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Tetraethyllead

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Tetraethyllead
Skeletal formula
Ball-and-stick model
Names
Preferred IUPAC name
Tetraethylplumbane
Other names
Lead tetraethyl

Tetraethyl lead

Tetra-ethyl lead
Identifiers
3D model (JSmol)
Abbreviations TEL
3903146
ChEBI
ChemSpider
ECHA InfoCard 100.000.979Edit this at Wikidata
EC Number
  • 201-075-4
68951
MeSH Tetraethyl+lead
RTECS number
  • TP4550000
UNII
UN number 1649
  • InChI=1S/4C2H5.Pb/c4*1-2;/h4*1H2,2H3;checkY
    Key: MRMOZBOQVYRSEM-UHFFFAOYSA-NcheckY
  • CC[Pb](CC)(CC)CC
Properties
C8H20Pb
Molar mass 323.4g·mol−1
Appearance Colorless liquid
Odor pleasant, sweet[1]
Density 1.653 g cm−3
Melting point −136 °C (−213 °F; 137 K)
Boiling point 84 to 85 °C (183 to 185 °F; 357 to 358 K) 15 mmHg
200parts per billion(ppb) (20 °C)[1]
Vapor pressure 0.2mmHg(20 °C)[1]
1.5198
Structure
Tetrahedral
0 D
Hazards
Occupational safety and health(OHS/OSH):
Main hazards
 Flammable, extremely toxic
GHSlabelling:
GHS06: ToxicGHS08: Health hazardGHS09: Environmental hazard
H300+H310+H330,H360,H373,H410
P201,P202,P260,P262,P264,P270,P271,P273,P280,P281,P284,P301+P310,P302+P350,P304+P340,P308+P313,P310,P314,P320,P321,P322,P330,P361,P363,P391,P403+P233,P405,P501
NFPA 704(fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g. diesel fuelInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazards (white): no code
4
2
3
Flash point 73 °C (163 °F; 346 K)
Explosive limits 1.8%–?[1]
Lethal doseor concentration (LD, LC):
35 mg/kg (rat, oral)
17 mg/kg (rat, oral)
12.3 mg/kg (rat, oral)[2]
30 mg/kg (rabbit, oral)
24 mg/kg (rat, oral)[2]
850 mg/m3(rat, 1 hr)[2]
650 mg/m3(mouse, 7 hr)[2]
NIOSH(US health exposure limits):
PEL(Permissible)
 TWA 0.075 mg/m3[skin][1]
REL(Recommended)
 TWA 0.075 mg/m3[skin][1]
IDLH(Immediate danger)
 40 mg/m3(as Pb)[1]
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa).

Tetraethyllead(commonly styledtetraethyl lead), abbreviatedTEL,is anorganolead compoundwith the formulaPb(C2H5)4.It was widely used as afueladditive for much of the 20th century, first being mixed withgasolinebeginning in the 1920s. This "leaded gasoline" had an increasedoctane ratingthat allowedengine compressionto be raised substantially and in turn increased vehicle performance and fuel economy.[3][4]TEL was firstsynthesisedby German chemistCarl Jacob Löwigin 1853. American chemical engineerThomas Midgley Jr.,who was working for the U.S. corporationGeneral Motors,was the first to discover its effectiveness as anantiknockagent in 1921, after spending several years attempting to find anadditivethat was both highly effective and inexpensive.

In the mid-20th century, scientists discovered TEL causedlead poisoningand was toxic to the human brain, especially in children.[5]TheUnited Statesand many other countries began phasing out the use of TEL in automotive fuel in the 1970s. By the early 2000s, most countries had completely banned the use of TEL in gasoline. Since 2011, leaded gasoline has been banned in every country. A 2011 study backed by the United Nations estimated that the removal of TEL had resulted in $2.4 trillion in annual benefits, and 1.2 million fewer premature deaths.[6]

Despite being banned from use in automotive fuel, TEL is sometimes still used in certain grades ofaviation fuel.Innospechas claimed to be the last firm legally making TEL but, as of 2013,TEL was being produced illegally by several companies in China.[7]In July 2021, the sale of leaded gasoline for cars was completely phased out worldwide, prompting theUnited Nations Environment Programme(UNEP) to declare an "official end" of its use in cars on August 30, 2021.[8]

Synthesis and properties

[edit]

TEL is produced by reactingchloroethanewith asodium–leadalloy.[9][10]

