Tetraethyllead (commonly styled tetraethyl lead), abbreviated TEL, is an
organolead compound
Organolead chemistry is the scientific study of the synthesis and properties of organolead compounds, which are organometallic compounds containing a chemical bond between carbon and lead. The first organolead compound was hexaethyldilead (Pb2(C2H5 ...
with the formula
Pb(
C2H5)
4. It was widely used as a
fuel
A fuel is any material that can be made to react with other substances so that it releases energy as thermal energy or to be used for work (physics), work. The concept was originally applied solely to those materials capable of releasing chem ...
additive for much of the 20th century, first being mixed with
gasoline
Gasoline ( North American English) or petrol ( Commonwealth English) is a petrochemical product characterized as a transparent, yellowish, and flammable liquid normally used as a fuel for spark-ignited internal combustion engines. When for ...
beginning in the 1920s. This "leaded gasoline" had an increased
octane rating
An octane rating, or octane number, is a standard measure of a liquid fuel, fuel's ability to withstand Compression ratio, compression in an internal combustion engine without causing engine knocking. The higher the octane number, the more compres ...
that allowed
engine compression to be raised substantially and in turn increased vehicle performance and fuel economy.
TEL was first
synthesized by German chemist
Carl Jacob Löwig
Carl Jacob Löwig (17 March 1803 – 27 March 1890) was a German chemist and discovered bromine independently of Antoine Jérôme Balard.
He received his PhD at the University of Heidelberg for his work with Leopold Gmelin.
During his research o ...
in 1853. American chemical engineer
Thomas Midgley Jr., who was working for the U.S. corporation
General Motors
General Motors Company (GM) is an American Multinational corporation, multinational Automotive industry, automotive manufacturing company headquartered in Detroit, Michigan, United States. The company is most known for owning and manufacturing f ...
, was the first to discover its effectiveness as an
knock inhibitor on December 9th, 1921, after spending six years attempting to find an
additive
Additive may refer to:
Mathematics
* Additive function, a function in number theory
* Additive map, a function that preserves the addition operation
* Additive set-function see Sigma additivity
* Additive category, a preadditive category with fin ...
that was both highly effective and inexpensive.
Of the some 33,000 substances in total screened,
lead
Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
was found to be the most effective antiknock agent, in that it necessitated the smallest concentrations necessary; a treatment of 1 part TEL to 1300 parts gasoline by weight is sufficient to suppress detonation. The four ethyl groups in the compound served to dissolve the active lead atom within the fuel.
When injected into the combustion chamber, tetraethyllead decomposed upon heating into ethyl
radicals
Radical (from Latin: ', root) may refer to:
Politics and ideology Politics
*Classical radicalism, the Radical Movement that began in late 18th century Britain and spread to continental Europe and Latin America in the 19th century
*Radical politics ...
, lead, and lead oxide. The
lead oxide
Lead oxides are a group of inorganic compounds with formulas including lead (Pb) and oxygen
Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), gr ...
scavenges radicals and therefore inhibits a flame from developing until full compression has been achieved, allowing the optimal timing of
ignition
Ignition may refer to:
Science and technology
* Firelighting, the human act of creating a fire for warmth, cooking and other uses
* Combustion, an exothermic chemical reaction between a fuel and an oxidant
* Fusion ignition, the point at which a ...
, as well as the lowering of fuel consumption.
Throughout the sixty year period from 1926 to 1985, an estimated 20 trillion liters of leaded gasoline at an average lead concentration of 0.4 g/L were produced and sold in the United States alone, or an equivalent of 8 million tons of inorganic lead, three quarters of which would have been emitted in the form of
lead chloride Lead chloride may refer to:
* Lead(II) chloride (plumbous chloride), mineral name: cotunnite
Cotunnite is the natural mineral form of lead(II) chloride (PbCl2). Unlike the pure compound, which is white, cotunnite can be white, yellow, or green. T ...
and
lead bromide. Estimating a similar amount of lead to have come from other countries' emissions, a total of more than 15 million tonnes of lead may have been released into the
atmosphere
An atmosphere () is a layer of gases that envelop an astronomical object, held in place by the gravity of the object. A planet retains an atmosphere when the gravity is great and the temperature of the atmosphere is low. A stellar atmosph ...
.
In the mid-20th century, scientists discovered that TEL caused
lead poisoning
Lead poisoning, also known as plumbism and saturnism, is a type of metal poisoning caused by lead in the body. Symptoms may include abdominal pain, constipation, headaches, irritability, memory problems, infertility, numbness and paresthesia, t ...
and was highly
neurotoxic
Neurotoxicity is a form of toxicity in which a biological, chemical, or physical agent produces an adverse effect on the structure or function of the central and/or peripheral nervous system. It occurs when exposure to a substance – specifical ...
to the human brain, especially in children.
Approximately 90% of the total lead in a human is present in the bones, deposited in the form of insoluble
Lead(II) phosphate
Lead(II) phosphate is an ionic compound with chemical formula Pb3( P O4)2. Lead(II) phosphate is a long-lived electronically neutral reagent chemical. Despite limited tests on humans, it has been identified as a carcinogen based on tests on anim ...
salt, with a half-life longer than twenty years. The
United States
The United States of America (USA), also known as the United States (U.S.) or America, is a country primarily located in North America. It is a federal republic of 50 U.S. state, states and a federal capital district, Washington, D.C. The 48 ...
and many other countries began phasing out the use of TEL in automotive fuel in the 1970s. With
EPA guidance and oversight, the US achieved the total elimination of sales of leaded gasoline for on-road vehicles on January 1st, 1996. By the early 2000s, most countries had banned the use of TEL in gasoline. In July 2021, the sale of leaded gasoline for cars was completely phased out worldwide following the termination of production by
Algeria
Algeria, officially the People's Democratic Republic of Algeria, is a country in the Maghreb region of North Africa. It is bordered to Algeria–Tunisia border, the northeast by Tunisia; to Algeria–Libya border, the east by Libya; to Alger ...
, prompting the
United Nations Environment Program
The United Nations Environment Programme (UNEP) is responsible for coordinating responses to environmental issues within the United Nations system. It was established by Maurice Strong, its first director, after the United Nations Conference on ...
(UNEP) to declare an "official end" of its use in cars on August 30, 2021.
In 2011, researchers retroactively estimated the annual impact of tetraethyl lead worldwide to be the following: 1.1 million excess deaths, 322 million lost IQ points, 60+ million crimes, and 4% of worldwide
GDP
Gross domestic product (GDP) is a monetary measure of the total market value of all the final goods and services produced and rendered in a specific time period by a country or countries. GDP is often used to measure the economic performance o ...
(around 2.4 trillion United States dollars per year).
Synthesis and properties
TEL is produced on an industrial scale by reacting
chloroethane
Chloroethane, commonly known as ethyl chloride, is a chemical compound with chemical formula CH3CH2Cl, once widely used in producing tetraethyllead, a gasoline additive. It is a colorless, flammable gas or refrigerated liquid with a faintly sweet ...
(ethyl chloride) with a
sodium
Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...
–
lead
Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
alloy
An alloy is a mixture of chemical elements of which in most cases at least one is a metal, metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Metallic alloys often have prop ...
.
