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'{{Use dmy dates|date=August 2011}} {{Chembox | Watchedfields = changed | verifiedrevid = 470603872 | ImageFile = Tetraethyllead-Skeletal-SVG.svg | ImageFile_Ref = {{Chemboximage|correct|??}} | ImageSize = 200 | ImageAlt = Skeletal formula | ImageFile1 = Tetraethyllead-3D-balls.png | ImageSize1 = 180 | ImageAlt1 = Ball-and-stick model | IUPACName = Tetraethylplumbane | SystematicName = <!-- Tetraethylplumbane (substitutive) OR Tetraethyllead (additive) --> | OtherNames = Lead tetraethyl<br /> Tetraethyl lead<br /> Tetra-ethyl lead |Section1={{Chembox Identifiers | Abbreviations = TEL | CASNo = 78-00-2 | CASNo_Ref = {{cascite|correct|CAS}} | PubChem = 6511 | ChemSpiderID = 6265 | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | EINECS = 201-075-4 | UNNumber = 1649 | MeSHName = Tetraethyl+lead | ChEBI_Ref = {{ebicite|correct|EBI}} | ChEBI = 30182 | RTECS = TP4550000 | Beilstein = 3903146 | Gmelin = 68951 | UNII_Ref = {{fdacite|correct|FDA}} | UNII = 13426ZWT6A | SMILES = CC[Pb](CC)(CC)CC | StdInChI = 1S/4C2H5.Pb/c4*1-2;/h4*1H2,2H3; | StdInChI_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey = MRMOZBOQVYRSEM-UHFFFAOYSA-N | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} }} |Section2={{Chembox Properties | C = 8 | H = 20 | Pb = 1 | Appearance = Colorless liquid | Odor = pleasant, sweet<ref name=PGCH/> | Density = 1.653 g cm⁻³ | MeltingPtC = −136 | BoilingPtC = 84 to 85 | BoilingPt_notes = 15&nbsp;mmHg | RefractIndex = 1.5198 | Solubility = 0.00002% (20&nbsp;°C)<ref name=PGCH/> | VaporPressure = 0.2 mmHg (20&nbsp;°C)<ref name=PGCH/> }} |Section3={{Chembox Structure | MolShape = Tetrahedral | Dipole = 0 D}} |Section4={{Chembox Hazards | EUClass = [[Image:GHS-pictogram-skull.svg|60px]][[Image:GHS-pictogram-pollu.svg|60px]] | RPhrases = {{R61}}, {{R26/27/28}}, {{R33}}, {{R50/53}}, {{R62}} | SPhrases = {{S53}}, {{S45}}, {{S60}}, {{S61}} | NFPA-H = 3 | NFPA-F = 2 | NFPA-R = 3 | FlashPtC = 73 | IDLH = 40 mg/m³ (as Pb)<ref name=PGCH>{{PGCH|0601}}</ref> | LC50 = 850 mg/m³ (rat, 1 hr)<ref name=IDLH>{{IDLH|78002|Tetraethyl lead}}</ref> | LD50 = 35 mg/kg (rat, oral)<br/>17 mg/kg (rat, oral)<br/>12.3 mg/kg (rat, oral)<ref name=IDLH/> | REL = TWA 0.075 mg/m³ [skin]<ref name=PGCH/> | PEL = TWA 0.075 mg/m³ [skin]<ref name=PGCH/> | ExploLimits = 1.8%–?<ref name=PGCH/> | LCLo = 650 mg/m³ (mouse, 7 hr)<ref name=IDLH/> | LDLo = 30 mg/kg (rabbit, oral)<br/>24 mg/kg (rat, oral)<ref name=IDLH/> }} |Section8={{Chembox Related | OtherCompounds = [[Tetraethylgermanium]]<br /> [[Tetraethyltin]]}} }} '''Tetraethyllead''' (commonly styled '''tetraethyl lead'''), abbreviated '''TEL''', is an [[organolead compound]] with the formula ([[ethyl group|CH₃CH₂]])₄[[lead|Pb]]. TEL was mixed with [[gasoline]] (petrol) beginning in the 1920s as a patented [[octane rating]] booster that allowed [[Compression ratio|engine compression]] to be raised substantially, which in turn increased vehicle performance or fuel economy.<ref name=BMJ1928>{{cite journal|title=TETRA-ETHYL LEAD AS AN ADDITION TO PETROL|journal=British Medical Journal|volume=1|issue=3504|pages=366–7|date=3 March 1928|pmid=20773729|pmc=2455205|doi=10.1136/bmj.1.3504.366}}</ref><ref>{{citation|title=After Lead?|work=[[Popular Science]]|page=94|edition=October 1987|url=https://books.google.com/books?id=oAAAAAAAMBAJ&&pg=PA94}}</ref> [[Ethanol]] was already known as a widely available, inexpensive, low toxicity octane booster, but TEL was promoted because it was uniquely profitable to the patent holders.<ref name="Kitman"/> TEL in automotive fuel was phased out starting in the U.S. in the mid-1970s because of its cumulative [[neurotoxicity]] and its damaging effect on [[catalytic converter]]s. When present in fuel, TEL is also the main cause of [[spark plug]] fouling.<ref>{{cite book |url=https://books.google.com/books?id=IHI-AAAAYAAJ&pg=SA2-PA15 |title=Operator's Manual: Army Model U-8F Aircraft |page=2−15<!-- not 2 through 15, but section 2 page 15. --> |publisher=Headquarters, Department of the Army (U.S.) |date=21 March 1978 }}</ref> TEL is still used as an additive in some grades of [[Avgas|aviation gasoline]], and in some developing countries. [[Innospec]] has claimed to be the last firm still making TEL, but {{as of|2013|lc=y}} TEL was apparently being produced illegally by several companies in China.<ref name=chinese-manufacturers>{{cite web|title=TEL for MOGAS manufacture in China|url=http://www.lead.org.au/TEL_for_MOGAS_manufacture_in_China_20130816.pdf|date=16 August 2013}}</ref> As of June 2016 only [[Algeria]], [[Yemen]], and [[Iraq]] continue widespread use of leaded gasoline.<ref name=":0" /> ==Synthesis and properties== TEL is produced by reacting [[chloroethane]] with a [[sodium]]–[[lead]] [[alloy]].<ref name="Seyferth">{{cite journal |author= Seyferth, D. |title= The Rise and Fall of Tetraethyllead. 2 |journal= [[Organometallics]] |year= 2003 |volume= 22 |pages= 5154–5178 |doi= 10.1021/om030621b |issue= 25}}</ref> : 4 NaPb + 4 CH₃CH₂Cl → (CH₃CH₂)₄Pb + 4 NaCl + 3 Pb TEL is also produced by reacting [[Ethylmagnesium Iodide]] with [[lead(II) chloride]]. :4C₂H₅Mg-I + 2PbCl₂ → (C₂H₅)₄Pb + Pb +4 MgICl The product is recovered by steam distillation, leaving a sludge of lead and sodium chloride. TEL is a [[Viscosity|viscous]] colorless [[liquid]]. Because TEL is charge neutral and contains an exterior of alkyl groups, it is highly [[Lipophilicity|lipophilic]] and soluble in petrol (gasoline). Despite decades of research, no reactions were found to improve upon this rather difficult process that involves metallic sodium and converts only 25% of the lead to TEL. A related compound, tetramethyllead, was commercially produced by a different electrolytic reaction.