Creosote

Some creosote types were used historically as a treatment for components of seagoing and outdoor wood structures to prevent rot (e.g., bridgework and railroad ties, see image). Samples may be found commonly inside chimney flues, where the coal or wood burns under variable conditions, producing soot and tarry smoke. Creosotes are the principal chemicals responsible for the stability, scent, and flavor characteristic of smoked meat; the name is derived from Greek κρέας (kreas) 'meat' and σωτήρ (sōtēr) 'preserver'.

The two main kinds recognized in industry are coal-tar creosote and wood-tar creosote. The coal-tar variety, having stronger and more toxic properties, has chiefly been used as a preservative for wood; coal-tar creosote was also formerly used as an escharotic, to burn malignant skin tissue, and in dentistry, to prevent necrosis, before its carcinogenic properties became known. The wood-tar variety has been used for meat preservation, ship treatment, and such medical purposes as an anaesthetic, antiseptic, astringent, expectorant, and laxative, though these have mostly been replaced by modern formulations.

Varieties of creosote have also been made from both oil shale and petroleum, and are known as oil-tar creosote when derived from oil tar, and as water-gas-tar creosote when derived from the tar of water gas. Creosote also has been made from pre-coal formations such as lignite, yielding lignite-tar creosote, and peat, yielding peat-tar creosote.

Creosote oils

The term creosote has a broad range of definitions depending on the origin of the coal tar oil and end-use of the material.

With respect to wood preservatives, the United States Environmental Protection Agency (EPA) considers the term creosote to mean a pesticide for use as a wood preservative meeting the American Wood Protection Association (AWPA) Standards P1/P13 and P2. The AWPA Standards require that creosote "shall be a pure coal tar product derived entirely from tar produced by the carbonization of bituminous coal."

Currently, all creosote-treated wood products—foundation and marine pilings, lumber, posts, railroad ties, timbers, and utility poles—are manufactured using this type of wood preservative. The manufacturing process can only be a pressure process under the supervision of a licensed applicator certified by the State Departments of Agriculture. No brush-on, spray, or non-pressure uses of creosote are allowed, as specified by the EPA-approved label for the use of creosote.

The use of creosote according to the AWPA Standards does not allow for mixing with other types of "creosote type" materials—such as lignite-tar creosote, oil-tar creosote, peat-tar creosote, water-gas-tar creosote, or wood-tar creosote. The AWPA Standard P3 does however, allow blending of a high-boiling petroleum oil meeting the AWPA Standard P4.

The information that follows describing the other various types of creosote materials and its uses should be considered as primarily being of only historical value. This history is important, because it traces the origin of these different materials used during the 19th and early 20th centuries. Furthermore, it must be considered that these other types of creosotes – lignite-tar, wood-tar, water-gas-tar, etc. – are not currently being manufactured and have either been replaced with more-economical materials, or replaced by products that are more efficacious or safer.

For some part of their history, coal-tar creosote and wood-tar creosote were thought to have been equivalent substances—albeit of distinct origins—accounting for their common name; the two were determined only later to be chemically different. All types of creosote are composed of phenol derivatives and share some quantity of monosubstituted phenols, but these are not the only active element of creosote. For their useful effects, coal-tar creosote relies on the presence of naphthalenes and anthracenes, while wood-tar creosote relies on the presence of methyl ethers of phenol. Otherwise, either type of tar would dissolve in water.

Creosote was first discovered in its wood-tar form in 1832, by Carl Reichenbach, when he found it both in the tar and in pyroligneous acids obtained by a dry distillation of beechwood. Because pyroligneous acid was known as an antiseptic and meat preservative, Reichenbach conducted experiments by dipping meat in a dilute solution of distilled creosote. He found that the meat was dried without undergoing putrefaction and had attained a smoky flavor. This led him to reason that creosote was the antiseptic component contained in smoke, and he further argued that the creosote he had found in wood tar was also in coal tar, as well as amber tar and animal tar, in the same abundance as in wood tar.

