Tar is a dark brown or black bituminous, odorous, viscous liquid obtained by the destructive distillation of organic materials such as wood, coal, or peat.[1] It is characterized by its heavy, oily consistency and high carbon content, distinguishing it from related substances like bitumen or pitch.[2]Produced through pyrolysis—intense heating of organic matter in the absence of oxygen—tar has been derived from diverse sources including trees, coal, bones, and petroleum residues for thousands of years.[3] Common types include wood tar, obtained from resinous woods like pine (Pinaceae family) or birch (Betulaceae), often containing turpentine and phenolic compounds; coal tar, a byproduct of coalcarbonization during coke and gas production; and plant tars from species in families such as Cupressaceae (e.g., juniper and cedar).[3][4][5]Historically, tar served practical purposes such as gluing materials, waterproofing boats and ropes, preserving wood against rot, and even decoration in ancient cultures across regions like Northern Europe, Morocco, and Turkey.[5] In modern applications, coal tar is primarily refined into chemicals, creosote for wood treatment, and pitch for binders in road paving, roofing, and pavement sealants, though its use has declined due to environmental concerns, including bans on coal-tar based sealants in several US jurisdictions such as New York, Maryland, and Virginia, with ongoing proposals in others as of 2025.[4][6][7][8] Wood tar and its pitch find roles in antiseptics, ointments for skin conditions like psoriasis, and manufacturing plastics, insulating materials, and caulking compounds.[3] Plant-derived tars retain ethnopharmacological value in traditional medicine and cosmetics for treating dermal diseases in both human and veterinary contexts.[5]Tar's chemical complexity—a mixture of aromatic hydrocarbons, phenols, and acids—underpins its versatility but also its hazards; coal tar and its derivatives are classified as carcinogenic due to polycyclic aromatic hydrocarbons (PAHs).[4] Significant production occurs in areas like Northern Europe for wood tar and industrial coke facilities worldwide for coal tar, with ongoing research into sustainable plant-based alternatives.[3][9][10]
Definition and Terminology
Etymology and Nomenclature
The word "tar" derives from Old Englishteoru, referring to the pitch or resin obtained from trees.[11] This term traces back to Proto-Germanic terwō and ultimately to the Proto-Indo-European rootderu-, which conveys notions of firmness, solidity, and tree or wood, reflecting tar's origins in tree resins and saps.[1] Cognates appear across Germanic languages, such as Old Norsetjara and Dutchteer, underscoring its ancient association with viscous, tree-derived substances used for sealing and preservation.[12]In nomenclature, tar is distinguished from related terms based on form and source; for instance, "pitch" denotes a denser, semi-solid residue derived from the distillation of tar, often used interchangeably but technically more solid and less fluid than liquid tar.[13] Specific variants include "Stockholm tar," a high-quality pine tar produced from destructive distillation of pine wood, named for the Swedish city of Stockholm due to a historical royal monopoly on its export, which ensured its standardization and reputation in shipbuilding and cordage. These distinctions help classify tars by production method and application, with wood-derived forms like Stockholm tar differentiated from coal or petroleum sources.Regional naming variations highlight cultural and linguistic adaptations; in Spanish, "brea" specifically means tar, as seen in place names like La Brea Tar Pits, where natural asphalt seeps were known to indigenous peoples and early settlers.[14] In French, "goudron" refers to tar generally, with "goudron de houille" denoting coal tar, a term rooted in industrial contexts for the byproduct of coalcarbonization.[15] Such terms reflect localized uses, from road surfacing to medicinal applications, while maintaining the core concept of a dark, viscous residue.