<ref name = Seyferth/> A process with [[lithium]] was developed, but 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]]s, {{nowrap|(CH₃CH₂)₄Pb}} decomposes completely into lead and lead oxides as well as combustible, short-lived ethyl [[Radical (chemistry)|radical]]s. Lead and lead oxide scavenge [[Radical (chemistry)|radical intermediates]] in [[combustion]] reactions. Engine knock is caused by a [[cool 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 TEL serves as a gasoline-soluble lead carrier.<ref name="Seyferth" /> When (CH₃CH₂)₄Pb burns, it produces not only carbon dioxide and water, but also lead: : (CH₃CH₂)₄Pb + 13 O₂ → 8 CO₂ + 10 H₂O + Pb This lead can oxidize further to give species such as [[lead(II) oxide]]: : 2 Pb + O₂ → 2 PbO Pb and PbO would quickly over-accumulate and destroy an engine. For this reason, the lead scavengers [[1,2-Dibromoethane|1,2-dibromoethane]] and [[1,2-Dichloroethane|1,2-dichloroethane]] are used in conjunction with TEL—these agents form volatile [[lead(II) bromide]] and [[lead(II) chloride]], respectively, which are flushed from the engine and into the air. ==In motor fuel== TEL was extensively used as a [[gasoline additive]] beginning in the 1920s,<ref name=Kovarik2005 /> wherein it served as an effective [[antiknock agent]] and prevented exhaust [[Poppet valve|valve]] and [[valve seat]] wear. ===Valve wear preventive=== Tetraethyl lead works as a buffer against microwelds forming between the hot exhaust valves and their [[Valve seat|seats]].<ref>{{cite web|url=http://www.imperialclub.com/Repair/Lit/Master/291/page13.htm|title=1972 Imperial & Chrysler Engine Performance Facts & Fixes ServiceBook (Session 291)|publisher=}}</ref> Once these valves reopen, the microwelds pull apart and leave the valves with a rough surface that would abrade the seats, leading to valve recession. When lead began to be phased out of motor fuel, the automotive industry began specifying hardened valve seats and upgraded exhaust valve materials to prevent valve recession without lead.<ref>{{cite web|url=http://www.imperialclub.com/Repair/Lit/Master/302/page04.htm|title=1973 Imperial and Chrysler Clean Air System Reference ServiceRepair Book from the Master Technician's Service Conference (Session 302)|publisher=}}</ref> ===Antiknock agent=== A gasoline-fueled reciprocating engine requires fuel of sufficient [[octane rating]] to prevent uncontrolled combustion known as [[engine knocking]] (''knock'' or ''ping'').<ref name="Seyferth" /> Antiknock agents allow the use of higher [[compression ratio]]s for greater [[fuel efficiency|efficiency]]<ref name="SAEtrans-hce1959">Caris, D. F. and Nelson, E. E. (1959). A New Look at High Compression Engines SAE Trans.</ref> and peak [[power (physics)|power]].<ref>{{cite journal|last1=Loeb|first1=A.P.|title=Birth of the Kettering Doctrine: Fordism, Sloanism and Tetraethyl Lead|journal=Business and Economic History|date=Fall 1995|volume=24|issue=2|url=http://www.thebhc.org/sites/default/files/beh/BEHprint/v024n1/p0072-p0087.pdf|archiveurl=https://web.archive.org/web/20151027191244/http://www.thebhc.org/sites/default/files/beh/BEHprint/v024n1/p0072-p0087.pdf|archivedate=2015-10-27|dead-url = no}}</ref> Adding varying amounts of additives like low percentage TEL or high percentage ethanol to gasoline, allowed easy, inexpensive control of octane ratings. TEL offered the business advantage of being commercially profitable because it could be patented.<ref name=Kovarik2005/> Aviation spirits with TEL used in WWII reached 150 octane to enable supercharged engines such as the [[Rolls-Royce Merlin]] and [[Rolls-Royce Griffon|Griffon]] to reach high horse power ratings at altitude.<ref>I Kept No Diary. Air Commodore F.R. Banks, 1978, ISBN 0-9504543-9-7</ref> In military aviation, TEL manipulation allowed a range of different fuels to be tailored for particular flight conditions. In 1935 the licence to produce TEL was given to [[I.G.Farben]] enabling the newly formed German [[Luftwaffe]] to 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.<ref>[[Rainer Karlsch]], Raymond G. Stokes: ''„Faktor Öl“. Die Mineralölwirtschaft in Deutschland 1859–1974.'' C. H. Beck, München, 2003, ISBN 3-406-50276-8, S. 187.</ref> ===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 [[Bioaccumulation|accumulative]] neurotoxicity [[Lead poisoning|of lead]]. The use of [[catalytic converter]]s, mandated in the US for 1975 and newer model-year cars to meet tighter emissions regulations, started a gradual phase-out of leaded gasoline in the US.<ref name=Kitman/> 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]] and [[iso-octane]] reduced the need to rely on TEL, as did other antiknock additives of varying toxicity including metallic compounds such as [[Methylcyclopentadienyl manganese tricarbonyl|MMT]] as well as [[oxygenate]]s including [[MTBE]], [[tert-Amyl methyl ether|TAME]], and [[ETBE]]. Lead-replacement additives were scientifically tested and some were approved by the Federation of British Historic Vehicle Clubs at the UK's [[Motor Industry Research Association]] in 1999. 