The product is recovered by steam distillation, leaving a sludge of lead and
sodium chloride
Sodium chloride , commonly known as Salt#Edible salt, edible salt, is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. It is transparent or translucent, brittle, hygroscopic, and occurs a ...
. TEL is a
viscous
Viscosity is a measure of a fluid's rate-dependent resistance to a change in shape or to movement of its neighboring portions relative to one another. For liquids, it corresponds to the informal concept of ''thickness''; for example, syrup h ...
colorless
liquid
Liquid is a state of matter with a definite volume but no fixed shape. Liquids adapt to the shape of their container and are nearly incompressible, maintaining their volume even under pressure. The density of a liquid is usually close to th ...
with a sweet odor. Because TEL is charge neutral and contains an exterior of alkyl groups, it is highly
lipophilic
Lipophilicity (from Greek language, Greek λίπος "fat" and :wikt:φίλος, φίλος "friendly") is the ability of a chemical compound to dissolve in fats, oils, lipids, and non-polar solvents such as hexane or toluene. Such compounds are c ...
and soluble in petrol (gasoline). This property, which allows it to dissolve so evenly and effectively in motor fuel, also allowed easy absorption by body fats and lipids and diffusion through the blood–brain barrier (BBB). The lead (II) ions (Pb
2+) would accumulate within the limbic forebrain, frontal cortex, and
hippocampus
The hippocampus (: hippocampi; via Latin from Ancient Greek, Greek , 'seahorse'), also hippocampus proper, is a major component of the brain of humans and many other vertebrates. In the human brain the hippocampus, the dentate gyrus, and the ...
.
Practically speaking, TEL is a "central nervous system toxin which produces an acute toxic psychosis."
There is no cure for direct poisoning by TEL. Inorganic lead compounds, such as those present in
engine exhausts, could be removed from the system through the administration of
chelating agents
Chelation () is a type of bonding of ions and their molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These l ...
, which bind to the inorganic lead and flush them out of the body. However, highly lipid-soluble TEL cannot be removed this way, and treatments are of a supportive nature.
Despite decades of research, no reactions were found to improve upon this process; it is rather difficult, involves reactive metallic sodium, and converts only 25% of the lead to TEL. A related compound,
tetramethyllead
Tetramethyllead, also called tetra methyllead and lead tetramethyl, is a chemical compound used as an antiknock additive for gasoline. It is a methyl radical synthon. Its use in gasoline is being phased out for environmental considerations.
Th ...
, was commercially produced by a different electrolytic reaction. However, tetramethyllead was even more difficult to make, and it did not find use beyond niche applications.
A highly efficient pathway utilizing ethyl chloride with a slight excess of
lithium
Lithium (from , , ) is a chemical element; it has chemical symbol, symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard temperature and pressure, standard conditions, it is the least dense metal and the ...
was developed, with a TEL yield over lead of over 90%. However, by then the fuel additive had started to fall out of favor and into disrepute, and the process was never put into practice.
Reactions
A noteworthy feature of TEL is the weakness of its four C–Pb bonds. At the temperatures found in
internal combustion engine
An internal combustion engine (ICE or IC engine) is a heat engine in which the combustion of a fuel occurs with an oxidizer (usually air) in a combustion chamber that is an integral part of the working fluid flow circuit. In an internal comb ...
s, TEL decomposes completely into lead as well as combustible, short-lived ethyl
radicals
Radical (from Latin: ', root) may refer to:
Politics and ideology Politics
*Classical radicalism, the Radical Movement that began in late 18th century Britain and spread to continental Europe and Latin America in the 19th century
*Radical politics ...
. Lead and lead oxide scavenge
radical intermediates in
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combustion ...
reactions. Engine knock is caused by a
cool flame
A cool flame is a flame having a typical temperature of about . In contrast to an ordinary hot flame, the reaction is not vigorous and releases little heat, light, or carbon dioxide. Cool flames are difficult to observe and are uncommon in everyday ...
, an oscillating low-temperature combustion reaction that occurs before the proper, hot ignition. Lead quenches the pyrolyzed radicals and thus kills the radical chain reaction that would sustain a cool flame, preventing it from disturbing the smooth ignition of the hot flame front. Lead itself is the reactive antiknock agent, and the ethyl groups serve as a gasoline-soluble carrier.
When TEL burns, it produces not only carbon dioxide and water, but also lead and lead(II) oxide:
[
Pb(C2H5)4 + 13 O2 -> 8 CO2 + 10 H2O + Pb
Pb(C2H5)4 + 27 O2 -> 16 CO2 + 20 H2O + 2 PbO
Pb and PbO would quickly over-accumulate and foul an engine. For this reason, ]1,2-dichloroethane
The chemical compound 1,2-dichloroethane, commonly known as ethylene dichloride (EDC), is a chlorinated hydrocarbon. It is a colourless liquid with a chloroform-like odour. The most common use of 1,2-dichloroethane is in the production of vinyl ...
and 1,2-dibromoethane
1,2-Dibromoethane, also known as ethylene dibromide (EDB), is an organobromine compound with the chemical formula . Although trace amounts occur naturally in the ocean, where it is probably formed by algae and kelp, substantial amounts are produc ...
were also added to gasoline as lead scavengers—these agents form volatile lead(II) chloride
Lead(II) chloride (PbCl2) is an inorganic compound which is a white solid under ambient conditions. It is poorly soluble in water. Lead(II) chloride is one of the most important lead-based reagents. It also occurs naturally in the form of the min ...
and lead(II) bromide
Lead(II) bromide is the inorganic compound with the formula PbBr2. It is a white powder. It is produced in the burning of typical leaded gasolines.Michael J. Dagani, Henry J. Barda, Theodore J. Benya, David C. Sanders "Bromine Compounds" in Ullman ...
, respectively, which flush the lead from the engine and into the air:
Pb(C2H5)4 + C2H4X2 + 16 O2 -> 10 CO2 + 12 H2O + PbX2
In motor fuel
TEL was extensively used as a gasoline additive
Gasoline additives may increase gasoline's octane rating, thus allowing the use of higher compression ratios for greater efficiency and power, or act as corrosion inhibitors or lubricants. Other additives include metal deactivators, oxygenates an ...
beginning in the 1920s, wherein it served as an effective antiknock agent
An antiknock agent (also: knock inhibitor) is a gasoline additive used to reduce engine knocking and increase the fuel's octane rating by raising the temperature and pressure at which auto-ignition occurs. The mixture known as gasoline or petrol, ...
and reduced exhaust valve
A valve is a device or natural object that regulates, directs or controls the flow of a fluid (gases, liquids, fluidized solids, or Slurry, slurries) by opening, closing, or partially obstructing various passageways. Valves are technically Pip ...
and valve seat
The valve seat in an internal combustion gasoline or diesel engine is the surface against which an intake or an exhaust valve rests during the portion of the engine operating cycle when that valve is closed. The valve seat is a critical component ...
wear. Concerns were raised in reputable journals of likely health outcomes of fine particles of lead in the atmosphere as early as 1924.
Valve wear preventive
Tetraethyllead helps cool intake valves and is an excellent buffer against microwelds forming between exhaust valves and their seats
A seat is a place to sit. The term may encompass additional features, such as back, armrest, head restraint but may also refer to concentrations of power in a wider sense (i.e " seat (legal entity)"). See disambiguation.