4 NaPb + 4 CH3CH2Cl → Pb(CH3CH2)4+ 4 NaCl + 3 Pb

The product is recovered by steam distillation, leaving a sludge of lead andsodium chloride.[11]TEL is aviscouscolorlessliquidwith a sweet odor.[12]Because TEL is charge neutral and contains an exterior of alkyl groups, it is highlylipophilicand soluble in petrol (gasoline). This property, which allows it to dissolve so evenly and effectively in motor fuel, also allows it to dissolve oils and fats well, and therefore, diffuse through the blood–brain barrier and accumulate within the limbic forebrain, frontal cortex, and hippocampus.[13]

Despite decades of research, no reactions were found to improve upon this process, which is rather difficult, involves metallic sodium, and converts only 25% of the lead to TEL. A related compound,tetramethyllead,was commercially produced by a different electrolytic reaction.[9]A process withlithiumwas developed but never put into practice.[14]

Reactions

[edit]

A noteworthy feature of TEL is the weakness of its four C–Pb bonds. At the temperatures found ininternal combustion engines,TEL decomposes completely into lead as well as combustible, short-lived ethylradicals.Lead and lead oxide scavengeradical intermediatesincombustionreactions. Engine knock is caused by acool flame,an oscillating low-temperature combustion reaction that occurs before the proper, hot ignition. Lead quenches the pyrolysed 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.[9]

When TEL burns, it produces not only carbon dioxide and water, but also lead and lead(II) oxide:[15]

Pb(C2H5)4+ 13 O2→ 8 CO2+ 10 H2O + Pb
2 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-dichloroethaneand1,2-dibromoethanewere also added to gasoline as lead scavengers—these agents form volatilelead(II) chlorideandlead(II) bromide,respectively, which flush the lead from the engine and into the air:[15]

Pb(C2H5)4+ C2H4Cl2+ 16 O2→ 10 CO2+ 12 H2O + PbCl2
Pb(C2H5)4+ C2H4Br2+ 16 O2→ 10 CO2+ 12 H2O + PbBr2

In motor fuel

[edit]

TEL was extensively used as agasoline additivebeginning in the 1920s,[16]wherein it served as an effectiveantiknock agentand reduced exhaustvalveandvalve seatwear. Concerns were raised in reputable journals of likely health outcomes of fine particles of lead in the atmosphere as early as 1924.[17][18][19]

Valve wear preventive

[edit]

Tetraethyllead helps cool intake valves and is an excellent buffer against microwelds forming between exhaust valves and theirseats.[20]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.[21]

Antiknock agent

[edit]

A gasoline-fuelled reciprocating engine requires fuel of sufficientoctane ratingto prevent uncontrolled combustion (preignition anddetonation).[9]Antiknock agents allow the use of highercompression ratiosfor greaterefficiency[22]and peakpower.[23]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.[16]Aviation fuels with TEL used in WWII reached octane ratings of 150 to enable turbocharged and supercharged engines such as theRolls-Royce MerlinandGriffonto reach high horsepower ratings at altitude.[24]In military aviation, TEL manipulation allowed a range of different fuels to be tailored for particular flight conditions.[citation needed]

In 1935 a licence to produce TEL was given toIG Farben,enabling the newly formed GermanLuftwaffeto use high-octane gasoline. A company, Ethyl GmbH, was formed that produced TEL at two sites in Germany with a government contract from 10 June 1936.[25]

In 1938 the United KingdomAir Ministrycontracted withICIfor 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.[26]

"Ethyl Fluid"

[edit]
Sign on an antique gasoline pump advertising tetraethyllead by theEthyl Corporation

For mi xing with raw gasoline, TEL was most commonly supplied in the form of "Ethyl Fluid", which consisted of TEL blended with 1,2-dichloroethane and 1,2-dibromoethane. 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.[27]

In the 1920s before safety procedures were strengthened, 17 workers for theEthyl Corporation,DuPont,andStandard Oildied from the effects of exposure to lead.[16]

Ethyl Fluid's formulation consisted of:[9]

Dichloroethane and dibromoethane act in a synergistic manner, where equal or approximately equal quantities of both provide the best scavenging ability.[9]

Phaseout and ban

[edit]

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 theaccumulativeneurotoxicityof lead.In the European Union, tetraethyllead has been classified as aSubstance of Very High Concernand placed on the Candidate List for Authorisation underRegistration, Evaluation, Authorisation and Restriction of Chemicals(REACH).[28]Potential use of TEL would need to be authorised through theREACH authorisation procedure.While not a complete ban, it introduces significant obligations such as a mandatory analysis of alternatives and socioeconomic analysis.[citation needed]