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.<ref>{{cite web|url=https://www.theguardian.com/theguardian/2011/jul/19/derek-bryce-smith-obituary|title=Derek Bryce-Smith obituary|work=the Guardian}}</ref> However, leaded motor fuel re-entered the [[United Kingdom|UK]] market in small quantities from 2000 in response to lobbying from classic-car organisations who contended their vehicles would be rendered useless without leaded fuel. The lead content is up to {{nobreak|0.15 grams per litre}}; Bayford & Co is the only wholesale supplier.{{Citation needed|date=January 2014}} Vehicles designed and built to run on leaded fuel may require modification to run on unleaded gasoline or [[autogas]]. 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 [[Hardening (metallurgy)|hardened]] exhaust valves and seats. Compatibility with reduced octane was addressed by reducing compression, generally by installing thicker cylinder [[head gasket]]s and/or rebuilding the engine with compression-reducing pistons. The availability of high-octane unleaded gasoline (or LPG) has reduced or eliminated the need to decrease compression ratios. Leaded gasoline remained legal as of late 2014<ref name=corrupt-executives>{{cite news | title=Corrupt Executives Sent To Prison For Pumping Toxic Leaded Fuel Overseas | url=http://www.huffingtonpost.com/2014/08/09/leaded-gas-corruption-innospec_n_5662418.html}}</ref> in parts of [[Algeria]], [[Iraq]], [[Yemen]], [[Myanmar]], [[North Korea]], and [[Afghanistan]]. It was available at the pump in most of these countries as of 2011, but very little was used in North Korea and it was not clear whether it was sold in Afghanistan.<ref>{{cite web|title=UNEP 10th general meeting strategy presentation|url=http://www.unep.org/transport/pcfv/PDF/10gpm_CHpresentation_strategy.pdf}}{{dead link|date=February 2017}}</ref><ref name=leadgroup>{{cite web |url= http://www.lead.org.au/fs/fst27.html |title= Countries where Leaded Petrol is Possibly Still Sold for Road Use |date= 17 June 2011 |author= Robert Taylor |publisher= The LEAD Group}}</ref> Specialty chemical company [[Innospec]] says that it is the world's only manufacturer of TEL<ref>{{cite web|url=http://www.innospecinc.com/our-markets/octane-additives/octane-additives|title=Octane Additives|publisher=}}</ref> and sells it for automotive use nowhere except to Algeria as of late 2014.<ref name=corrupt-executives /> Innospec previously sold TEL to Iraq and Yemen as of 2011, but remains unclear after head executives were charged for bribing various government state owned oil companies, to approve the sale of their TEL products.<ref name=leadgroup /><ref>{{cite web|url=http://www.fcpaprofessor.com/first-enforcement-action-of-2011-involves-a-former-executive-officer|title=First Enforcement Action of 2011 Involves a Former Executive Officer|work=FCPA Professor}}</ref> North Korea and Myanmar buy their TEL from China.<ref name="chinese-manufacturers"/> The governments of Algeria and Iraq have scheduled the final elimination of leaded gasoline in their countries in 2015, after refinery upgrades. The status in Afghanistan, Yemen, and Myanmar is unclear. {{as of|2016|6}} [[United Nations Environment Programme|UNEP]]-sponsored phase-out is nearly complete: only [[Algeria]], [[Yemen]], and [[Iraq]] continue widespread use of leaded gasoline. None use it exclusively.<ref name=":0">{{Cite web|url=http://www.unep.org/Transport/new/PCFV/pdf/Maps_Matrices/world/lead/MapWorldLead_June2016.pdf|title=UNEP - Transport - Partnership for Clean Fuels and Vehicles|website=Leaded Petrol Phase-out: Global Status as at June 2016|access-date=2016-06-06}}{{dead link|date=February 2017}}</ref> ====Leaded-fuel bans ==== Leaded-fuel bans for road vehicles came into effect as follows: {{Col-begin}} {{Col-break}} ;Europe *Austria: 1989 *Bosnia and Herzegovina: 2009 *Czech Republic: 2001<ref>{{cite book|url=https://books.google.com/books?id=L4_VAgAAQBAJ|title=OECD Environmental Performance Reviews OECD Environmental Performance Reviews: Czech Republic 2005|first=|last=OECD|date=11 October 2005|publisher=OECD Publishing|via=Google Books}}</ref> *Denmark: 1994<ref>{{cite web|url=http://mst.dk/borger/luftforurening/biler-busser-og-andre-koeretoejer/regulering-af-braendstoffer/|title=Regulering af brændstoffer|language=Danish|access-date=2016-03-13}}</ref> *[[European Union|EU]]: 1 January 2000 (Member states which had not already withdrawn it from sale. Earlier regulation had prevented the sale or production of cars using leaded petrol after 1992) *France: 2000<ref>{{cite book|url=https://books.google.pl/books?id=OYbVAgAAQBAJ&pg=PA98&dq=oecd+environmental+performance+reviews+france+leaded&hl=pl&sa=X&ved=0ahUKEwilt-KqipTLAhVlMJoKHdOMBMoQ6AEIJTAA#v=onepage&q=leaded%20petrol&f=false|title=OECD Environmental Performance Reviews OECD Environmental Performance ...