Types of seat
The ...
. Once these valves reopen, the microwelds pull apart and abrade the valves and seats, leading to valve recession. When TEL began to be phased out, the automotive industry began specifying hardened valve seats and upgraded materials which allow for high wear resistance without requiring lead.
Antiknock agent
A gasoline-fueled reciprocating engine requires fuel of sufficient octane rating
An octane rating, or octane number, is a standard measure of a liquid fuel, fuel's ability to withstand Compression ratio, compression in an internal combustion engine without causing engine knocking. The higher the octane number, the more compres ...
to prevent uncontrolled combustion (pre-ignition and detonation
Detonation () is a type of combustion involving a supersonic exothermic front accelerating through a medium that eventually drives a shock front propagating directly in front of it. Detonations propagate supersonically through shock waves with ...
). Antiknock agents allow the use of higher compression ratio
The compression ratio is the ratio between the maximum and minimum volume during the compression stage of the power cycle in a piston or Wankel engine.
A fundamental specification for such engines, it can be measured in two different ways. Th ...
s for greater efficiency
Efficiency is the often measurable ability to avoid making mistakes or wasting materials, energy, efforts, money, and time while performing a task. In a more general sense, it is the ability to do things well, successfully, and without waste.
...
and peak power
Power may refer to:
Common meanings
* Power (physics), meaning "rate of doing work"
** Engine power, the power put out by an engine
** Electric power, a type of energy
* Power (social and political), the ability to influence people or events
Math ...
. Adding varying amounts of additives to gasoline allowed easy, inexpensive control of octane ratings. TEL offered the business advantage of being commercially profitable because its use for this purpose could be patented. Aviation fuels with TEL used in WWII reached octane ratings of 150 to enable turbocharged and supercharged engines such as the Rolls-Royce Merlin
The Rolls-Royce Merlin is a British Coolant#Liquids, liquid-cooled V12 engine, V-12 Reciprocating engine, piston aero engine of 27-litre (1,650 cu in) Engine displacement, capacity. Rolls-Royce Limited, Rolls-Royce designed the engine an ...
and Griffon to reach high horsepower ratings at altitude. In military aviation, TEL manipulation allowed a range of different fuels to be tailored for particular flight conditions.
In 1935 a license to produce TEL was given to IG Farben
I. G. Farbenindustrie AG, commonly known as IG Farben, was a German Chemical industry, chemical and Pharmaceutical industry, pharmaceutical conglomerate (company), conglomerate. It was formed on December 2, 1925 from a merger of six chemical co ...
, enabling the newly formed German to use high-octane gasoline for high altitude flight. A company, Ethyl GmbH, was formed that produced TEL at two sites in Germany with a government contract from 10 June 1936.
In 1938 the United Kingdom Air Ministry
The Air Ministry was a department of the Government of the United Kingdom with the responsibility of managing the affairs of the Royal Air Force and civil aviation that existed from 1918 to 1964. It was under the political authority of the ...
contracted with ICI for the construction and operation of a TEL plant. A site was chosen at Holford Moss, near Plumley in Cheshire. Construction started in April 1939 and TEL was being produced by September 1940.
"Ethyl Fluid"
For mixing with raw gasoline, TEL was most commonly supplied in the form of "Ethyl Fluid", consisting of TEL blended with 1,2-dichloroethane and 1,2-dibromoethane, which prevent lead from building up in the engine. Ethyl Fluid also contained a reddish dye to distinguish treated from untreated gasoline and discourage the use of leaded gasoline for other purposes such as cleaning.
In the 1920s, before safety procedures were strengthened, 17 workers for the Ethyl Corporation
Ethyl Corporation is a fuel additive company headquartered in Richmond, Virginia, in the United States. The company is a distributor of fuel additives. Among other products, Ethyl Corporation distributes tetraethyl lead, an additive used to make ...
, DuPont
Dupont, DuPont, Du Pont, duPont, or du Pont may refer to:
People
* Dupont (surname) Dupont, also spelled as DuPont, duPont, Du Pont, or du Pont is a French surname meaning "of the bridge", historically indicating that the holder of the surname re ...
, and Standard Oil
Standard Oil Company was a Trust (business), corporate trust in the petroleum industry that existed from 1882 to 1911. The origins of the trust lay in the operations of the Standard Oil of Ohio, Standard Oil Company (Ohio), which had been founde ...
died from the effects of exposure to lead. The grim news was not well received by US legislators and a brief ban was put into place. However, it was lifted on recommendation of the United States Surgeon General
Surgeon general (: surgeons general) is a title used in several Commonwealth countries and most NATO nations to refer either to a senior military medical officer or to a senior uniformed physician commissioned by the government and entrusted with p ...
and a panel of scientists in 1929, after extensive lobbying
Lobbying is a form of advocacy, which lawfully attempts to directly influence legislators or government officials, such as regulatory agency, regulatory agencies or judiciary. Lobbying involves direct, face-to-face contact and is carried out by va ...
efforts by the aforementioned companies. It would be another half century until a similar effort was made to rein in the additive, spearheaded by the EPA in the 1980s. This time, concerns for health and the environment were aided by the increasing use of catalytic converter
A catalytic converter part is an vehicle emissions control, exhaust emission control device which converts toxic gases and pollutants in exhaust gas from an internal combustion engine into less-toxic pollutants by catalysis, catalyzing a redox ...
s, which cannot tolerate TEL.
Ethyl Fluid's formulation consisted of:
* 61.45% tetraethyllead
* 18.80% 1,2-dichloroethane
The chemical compound 1,2-dichloroethane, commonly known as ethylene dichloride (EDC), is a chlorinated hydrocarbon. It is a colourless liquid with a chloroform-like odour. The most common use of 1,2-dichloroethane is in the production of vinyl ...
* 17.85% 1,2-dibromoethane
1,2-Dibromoethane, also known as ethylene dibromide (EDB), is an organobromine compound with the chemical formula . Although trace amounts occur naturally in the ocean, where it is probably formed by algae and kelp, substantial amounts are produc ...
* 1.90% inerts, preservatives, and dyes
It was found that dichloroethane and dibromoethane act in a synergistic manner, in that approximately equal quantities of both provide the best scavenging ability, thus preventing engines from fouling up due to deposits of inorganic lead within the pistons and exhausts.
Phaseout and ban
In most industrialized countries, a phaseout of TEL from road vehicle fuels was completed by the early 2000s because of concerns over air and soil lead levels and the accumulative neurotoxicity of lead. In the European Union, tetraethyllead has been classified as a Substance of Very High Concern
A substance of very high concern (SVHC) is a chemical substance (or part of a group of chemical substances) which has been proposed as a candidate for inclusion on the Authorization or Restriction list (seeECHA Lists of REACH.
The addition of a ...
and placed on the Candidate List for Authorization under (REACH). Potential use of TEL would need to be authorized through the REACH authorization procedure. While not a complete ban, it introduces significant obligations such as a mandatory analysis of alternatives and socioeconomic analysis.