Soon afterward, in 1834, Friedrich Ferdinand Runge discovered carbolic acid (phenol) in coal-tar, and Auguste Laurent obtained it from "phenylhydrate", which was soon determined to be the same compound. There was no clear view on the relationship between carbolic acid and creosote; Runge described it as having similar caustic and antiseptic properties, but noted that it was different, in that it was an acid and formed salts. Nonetheless, Reichenbach argued that creosote was also the active element, as it was in pyroligneous acid. Despite evidence to the contrary, his view held sway with most chemists, and it became commonly accepted wisdom that creosote, carbolic acid, and phenylhydrate were identical substances, with different degrees of purity.

Carbolic acid was soon commonly sold under the name "creosote", and the scarcity of wood-tar creosote in some places led chemists to believe that it was the same substance as that described by Reichenbach. In the 1840s, Eugen Freiherr von Gorup-Besanez, after realizing that two samples of substances labelled as creosote were different, started a series of investigations to determine the chemical nature of carbolic acid, leading to a conclusion that it more resembled chlorinated quinones and must have been a different, entirely unrelated substance.

Independently, there were investigations into the chemical nature of creosote. A study by F.K. Völkel revealed that the smell of purified creosote resembled that of guaiacol, and later studies by Heinrich Hlasiwetz identified a substance common to guaiacum and creosote that he called creosol, and he determined that creosote contained a mixture of creosol and guaiacol. Later investigations by Gorup-Besanez, A.E. Hoffmann, and Siegfried Marasse showed that wood-tar creosote also contained phenols, giving it a feature in common with coal-tar creosote.

Historically, coal-tar creosote has been distinguished from what was thought of as creosote proper—the original substance of Reichenbach's discovery—and it has been referred to specifically as "creosote oil". But, because creosote from coal-tar and wood-tar are obtained from a similar process and have some common uses, they have also been placed in the same class of substances, with the terms "creosote" or "creosote oil" referring to either product.

Wood-tar creosote

Wood-tar creosote is a colourless to yellowish greasy liquid with a smoky odor, produces a sooty flame when burned, and has a burned taste. It is non-buoyant in water, with a specific gravity of 1.037 to 1.087, retains fluidity at a very low temperature, and boils at 205-225 °C. In its purest form, it is transparent. Dissolution in water requires up to 200 times the amount of water as the base creosote. This creosote is a combination of natural phenols: primarily guaiacol and creosol (4-methylguaiacol), which typically constitutes 50% of the oil; second in prevalence are cresol and xylenol; the rest being a combination of monophenols and polyphenols.

The simple phenols are not the only active element in wood-tar creosote. In solution, they coagulate albumin, which is a water-soluble protein found in meat, so they serve as a preserving agent, but also cause denaturation. Most of the phenols in the creosote are methoxy derivatives: they contain the methoxy group (−O−CH₃) linked to the benzene nucleus. The high level of methyl derivates created from the action of heat on wood (also apparent in the methyl alcohol produced through distillation) make wood-tar creosote substantially different from coal-tar creosote. Guaiacol is a methyl ether of pyrocatechin, while creosol is a methyl ether of methyl-pyrocatechin, the next homolog of pyrocatechin. Methyl ethers differ from simple phenols in being less hydrophilic, caustic, and poisonous. This allows meat to be successfully preserved without tissue denaturation, and allows creosote to be used as a medical ointment.

Because wood-tar creosote is used for its guaiacol and creosol content, it is generally derived from beechwood rather than other woods, since it distills with a higher proportion of those chemicals to other phenolics. The creosote can be obtained by distilling the wood tar and treating the fraction heavier than water with a sodium hydroxide solution. The alkaline solution is then separated from the insoluble oily layer, boiled in contact with air to reduce impurities, and decomposed by diluted sulfuric acid. This produces a crude creosote, which is purified by re-solution in alkali, re-precipitation with acid, then redistilled with the fraction passing over between 200° and 225° constituting the purified creosote.

When ferric chloride is added to a dilute solution, it will turn green: a characteristic of ortho-oxy derivatives of benzene. It dissolves in sulfuric acid to a red liquid, which slowly changes to purple-violet. Shaken with hydrochloric acid in the absence of air, it becomes red, the color changing in the presence of air to dark brown or black.

