The Rise And Fall Of Organometallic Additives In Automotive Gasoline

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Environmental Forensics, 11:17–49, 2010
C Taylor & Francis Group, LLC
Copyright !
ISSN: 1527–5922 print / 1527–5930 online
DOI: 10.1080/15275920903346794
The Rise and Fall of Organometallic Additives in Automotive
Gasoline
Gil Oudijk
Triassic Technology, Inc., Hopewell, NJ, USA
Downloaded By: [Oudijk, Gil] At: 22:54 17 March 2010
Refiners have used numerous gasoline additives since the 1920s to increase automotive performance and correct deficiencies. The
history of organometallic additives, in particular lead-, manganese- and iron-containing compounds is discussed. Some of these
additives can be helpful to environmental investigators for fingerprinting and age-dating leaded-gasoline releases. Knowing their
history, investigators can decipher these releases more efficiently.
Keywords: age-dating techniques, cymantrene, environmental litigation, Ethyl Corporation, ethylene dibromide (EDB), ethylene
dichloride (EDC), ferrocene, fingerprinting techniques, gasoline, gasoline additives, groundwater contamination, iron
carbonyl, leaded gasoline, methyl cyclopentadienyl manganese tricarbonyl (MMT), mixed leads, tetraethyl lead (TEL),
tetramethyl lead (TML), unleaded gasoline
By 1920, gasoline was the favorite automotive fuel, but as the
compression ratios of automotive engines increased, knocking
became prevalent. The compression ratio is the piston displacement plus clearance volume, divided by the clearance volume
(Owen and Coley, 1995). A higher ratio will impart greater
power to the engine (Cramer and Campbell, 1949). Today, ratios can be higher than 11:1, whereas in the 1920s ratios were
closer to 4:1. Knocking is the premature detonation of fuel in the
pistons and heard as a ping or knock, causing power loss, overheating, poor fuel economy, and possible engine damage (Ethyl
Corporation, 1957). Because of this handicap, gasoline-powered
engines could not fulfill their potential. Additives, in particular the organometallics, were developed to alleviate knocking
(Kettering, 1919; Walsh, 1954).
Gasoline additives are compounds introduced into gasoline
after refining to improve automotive performance or correct
deficiencies (Gibbs, 1990). Use of additives began commercially
in 1923, and, in the following 90 years, many varieties were
developed. An important use for additives is reducing engine
knock, and, for more than 70 years, organometallics were the
additives of choice.
For environmental investigators, additives can help fingerprint and date gasoline releases. The type of additives present,
their environmental distribution, and their concentration can often help investigators date or fingerprint leaded-gasoline spills,
thereby identifying potential responsible parties. Many articles
exist detailing these additives and their history (Kaplan, 2003;
Received 1 May 2009; accepted 1 October 2009
Address correspondence to Gil Oudijk, Triassic Technology, Inc., 57 Hamilton Avenue, Hopewell, NJ 08525. E-mail:
[email protected]
Kaplan et al., 1997; Morrison, 2000a; Morrison, 2000b; Oudijk,
2005, 2006; Galperin and Kaplan, 2008); however, none provide
a comprehensive historical overview. This article provides a historical description of organometallic additives and their associated scavengers; their usage time frames, and details on their
phase-out. It is not intended to be a guide for the forensic investigation of leaded-gasoline releases; however, such information
is commonly helpful in environmental litigation.
In this article, the use of organometallic additives in the
United States (US) is emphasized; however, some information on international usage is included. Dates of introduction
of leaded and unleaded gasoline—different and diverse octane
grades or types of gasoline—are based on corporate histories,
trade journal articles, newspaper accounts, oil-company and
chemical-manufacturer advertisements and collectibles with
known time frames. The oil companies discussed in this article
are described in Table 1.