The use ofcatalytic converters,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.[29]The need for TEL was lessened by several advances in automotive engineering and petroleum chemistry. Safer methods for making higher-octane blending stocks such asreformateandiso-octanereduced the need to rely on TEL, as did other antiknock additives of varying toxicity including metallic compounds such asmethylcyclopentadienyl manganese tricarbonyl(MMT) as well asoxygenatesincludingmethyl tertiary-butyl ether(MTBE),tert-amyl methyl ether(TAME), andethyltert-butyl ether(ETBE).[citation needed]

The first country to completely ban leaded gasoline wasJapanin 1986.[30]

Since January 1993 all gasoline powered cars sold in theEuropean Unionand theUnited Kingdomhave been required to use unleaded fuel. This was to comply with theEuro 1 emission standardswhich mandated that all new cars to be fitted with acatalytic converter.[31]Unleaded fuel was first introduced in the United Kingdom in June 1986.[32]

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.[33][34]An exemption to the ban exists for owners of classic cars.[citation needed]

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 ofhardenedexhaust valves and seats. Compatibility with reduced octane was addressed by reducing compression, generally by installing thicker cylinderhead gasketsand/or rebuilding the engine with compression-reducing pistons, although modern high-octane unleaded gasoline has eliminated the need to decrease compression ratios.[citation needed]

Leaded gasoline remained legal as of late 2014[35]in parts ofAlgeria,Iraq,Yemen,Myanmar,North Korea,andAfghanistan.[36][37][needs update]North Korea and Myanmar purchased their TEL from China, while Algeria, Iraq, and Yemen purchased it from the specialty chemical companyInnospec,the world's sole remaining legal manufacturer of TEL.[38]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.[37][39]

As of June 2016theUNEP-sponsored phase-out was nearly complete: only Algeria, Iraq, and Yemen continued widespread use of leaded gasoline, although not exclusively.[40]In July 2021, Algeria had halted its sale.[8]

Leaded-fuel bans

[edit]

Leaded-fuel bans for road vehicles came into effect as follows:

Africa
[edit]
  • 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.[78]However, in Algeria refineries needed to be altered; as a result, leaded fuel remained available in parts ofAlgeria,[37]with phaseout scheduled for 2016. After the Algerian Government outlawed the sale of leaded petrol throughout all of Algeria, leaded petrol has now been effectively phased out.[79][80]

In motor racing

[edit]

Leaded fuel was commonly used in professionalmotor racing,until its phase out beginning in the 1990s. Since 1992,Formula Oneracing cars have been required to use fuel containing no more than 5 mg/L of lead.[81][verification needed]

NASCARbegan experimentation in 1998 with an unleaded fuel, and in 2006 began switching the national series to unleaded fuel, completing the transition at theFontana round in February 2007when the premier class switched. This was influenced after blood tests of NASCAR teams revealed elevated blood lead levels.[82][83]

Aviation gasoline

[edit]
Main article:Avgas

TEL remains an ingredient of 100octaneavgasfor piston-engine aircraft. The current formulation of 100LL (low lead, blue) aviation gasoline contains 2.12 grams per US gallon (0.56 g/L) of TEL, half the amount of the previous 100/130 (green) octane avgas (at 4.24 grams per gallon),[84]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.[85]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.[86]

Alternative antiknock agents

[edit]

Antiknock agents are classed ashigh-percentageadditives, such as alcohol, andlow-percentageadditives based onheavy elements.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(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,anorganometalliccompound ofiron,is also used as an antiknock agent although with some significant drawbacks.[87]

High-percentage additives areorganic compoundsthat do not contain metals, but require much higher blending ratios, such as 20–30% forbenzeneandethanol.It had been established by 1921 that ethanol was an effective antiknock agent, but TEL was introduced instead mainly for commercial reasons.[29]Oxygenatessuch asTAMEderived from natural gas,MTBEmade from methanol, and ethanol-derivedETBE,have largely supplanted TEL. MTBE has environmental risks of its own and there are also bans on its use.[citation needed]

Improvements to gasoline itself decrease the need for antiknock additives. Syntheticiso-octaneandalkylateare examples of such blending stocks. Benzene and other high-octanearomaticscan be also blended to raise the octane number, but they are disfavored today because oftoxicityandcarcinogenicity.[citation needed]

Toxicity

[edit]

6 mL of tetraethyllead is enough to induce severelead poisoning.[88]The hazards of TEL content are heightened due to the compound's volatility and highlipophilicity,enabling it to easily cross theblood–brain barrier.