|publisher=}}</ref> *Germany: 1988 *Greece: 2002<ref>{{cite book|url=https://books.google.com/books?id=hWt0uW_a2GIC|title=OECD Environmental Performance Reviews OECD Environmental Performance Reviews: Greece 2009|first=|last=OECD|date=15 March 2010|publisher=OECD Publishing|via=Google Books}}</ref> *Hungary: 1999 *Ireland: 1 January 2000 *Italy: 1 January 2002<ref>{{cite book|url=https://books.google.com/books?id=Q4bYAgAAQBAJ|title=OECD Environmental Performance Reviews OECD Environmental Performance Reviews: Italy 2002|first=|last=OECD|date=29 January 2003|publisher=OECD Publishing|via=Google Books}}</ref> *Monaco: 2000 *Netherlands: 1998<ref>{{cite book|url=https://books.google.pl/books?id=G1rWAgAAQBAJ&pg=PA207&dq=oecd+environmental+performance+reviews+norway+leaded&hl=pl&sa=X&ved=0ahUKEwjq8eaWiZTLAhWkO5oKHXgiBN0Q6AEIOzAE#v=onepage&q=187&f=false|title=OECD Environmental Performance Reviews OECD Environmental Performance ...|publisher=}}</ref> *Norway: 1988 *Poland: 2005 *Slovenia: 2001<ref>{{cite book|url=https://books.google.com/books?id=FOrUeREpU5IC|title=OECD Environmental Performance Reviews OECD Environmental Performance Reviews: Slovenia 2012|first=|last=OECD|date=6 June 2012|publisher=OECD Publishing|via=Google Books}}</ref> *Spain: 2001<ref>{{cite web|url=http://www.minetur.gob.es/energia/petroleo/Carburantes/Paginas/informacion.aspx|title=Prohibición de la venta de gasolina con plomo - El Petróleo - Energía - Mº de Industria, Energía y Turismo|publisher=}}</ref> *Portugal: 1999 *Romania: 2005<ref>{{cite news |publisher= [[Evenimentul Zilei]] |url= http://www.evz.ro/detalii/stiri/dispare-benzina-cu-plumb-657363.html |title= ''Dispare benzina cu plumb'' |date= 27 July 2004}}</ref> *Russia: 2002<ref>{{cite web|url=http://www.lawrussia.ru/texts/legal_149/doc149a777x242.htm|title=Постановление ГД ФС РФ от 15.11.2002 N 3302-III ГД "О проекте Федерального закона N 209067-3 "Об ограничении оборота этилированного бензина в Российской Федерации"|archiveurl=http://www.webcitation.org/6DR9WXtsJ|archivedate=5 January 2013}}</ref> *Serbia: 2010 *Sweden: 1992 *Switzerland: 2000 *Turkey: 2006 *Ukraine: 2003 {{Col-break}} ;North America *Canada: 1993 *USA: 1996 **California: 1992 *Bahamas: *Belize: *Bermuda: *Costa Rica: *Dominican Republic: *El Salvador: *Guatemala: *Haiti: *Honduras: *Mexico: 1998 *Nicaragua: *Puerto Rico: 1 January 1996 (USA) *Trinidad and Tobago: 2000 {{Col-break}} ;South America *Argentina: 1998 *Bolivia: *Brazil: 1989 *Chile: 2001<ref>{{cite web|title=ENAP dejará de distribuir gasolina con plomo el sabado|url=http://www.emol.com/noticias/economia/2001/03/26/50211/enap-dejara-de-distribuir-gasolina-con-plomo-el-sabado.html|accessdate=1 August 2014}}</ref> *Colombia: 1991<ref>{{cite news |publisher= [[El Tiempo (Colombia)|El Tiempo]] |url= http://www.eltiempo.com/archivo/documento/MAM-615546 |title= ''La gasolina no tiene plomo'' |author=Gabriel Reyes Aldana |date= 10 July 1997}}</ref> *Peru: 2004 *Venezuela: 2005 {{Col-break}} ;Asia *Japan: 1986 *Hong Kong: 1999 *Malaysia: 2000 *Singapore: 1998 *South Korea: 1993 *Sri Lanka: 1999 *Thailand: 1996 *Bangladesh: *Taiwan: 2000 *China: 2000 *Philippines: 2000 *India: March 2000<ref name="blogs.wsj.com">{{cite web|last1=Venkatesh|first1=Thuppil|title=A Surprising Source of Lead Poisoning: India’s Idols|url=http://blogs.wsj.com/indiarealtime/2015/06/04/an-unlikely-source-of-lead-poisoning-indias-idols/|website=WSJ|accessdate=18 April 2016}}</ref> *Iran: 2003 *Nepal: 2000 *Pakistan: 2001<ref>{{cite journal|title=Status of children’s blood lead levels in Pakistan: implications for research and policy| pmc=2494596 | pmid=18359052|doi=10.1016/j.puhe.2007.08.012|volume=122|year=2008|pages=708–15 | author = Kadir MM, Janjua NZ, Kristensen S, Fatmi Z, Sathiakumar N| journal=Public Health}}</ref> *Indonesia: 2006 {{Col-break}} ;'''Oceania''' *Australia: 2002<ref>{{cite news|url=http://www.ens-newswire.com/ens/jul2004/2004-07-26-04.asp|title=Australia Cuts Sulfur Content in Transport Fuels|first=|last=staff|publisher=}}</ref> *New Zealand: 1996 *Guam: 1 January 1996 (USA) {{col-end}} ===== Africa ===== Leaded petrol was supposed to be completely phased out continent-wide on 1 January 2006, following a ban initiated from the 2002 Earth Summit.<ref>{{cite news |publisher= [[The Independent]] |url= http://www.independent.co.uk/environment/un-hails-green-triumph-as-leaded-petrol-is-banned-throughout-africa-521255.html |title= UN hails green triumph as leaded petrol is banned throughout Africa |author= Geoffrey Lean |date = 1 January 2006}}</ref> However, in Algeria refineries needed to be altered; as a result, leaded fuel remains available in parts of [[Algeria]],<ref name=leadgroup/> with phaseout scheduled for 2015.<ref>{{cite news | url=http://www.downtoearth.org.in/content/africa-adopts-continent-wide-sustainable-transport-agenda | title=Africa adopts continent-wide sustainable transport agenda}}</ref> ====In race vehicles==== Leaded fuel was commonly used in professional [[auto racing]], until its phase out beginning in the 1990s. Since 1993, [[Formula One]] racing cars have been required to use normal unleaded ''super'' petrol compliant with EU standards—the same petrol provided by ordinary petrol stations.<ref>{{cite web|url=http://www.f1technical.net/articles/19|title=Fuel|publisher=}}</ref> [[NASCAR]] began experimentation in 1998 with an unleaded fuel, and in 2006 began switching the national series to unleaded fuel, completing the transition at the [[2007 Auto Club 500|Fontana round in February 2007]] when the premier class switched. This was influenced after blood tests of NASCAR teams revealed elevated blood lead levels.