honey or gum were also used in mixtures with pigment (Taft and Mayer 2000; Vetter 2019). Second and third hand ethnographic information on rock art from Southern Namibia show that paint mixtures included fat, honey and gum Arabic. Honey was used exclusively as the media or vehicle by being applied directly to the rock surface, unmixed, using the rock as a crayon (Escott 2011).

    The Egyptian, Roman and Chinese civilizations discovered how to make refined man-made colors, deriving them from organic and inorganic (not living) pigments found in nature. The pigments were generally mixed with chalk or a honey binder (Bouherour 2001; Gooch 2002). Other binders used at the time included egg whites, mixed with combinations of honey, gum arabic and other plant gums (Rene de la Rie 1989).

    Mineral Binders

    Lime-paint

    Lime-paint was a technique used in antiquity to make frescoes on walls. The process involves mixing a lime-water solution called “slaked lime” with pigment, which is applied to dry plaster.

    To make slaked lime, the lime is added to water, and the resulting chemical reaction produces calcium hydroxide, which is responsible for the carbonization of paint (Botticelli 1992; Piovesan et al. 2012).

    Water and lime create a chemical reaction as the paint dries, which results in the pigment being surrounded and protected by lime crystals (CaCO3)).

    Lime-paint was used to paint Egyptian mummy coffins sealed with varnish (Gooch 2002).

    Gypsum

    Gypsum has been used since ancient Egyptian and Biblical times as a base in paint.

    Beeswax, gelatin, gum arabic, egg, white and yolk were added to gypsum, along with lime plaster and plaster of Paris to create a binding agent with the pigment.

    (Huntley et al. 2015; Gooch 2012).

    Quartz / Feldspar / Whewellite

    The Egyptian, Roman and Chinese civilizations created synthetic paints including Egyptian Blue, Chinese blue, and Chinese purple. The colors were identified from the 6th Dynasty through to the Roman era in eleven original specimens. Quartz and mica were found to be frequently used as a common paint additive in Egyptian Blue and Chinese Blue and Purple synthetic paint mixtures. Egyptian samples from tombs revealed that the starting components for Egyptian Blue were normally calcite, quartz and copper containing substances. These could include minerals such as malachite, copper metal or azurite in combination with a flux to purify and prevent oxidation of the metals . Cuprorivaite and wollastonite and libethenite as synthetic ingredients in a paint mixture for a greenish-blue hue of Egyptian Blue (Bouherour 2001).

    Some of these man-made paints were used in the form of paint sticks as found in the specimens from the Chinese Terracottoa army. Paint sticks also contained synthetic additives of barium-lead and a barium-copper-silicate mixture in the synthetic ancient Chinese paint mixtures use on the Terracotta Army figures (Bouherour 2001).

    Analysis of rock art from ancient sites in Australia has described the use of minerals as binders in pictographs. Analysis of this “mulberry ocher paint,” apparently demonstrated that minerals such as quartz, anorthite (feldspar), hematite and others were used both as pigments and binding materials in the paint (Huntley et al. 2015).

    Naturally occurring mulberry hematite paint mixtures are mostly made up of inorganic jarosite minerology, red paints with hematite, a blood binder and an organic base, possibly tree sap. The minerology was detected to be gypsum, quartz, anorthite (feldspar), hematite and the colorant was thought to be hematite. Mineral silica accretions were investigated to contain salts, phosphate salts, clays, and oxalates such as whewellite. In reading this article, there is some scepticism as to where whewellite was intentionally mixed into a paint recipe and where it occurred naturally as a crystalline material developing from environmental conditions (Huntley et al. 2015).

    Synthetic Binders

    Acrylic binders

    Acrylic medium, a polymer emulsion, has been employed since the 1930s. Its ability to be used as a water-based binder and extender with fast drying properties has made it popular as artists and commercial paint companies. This new, synthetic medium created an explosion of experiments and possibilities. It can be built up thickly with a palette knife, or diluted and applied with a brush like watercolor.

    Beginning in the 1950s, mural painters found acrylic medium a versatile addition to make workable paint for large scale projects (Taft and Mayer 2000).

    Conclusion

    Because of advances in modern scientific technologies, we have a better understanding of binders and carriers used in paint media throughout time and around the world. We can look to both the past and to more recent testing to confirm or refine our thinking about the compositions of historic pigments, binders and carriers in paint. For instance,

    a study done by Reese in 1996 using PCR and phylogenetic analysis, hypothesized that the origin of the binder used in Lower Pecos River rock art was a unique and extinct animal similar to a deer, from the order Artiodactyla. This study, which was repeated by Mawk & Hyman et al. in 2001 using a variety of DNA testing, determined that the previous 1996 study sample by Reese was contaminated and was therefore inconclusive as to the animal source of the binder. That source will have to be determined in a future study,

    My future research interests are to identify and analyze plant, tree sap and animal binders in the rock art of the Lower Pecos River region, in the southwest US and adjacent Mexican areas. Since these rock art paintings are approximately 4,000 years old, my future research plans would include investigating how these binders helped the images, exposed to environmental vagaries, last so long, especially compared to European painting medias which only lasted roughly 500 years.

  • Learn to make your own paint binders from Northwest artist and paint specialist, Theodora Jonsson. Resin and mastics have been used since ancient times to make the paint used in honor of sacred shrines, cathedrals and temples. The smell alone can raise one to embody a mental painting space of the sacred. Learn about the making and use of ancient paint binders including their history, mythology, religious and contemporary sources. Experiment with your artwork in the making of these sacred paint recipes. Outdoor spaces recommended and only within proper ventilated areas.

  • From the Silk Road to the present day artist’s palette, we explore the studio practices of color making one color at a time through historical, literary and travel notes as these resources delve into the fascinating, cross cultural and cross era evolution of color for artists and textile workers.

  • Learn the exotic histories of color and secrets on how to mix the colors of the Skagit Valley. Join me to learn how to mix the colors and hue combinations to make the sky and water pop! Each week we will explore the history of one color. In a brief slideshow presentation, following the creation of pigments and the stories of their inventors. This class explores the art and cultural history of color as well as teaches practical painting technique, color mixing and use. Color theory inspired from conversations with Norman Lundin.

    The full spectrum of classes span from red to violet over twelve sessions. Sign up one month at a time.

Juniper tree resin forms hard crystals which can be gathered.

 

Making tree resin mediums involves soaking the dried resin in white spirits for 24 hours and playing with the recipes to get the right consistency and flow for the paint.

Pacific Northwest Cedar and Douglas Fir trees have had spiritual significance for centuries, some are culturally modified to signify rites of passage, harvesting and hunting grounds by the Nuwha’ha, Upper Skagit, and Nooksack Tribes.