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 includepulmonary edema,anemia,ataxia, convulsions, severe weight loss,delirium,irritability, hallucinations, nightmares, fever, muscle and joint pain,swelling of the brain,coma, and damage to cardiovascular and renal organs.[89] Chronic exposure to TEL can cause long-term negative effects such asmemory loss,delayed reflexes, neurological problems, insomnia, tremors, psychosis, loss of attention, and an overall decrease in IQ and cognitive function.[90]

Thecarcinogenityof tetraethyllead is debatable. It is believed to harm the male reproductive system and cause birth defects.[91]

Concerns over thetoxicity of lead[92]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.[93]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".[94][95]

History

[edit]

In 1853, German chemistKarl Jacob Löwig(1803–1890) first prepared what he claimed was Pb2(C2H5)3fromethyl iodideand an alloy of lead and sodium.[96]In 1859, English chemistGeorge Bowdler Buckton(1818–1905) reported what he claimed was Pb(C2H5)2fromzinc ethyl(Zn(C2H5)2) andlead(II) chloride.[97]Later authors credit both methods of preparation with producing tetraethyl lead.[98]

In fuel

[edit]

TEL remained unimportant commercially until the 1920s.[29]In 1921, at the direction of DuPont Corporation, which manufactured TEL, it was found to be an effectiveantiknock agentbyThomas Midgley,working underCharles KetteringatGeneral Motors CorporationResearch.[99]General Motorspatentedthe 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".[29]Early research into "engine knocking"(also called" pinging "or" pinking ") was also led by A.H. Gibson andHarry Ricardoin England and Thomas Boyd in the United States. The discovery thatleadadditives modified this behavior led to the widespread adoption of their use in the 1920s, and therefore more powerful, higher-compression engines.[16]In 1924,Standard Oil of New Jersey(ESSO/EXXON) and General Motors created theEthyl Gasoline Corporationto produce and market TEL. Deepwater, New Jersey, across the river from Wilmington, was the site for production of some of DuPont's most important chemicals, particularly TEL. After TEL production at theBayway Refinerywas 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.[100]

Initial controversy

[edit]

The toxicity of concentrated TEL was recognized early on, as lead had been recognized since the 19th century as a dangerous substance that could causelead poisoning.In 1924, a public controversy arose over the "loony gas", after five[101]workers died, and many others were severely injured, in Standard Oil refineries in New Jersey.[102]There had also been a private controversy for two years prior to this controversy; several public health experts, includingAlice HamiltonandYandell Henderson,engaged Midgley and Kettering with letters warning of the dangers to public health.[16]After the death of the workers, dozens of newspapers reported on the issue.[103]The New York Timeseditorialized in 1924 that the deaths should not interfere with the production of more powerful fuel.[16]

To settle the issue, theU.S. Public Health Serviceconducted a conference in 1925, and the sales of TEL were voluntarily suspended for one year to conduct a hazard assessment.[9][29][104]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.[16]The low concentrations present in gasoline and exhaust were not perceived as immediately dangerous. AU.S. Surgeon Generalcommittee 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.[29]In the years that followed, research was heavily funded by the lead industry; in 1943,Randolph Byersfound children with lead poisoning had behavior problems, but theLead Industries Associationthreatened him with a lawsuit and the research ended.[16][105]

In the late 1920s,Robert A. Kehoeof theUniversity of Cincinnatiwas 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's work on human lead burdens (see below) and other studies.[29]In 1928, Dr. Kehoe expressed the opinion that there was no basis for concluding that leaded fuels posed any health threat.[29]He convinced theSurgeon Generalthat thedose–response relationshipof lead had "no effect" below a certain threshold.[106]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.[citation needed]

In the late 1940s and early 1950s,Clair Cameron Pattersonaccidentally discovered the pollution caused by TEL in the environment while determining theage of the Earth.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 acleanroomto 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 asGreenland.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.[107][108]

In the 1960s, the first clinical works were published proving the toxicity of this compound in humans, e.g. byMirosław Jan Stasik.[89]

Modern findings

[edit]

In the 1970s,Herbert Needlemanfound 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.[16]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.[109]

In the U.S. in 1973, theUnited States Environmental Protection Agencyissued 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 theClean Air Act,as amended 1970. The Ethyl Corp challenged the EPA regulations in Federal court. Although the EPA's regulation was initially invalidated,[16]the EPA won the case on appeal, so the TEL phasedown began to be implemented in 1976. Leaded gas was banned in vehicles withcatalytic convertersin 1975 due to damage of catalytic converters but it continued to be sold for vehicles without catalytic converters.[110]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.[111]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.[112]The U.S. phasedown regulations also were due in great part to studies conducted byPhilip J. Landrigan.[113]

In Europe, ProfessorDerek Bryce-Smithwas among the first to highlight the potential dangers of TEL and became a leading campaigner for removal of lead additives from petrol.[114]