The use of catalytic converter
A catalytic converter part is an vehicle emissions control, exhaust emission control device which converts toxic gases and pollutants in exhaust gas from an internal combustion engine into less-toxic pollutants by catalysis, catalyzing a redox ...
s, mandated in the United States for 1975 and later model-year cars to meet tighter emissions regulations, started a gradual phase-out of leaded gasoline in the U.S. The need for TEL was lessened by several advances in automotive engineering and petroleum chemistry. Safer methods for making higher-octane blending stocks such as reformate
Catalytic reforming is a chemical process used to convert naphthas from crude oil into liquid products called reformates, which are premium "blending stocks" for high-octane gasoline. The process converts low-octane linear hydrocarbons (paraffins ...
and iso-octane
2,2,4-Trimethylpentane, also known as isooctane or iso-octane, is an organic compound with the formula (CH3)3CCH2CH(CH3)2. It is one of several isomers of octane (C8H18). This particular isomer is the standard 100 point on the octane rating scale ...
reduced the need to rely on TEL, as did other antiknock additives of varying toxicity including metallic compounds such as methylcyclopentadienyl manganese tricarbonyl
Methylcyclopentadienyl manganese tricarbonyl (MMT or MCMT) is an organomanganese compound with the formula (C5H4CH3)Mn(CO)3. Initially marketed as a supplement for use in leaded gasoline, MMT was later used in unleaded gasoline to increase the oc ...
(MMT) as well as oxygenate
In the liquid fuel industry, oxygenates are hydrocarbon-derived fuel additives containing at least one oxygen atom to promote complete combustion. Absent oxygenates, fuel combustion is usually incomplete, and the exhaust stream pollutes the air ...
s including methyl ''tert''-butyl ether (MTBE), ''tert''-amyl methyl ether (TAME), and ethyl ''tert''-butyl ether (ETBE).
The first country to completely ban leaded gasoline was Japan
Japan is an island country in East Asia. Located in the Pacific Ocean off the northeast coast of the Asia, Asian mainland, it is bordered on the west by the Sea of Japan and extends from the Sea of Okhotsk in the north to the East China Sea ...
in 1986.
Since January 1993, all gasoline powered cars sold in the European Union
The European Union (EU) is a supranational union, supranational political union, political and economic union of Member state of the European Union, member states that are Geography of the European Union, located primarily in Europe. The u ...
and the United Kingdom
The United Kingdom of Great Britain and Northern Ireland, commonly known as the United Kingdom (UK) or Britain, is a country in Northwestern Europe, off the coast of European mainland, the continental mainland. It comprises England, Scotlan ...
have been required to use unleaded fuel. This was to comply with the Euro 1 emission standards which mandated that all new cars to be fitted with a catalytic converter
A catalytic converter part is an vehicle emissions control, exhaust emission control device which converts toxic gases and pollutants in exhaust gas from an internal combustion engine into less-toxic pollutants by catalysis, catalyzing a redox ...
. Unleaded fuel was first introduced in the United Kingdom in June 1986.
Leaded gasoline was removed from the forecourts in the United Kingdom on January 1, 2000, and a Lead Replacement Petrol was introduced although this was largely withdrawn by 2003 due to dwindling sales. An exemption to the ban exists for owners of classic cars.
Vehicles designed and built to run on leaded fuel often require modification to run on unleaded gasoline. These modifications fall into two categories: those required for physical compatibility with unleaded fuel, and those performed to compensate for the relatively low octane of early unleaded fuels. Physical compatibility requires the installation of hardened exhaust valves and seats. Compatibility with reduced octane was addressed by reducing compression, generally by installing thicker cylinder head gasket
In an internal combustion engine, a head gasket provides the seal between the engine block and cylinder head(s).
Its purpose is to seal the combustion gases within the cylinders and to avoid coolant or engine oil leaking into the cylinders. Leak ...
s and/or rebuilding the engine with compression-reducing pistons, although modern high-octane unleaded gasoline has eliminated the need to decrease compression ratios.
Leaded gasoline remained legal as of late 2014 in parts of Algeria
Algeria, officially the People's Democratic Republic of Algeria, is a country in the Maghreb region of North Africa. It is bordered to Algeria–Tunisia border, the northeast by Tunisia; to Algeria–Libya border, the east by Libya; to Alger ...
, Iraq
Iraq, officially the Republic of Iraq, is a country in West Asia. It is bordered by Saudi Arabia to Iraq–Saudi Arabia border, the south, Turkey to Iraq–Turkey border, the north, Iran to Iran–Iraq border, the east, the Persian Gulf and ...
, Yemen
Yemen, officially the Republic of Yemen, is a country in West Asia. Located in South Arabia, southern Arabia, it borders Saudi Arabia to Saudi Arabia–Yemen border, the north, Oman to Oman–Yemen border, the northeast, the south-eastern part ...
, Myanmar
Myanmar, officially the Republic of the Union of Myanmar; and also referred to as Burma (the official English name until 1989), is a country in northwest Southeast Asia. It is the largest country by area in Mainland Southeast Asia and has ...
, North Korea
North Korea, officially the Democratic People's Republic of Korea (DPRK), is a country in East Asia. It constitutes the northern half of the Korea, Korean Peninsula and borders China and Russia to the north at the Yalu River, Yalu (Amnok) an ...
, and Afghanistan
Afghanistan, officially the Islamic Emirate of Afghanistan, is a landlocked country located at the crossroads of Central Asia and South Asia. It is bordered by Pakistan to the Durand Line, east and south, Iran to the Afghanistan–Iran borde ...
. North Korea and Myanmar purchased their TEL from China, while Algeria, Iraq, and Yemen purchased it from the specialty chemical company Innospec, the world's sole remaining legal manufacturer of TEL. In 2011 several Innospec executives were charged and imprisoned for bribing various government state-owned oil companies to approve the sale of their TEL products.
the UNEP
The United Nations Environment Programme (UNEP) is responsible for coordinating responses to environmental issues within the United Nations system. It was established by Maurice Strong, its first director, after the Declaration of the United Nati ...
-sponsored phase-out was nearly complete: only Algeria, Iraq, and Yemen continued widespread use of leaded gasoline, although not exclusively. In July 2021, Algeria had halted its sale.
Leaded-fuel bans
Leaded-fuel bans for road vehicles came into effect as follows:
= Europe
=
*Armenia: 2001
*Austria: 1989
*Belarus: 1998
*Bulgaria: 2002
*Bosnia and Herzegovina: 2009
*Croatia: 2006
*Cyprus: 2004
*Czech Republic: 2001
*Denmark: 1994
*European Union
The European Union (EU) is a supranational union, supranational political union, political and economic union of Member state of the European Union, member states that are Geography of the European Union, located primarily in Europe. The u ...