Physical and Chemical Properties
Tar exhibits a dark brown to black coloration and exists as a viscous liquid or semisolid at room temperature, depending on its specific composition and source material.[16] Its density typically ranges from 1.0 to 1.2 g/cm³, reflecting the dense packing of its hydrocarbon components.[17] The boiling point of tar components spans a broad range, generally from 150°C to 400°C, as it is a complex mixture rather than a single compound, allowing distillation over varying temperatures.[18]A defining characteristic of tar is its high viscosity, which can reach up to 10,000 cP or more, contributing to its flow resistance and utility in applications requiring adhesion.[19] Tar demonstrates solubility in organic solvents such as benzene, ether, alcohol, and acetone, but it is insoluble in water, which underscores its hydrophobic nature derived from non-polar hydrocarbons.[20] This solubility profile, combined with its viscous consistency, imparts strong adhesive qualities, primarily due to the presence of polymeric hydrocarbons that enable binding to surfaces.[21]Chemically, tar shows basic stability with resistance to mild oxidation under ambient conditions, making it suitable for preservative uses, though it can undergo polymerization when exposed to elevated temperatures, leading to increased rigidity and the formation of pitch-like residues. This thermal polymerization arises from reactions among its aromatic and aliphatic components, altering its molecular structure without complete decomposition.[22]
History
Ancient and Pre-Industrial Uses
Evidence of tar use dates back to prehistoric times, with archaeological findings indicating its application in mummification processes in ancient Egypt around 3500 BCE. Analysis of a naturally mummified body from the predynastic period reveals the presence of complex balms containing resins and tars, likely sourced from petroleum bitumen, used to preserve soft tissues and inhibit bacterial growth.[23] This practice evolved over millennia, though petroleum bitumen was not universally employed and became more prominent in later periods.[24]In Neolithic Europe, particularly Scandinavia, birch-bark tar served as a versatile adhesive and waterproofing agent, applied to seal canoes and boats constructed from wood or animal skins. Produced by heating birch bark in low-oxygen conditions, this tar was used to mend pottery, haft tools, and caulk vessels, facilitating maritime activities such as fishing and trade across the Baltic Sea around 5000–2500 BCE.[25] Archaeological residues on flint blades and pottery from sites in northern Europe confirm its role in waterproofing wooden watercraft during this era.[26]Among ancient civilizations, tar found widespread use in maritime and construction applications. In Greek and Roman societies, pitch derived from pine resin or natural bitumen was applied to caulk ship hulls and coat bottoms, preventing water ingress and biofouling on wooden vessels.[27] The Romans also employed bitumen for sealing aqueducts, reservoirs, and early road surfaces, drawing from Greek terminology "asphaltos" meaning "secure."[28] Biblical texts in the Old Testament reference tar similarly; Genesis 6:14 instructs the use of "pitch" (zepheth, denoting a bituminous substance) to waterproof Noah's ark inside and out, reflecting common Near Eastern waterproofing techniques of the period.[29]Before 1800, pre-industrial extraction of tar in Europe and Asia relied on rudimentary methods, including collection from natural seeps and distillation of pine resin. In the Near East and parts of Asia, communities gathered viscous bitumen from surface seeps for use in building and sealing, a practice documented in Mesopotamian records and continuing into Ottoman times.[30] In Scandinavia and central Europe, pine tar was produced by slow pyrolysis of pine wood in earthen kilns or pits, yielding a dark, sticky byproduct for local trade and ship maintenance as early as the Viking Age.[31] In Anatolia, traditional production from black pine involved heating resinous wood, supporting regional economies through the 18th century.[32]
Development of Industrial Production
The development of industrial tar production began in the 18th and 19th centuries, building on ancient uses of tar for preservation and waterproofing as precursors to scaled manufacturing. In Europe, particularly Britain, coal tar emerged as a significant byproduct during the early 1800s from the carbonization of coal for manufactured gas used in urban lighting. The first commercial gas works, established in London in 1813, produced coal tar as a waste material initially discarded into rivers, but by the 1830s, its potential for industrial applications prompted collection and basic processing.[33][34]Concurrently, wood tar production industrialized in Sweden during the 18th and 19th centuries to supply naval stores for European shipbuilding, utilizing kiln-based methods by small landowners in northern regions. These kilns, often constructed from earth and wood, processed pine resin to yield tar essential for caulking and rope preservation, with Sweden dominating exports to the Royal Navy until the mid-18th century when colonial sources began competing. Key innovations in the mid-19th century included the expansion of coke oven operations around the 1850s, which generated substantial coal tar volumes as byproducts during iron and steel production; this led to the establishment of dedicated coal tar refineries, such as the 1843 facility at Crew’s Hole in Bristol, focused on extracting creosote and pitch for timber treatment.[35][34]In the 20th century, particularly post-World War II, tar production shifted toward petroleum sources, with refined bitumen and asphalt derivatives supplanting coal tar for applications like road paving due to the booming oil industry and wartime advancements in refining. This transition reflected broader energy trends, as petroleum output surged to meet reconstruction demands, reducing reliance on coal-derived tars. Economically, tar's role fueled the chemical industry boom, enabling dyes, pharmaceuticals, and synthetics; by 1900, global coal tardistillation reached approximately 3 million tons annually, scaling from artisanal levels and contributing to the second industrial revolution's growth in organic chemicals.[36][37]