<ref>{{cite journal |last1= O'Neil |pmid= 16361219 |first1= J |year= 2006 |pages= 67–71 |issue= 2 |last2= Steele |volume= 3 |journal= Journal of occupational and environmental hygiene |first2= G |last3= McNair |first3= CS |last4= Matusiak |first4= MM |last5= Madlem |first5= J |title= Blood lead levels in NASCAR Nextel Cup Teams |doi= 10.1080/15459620500471221}}</ref><ref>{{cite web |url= http://nascar.about.com/od/cars/a/unleaded08.htm |title= NASCAR to Use Unleaded Fuel in 2008}}</ref> ====Aviation gasoline==== {{main|Avgas}} TEL remains an ingredient of 100 [[octane rating|octane]] [[avgas]] for piston-engine aircraft. The current formulation of 100LL (low lead, blue) aviation gasoline contains 2.12 grams of TEL per gallon, half the amount of the previous 100/130 (green) octane avgas (at 4.24 grams per gallon),<ref>{{cite web |url= http://www.aopa.org/whatsnew/regulatory/reglead.html |title= Issues Related to Lead in Avgas |publisher= Aircraft Owners and Pilots Association}}</ref> but only slightly less than the 2.2 grams per gallon historically permitted in automotive leaded gasoline and substantially greater than the allowed 0.001 grams per gallon in automotive unleaded gasoline sold in the United States today.<ref>{{cite web |url= http://www.autofuelstc.com/autofuelstc/pa/Information.html |title= Modifications / Octane / Lead Content / Fuel Specs / Limitations / Certification | publisher = Petersen Aviation Inc}}</ref> 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.<ref>{{cite news |url=http://www.runwaygirlnetwork.com/2014/07/30/us-leads-avgas-effort-for-lead-free-air/ |title=US leads Avgas effort for lead-free air |last1=Bryan |first1=Chelsea |date=30 July 2014 |website=www.runwaygirlnetwork.com |publisher=Kirby Media Group |accessdate=31 July 2014}}</ref> ====Alternative antiknock agents==== Antiknock agents are classed as ''high-percentage'' additives, such as alcohol, and ''low-percentage'' additives based on [[Heavy metal (chemistry)|heavy 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]], an [[Organometallic chemistry|organometallic]] compound of [[iron]], is also used as an antiknock agent although with some significant drawbacks.<ref>[http://www.osd.org.tr/14.pdf Application of fuel additives]</ref> High-percentage additives are [[organic compound]]s that do not contain metals, but require much higher blending ratios, such as 20–30% for [[benzene]] and [[ethanol]]. It had been established by 1921 that ethanol was an effective antiknock agent, but TEL was introduced instead mainly for commercial reasons.<ref name="Kitman"/> [[Oxygenate]]s such as [[tert-Amyl methyl ether|TAME]] derived from natural gas, [[MTBE]] made from methanol, and ethanol-derived [[ETBE]], 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]] and [[alkylate]] are examples of such blending stocks. Benzene and other high-octane [[Aromatic hydrocarbon|aromatics]] can be also blended to raise the octane number, but they are disfavored today because of toxicity and carcinogenicity. ==Formulation of ethyl fluid== [[File:EthylCorporationSign.jpg|thumb|upright|Sign on an antique gasoline pump advertising tetraethyllead by the Ethyl Corporation]] TEL was supplied for mixing with raw gasoline in the form of '''ethyl fluid''', which was TEL blended with the lead scavengers [[1,2-Dibromoethane|1,2-dibromoethane]] and [[1,2-Dichloroethane|1,2-dichloroethane]]. 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 yet developed, 17 workers for the Ethyl Corporation, DuPont, and Standard Oil died from the effects of exposure to lead.<ref name=Kovarik2005 /> The formula for ethyl fluid is:<ref name="Seyferth" /> * Tetraethyllead 61.45% * [[1,2-Dibromoethane]] 17.85% * [[1,2-Dichloroethane]] 18.80% * Inerts & dye 1.90% Dibromoethane and dichloroethane act in a synergistic manner, where a particular mixing ratio provides the best lead scavenging ability.<ref name="Seyferth"/> ==Toxicity== Lead pollution from engine exhaust is dispersed into the air and into the vicinity of roads and easily inhaled. Contact with concentrated TEL leads to acute [[lead poisoning]]. Lead is a [[toxic metal]] that accumulates in the body and is associated with subtle and insidious [[neurotoxic]] effects especially at low exposure levels, such as low IQ and antisocial behavior.<ref>{{Cite web |url=http://www.rachel.org/files/document/Bone_Lead_Levels_and_Delinquent_Behavior.pdf |title=Bone Lead Levels and Delinquent Behavior |author=Julie A. Reiss |date=7 February 1996 |accessdate=19 March 2013}}</ref><ref>{{Cite web |url=http://dx.doi.org/10.1016/S0892-0362(01)00184-2 |title=Early exposure to lead and juvenile delinquency |author=Kim N. Dietrich |date=November–December 2001 |accessdate=19 March 2013}}</ref><ref>{{Cite web |url=http://dx.doi.org/10.1016/S0165-0173(98)00011-3 |title=Low-level lead-induced neurotoxicity in children: an update on central nervous system effects |author=Yoram Finkelstein|date=July 1998 |accessdate=19 March 2013}}</ref> It has particularly harmful effects on children. These concerns 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 μみゅーg/dL in 1976 to only 3 μみゅーg/dL in 1991.<ref name="Reyes" /> The US Centers for Disease Control considered blood lead levels "elevated" when they were above 10 μみゅーg/dL. Lead exposure affects the [[intelligence quotient]] (IQ) such that a blood lead level of 30 μみゅーg/dL is associated with a 6.9-point reduction of IQ, with most reduction (3.9 points) occurring below 10 μみゅーg/dL.