From 1 January 1996, theU.S. Clean Air Actbanned 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.[115]Thus, what had begun in the U.S. as a phasedown 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'sbloodstreams.[116][117]

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.[118]

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.[29]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.[119]Indiabanned leaded petrol in March 2000.[69]

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 Programme said.[6][120]The announcement was slightly premature, as a few countries still had leaded gasoline for sale as of 2017.[40]On 30 August 2021 theUnited Nations Environment Programmeannounced 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.[121][122]

Effect on crime rates

[edit]
Main article:Lead–crime hypothesis

Reduction in the average blood lead level is believed to have been a major cause for falling violent crime rates in the United States.[123]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.[93][124]After the ban on TEL, blood lead levels in U.S. children dramatically decreased.[93]Researchers includingAmherst Collegeeconomist Jessica Wolpaw Reyes,Department of Housing and Urban Developmentconsultant Rick Nevin, and Howard Mielke ofTulane Universitysay that declining exposure to lead is responsible for an up to 56% decline in crime from 1992 to 2002.[125]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.[126][127]

Lingering issues over time

[edit]

Although leaded gasoline has long since ended its history of regular use in U.S. transportation, it has left high concentrations of lead in thesoiladjacent 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 getbreathed in.Children, especially those inpoverty inside of the U.S.,are particularly at risk.[128]

See also

[edit]

References

[edit]
  1. ^abcdefgNIOSH Pocket Guide to Chemical Hazards."#0601".National Institute for Occupational Safety and Health(NIOSH).
  2. ^abcd"Tetraethyl lead".Immediately Dangerous to Life or Health Concentrations (IDLH).National Institute for Occupational Safety and Health(NIOSH).
  3. ^"Tetra-Ethyl Lead as an Addition to Petrol".British Medical Journal.1(3504): 366–7. 3 March 1928.doi:10.1136/bmj.1.3504.366.PMC2455205.PMID20773729.
  4. ^"After Lead?",Popular Science(October 1987 ed.), Bonnier Corporation, p. 94, October 1987,archivedfrom the original on 13 July 2024,retrieved23 August2020
  5. ^"LEAD EXPOSURE IN CHILDHOOD LINKED TO LOWER IQ, LOWER STATUS: Leaded gasoline creates a natural experiment in long-term study".Duke University. 28 March 2017.Archivedfrom the original on 13 July 2024.Retrieved11 March2022.
  6. ^ab"Phase-out of leaded petrol brings huge health and cost benefits".UN News.27 October 2011.Archivedfrom the original on 27 January 2022.Retrieved28 November2020.
  7. ^Chung, Kevin (16 August 2013).TEL for MOGAS manufacture in China(PDF)(Report). Summer Hill, NSW, Australia: The LEAD Group, Inc.Archived(PDF)from the original on 22 March 2018.Retrieved14 January2018.
  8. ^ab"It's official: You can't buy leaded gasoline for cars anywhere on Earth".cbc.ca.CBC News. 30 August 2021.Archivedfrom the original on 30 August 2021.Retrieved30 August2021.
  9. ^abcdefgSeyferth, D. (2003). "The Rise and Fall of Tetraethyllead. 2".Organometallics.22(25): 5154–5178.doi:10.1021/om030621b.
  10. ^Jewkes, John; Sawers, David; Richard, Richard (1969).The sources of invention(2nd ed.). New York: W. W. Norton. pp.235–237.ISBN978-0-393-00502-8.Retrieved11 July2018.
  11. ^Davis, William E. (1973).Emission Study of Industrial Sources of Lead Air Pollutants, 1970.United States: Environmental Protection Agency. p. 57.Archivedfrom the original on 7 June 2023.Retrieved22 March2023.
  12. ^Dara, S.S.; Shete, S.D.S. Chand's Applied Chemistry Volume 2 (For 2nd Semester of Mumbai University).S. Chand Publishing. p. 93.ISBN978-81-219-3495-4.Archivedfrom the original on 7 June 2023.Retrieved22 March2023.
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Further reading

[edit]
  • Filella, Montserrat; Bonet, Josep (2017). "Chapter 14. Environmental Impact of Alkyl Lead(IV) Derivatives: Perspective after Their Phase-out". In Astrid, S.; Helmut, S.; Sigel, R. K. O. (eds.).Lead: Its Effects on Environment and Health.Metal Ions in Life Sciences. Vol. 17. de Gruyter. pp. 471–490.doi:10.1515/9783110434330-014.ISBN978-3-11-043433-0.PMID28731307.
[edit]

Media articles

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Official documents

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Scientific papers and journal articles

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