Types of Tar
Wood Tar
Wood tar is derived from the pyrolysis of resin-rich woods, primarily pine (Pinus spp.), beech (Fagus sylvatica), and birch (Betula spp.), where the wood is heated in low-oxygen conditions to yield a viscous distillate.[38][39][35] This process, known as destructive distillation, breaks down the lignocellulosic components into condensable vapors that form the tar, along with byproducts like char and gases. Historical production was centered in Scandinavia, where pine stumps and roots—naturally high in resin—were preferred raw materials, and in Russia, where similar methods supported large-scale output for export.[40][35]Distinct from coal tar's heavier, black composition, wood tar exhibits a lighter golden to dark brown color and a characteristic smoky, empyreumatic aroma due to its phenolic and terpenoid components.[41][42] Its higher resin content, including guaiacol, creosol, and terpene oils, contributes to adhesive properties, making it suitable for binding materials in traditional applications like stone repair and woodworking.[43][42]Key variants include pine tar, produced via kiln-burning of pine wood, which is notably rich in turpentine and volatile oils, enhancing its fluidity and preservative qualities.[35][42]Juniper tar (Juniperus spp.), obtained similarly from juniper wood or bark, has been employed in folk medicine for its antiseptic and anti-inflammatory effects, treating skin conditions and wounds historically across Europe and beyond.[44]
Coal Tar
Coal tar is a viscous, black liquid obtained as a byproduct during the carbonization of coal, primarily in the production of coke for steelmaking and coal gas.[45] This process involves heating coal in the absence of air, known as destructive distillation, which yields coke as the main product while coal tar condenses from the volatile matter released.[46] Historically, coal tar was first isolated in significant quantities in the 19th century from gasworks, where coal was carbonized to produce town gas for lighting and heating urban areas.[37]Characterized by its thick, black appearance and pungent naphthalene-like odor, coal tar is a complex mixture dominated by high concentrations of aromatic hydrocarbons, including polycyclic aromatic compounds that distinguish it from other tars.[47] Upon fractional distillation, it yields valuable sub-products such as creosote oil, used for wood preservation, and naphthalene, a key intermediate for chemical synthesis.[48] These aromatic-rich fractions contribute to its industrial utility, though they also impart potential health risks due to carcinogenic components.[49]Coal tar played a pivotal historical role as the foundation for the synthetic organic chemicals industry, particularly through its derivatives like aniline. In 1856, William Henry Perkin discovered mauveine, the first synthetic dye, while experimenting with aniline derived from coal tar in an attempt to synthesize quinine.[50] This serendipitous breakthrough, conducted in Perkin's home laboratory, transformed coal tar from a mere waste product of gasworks into a vital source of dyes, pharmaceuticals, and other compounds, sparking the modernchemical industry.[51]
Petroleum and Bitumen Derivatives
Petroleum tars, also known as asphaltic tars or bitumen, are primarily derived from the vacuum distillation of crude oil residues following atmospheric distillation.[52] These heavy fractions consist of complex hydrocarbons with carbon numbers predominantly greater than 40, forming a semi-solid or viscous material at ambient temperatures.[52] Natural bitumen deposits, such as Trinidad Lake Asphalt, represent another key source, occurring as a naturally formed, semi-solid emulsion of bitumen and mineral matter in lake-like formations.[53]These tars are characterized by high asphaltene content, typically comprising 5-25% of the composition, which contributes to their structural complexity and colloidal stability.[54]Asphaltenes, being polar, high-molecular-weight polycyclic aromatic hydrocarbons with heteroatoms, enhance the material's resistance to phase separation and provide greater thermal and oxidative stability compared to more volatile tars from other origins.[55] Their lower volatility stems from the predominance of high-boiling-point aliphatic and naphthenic components, making them suitable for durable, long-lasting applications.[54]Common variants include road tars, formulated for pavement binding with penetration grades typically between 60/70 and 200/300, and roofing asphalts, which are oxidized to achieve higher softening points around 85-105°C for weather resistance.[56] These petroleum-derived products are aliphatic-rich, emphasizing saturated hydrocarbons over aromatics, which supports their use in structural paving rather than chemical feedstocks.[54]Global production of petroleum bitumen occurs in major refining regions, with Middle Eastern countries such as Saudi Arabia and Iran being significant producers alongside others like Canada and those in Asia-Pacific, which accounts for the largest share. As of 2024, global production was approximately 128 million metric tons.[57][58] This reflects the scalability of refinery processes in oil-rich areas since the mid-20th century, shifting from earlier sources like coal.