<ref name="Lanphear 2005">{{Cite journal | last1 = Lanphear | first1 = B. P. | last2 = Hornung | first2 = R. | last3 = Khoury | first3 = J. | last4 = Yolton | first4 = K. | last5 = Baghurst | first5 = P. | last6 = Bellinger | first6 = D. C. | last7 = Canfield | first7 = R. L. | last8 = Dietrich | first8 = K. N. | last9 = Bornschein | first9 = R. | last10 = Greene | doi = 10.1289/ehp.7688 | first10 = T. | last11 = Rothenberg | first11 = S. J. | last12 = Needleman | first12 = H. L. | last13 = Schnaas | first13 = L. | last14 = Wasserman | first14 = G. | last15 = Graziano | first15 = J. | last16 = Roberts | first16 = R. | title = Low-Level Environmental Lead Exposure and Children's Intellectual Function: An International Pooled Analysis | journal = Environmental Health Perspectives | volume = 113 | issue = 7 | pages = 894–899 | year = 2005 | pmid = 16002379| pmc =1257652 }}</ref> Reduction in the average blood lead level is believed to have been a major cause for falling violent crime rates in the United States<ref name="WashingtonPostCrime">{{cite web | url=http://www.washingtonpost.com/blogs/wonkblog/wp/2013/04/22/lead-abatement-alcohol-taxes-and-10-other-ways-to-reduce-the-crime-rate-without-annoying-the-nra/ | title=Lead abatement, alcohol taxes and 10 other ways to reduce the crime rate without annoying the NRA | publisher=Washington Post | date=22 April 2013 | accessdate=23 May 2013 | author=Matthews, Dylan}}</ref> and South Africa.<ref name="BusinessDayCrime">{{cite web | url=http://www.bdlive.co.za/opinion/columnists/2013/01/22/ban-on-lead-may-yet-give-us-respite-from-crime | title=Ban on lead may yet give us respite from crime | publisher=Business Day | date=22 January 2013 | accessdate=23 May 2013 | author=Marrs, Dave}}</ref> 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 up to a 56% decline in crime from 1992 to 2002.<ref>{{cite web|url=http://www.chicagotribune.com/news/watchdog/ct-lead-poisoning-science-met-20150605-story.html|title=Lead poisoning linked to violent crime - Chicago Tribune|author=Chicago Tribune|date=6 June 2015|work=chicagotribune.com}}</ref> Including other factors that are believed to have increased crime rates over that period Reyes found that this led to an actual decline of 34% over that period.<ref name="AmherstCrime">{{cite web | url=http://www3.amherst.edu/~jwreyes/papers/LeadCrimeNBERWP13097.pdf | title=ENVIRONMENTAL POLICY AS SOCIAL POLICY? THE IMPACT OF CHILDHOOD LEAD EXPOSURE ON CRIME | publisher=NATIONAL BUREAU OF ECONOMIC RESEARCH | date=May 2007 | accessdate=23 May 2013 | author=Wolpaw Reyes, Jessica}}</ref> A statistically significant correlation has been found between the usage rate of leaded gasoline and violent crime: taking into account a 22-year time lag, the violent crime curve virtually tracks the lead exposure curve.<ref name="Reyes">Reyes, J. W. (2007). [http://www.amherst.edu/~jwreyes/papers/LeadCrimeNBERWP13097.pdf "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.</ref><ref>{{cite web|url=http://www.independent.co.uk/environment/green-living/ban-on-leaded-petrol-has-cut-crime-rates-around-the-world-398151.html|title=Ban on leaded petrol 'has cut crime rates around the world'|author=Geoffrey Lean, Environment Editor|date=27 October 2007|work=The Independent}}</ref> After the ban on TEL, blood lead levels in US children dramatically decreased.<ref name="Reyes" /> Although leaded gasoline is largely gone in North America, it has left high concentrations of lead in the soil adjacent to roads that were constructed prior to its phaseout. Children are particularly at risk if they consume this.<ref>{{Cite web |url=http://www.motherjones.com/environment/2013/01/lead-crime-link-gasoline |title=America's Real Criminal Element: Lead |author=Kevin Drum |work=[[Mother Jones (magazine)|Mother Jones]] |date=January–February 2013 |accessdate=4 January 2013 }}</ref> ==History== In 1853, German chemist [[Carl Jacob Löwig|Karl Jacob Löwig]] (1803–1890) first prepared what he claimed was Pb₂(C₂H₅)₃ from [[ethyl iodide]] and an alloy of lead and sodium.<ref>Löwig (1853) [https://books.google.com/books?id=14M8AAAAIAAJ&pg=RA1-PA318#v=onepage&q&f=false "''Ueber Methplumbäthyl''"] (On meta-lead ethyl) ''Annalen der Chemie und Pharmacie'', '''88''' : 318-322.</ref> In 1859, English chemist [[George Bowdler Buckton]] (1818–1905) reported what he claimed was Pb(C₂H₅)₂ from [[zinc ethyl]] (Zn(C₂H₅)₂) and [[lead(II) chloride]].<ref>George Bowdler Buckton (1859) [http://www.jstor.org/stable/111509?seq=1 "Further remarks on the organo-metallic radicals, and observations more particularly directed to the isolation of mercuric, plumbic, and stannic ethyl,"] ''Proceedings of the Royal Society of London'', '''9''' : 309-316. For Buckton's preparation of tetraethyl lead, see pages 312-314.</ref> Later authors credit both methods of preparation with producing tetraethyl lead.<ref>See, for example: * H. E. Roscoe and C. Schorlemmer, ''A Treatise on Chemistry'', Volume 3, Part 1 (New York, New York: D. Appleton and Co., 1890), [https://books.google.com/books?id=zs0cAQAAIAAJ&pg=PA466#v=onepage&q&f=false page 466]. * Frankland and Lawrence credit Buckton with synthesizing tetraethyl lead in: E. Frankland and Awbrey Lawrance (1879) "On plumbic tetrethide," ''Journal of the Chemical Society, Transactions'', '''35''' : 244-249.