In preparation of food by smoking, guaiacol contributes mainly to the smoky taste, while the dimethyl ether of pyrogallol, syringol, is the main chemical responsible for the smoky aroma.

Historical uses

Industrial

Soon after it was discovered and recognized as the principle of meat smoking, wood-tar creosote became used as a replacement for the process. Several methods were used to apply the creosote. One was to dip the meat in pyroligneous acid or a water of diluted creosote, as Reichenbach did, or brush it over with them, and within one hour the meat would have the same quality as that of traditionally smoked preparations. Sometimes the creosote was diluted in vinegar rather than water, as vinegar was also used as a preservative. Another was to place the meat in a closed box, and place with it a few drops of creosote in a small bottle. Because of the volatility of the creosote, the atmosphere was filled with a vapour containing it, and it would cover the flesh.

The application of wood tar to seagoing vessels was practiced through the 18th century and early 19th century, before the creosote was isolated as a compound. Wood-tar creosote was found not to be as effective in wood treatments, because it was harder to infuse the creosote into the wood cells, but still experiments were done, including by many governments, because it proved to be less expensive on the market.

Medical

Even before creosote as a chemical compound was discovered, it was the chief active component of medicinal remedies in different cultures around the world.

In antiquity, pitches and resins were used commonly as medicines. Pliny mentions a variety of tar-like substances being used as medicine, including cedria and pissinum. Cedria was the pitch and resin of the cedar tree, being equivalent to the oil of tar and pyroligneous acid which are used in the first stage of distilling creosote. He recommends cedria to ease the pain in a toothache, as an injection in the ear in case of hardness of hearing, to kill parasitic worms, as a preventive for infusion, as a treatment for phthiriasis and porrigo, as an antidote for the poison of the sea hare, as a liniment for elephantiasis, and as an ointment to treat ulcers both on the skin and in the lungs. He further speaks of cedria being used as the embalming agent for preparing mummies. Pissinum was a tar water that was made by boiling cedria, spreading wool fleeces over the vessels to catch the steam, and then wringing them out.

The Pharmacopée de Lyon, published in 1778, says that cedar tree oil is believed to cure vomiting and help medicate tumors and ulcers. Physicians contemporary to the discovery of creosote recommended ointments and pills made from tar or pitch to treat skin diseases. Tar water had been used as a folk remedy since the Middle Ages to treat affections like dyspepsia. George Berkeley wrote several works on the medical virtues of tar water, including a philosophical work in 1744 titled Siris: a chain of philosophical reflexions and inquiries concerning the virtues of tar water, and divers other subjects connected together and arising one from another, and a poem where he praised its virtues. Pyroligneous acid was also used at the time in a medicinal water called Aqua Binelli (Binelli's water), a compound which its inventor, the Italian Fedele Binelli, claimed to have hemostatic properties in his research published in 1797. These claims have since been disproven.

Given this history, and the antiseptic properties known to creosote, it became popular among physicians in the 19th century. A dilution of creosote in water was sold in pharmacies as Aqua creosoti, as suggested by the previous use of pyroligneous acid. It was prescribed to quell the irritability of the stomach and bowels and detoxify, treat ulcers and abscesses, neutralize bad odors, and stimulate the mucous tissues of the mouth and throat. Creosote in general was listed as an irritant, styptic, antiseptic, narcotic, and diuretic, and in small doses when taken internally as a sedative and anaesthetic. It was used to treat ulcers, and as a way to sterilize the tooth and deaden the pain in case of a tooth-ache.

Creosote was suggested as a treatment for tuberculosis by Reichenbach as early as 1833. Following Reichenbach, it was argued for by John Elliotson and Sir John Rose Cormack. Elliotson, inspired by the use of creosote to arrest vomiting during an outbreak of cholera, suggested its use for tuberculosis through inhalation. He also suggested it for epilepsy, neuralgia, diabetes, and chronic glanders. The idea of using it for tuberculosis failed to be accepted. Use for this purpose was dropped, until the idea was revived in 1876 by British doctor G. Anderson Imlay, who suggested it be applied locally by spray to the bronchial mucous membrane. This was followed up in 1877 when it was argued for in a clinical paper by Charles Bouchard and Henri Gimbert. Germ theory had been established by Pasteur in 1860, and Bouchard, arguing that a bacillus was responsible for the disease, sought to rehabilitate creosote for its use as an antiseptic to treat it. He began a series of trials with Gimbert to convince the scientific community, and claimed a promising cure rate. A number of publications in Germany confirmed his results in the following years.