Production Methods
Destructive Distillation Processes
Destructive distillation is a thermal decomposition process in which organic materials such as wood or coal are heated in low-oxygen retorts, resulting in the production of tar, combustible gases, and solid char as primary outputs. For wood, temperatures typically range from 350–500°C, while for coal, primary pyrolysis occurs at 400–600°C, though the overall coking process reaches 900–1100°C.[59]) This method relies on pyrolysis, where the absence of sufficient air prevents complete combustion and instead promotes the breakdown of complex organic structures into volatile condensable liquids, including tar.[60] Historically, the process was conducted in sealed vessels or kilns to capture the evolving vapors, which condense to form the viscous tar fraction.The process unfolds in distinct stages, beginning with primary pyrolysis, during which the organic matter—such as lignins and cellulose in wood or bituminous components in coal—undergoes initial thermaldegradation. This stage produces primary char and volatile compounds, including water vapor, carbon dioxide, and initial hydrocarbons, as the large molecular structures break down. Secondary cracking follows as these volatiles are further heated, leading to the formation of aromatic compounds and heavier tar precursors through recombination and dehydration reactions.[61] The resulting tar is collected by condensing the vapors in cooled chambers, separating it from non-condensable gases.[59]Efficiency in destructive distillation varies with feedstock and conditions, with typical tar yields ranging from 10 to 20% of the dry wood weight under historical batch processes, though actual outputs depend on factors like heating rate and moisture content.[62] For coal, yields are lower, around 3 to 5% by weight, due to its higher carbon content and denser structure.[63] Pre-1900 equipment, such as cylindrical iron retorts or masonrykilns for wood and horizontal retorts in gasworks for coal, facilitated controlled heating, while beehive ovens were employed in early coal processing to produce coke with incidental tar recovery.[64] These methods allowed for scaling in industrial settings, particularly during the 19th century when demand for tar in preservation and chemicals grew.
Modern Refining Techniques
Modern refining techniques for tar production prioritize continuous, high-efficiency processes that enhance product purity and minimize environmental impact, primarily through integration with petroleum and biomass operations. Vacuum distillation, commonly employed in petroleum refineries, processes heavy residues such as bitumen-derived tar under reduced pressure to lower boiling points and prevent thermal decomposition, enabling the separation of valuable fractions like vacuum gas oil and pitch while achieving high purity levels.[65] This method is particularly effective for oil sands bitumen, where it facilitates the isolation of tar components at temperatures below 400°C, improving yield and reducing energy consumption compared to atmospheric distillation.[66]Hydrocracking represents another key advancement, involving catalytic hydrogenation under high pressure and temperature to break down complex tar fractions into lighter hydrocarbons, such as diesel and gasoline precursors, with conversion efficiencies exceeding 90% for heavy coal tar feeds.[67] In this process, bifunctional catalysts like nickel-molybdenum on alumina promote hydrogen addition and cracking, effectively separating and upgrading polycyclic aromatic structures prevalent in tar, resulting in reduced viscosity and enhanced stability of the output.[68] For coal tar specifically, hydrocracking operates at 350-450°C and 10-20 MPa, yielding up to 70% middle distillates while minimizing coke formation.[67]Fluidized bed pyrolysis has emerged as a preferred method for biomass-derived tar, utilizing a bed of inert particles like sand to ensure uniform heating and rapid vapor release at 450-550°C, producing tar yields of 30-50% by weight under optimized conditions.[69] The fluidized state enhances heat and mass transfer, allowing for shorter residence times (seconds) that preserve volatile tar components, with bio-oil outputs rich in phenolic compounds suitable for further refining. Catalysts such as zeolites integrated into the bed can further boost selectivity toward desired tar fractions by promoting deoxygenation.[70]Since the post-1950s, automation in refining operations, including real-timeprocesscontrol systems and advanced monitoring, has significantly reduced emissions in tar production by optimizing energy use and minimizing waste, with reported decreases of up to 20-30% in volatile organic compound releases through precise temperature and pressure regulation.[71] The use of catalysts in these modern processes has improved overall yields to 30-50% for tar fractions, particularly in biomass and coal applications, by enhancing cracking efficiency and reducing side reactions.[70] Global annual tar output exceeds 200 million tons as of 2024, driven largely by oil sandsbitumen production of approximately 180 million tons and global coal tar production of around 20–25 million tons, alongside outputs from coal gasification.[72][73]Building briefly on the legacy of destructive distillation as a foundational pyrolysis approach, contemporary methods emphasize scalable, catalyst-enhanced operations for sustainable tar generation.[69]