: 1 January 2000
*Finland: 1994
*France: 2000
*Germany: 1996
*Gibraltar: 2001
*Greece: 2002
*Hungary: 1999
*Ireland: 1 January 2000
*Italy: 1 January 2002
*Malta: 2003
*Monaco: 2000
*Netherlands: 1998
*Norway: 1997
*Poland: December 2000
*Slovenia: 2001
*Spain: 1 August 2001
*Portugal: 1999
*Romania: 2005
*Russia: 2003
*Serbia: 2010
*Sweden: 1995
*Switzerland: 2000
*Ukraine: 2003
*United Kingdom: 1 January 2000
= North America
=
*Anguilla: 1998
*Antigua and Barbuda: 1991
*Aruba: 1997
*Bahamas: 1996
*Belize: 1997
*Bermuda: 1990
*Cayman Islands: 1999
*Canada: December 1990
*Costa Rica: 1996
*Dominican Republic: 1999
*El Salvador: 1992
*Guatemala: 1991
*Haiti: 1998
*Honduras: 1996
*Jamaica: 2000
*Mexico: 1998
*Nicaragua: 1995
*Panama: 2002
*Trinidad and Tobago: 2000
*United States (including Puerto Rico): 1 January 1996
**California: 1992
= South America
=
*Argentina: 1998
*Bolivia: 1995
*Brazil: 1989 or 1991
*Chile: 2001 or 2005
*Colombia: 1991
*Guyana: 2000
*Peru: 2004
*Suriname: 2001
*Uruguay: 2004
*Venezuela: 2005
= Asia
=
*Afghanistan: 2016
*Bangladesh: 1999
*China: 2000
*Hong Kong: 1999
*India: March 2000
*Saudi Arabia: 2001
*Indonesia: 2006
*Iran: 2003
*Iraq: 2018
*Japan: 1986
*Malaysia: 2000
*Myanmar: 2016
*Nepal: 2000
*North Korea: 2016
*Pakistan: 2001
*Philippines: 2000
*Singapore: 1998
*South Korea: 1993
*Sri Lanka: 1999
*Taiwan: 2000
*Thailand: 1996
*Turkey: 2006
*United Arab Emirates: 2003
*Vietnam: 2001
*Yemen: 2018
= Oceania
=
*Australia: 2002
*New Zealand: 1996
*Guam: 1 January 1996 (USA)
*Samoa: 2001
= Africa
=
*Egypt: 1999
*South Africa: 2006
*Leaded petrol was supposed to be completely phased out continent-wide on 1 January 2006, following a ban initiated from the 2002 Earth Summit. However, in Algeria refineries needed to be altered; as a result, leaded fuel remained available in parts of Algeria
Algeria, officially the People's Democratic Republic of Algeria, is a country in the Maghreb region of North Africa. It is bordered to Algeria–Tunisia border, the northeast by Tunisia; to Algeria–Libya border, the east by Libya; to Alger ...
, with phaseout scheduled for 2016. After the Algerian Government outlawed the sale of leaded petrol throughout all of Algeria, leaded petrol was finally phased out by July 2021.
In motor racing
Leaded fuel was commonly used in professional motor racing
An engine or motor is a machine designed to convert one or more forms of energy into mechanical energy.
Available energy sources include potential energy (e.g. energy of the Earth's gravitational field as exploited in hydroelectric power gene ...
, until its phase out beginning in the 1990s. Since 1992, Formula One
Formula One (F1) is the highest class of worldwide racing for open-wheel single-seater formula Auto racing, racing cars sanctioned by the Fédération Internationale de l'Automobile (FIA). The FIA Formula One World Championship has been one ...
racing cars have been required to use fuel containing no more than 5 mg/L of lead.
NASCAR
The National Association for Stock Car Auto Racing, LLC (NASCAR) is an American auto racing sanctioning and operating company that is best known for stock car racing. It is considered to be one of the top ranked motorsports organizations in ...
began experimentation in 1998 with an unleaded fuel, and in 2006 began switching the national series to unleaded fuel, completing the transition at the Fontana round in February 2007 when the premier class switched. This was influenced after blood tests of NASCAR teams revealed elevated blood lead levels.
Aviation gasoline
TEL remains an ingredient of 100 octane
Octane is a hydrocarbon and also an alkane with the chemical formula C8H18, and the condensed structural formula CH3(CH2)6CH3. Octane has many structural isomers that differ by the location of branching in the carbon chain. One of these isomers ...
avgas
Avgas (aviation gasoline, also known as aviation spirit in the United Kingdom, UK) is an aviation fuel used in aircraft with spark-ignited internal combustion engines. ''Avgas'' is distinguished from conventional gasoline (petrol) used in moto ...
for piston-engine aircraft. The current formulation of 100LL (low lead, blue) aviation gasoline contains of TEL, half the amount of the previous 100/130 (green) octane avgas (at 4.24 grams per gallon), and twice as much as the 1 gram per gallon permitted in regular automotive leaded gasoline prior to 1988 and substantially greater than the allowed 0.001 grams per gallon in automotive unleaded gasoline sold in the United States today. The United States Environmental Protection Agency, FAA, and others are working on economically feasible replacements for leaded avgas, which still releases 100 tons of lead every year.
Alternative antiknock agents
Antiknock agents are classed as ''high-percentage'' additives, such as alcohol, and ''low-percentage'' additives based on heavy elements
upright=1.2, Crystals of lead.html" ;"title="osmium, a heavy metal nearly twice as dense as lead">osmium, a heavy metal nearly twice as dense as lead
Heavy metals is a controversial and ambiguous term for metallic elements with relatively h ...
. Since the main problem with TEL is its lead content, many alternative additives that contain less poisonous metals have been examined. A manganese-carrying additive, methylcyclopentadienyl manganese tricarbonyl
Methylcyclopentadienyl manganese tricarbonyl (MMT or MCMT) is an organomanganese compound with the formula (C5H4CH3)Mn(CO)3. Initially marketed as a supplement for use in leaded gasoline, MMT was later used in unleaded gasoline to increase the oc ...
(MMT or methylcymantrene), was used for a time as an antiknock agent, though its safety is controversial and it has been the subject of bans and lawsuits. Ferrocene
Ferrocene is an organometallic chemistry, organometallic compound with the formula . The molecule is a Cyclopentadienyl complex, complex consisting of two Cyclopentadienyl anion, cyclopentadienyl rings sandwiching a central iron atom. It is an o ...
, an organometallic
Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and so ...
compound of iron
Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...
, is also used as an antiknock agent although with some significant drawbacks.
High-percentage additives are organic compound
Some chemical authorities define an organic compound as a chemical compound that contains a carbon–hydrogen or carbon–carbon bond; others consider an organic compound to be any chemical compound that contains carbon. For example, carbon-co ...
s that do not contain metals, but require much higher blending ratios, such as 20–30% for benzene
Benzene is an Organic compound, organic chemical compound with the Chemical formula#Molecular formula, molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar hexagonal Ring (chemistry), ring with one hyd ...
and ethanol
Ethanol (also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound with the chemical formula . It is an Alcohol (chemistry), alcohol, with its formula also written as , or EtOH, where Et is the ps ...
. It had been established by 1921 that ethanol was an effective antiknock agent, but TEL was introduced instead mainly for commercial reasons. Oxygenate
In the liquid fuel industry, oxygenates are hydrocarbon-derived fuel additives containing at least one oxygen atom to promote complete combustion. Absent oxygenates, fuel combustion is usually incomplete, and the exhaust stream pollutes the air ...
s such as TAME
Tame may refer to:
*Taming, the act of training wild animals
* River Tame, Greater Manchester
*River Tame, West Midlands and the Tame Valley
* Tame, Arauca, a Colombian town and municipality
* "Tame" (song), a song by the Pixies from their 1989 a ...
derived from natural gas, MTBE
Methyl ''tert''-butyl ether (MTBE), also known as ''tert''-butyl methyl ether, is an organic compound with a structural formula (CH3)3COCH3. MTBE is a volatile, flammable, and colorless liquid that is sparingly soluble in water. Primarily used as ...
made from methanol, and ethanol-derived ETBE
Ethyl ''tertiary''-butyl ether (ETBE), also known as ethyl ''tert''-butyl ether, is commonly used as an oxygenate gasoline additive in the production of gasoline from crude oil. ETBE offers equal or greater air quality benefits than ethan ...