</ref> ===History of TEL in fuels=== Regardless of the details of the chemical discoveries, tetraethyl lead remained unimportant commercially until the 1920s.<ref name="Kitman">Kitman, J. (2 March 2000). [http://www.thenation.com/article/secret-history-lead?page=full "The Secret History of Lead."] ''[[The Nation]]''. Retrieved 17 August 2009.</ref> In 1921, at the direction of Dupont Corporation which manufactured TEL, it was found to be an effective antiknock agent by [[Thomas Midgley, Jr.|Thomas Midgley]], working under [[Charles Kettering]] at [[General Motors Corporation]] Research.<ref>"Leaded Gasoline, Safe Refrigeration, and Thomas Midgley, Jr." Chapter 6 in S. Bertsch McGrayne. ''Prometheans in the Lab''. McGraw-Hill: New York, 2002. ISBN 0-07-140795-2</ref> General Motors [[patent]]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".<ref name="Kitman"/> Early research into "[[engine knocking]]" (also called "pinging" or "pinking") was also led by A.H. Gibson and [[Harry Ricardo]] in England and Thomas Boyd in the United States. The discovery that [[lead]] additives modified this behavior led to the widespread adoption of their use in the 1920s, and therefore more powerful, higher compression engines.<ref name=Kovarik2005>{{cite journal |author=Kovarik W |title=Ethyl-leaded gasoline: how a classic occupational disease became an international public health disaster |journal=Int J Occup Environ Health |volume=11 |issue=4 |pages=384–97 |year=2005 |pmid=16350473 |doi= 10.1179/oeh.2005.11.4.384|url=http://www.radford.edu/~wkovarik/ethylwar/IJOEH.pdf}}</ref> In 1924, [[Standard Oil of New Jersey]] (ESSO/EXXON) and General Motors created the [[Ethyl Corporation|Ethyl Gasoline Corporation]] to produce and market TEL. Deepwater, NJ across the river from Wilmington, was the site for production of some of DuPont's most important chemicals, particularly tetraethyl lead (TEL). After TEL production at the [[Bayway Refinery]] 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.<ref>{{cite web|url=http://www2.dupont.com/Phoenix_Heritage/en_US/1914_a_detail.html|title=Innovation Starts Here - DuPont USA|author=zk4540|publisher=}}</ref> ===History of controversy and phase-out=== {{seealso|Lead and crime hypothesis}} 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]]. In 1924, a public controversy arose over the "loony gas," after at least 17 workers died, and many others were severely injured, in Standard and DuPont 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]] and [[Yandell Henderson]], engaged Midgley and Kettering with letters warning of the dangers to public health.<ref name=Kovarik2005/> After the death of the workers, dozens of newspapers reported on the issue.<ref>{{cite web|url=http://yarchive.net/chem/tetraethyl_lead.html|title=Tetraethyl lead(Bruce Hamilton)|publisher=}}</ref> ''The New York Times'' editorialized in 1924 that the deaths should not interfere with the production of more powerful fuel.<ref name=Kovarik2005 /> To settle the issue, the [[U.S. Public Health Service]] conducted a conference in 1925, and the sales of TEL were voluntarily suspended for one year to conduct a hazard assessment.<ref name="Seyferth" /><ref name="Kitman"/><ref>Alan P. Loeb, "Paradigms Lost: A Case Study Analysis of Models of Corporate Responsibility for the Environment," Business and Economic History, Vol. 28, No. 2, Winter 1999, at 95.</ref> 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.<ref name=Kovarik2005/> The low concentrations present in gasoline and exhaust were not perceived as immediately dangerous. A [[U.S. Surgeon General]] 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.<ref name="Kitman"/> 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 he was threatened with a lawsuit and the research ended.<ref name=Kovarik2005/> In the late 1920s, [[Robert A. Kehoe]] of the [[University of Cincinnati]] 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 Cameron Patterson|Clair Patterson]]'s work on human lead burdens (see below) and other studies.<ref name="Kitman"/> In 1928, Dr. Kehoe expressed the opinion that there was no basis for concluding that leaded fuels posed any health threat.<ref name="Kitman" /> He convinced the [[Hugh S. Cumming|Surgeon General]] that the [[dose–response relationship]] of lead was "no effect" below a certain threshold.<ref>Bryson, Christopher (2004). ''The Fluoride Deception'', p. 41. Seven Stories Press. Citing historian Lynne Snyder.</ref> 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]]. 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]] 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]]. 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 opponents of its use.<ref>{{ cite book | author = Bryson, B. | year = 2003 | chapter = 10. Getting the Lead Out | title = A Short History of Nearly Everything | publisher = Broadway Books | location = New York | isbn = 0-7679-0818-X }}</ref> In the 1960s, the first clinical works were published proving the toxicity of this compound in humans, e.g. by [[Mirosław Jan Stasik]].