Chemical Composition
Hydrocarbon Components
Tar consists primarily of hydrocarbon compounds, which form the backbone of its organic composition, derived from the pyrolysis or distillation of organic materials such as wood, coal, or petroleum residues. The major classes of hydrocarbons in tar include aliphatics (primarily paraffins and olefins), aromatics (such as benzenes and naphthalenes), and polycyclic aromatic hydrocarbons (PAHs). Aliphatics typically account for 2-10% of the hydrocarbon fraction in low-temperature tars, and less in high-temperature varieties, contributing to the saturated and unsaturated chain structures, while aromatics dominate at 40-60%, providing the characteristic stability and viscosity of tar. Olefins, as unsaturated aliphatics, are present in smaller amounts, often linked to incomplete carbonization processes.[74]Among the aromatics, PAHs are particularly prominent, featuring fused ring structures like anthracene (C_{14}H_{10}), naphthalene (C_{10}H_{8}), and phenanthrene, which arise from the thermal decomposition of complex precursors. These compounds exhibit average molecular weights ranging from 200 to 1000 Da, influencing tar's solubility and reactivity; for instance, lighter PAHs (e.g., naphthalene at 128 Da) distill at lower temperatures, while heavier ones contribute to the pitch-like residues. The structural diversity, including alkyl-substituted and oxygenated variants, underscores the heterogeneity of tar as a mixture rather than a single entity.[75][76]Variations in hydrocarbon composition occur depending on the source material and production method. In coal tar, particularly from high-temperature coking, PAHs can constitute up to 70% of the total hydrocarbons, with naphthalene comprising 8-12% and anthracene 1.5-1.8% by weight, reflecting the aromatic-rich nature of coal precursors. Conversely, wood tar features a higher proportion of alicyclics, such as terpenes and cyclic paraffins, which form from the resinous components of lignocellulosic materials; these can reach significant levels alongside lower PAH contents (e.g., 5% aromatics in organic-soluble fractions). Petroleum-derived tars, or bitumen derivatives, show intermediate profiles with more aliphatic chains (10-20%) balanced by aromatic cores. These differences affect tar's physical traits, such as the darker color in coal tar due to extended PAH conjugation.[74][77][78]
Non-Hydrocarbon Elements and Impurities
Tar, derived from sources such as coal, wood, or petroleum, incorporates non-hydrocarbon elements that alter its chemical reactivity, stability, and suitability for industrial applications. Sulfur is a prominent heteroatom in coal tar, with concentrations typically ranging from 0.5% to 2% by weight, often existing in thiophenic and sulfidic forms that enhance the material's viscosity but also promote corrosiveness through the formation of sulfur oxides during heating or combustion.[79]Nitrogen appears at levels of 0.1% to 1.5%, predominantly in pyridinic and pyrrolic structures, which can interfere with downstream hydrogenation processes by poisoning catalysts.[80][81] Oxygen content is higher in low-temperature coal tars, largely bound in phenolic hydroxyl groups, contributing to the tar's acidic nature with pH values around 6.5.[82][83]Trace metals represent key impurities, particularly in petroleum and bitumen-derived tars, where vanadium concentrations can reach 350 to 2500 ppm, originating from porphyrin complexes in crude oils and leading to catalyst deactivation in refining.[84] Other metals like nickel may co-occur at similar levels, exacerbating processing challenges. Ash residues, consisting of inorganic minerals such as silica and alumina, comprise 0.1% to 1% in refined tars, though higher in crude forms up to several percent, resulting from incomplete separation during production.[85]Water content, often emulsified and ranging from 0.5% to 5% in raw tar, promotes instability and microbial growth if not addressed.[86]These elements and impurities impact tar's performance: sulfur and nitrogen compounds increase corrosiveness and environmental emissions, while phenolic oxygen functionalities enhance solubility in alkaline media but lower pH, affecting storage and handling. Purification via fractional distillation effectively separates heteroatomic fractions, removing up to 90% of sulfur in some oxidative-distillation hybrids and substantially reducing ash and water to below 0.1% and 0.5%, respectively, yielding higher-purity products for applications like pitch production.[79][86]
Applications and Uses
Industrial and Construction Uses