, have largely supplanted TEL. MTBE has environmental risks of its own and there are also bans on its use.
Improvements to gasoline itself decrease the need for antiknock additives. Synthetic iso-octane
2,2,4-Trimethylpentane, also known as isooctane or iso-octane, is an organic compound with the formula (CH3)3CCH2CH(CH3)2. It is one of several isomers of octane (C8H18). This particular isomer is the standard 100 point on the octane rating scale ...
and alkylate
An alkylation unit (alky) is one of the conversion processes used in petroleum refineries. It is used to convert isobutane and low-molecular-weight alkenes (primarily a mixture of propene and butene) into alkylate, a high octane gasoline componen ...
are examples of such blending stocks. Benzene and other high-octane aromatics
Aromatic compounds or arenes are organic compounds "with a chemistry typified by benzene" and "cyclically conjugated."
The word "aromatic" originates from the past grouping of molecules based on odor, before their general chemical properties were ...
can be also blended to raise the octane number, but they are disfavored today because of toxicity
Toxicity is the degree to which a chemical substance or a particular mixture of substances can damage an organism. Toxicity can refer to the effect on a whole organism, such as an animal, bacteria, bacterium, or plant, as well as the effect o ...
and carcinogen
A carcinogen () is any agent that promotes the development of cancer. Carcinogens can include synthetic chemicals, naturally occurring substances, physical agents such as ionizing and non-ionizing radiation, and biologic agents such as viruse ...
icity.
Toxicity
6 mL of tetraethyllead is enough to induce severe lead poisoning
Lead poisoning, also known as plumbism and saturnism, is a type of metal poisoning caused by lead in the body. Symptoms may include abdominal pain, constipation, headaches, irritability, memory problems, infertility, numbness and paresthesia, t ...
. The hazards of TEL content are heightened due to the compound's volatility and high lipophilicity
Lipophilicity (from Greek λίπος "fat" and φίλος "friendly") is the ability of a chemical compound to dissolve in fats, oils, lipids, and non-polar solvents such as hexane or toluene. Such compounds are called lipophilic (translated ...
, enabling it to easily cross the blood–brain barrier
The blood–brain barrier (BBB) is a highly selective semipermeable membrane, semipermeable border of endothelium, endothelial cells that regulates the transfer of solutes and chemicals between the circulatory system and the central nervous system ...
.
Early symptoms of acute exposure to tetraethyllead can manifest as irritation of the eyes and skin, sneezing, fever, vomiting, and a metallic taste in the mouth. Later symptoms of acute TEL poisoning include pulmonary edema
Pulmonary edema (British English: oedema), also known as pulmonary congestion, is excessive fluid accumulation in the tissue or air spaces (usually alveoli) of the lungs. This leads to impaired gas exchange, most often leading to shortness ...
, anemia
Anemia (also spelt anaemia in British English) is a blood disorder in which the blood has a reduced ability to carry oxygen. This can be due to a lower than normal number of red blood cells, a reduction in the amount of hemoglobin availabl ...
, ataxia, convulsions, severe weight loss, delirium
Delirium (formerly acute confusional state, an ambiguous term that is now discouraged) is a specific state of acute confusion attributable to the direct physiological consequence of a medical condition, effects of a psychoactive substance, or ...
, irritability, hallucinations, nightmares, fever, muscle and joint pain, swelling of the brain, coma, and damage to cardiovascular and renal organs.
Chronic exposure to TEL can cause long-term negative effects such as memory loss
Amnesia is a deficit in memory caused by brain damage or brain diseases,Gazzaniga, M., Ivry, R., & Mangun, G. (2009) Cognitive Neuroscience: The biology of the mind. New York: W.W. Norton & Company. but it can also be temporarily caused by t ...
, delayed reflexes, neurological problems, insomnia, tremors, psychosis, loss of attention, and an overall decrease in IQ and cognitive function.
The carcinogenity
A carcinogen () is any agent that promotes the development of cancer. Carcinogens can include synthetic chemicals, naturally occurring substances, physical agents such as ionizing and non-ionizing radiation, and biologic agents such as viruse ...
of tetraethyllead is debatable. It is believed to harm the male reproductive system and cause birth defects.
Concerns over the toxicity of lead eventually led to the ban on TEL in automobile gasoline in many countries. Some neurologists have speculated that the lead phaseout may have caused average IQ levels to rise by several points in the US (by reducing cumulative brain damage throughout the population, especially in the young). For the entire US population, during and after the TEL phaseout, the mean blood lead level dropped from 16 μg/dL in 1976 to only 3 μg/dL in 1991. The U.S. Centers of Disease control previously labelled children with 10 μg/dL or more as having a "blood lead level of concern". In 2021, the level was lowered in accordance with the average lead level in the U.S. decreasing to 3.5 μg/dL or more as having a "blood lead level of concern".
History
In 1853, German chemist Karl Jacob Löwig (1803–1890) first prepared what he claimed was Pb2(C2H5)3 from ethyl iodide
Ethyl iodide (also iodoethane) is a transparency and translucency, colorless flammable chemical compound. It has the chemical formula C2H5I and is prepared by heating ethanol with iodine and phosphorus.''Merck Index of Chemicals and Drugs'', 9th e ...
and an alloy of lead and sodium. In 1859, English chemist George Bowdler Buckton
George Bowdler Buckton (24 May 1818, London – 25 September 1905, Haslemere, Surrey) was an England, English chemist and entomologist who specialised in aphids.
Early life
Buckton was born in London and lived in Hornsey, England. He was the ...
(1818–1905) reported what he claimed was Pb(C2H5)2 from zinc ethyl (Zn(C2H5)2) and lead(II) chloride
Lead(II) chloride (PbCl2) is an inorganic compound which is a white solid under ambient conditions. It is poorly soluble in water. Lead(II) chloride is one of the most important lead-based reagents. It also occurs naturally in the form of the min ...
. Later authors credit both methods of preparation with producing tetraethyl lead.
In fuel
TEL remained unimportant commercially until the 1920s.[Kitman, J. (2 March 2000)]
"The Secret History of Lead."
''The Nation
''The Nation'' is a progressive American monthly magazine that covers political and cultural news, opinion, and analysis. It was founded on July 6, 1865, as a successor to William Lloyd Garrison's '' The Liberator'', an abolitionist newspaper ...
''. Retrieved 17 August 2009. In 1921, at the direction of DuPont Corporation, which manufactured TEL, it was found to be an effective antiknock agent
An antiknock agent (also: knock inhibitor) is a gasoline additive used to reduce engine knocking and increase the fuel's octane rating by raising the temperature and pressure at which auto-ignition occurs. The mixture known as gasoline or petrol, ...
by Thomas Midgley, working under Charles Kettering
Charles Franklin Kettering (August 29, 1876 – November 25, 1958) sometimes known as Charles Fredrick Kettering was an American inventor, engineer, businessman, and the holder of 186 patents.