Later, a period of experimentation with different techniques and chemicals using creosote in treating tuberculosis lasted until about 1910, when radiation therapy seemed more promising. Guaiacol, instead of a full creosote solution, was suggested by Hermann Sahli in 1887. He argued it had the active chemical of creosote and had the advantage of being of definite composition and having a less unpleasant taste and odor. A number of solutions of both creosote and guaiacol appeared on the market, such as phosphotal and guaicophosphal, phosphites of creosote and guaiacol; eosot and geosot, valerinates of creosote and guaicol; phosot and taphosot, phosphate and tannophospate of creosote; and creosotal and tanosal, tannates of creosote. Creosote and eucalyptus oil were also a remedy used together, administered through a vaporizor and inhaler. Since then, more effective and safer treatments for tuberculosis have been developed.

In the 1940s, Canadian-based Eldon Boyd experimented with guaiacol and a recent synthetic modification—glycerol guaiacolate (guaifenesin)—on animals. His data showed that both drugs were effective in increasing secretions into the airways in laboratory animals, when high-enough doses were given.

Current uses

Industrial

Wood-tar creosote is to some extent used for wood preservation, but it is generally mixed with coal-tar creosote, since the former is not as effective. Commercially available preparations of "liquid smoke", marketed to add a smoked flavour to meat and aid as a preservative, consist primarily of creosote and other constituents of smoke. Creosote is the ingredient that gives liquid smoke its function; guaicol lends to the taste and the creosote oils help act as the preservative. Creosote can be destroyed by treatment with chlorine, either sodium hypochlorite, or calcium hypochlorite solutions . The phenol ring is essentially opened, and the molecule is then subject to normal digestion and normal respiration.

Medical

The guaifenesin developed by Eldon Boyd is still commonly used today as an expectorant, sold over the counter, and usually taken by mouth to assist the bringing up of phlegm from the airways in acute respiratory tract infections. Guaifenesin is a component of Mucinex, Robitussin DAC, Cheratussin DAC, Robitussin AC, Cheratussin AC, Benylin, DayQuil Mucous Control, Meltus, and Bidex 400.

Seirogan is a popular Kampo medicine in Japan, used as an anti-diarrheal, and has 133 mg wood creosote from beech, pine, maple or oak wood per adult dose as its primary ingredient. Seirogan was first used as a gastrointestinal medication by the Imperial Japanese Army in Russia during the Russo-Japanese War of 1904 to 1905.

Creomulsion is a cough medicine in the United States, introduced in 1925, that is still sold and contains beechwood creosote. Beechwood creosote is also found under the name kreosotum or kreosote.

Coal-tar creosote

Coal-tar creosote is greenish-brown liquid, with different degrees of darkness, viscosity, and fluorescence depending on how it is made. When freshly made, the creosote is a yellow oil with a greenish cast and highly fluorescent, and the fluorescence is increased by exposure to air and light. After settling, the oil is dark green by reflected light and dark red by transmitted light. To the naked eye, it generally appears brown. The creosote (often called "creosote oil") consists almost wholly of aromatic hydrocarbons, with some amount of bases and acids and other neutral oils. The flash point is 70–75 °C and burning point is 90–100 °C, and when burned it releases a greenish smoke. The smell largely depends on the naphtha content in the creosote. If there is a high amount, it will have a naphtha-like smell, otherwise it will smell more of tar.

In the process of coal-tar distillation, the distillate is collected into four fractions; the "light oil", which remains lighter than water, the "middle oil" which passes over when the light oil is removed; the "heavy oil", which sinks; and the "anthracene oil", which when cold is mostly solid and greasy, of a buttery consistence. Creosote refers to the portion of coal tar which distills as "heavy oil", typically between 230 and 270 °C, also called "dead oil"; it sinks into water but still is fairly liquid. Carbolic acid is produced in the second fraction of distillation and is often distilled into what is referred to as "carbolic oil".