Tar plays a pivotal role in construction, particularly in road surfacing where asphalt—a petroleum-derived tar blend—forms the primary material for durable pavements. In the United States, approximately 94% of the 2.7 million miles of paved roads are surfaced with asphalt, providing a flexible and cost-effective solution for high-traffic infrastructure.[87] This widespread adoption stems from asphalt's ability to withstand heavy loads and weather variations, with modern formulations incorporating tar binders to enhance adhesion between aggregates. Historically, tar-based mixtures like tarmacadam were used in early 19th-century paving to bind stones and reduce dust on roads.[88]Beyond roadways, tar derivatives are essential in roofing and waterproofing applications, where roofing felts or tar paper serve as underlayments to protect structures from moisture infiltration. These materials, typically composed of fiberglass or paper saturated with bitumen or asphalt, create a secondary barrier beneath shingles or membranes, preventing leaks and extending roof longevity in residential and commercialbuildings.[89]Bitumen-impregnated felts are valued for their tear resistance and impermeability, commonly applied in flat or low-slope roofs to ensure long-term waterproofing performance.[90]In industrial applications, coal tar pitch functions as a critical binder in manufacturing carbon anodes for aluminum production, where it is mixed with petroleum coke and baked to form electrodes used in electrolytic smelting processes. This binder ensures structural integrity and electrical conductivity, accounting for a significant portion of global aluminum output through the Hall-Héroult method.[91] Similarly, coal tar pitch serves as an effective binder in coal briquettes, enhancing cohesion during compression and carbonization to produce high-strength fuel products from fine coal particles, particularly in regions with abundant coal byproducts.[92]Tar derivatives also contribute to wood preservation, with creosote—a distillate from coal tar—applied to treat timber for outdoor and marine uses, such as railway ties, utility poles, and bridge components. Creosote penetrates wood fibers to repel insects, fungi, and decay, providing decades of protection in harsh environments and remaining a standard in industrial timber treatment. However, its use is restricted to industrial and commercial applications under regulations such as those from the U.S. EPA, due to health concerns.[93]The global market for tar and its derivatives was valued at approximately USD 68 billion in 2025, driven primarily by petroleum-based products like asphalt and bitumen, which dominate over 70% of industrial and construction applications due to their scalability and versatility in infrastructure projects.[94] Coal tar variants, while essential in niche sectors like electrode production, represent a smaller but stable segment, with the overall market reflecting tar's indispensable role in modern manufacturing and building.[95]
Medical and Traditional Applications
Tar has a long history in traditional medicine, particularly wood tar derived from pine, which indigenous peoples across North America incorporated into salves and ointments to treat skin infections and inflammatory conditions such as wounds and rashes due to its antiseptic and soothing properties.[96] In the 19th century, coal tar emerged as a key component in antiseptics, with its derivative carbolic acid (phenol) revolutionizing surgical practices by reducing post-operative infections when applied to wounds and instruments, as pioneered by Joseph Lister.[97]In modern medicine, coal tar remains a standard topical treatment for psoriasis, applied in shampoos, creams, or solutions typically containing 2-10% coal tar to reduce scaling, itching, and inflammation by slowing skin cell growth.[98] Similarly, pine tar is commonly used in soaps and bath additives for managing eczema, leveraging its anti-inflammatory, antibacterial, and antifungal effects to alleviate dryness, irritation, and flare-ups in sensitive skin.[42]Regulatory oversight ensures safe application; the U.S. Food and Drug Administration (FDA) classifies coal tar as safe and effective for over-the-counter topical use in concentrations up to 5% for psoriasis and related dermatoses, with higher strengths available by prescription.[99] Historically, Victorian-era medicine featured complex mixtures incorporating opium with tar derivatives for pain relief and cough suppression, though such combinations have been discontinued due to safety concerns.[100]
Health, Safety, and Environmental Impacts
Toxicity and Health Risks