For the list of patents issued to Kettering, see, Le ...
at General Motors Corporation
General Motors Company (GM) is an American multinational automotive manufacturing company headquartered in Detroit, Michigan, United States. The company is most known for owning and manufacturing four automobile brands: Chevrolet, Buick, GMC, ...
Research. General Motors patent
A patent is a type of intellectual property that gives its owner the legal right to exclude others from making, using, or selling an invention for a limited period of time in exchange for publishing an sufficiency of disclosure, enabling discl ...
ed the use of TEL as an antiknock agent and used the name "Ethyl" that had been proposed by Kettering in its marketing materials, thereby avoiding the negative connotation of the word "lead". Early research into "engine knocking
In spark-ignition internal combustion engines, knocking (also knock, detonation, spark knock, pinging or pinking) occurs when combustion of some of the air/fuel mixture in the cylinder does not result from propagation of the flame front ignite ...
" (also called "pinging" or "pinking") was also led by A.H. Gibson and Harry Ricardo
Sir Harry Ralph Ricardo (26 January 1885 – 18 May 1974) was an English engineer who was one of the foremost engine designers and researchers in the early years of the development of the internal combustion engine.
Among his many other works, ...
in England and Thomas Boyd in the United States. The discovery that lead
Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
additives modified this behavior led to the widespread adoption of their use in the 1920s, and therefore more powerful, higher-compression engines. In 1924, Standard Oil of New Jersey
Exxon Mobil Corporation ( ) is an American multinational oil and gas corporation headquartered in Spring, Texas, a suburb of Houston. Founded as the largest direct successor of John D. Rockefeller's Standard Oil, the modern company was formed ...
(ESSO/EXXON) and General Motors created the Ethyl Gasoline Corporation
Ethyl Corporation is a fuel additive company headquartered in Richmond, Virginia, in the United States. The company is a distributor of fuel additives. Among other products, Ethyl Corporation distributes tetraethyl lead, an additive used to make ...
to produce and market TEL. Deepwater, New Jersey
New Jersey is a U.S. state, state located in both the Mid-Atlantic States, Mid-Atlantic and Northeastern United States, Northeastern regions of the United States. Located at the geographic hub of the urban area, heavily urbanized Northeas ...
, across the river from Wilmington, was the site for production of some of DuPont's most important chemicals, particularly TEL. After TEL production at the Bayway Refinery
Bayway Refinery is a refining facility in the Port of New York and New Jersey, owned by Phillips 66. Located in Linden and Elizabeth, New Jersey, and bisected by Morses Creek, it is the northernmost refinery on the East Coast of the United State ...
was shut down, Deepwater was the only plant in the Western hemisphere producing TEL up to 1948, when it accounted for the bulk of the Dupont/Deepwater's production.
Initial controversy
The toxicity of concentrated TEL was recognized early on, as lead had been recognized since the 19th century as a dangerous substance that could cause lead poisoning
Lead poisoning, also known as plumbism and saturnism, is a type of metal poisoning caused by lead in the body. Symptoms may include abdominal pain, constipation, headaches, irritability, memory problems, infertility, numbness and paresthesia, t ...
. In 1924, a public controversy arose over the "loony gas", after five workers died, and many others were severely injured, in Standard Oil refineries in New Jersey. There had also been a private controversy for two years prior to this controversy; several public health experts, including Alice Hamilton
Alice Hamilton (February 27, 1869 – September 22, 1970) was an American physician, research scientist, and author. She was a leading expert in the field of occupational health, laid the foundation for health and safety protections, and a pione ...
and Yandell Henderson, engaged Midgley and Kettering with letters warning of the dangers to public health. After the death of the workers, dozens of newspapers reported on the issue. ''The New York Times'' editorialized in 1924 that the deaths should not interfere with the production of more powerful fuel.
To settle the issue, the U.S. Public Health Service
The United States Public Health Service (USPHS or PHS) is a collection of agencies of the Department of Health and Human Services which manages public health, containing nine out of the department's twelve operating divisions. The assistant se ...
conducted a conference in 1925, and the sales of TEL were voluntarily suspended for one year to conduct a hazard assessment. The conference was initially expected to last for several days, but reportedly the conference decided that evaluating presentations on alternative anti-knock agents was not "its province", so it lasted a single day. Kettering and Midgley stated that no alternatives for anti-knocking were available, although private memos showed discussion of such agents. One commonly discussed agent was ethanol. The Public Health Service created a committee that reviewed a government-sponsored study of workers and an Ethyl lab test, and concluded that while leaded gasoline should not be banned, it should continue to be investigated. The low concentrations present in gasoline and exhaust were not perceived as immediately dangerous. A U.S. Surgeon General
The surgeon general of the United States is the operational head of the United States Public Health Service Commissioned Corps (PHSCC) and thus the leading spokesperson on matters of public health in the federal government of the United States. T ...
committee issued a report in 1926 that concluded there was no real evidence that the sale of TEL was hazardous to human health but urged further study. In the years that followed, research was heavily funded by the lead industry; in 1943, Randolph Byers found children with lead poisoning had behavior problems, but the Lead Industries Association
The Lead Industries Association (LIA) was a trade organization that in 1925 made it possible for tetraethyllead to be an additive of commercial gasoline and later incorporated in 1928 to promote the interests of the lead industry. The National Lea ...
threatened him with a lawsuit and the research ended.
In the late 1920s, Robert A. Kehoe of the University of Cincinnati
The University of Cincinnati (UC or Cincinnati, informally Cincy) is a public university, public research university in Cincinnati, Ohio, United States. It was founded in 1819 and had an enrollment of over 53,000 students in 2024, making it the ...
was the Ethyl Corporation's chief medical consultant and one of the lead industry's staunchest advocates, who would not be discredited until decades later by Dr. Clair Patterson
Clair Cameron Patterson (June 2, 1922 – December 5, 1995) was an American geochemist. Born in Mitchellville, Iowa, Patterson graduated from Grinnell College. He later received his Ph.D. from the University of Chicago and spent his entire pro ...
's work on human lead burdens (see below) and other studies. In 1928, Dr. Kehoe expressed the opinion that there was no basis for concluding that leaded fuels posed any health threat. He convinced the Surgeon General
Surgeon general (: surgeons general) is a title used in several Commonwealth countries and most NATO nations to refer either to a senior military medical officer or to a senior uniformed physician commissioned by the government and entrusted with p ...
that the dose–response relationship
The dose–response relationship, or exposure–response relationship, describes the magnitude of the Stimulus–response model, response of an organism, as a Function (mathematics), function of exposure (or Dose (biochemistry), doses) to a Sti ...
of lead had "no effect" below a certain threshold. As the head of Kettering Laboratories for many years, Kehoe would become a chief promoter of the safety of TEL, an influence that did not begin to wane until about the early 1960s. But by the 1970s, the general opinion of the safety of TEL would change, and by 1976 the U.S. government would begin to require the phaseout of this product.
In the late 1940s and early 1950s, Clair Cameron Patterson accidentally discovered the pollution caused by TEL in the environment while determining the age of the Earth
The age of Earth is estimated to be 4.54 ± 0.05 billion years. This age may represent the age of Earth's accretion (astrophysics), accretion, or Internal structure of Earth, core formation, or of the material from which Earth formed. This dating ...