Commercial creosote contains substances from six groups. The two groups occur in the greatest amounts and are the products of the distillation process—the "tar acids", which distill below 205 °C and consist mainly of phenols, cresols, and xylenols, including carbolic acid—and aromatic hydrocarbons, which divide into naphthalenes, which distill approximately between 205 and 255 °C, and constituents of an anthracene nature, which distill above 255 °C. The quantity of each varies based on the quality of tar and temperatures used, but generally, the tar acids won't exceed 5%, the naphthalenes make up 15 to 50%, and the anthracenes make up 45% to 70%. The hydrocarbons are mainly aromatic; derivatives of benzene and related cyclic compounds such as naphthalene, anthracene, phenanthrene, acenaphthene, and fluorene. Creosotes from vertical-retort and low temperature tars contain, in addition, some paraffinic and olefinic hydrocarbons. The tar-acid content also depends on the source of the tar—it may be less than 3% in creosote from coke-oven tar and as high as 32% in creosote from vertical retort tar. All of these have antiseptic properties. The tar acids are the strongest antiseptics but have the highest degree of solubility in water and are the most volatile; so, like with wood-tar creosote, phenols are not the most valued component, as by themselves they would lend to being poor preservatives. In addition, creosote contains several products naturally occurring in coal—nitrogen-containing heterocycles, such as acridines, carbazoles, and quinolines, referred to as the "tar bases" and generally make up about 3% of the creosote—sulfur-containing heterocycles, generally benzothiophenes—and oxygen-containing heterocycles, dibenzofurans. Lastly, creosote contains a small number of aromatic amines produced by the other substances during the distillation process and likely resulting from a combination of thermolysis and hydrogenation. The tar bases are often extracted by washing the creosote with aqueous mineral acid, although they're also suggested to have antiseptic ability similar to the tar acids.

Commercially used creosote is often treated to extract the carbolic acid, naphthalene, or anthracene content. The carbolic acid or naphthalene is generally extracted to be used in other commercial products. In the early 20th century, American-produced creosote oils typically had low amounts of anthracene and high amounts of naphthalene, because when forcing the distillate at a temperature that produces anthracene the soft pitch will be ruined and only the hard pitch will remain; this ruined it for use in roofing purposes (which was common before widespread availability of cheap oil bitumen) and only left a product which wasn't commercially useful.

Historical uses

Industrial

The use of coal-tar creosote on a commercial scale began in 1838, when a patent covering the use of creosote oil to treat timber was taken out by inventor John Bethell. The "Bethell process"—or as it later became known, the full-cell process—involves placing wood to be treated in a sealed chamber and applying a vacuum to remove air and moisture from wood "cells". The wood is then pressure-treated to imbue it with creosote or other preservative chemicals, after which vacuum is reapplied to separate the excess treatment chemicals from the timber. Alongside the zinc chloride-based "Burnett process", use of creosoted wood prepared by the Bethell process became a principal way of preserving railway timbers (most notably railway sleepers) to increase the lifespan of the timbers, and avoiding having to regularly replace them.

Besides treating wood, it was also used for lighting and fuel. In the beginning, it was only used for lighting needed in harbour and outdoor work, where the smoke that was produced from burning it was of little inconvenience. By 1879, lamps had been created that ensured a more complete combustion by using compressed air, removing the drawback of the smoke. Creosote was also processed into gas and used for lighting that way. As a fuel, it was used to power ships at sea and blast furnaces for different industrial needs, once it was discovered to be more efficient than unrefined coal or wood. It was also used industrially for the softening of hard pitch, and burned to produce lamp black. By 1890, the production of creosote in the United Kingdom totaled approximately 29,900,000 gallons per year.

In 1854, Alexander McDougall and Robert Angus Smith developed and patented a product called McDougall's Powder as a sewer deodorant; it mainly consisted of carbolic acid derived from creosote. McDougall, in 1864, experimented with his solution to remove entozoa parasites from cattle pasturing on a sewage farm. This later led to widespread use of creosote as a cattle wash and sheep dip. External parasites would be killed in a creosote diluted dip, and drenching tubes would be used to administer doses to the animals' stomachs to kill internal parasites.