<ref>{{ cite journal |author1=Stasik, M. |author2=Byczkowska, Z. |author3=Szendzikowski, S. |author4=Fiedorczuk, Z. | title = Acute Tetraethyllead Poisoning | journal = Arch. Toxikol. | year = 1969 | volume = 24 | issue = 4 | pages = 283–291 | doi = 10.1007/BF00577576 }}</ref> 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.<ref name=Kovarik2005/> Needleman also wrote the average US child's blood lead level was 13.7 μみゅーg/dl in 1976 and that Patterson believed that everyone was to some degree poisoned by TEL in gasoline.<ref name="Needleman1999">{{Cite journal | doi = 10.1006/enrs.2000.4069| pmid = 10991779| title = The Removal of Lead from Gasoline: Historical and Personal Reflections| journal = Environmental Research| volume = 84| issue = 1| pages = 20–35| year = 2000| last1 = Needleman | first1 = H. }}</ref> 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 dismissed,<ref name=Kovarik2005/> the EPA won the case on appeal, so the TEL phasedown began to be implemented in 1976. 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.<ref>{{cite web |url=http://yosemite.epa.gov/ee/epa/eed.nsf/fa6512c6e51c4a208525766200639df2/df94392f72ebb26085257746000aff52!OpenDocument |title=Lead Credit Trading |author=<!--Staff writer(s); no by-line.--> |date=c. 2006 |website=National Center for Environmental Economics |publisher=US EPA |accessdate=3 October 2014}}</ref> Then 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.<ref>{{cite journal |author1=Pirkle, J. L. |author2=Brody, D. J. |author3=Gunter, E. W. | title = The Decline in Blood Lead Levels in the United States: The National Health and Nutrition Examination Surveys (NHANES) |journal= [[JAMA (journal)|JAMA]] |year= 1994 |volume= 272 |pages= 284–291 |doi= 10.1001/jama.1994.03520040046039 |issue= 4|display-authors=etal}}</ref> The U.S. phasedown regulations also were due in great part to studies conducted by [[Philip J. Landrigan]]. In 1995, leaded fuel accounted for only 0.6% of total gasoline sales and less than 2000 [[short tons]] (1814 t) of lead per year. 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. Thus, what had begun in the U.S. as a phasedown ultimately ended in a phase-out. Similar bans in other countries have resulted in lowering levels of lead in people's [[blood]]streams.<ref>{{Cite journal| title = Blood Lead Secular Trend in a Cohort of Children in Mexico City (1987–2002) | author = Lourdes Schnaas, Stephen J. Rothenberg, María-Fernanda Flores, Sandra Martínez, Carmen Hernández, Erica Osorio,1 and Estela Perroni | journal = [[Environ. Health Perspect.]] | year = 2004 | volume = 112 | issue = 10 | pages = 1110–1115 | doi = 10.1289/ehp.6636 | pmid = 15238286 | pmc = 1247386 }}</ref><ref>{{Cite journal| journal = [[Archives of Environmental Health]] | volume = 59 | issue = 4 | year = 2004 | pages = 182–187 | doi = 10.3200/AEOH.59.4.182-187 | title = Rapid Drop in Infant Blood Lead Levels during the Transition to Unleaded Gasoline Use in Santiago, Chile | author = Paulina Pino, Tomás Walter; Manuel J. Oyarzún A3, Matthew J. Burden; Betsy Lozoff}}</ref> 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.<ref>Valerie Franchi, "Getting the Lead Out," ''Front Lines'', published by the U.S. Agency for International Development, Oct. 1997.</ref> 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.<ref name="Kitman"/> Leaded gasoline was withdrawn entirely from the European Union market on 1 January 2000, although it had been banned much earlier in most member states. Other countries also phased out TEL.<ref name=meca2003>{{cite web|url=http://www.meca.org/galleries/default-file/lead0103_%28final%29.pdf |title=The Case for Banning Lead in Gasoline |date=January 2003 |publisher=Manufacturers of Emission Controls Association (MECA) |accessdate=7 June 2012}}</ref> [[India]] banned leaded petrol in March 2000.<ref name="blogs.wsj.com"/> 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.<ref>{{cite web|url=http://www.un.org/apps/news/story.asp?NewsID=40226&Cr=pollutant&Cr1=#.UZdkooJAsR4 |title=Phase-out of leaded petrol brings huge health and cost benefits |date=27 October 2011}}</ref><ref>{{cite web| url= http://www.unep.org/transport/pcfv/PDF/Hatfield_Global_Benefits_Unleaded.pdf|vauthors=Tsai PL, Hatfield TH |title=Global Benefits From the Phaseout of Leaded Fuel| journal=Journal of Environmental Health |volume=74 |number=5 |pages=8–14 |date=December 2011| pmid=}}</ref> The announcement was slightly premature, as a few countries still have leaded gasoline for sale as of 2013 (see above). ==See also== {{Portal|Chemistry}} * [[Elmer Keiser Bolton#World War I and E.I. du Pont de Nemours and Company|Elmer Keiser Bolton]] * [[Ethyl Corporation]] * [[Lead]] ** [[Ethyl tert-butyl ether]] (ETBE) ** [[Lead abatement]] ** [[Lead and crime hypothesis]] ** [[Methyl tert-butyl ether]] (MTBE) ** [[Organolead chemistry]] ** [[Poisoning from lead]] ** [[Tert-Amyl methyl ether]] (TAME) * [[List of petrol additives]] ==References== {{Reflist|30em}} ==External links== *U.S. Gov't, National Institute for Occupational Safety and Health. [http://www.cdc.gov/niosh/npg/npgd0601.html NIOSH Pocket Guide to Chemical Hazards] *Kovarik, Bill (1999). [http://www.radford.edu/~wkovarik/papers/kettering.html Charles F. Kettering and the 1921 Discovery of Tetraethyl Lead] *[http://www.aopa.org/whatsnew/regulatory/regunlead.html True unleaded alternative for 100LL needed for general aviation] {{Motor fuel}} [[Category:Organolead compounds]] [[Category:Antiknock agents]]'