Exposure to tar, particularly coal tar and its derivatives, can cause acute health effects primarily through direct contact and inhalation of fumes. Skin contact with tar often leads to irritation, burns, and dermatitis, characterized by redness, itching, and potential blistering due to its irritant and phototoxic properties.[101][102] Inhalation of tar vapors, which may contain benzene and other volatile compounds, can result in respiratory irritation, coughing, sneezing, headache, dizziness, and fatigue; the Occupational Safety and Health Administration (OSHA) sets a permissible exposure limit of 1 ppm for benzene over an 8-hour workday to mitigate these risks. Eye exposure may cause conjunctivitis and corneal damage from acute fume inhalation.The primary routes of tar exposure in occupational settings are inhalation of fumes and vapors, accounting for a significant portion of cases, and dermal absorption through skin contact with tar or contaminated surfaces.[4][103]Inhalation is particularly prevalent during heating or application processes, while dermal exposure occurs via direct handling, often leading to systemic absorption of polycyclic aromatic hydrocarbons (PAHs). Ingestion is less common but possible through hand-to-mouth transfer. These routes contribute to both immediate and prolonged health hazards in industries like paving and roofing.[104]Chronic exposure to tar poses substantial carcinogenic risks, largely attributed to PAHs such as benzopyrene, which the International Agency for Research on Cancer (IARC) classifies as Group 1 carcinogens; coal tar itself and coal-tar pitch are also designated Group 1 due to sufficient evidence of carcinogenicity in humans.[105] Occupational studies have linked prolonged tar exposure to elevated lung cancer risk, with standardized mortality ratios indicating up to 1.5-fold increases among tar-distillery and coal gas workers, and historical data from the early 20th century suggesting even higher relative risks in exposed cohorts.[106] Skin, bladder, and kidney cancers are also associated with long-term dermal and inhalational exposure.[4]Mitigation of tar-related health risks relies on personal protective equipment (PPE) and adherence to standards established by OSHA since the 1970s, including respirators for fume inhalation and impervious gloves, clothing, and eye protection to prevent dermal absorption.[6] Regular monitoring and engineering controls further reduce exposure levels in controlled industrial environments, though tar's use in some medical applications requires similar precautions to minimize risks.
Environmental Concerns and Regulations
Tar, particularly coal tar and petroleum-derived variants, poses significant environmental risks through contamination of soil and water bodies. Spills and leaks from tar storage or application sites lead to persistent pollution, as tar's viscous nature allows it to infiltrate soil pores, reducing permeability and altering microbial activity. In aquatic environments, tar residues introduce polycyclic aromatic hydrocarbons (PAHs), which are hydrophobic and adsorb to sediments, contaminating groundwater and surface water over extended periods.[107] PAHs from tar exhibit high bioaccumulation potential in aquatic organisms, concentrating in fish tissues and magnifying through food chains, which can indirectly affect human health via seafood consumption.[108][109]Air emissions from tar production, use, and weathering contribute to atmospheric pollution, including particulate matter and volatile PAHs that participate in smog formation. During coal tar application or erosion from paved surfaces, PAHs volatilize or become airborne as dust, reacting with other pollutants to form secondary aerosols that exacerbate urban smog. These emissions are particularly notable in industrial and urban settings where tar-based materials like sealants are prevalent.[110][111]Notable incidents highlight tar's ecological footprint. The 1989 Exxon Valdez oil spill released approximately 11 million gallons of crude oil into Prince William Sound, Alaska, which weathered into tar balls and residues persisting in sediments for decades, causing ongoing contamination of intertidal zones and affecting marine ecosystems. In urban areas, coal tar runoff from sealed pavements has polluted stormwater ponds and nearby water bodies; for instance, studies in the U.S. Midwest found coal tar sealants accounting for up to 67% of PAHs in metro-area sediments, leading to groundwater infiltration and broader aquatic toxicity.[112][113]Regulatory frameworks address these concerns through restrictions on tar and its components. In the European Union, the REACH regulation (Annex XVII, Entry 50) since 2013 limits eight carcinogenic PAHs in consumer articles, including those derived from coal tar, to 1 mg/kg to prevent environmental release via products like tires and sealants. In the United States, the EPA's land disposal restrictions under 40 CFR Part 268 classify certain tar wastes as hazardous if they exhibit toxicity characteristics, requiring treatment to meet standards before disposal, including wastewater sludges containing tar-derived PAHs. These measures encourage a shift to bio-based alternatives, such as lignin-derived binders from forestry residues, which reduce PAH emissions and comply with sustainability mandates in regions banning coal tar sealants.[114][115][116]