Creosoted wood blocks were a common road-paving material in the late 19th and early 20th centuries, but ultimately fell out of favor because they did not generally hold up well enough over time.

Two later methods for creosoting wood were introduced after the turn of the century, referred to as empty-cell processes, because they involve compressing the air inside the wood so that the preservative can only coat the inner cell walls rather than saturating the interior cell voids. This is a less effective, though usually satisfactory, method of treating the wood, but is used because it requires less of the creosoting material. The first method, the "Rüping process" was patented in 1902, and the second, the "Lowry process" was patented in 1906. Later in 1906, the "Allardyce process" and "Card process" were patented to treat wood with a combination of both creosote and zinc chloride. In 1912, it was estimated that a total of 150,000,000 gallons were produced in the US per year.

Medical

Coal-tar creosote, despite its toxicity, was used as a stimulant and escharotic, as a caustic agent used to treat ulcers and malignancies, cauterize wounds, and prevent infection and decay. It was particularly used in dentistry to destroy tissues and arrest necrosis.

Current uses

Industrial

Coal-tar creosote is the most widely used wood treatment today; both industrially, processed into wood using pressure methods such as "full-cell process" or "empty-cell process", and more commonly applied to wood through brushing. In addition to toxicity to fungi, insects, and marine borers, it serves as a natural water repellent. It is commonly used to preserve and waterproof railroad ties, pilings, telephone poles, power line poles, marine pilings, and fence posts. Although suitable for use in preserving the structural timbers of buildings, it is not generally used that way because it is difficult to apply. There are also concerns about the environmental impact of the leaching of creosote into aquatic ecosystems.

Due to its carcinogenic character, the European Union has regulated the quality of creosote for the EU market and requires that the sale of creosote be limited to professional users. The United States Environmental Protection Agency regulates the use of coal-tar creosote as a wood preservative under the provisions of the Federal Insecticide, Fungicide, and Rodenticide Act. Creosote is considered a restricted-use pesticide and is only available to licensed pesticide applicators.

Oil-tar creosote

Oil-tar creosote is derived from the tar that forms when using petroleum or shale oil in the manufacturing of gas. The distillation of the tar from the oil occurs at very high temperatures; around 980 °C. The tar forms at the same time as the gas, and once processed for creosotes contains a high percentage of cyclic hydrocarbons, a very low amount of tar acids and tar bases, and no true anthracenes have been identified. Historically, this has mainly been produced in the United States on the Pacific coast, where petroleum has been more abundant than coal. Limited quantities have been used industrially, either alone, mixed with coal-tar creosote, or fortified with pentachlorophenol.

Water-gas-tar creosote

Water-gas-tar creosote is also derived from petroleum oil or shale oil, but by a different process; it is distilled during the production of water gas. The tar is a by-product resulting from enrichment of water gas with gases produced by thermal decomposition of petroleum. Of the creosotes derived from oil, it is practically the only one used for wood preservation. It has the same degree of solubility as coal-tar creosote and is easy to infuse into wood. Like standard oil-tar creosote, it has a low amount of tar acids and tar bases, and has less antiseptic qualities. Petri dish tests have shown that water-gas-tar creosote is one-sixth as anti-septically effective as that of coal-tar.

Lignite-tar creosote

Lignite-tar creosote is produced from lignite rather than bituminous coal, and varies considerably from coal-tar creosote. Also called "lignite oil", it has a very high content of tar acids, and has been used to increase the tar acids in normal creosote when necessary. When it has been produced, it has generally been applied in mixtures with coal-tar creosote or petroleum. Its effectiveness when used alone has not been established. In an experiment with southern yellow pine fence posts in Mississippi, straight lignite-tar creosote was giving good results after about 27 years exposure, although not as good as the standard coal-tar creosote used in the same situation.

Peat-tar creosote

There have also been attempts to distill creosote from peat-tar, although mostly unsuccessful due to the problems with winning and drying peat on an industrial scale. Peat tar by itself has in the past been used as a wood preservative.