. As he attempted to measure lead content of very old rocks, and the time it took uranium to decay into lead, the readings were made inaccurate by lead in the environment that contaminated his samples. He was then forced to work in a cleanroom
A cleanroom or clean room is an engineered space that maintains a very low concentration of airborne particulates. It is well-isolated, well-controlled from contamination, and actively cleansed. Such rooms are commonly needed for scientifi ...
to keep his samples uncontaminated by environmental pollution of lead. After coming up with a fairly accurate estimate of the age of the Earth, he turned to investigating the lead contamination problem by examining ice cores from countries such as Greenland
Greenland is an autonomous territory in the Danish Realm, Kingdom of Denmark. It is by far the largest geographically of three constituent parts of the kingdom; the other two are metropolitan Denmark and the Faroe Islands. Citizens of Greenlan ...
. He realized that the lead contamination in the environment dated from about the time that TEL became widely used as a fuel additive in gasoline. Being aware of the health dangers posed by lead and suspicious of the pollution caused by TEL, he became one of the earliest and most effective proponents of removing it from use.
In the 1960s, the first clinical works were published proving the toxicity of this compound in humans, e.g. by Mirosław Jan Stasik.
Modern findings
In the 1970s, Herbert Needleman found that higher lead levels in children were correlated with decreased school performance. Needleman was repeatedly accused of scientific misconduct by individuals within the lead industry, but he was eventually cleared by a scientific advisory council. Needleman also wrote the average US child's blood lead level was 13.7 μg/dL in 1976 and that Patterson believed that everyone was to some degree poisoned by TEL in gasoline.
In the U.S. in 1973, the United States Environmental Protection Agency issued regulations to reduce the lead content of leaded gasoline over a series of annual phases, which therefore came to be known as the "lead phasedown" program. EPA's rules were issued under section 211 of the Clean Air Act (United States), Clean Air Act, as amended 1970. The Ethyl Corp challenged the EPA regulations in Federal court. Although the EPA's regulation was initially invalidated, the EPA won the case on appeal, so the TEL phasedown began to be implemented in 1976. Leaded gas was banned in vehicles with catalytic converters in 1975 due to damage of catalytic converters but it continued to be sold for vehicles without catalytic converters. Additional regulatory changes were made by EPA over the next decade (including adoption of a trading market in "lead credits" in 1982 that became the precursor of the Acid Rain Allowance Market, adopted in 1990 for SO2), but the decisive rule was issued in 1985. The EPA mandated that lead additive be reduced by 91 percent by the end of 1986. A 1994 study had indicated that the concentration of lead in the blood of the U.S. population had dropped 78% from 1976 to 1991. The U.S. phasedown regulations also were due in great part to studies conducted by Philip J. Landrigan.
In Europe, Professor Derek Bryce-Smith was among the first to highlight the potential dangers of TEL and became a leading campaigner for removal of lead additives from petrol.
From 1 January 1996, the Clean Air Act (United States), U.S. Clean Air Act banned the sale of leaded fuel for use in on-road vehicles although that year the US EPA indicated that TEL could still be used in aircraft, racing cars, farm equipment, and marine engines. Thus, what had begun in the U.S. as a phase down ultimately ended in a phase-out for on-road vehicle TEL. Similar bans in other countries have resulted in lowering levels of lead in people's bloodstreams.
Taking cue from the domestic programs, the U.S. Agency for International Development undertook an initiative to reduce tetraethyl lead use in other countries, notably its efforts in Egypt begun in 1995. In 1996, with the cooperation of the U.S. AID, Egypt took almost all of the lead out of its gasoline. The success in Egypt provided a model for AID efforts worldwide.
By 2000, the TEL industry had moved the major portion of their sales to developing countries whose governments they lobbied against phasing out leaded gasoline. Leaded gasoline was withdrawn entirely from the European Union market on 1 January 2000, although it had been banned earlier in most member states. Other countries also phased out TEL. India banned leaded petrol in March 2000.
By 2011, the United Nations announced that it had been successful in phasing out leaded gasoline worldwide. "Ridding the world of leaded petrol, with the United Nations leading the effort in developing countries, has resulted in $2.4 trillion in annual benefits, 1.2 million fewer premature deaths, higher overall intelligence and 58 million fewer crimes", the United Nations Environmental Program said. The announcement was slightly premature, as a few countries still had leaded gasoline for sale as of 2017. On 30 August 2021 the United Nations Environment Program
The United Nations Environment Programme (UNEP) is responsible for coordinating responses to environmental issues within the United Nations system. It was established by Maurice Strong, its first director, after the United Nations Conference on ...
announced that leaded gasoline had been eliminated. The final stocks of the product were used up in Algeria, which had continued to produce leaded gasoline until July 2021.
Effect on crime rates
Reduction in the average blood lead level is believed to have been a major cause for falling violent crime rates in the United States. A statistically significant correlation has been found between the usage rate of leaded gasoline and violent crime: the violent crime curve virtually tracks the lead exposure curve with a 22-year time lag.[Reyes, J. W. (2007)]
"The Impact of Childhood Lead Exposure on Crime". National Bureau of Economic Research.
"a" ref citing Pirkle, Brody, et. al (1994). Retrieved 17 August 2009. After the ban on TEL, blood lead levels in U.S. children dramatically decreased. Researchers including Amherst College economist Jessica Wolpaw Reyes, Department of Housing and Urban Development consultant Rick Nevin, and Howard Mielke of Tulane University say that declining exposure to lead is responsible for an up to 56% decline in crime from 1992 to 2002. Taking into consideration other factors that are believed to have increased crime rates over that period, Reyes found that the reduced exposure to lead led to an actual decline of 34% over that period.
Lingering issues over time
Although leaded gasoline has long since ended its history of regular use in U.S. transportation, it has left high concentrations of lead in the soil adjacent to roads that were heavily used prior to its phaseout. These contaminated materials present health dangers even when merely touched or when components of it get Breathing, breathed in. Children, especially those in Poverty in the United States, poverty inside of the U.S., are particularly at risk.
See also
* Elmer Keiser Bolton#World War I and E.I. du Pont de Nemours and Company, Elmer Keiser Bolton
* Lead abatement
* List of petrol additives
References
Further reading
*
External links
Media articles
The Man Who Warned the World About Lead
(PBS / NOVA)
The Most Important Scientist You’ve Never Heard Of
BY Lucas Reilly, May 17, 2017, mentalfloss.com
The World Has Finally Stopped Using Leaded Gasoline. Algeria Used The Last Stockpile
August 30, 2021, Heard on All Things Considered, Camila Domonoske, NPR.
Official documents
*U.S. Gov't, National Institute for Occupational Safety and Health
Scientific papers and journal articles
*Kovarik, Bill (1999)
*[https://www.aopa.org/advocacy/advocacy-briefs/regulatory-brief-avgas-100ll-alternatives True unleaded alternative for 100LL needed for general aviation]
*Jamie Lincoln Kitman:
The Secret History of Lead
'. In: The Nation, 2 March 2000.
{{Authority control
Organolead compounds
Antiknock agents
Ethyl compounds