The Tetraethyl Lead-Based Additives
General Motors’ Discovery of Tetraethyl Lead
Octane rating is a measure of a gasoline’s resistance to detonation in the spark-ignition engine (knocking) and is reported
in terms of octane numbers (Gibbs, 1993). The octane scale
is arbitrary and two ratings are used: research octane number
(RON) and motor octane number (MON). RON was developed
in 1927 and MON in 1932 (Hamilton and Falkiner, 2003). The
antiknock index (AKI) used in the US since 1971 is defined as
the average of RON and MON or (R+M/2)(Gibbs, 1990).
General Motors (GM, Detroit, MI) developed tetraethyl lead
(TEL) as an anti-knock agent in 1921 (Sloan Jr., 1963). GM
had tested organic formulations of iron, tin, bismuth, arsenic,
17
18
Oudijk
Table 1. The oil companies discussed in this article that sold leaded gasoline, their former names and their present owner
Company
Amoco
Anglo-American (UK)
Arco
Ashland
Associated
Atlantic
Atlantic-Union (AUS)
Beacon
BP (UK)
British-American (CAN)
California Standard
Canadian (CAN)
Chevron
Cities Service
Citgo
Clark
Commonwealth (AUS)
Conoco
Enarco
Exxon
Fleet-Wing
Getty
Gulf
Hess
Humble
Imperial (CAN)
Indiana Standard
Irving (CAN)
Jersey Standard
Kentucky Standard
Kerr-McGee
Leonard
Louisiana Standard
Marathon
McColl-Frontenac (CAN)
Mobil
Murphy
Nebraska Standard
New York Standard
Ohio Standard
Pemex (MX)
Pennsylvania Standard
Pennzoil
Phillips
Powerine
Pure
Quaker State
Refiners
Richfield
Description
See Indiana Standard
Known as the Anglo-American Oil Company, Jersey Standard’s affiliate in the UK. Now known as Esso (as of 1951)
See Atlantic and Richfield
Known as the Ashland Oil & Refining Company. Merged with Marathon in 1998
Known as Associated Oil Company, acquired by Jersey Standard in 1931, acquired by J. Paul Getty in 1937. Merged
with Tide Water in 1938 becoming Tide Water–Associated Oil Company, used the Flying A and Tydol trademarks, and
now part of Chevron
Known as the Atlantic Refining Company, merged with Richfield in 1966 to become Arco and acquired by BP in 2000
Known as the Atlantic-Union Oil Company, a joint venture between Atlantic and Union in Australia
Also known as Beacon Oil Company, merged with Colonial Oil Company in 1928 to become Colonial Beacon Oil
Company and acquired by Jersey Standard in 1929
Formerly known as the Anglo-Persian Oil Company, Anglo-Iranian Oil Company (as of 1935), British Petroleum (as of
1954) and BPAmoco Corporation (as of 1999). Known as BP Corporation as of 2000
Known as the British-American Oil Company and acquired by Gulf in 1969
Known as the Standard Oil Company (California) or SoCal and later renamed Chevron (as of 1984)
Known as Canadian Oil Company, Ltd., purchased Enarco in 1908, independent in 1938, but purchased by Shell in 1963
See California Standard
Formerly known as Cities Service Company, known as the Citgo Petroleum Corporation as of 1965 and acquired by
Petróleos de Venezuela, SA (PDVSA) in 1990
See Cities Service
Known as Clark Oil & Refining Company and acquired by Premcor in 1999
Known as Commonwealth Oil Refineries or COR and acquired by BP in 1952
Known as Continental Oil Company and merged with Phillips in 2002
Known as National Refining Company and acquired by Ashland in 1950
See Jersey Standard
Known as Fleet-Wing Petroleum Corporation, previously known as the Spears & Riddle, purchased by Sohio in 1928,
but continued to operate Fleet-Wing branded filling stations. Acquired by Pennzoil in 1968
Known as Getty Oil Company, until 1956 known as Pacific Western Oil Company and purchased by Texaco in 1984.
Much of the remnants of Getty are now owned by Lukoil and Chevron
Known as Gulf Oil Company and acquired by California Standard in 1984
Known as Hess Corporation and prior to 2006 known as the Amerada-Hess Corporation
Known as Humble Oil & Refining Company. Jersey Standard owned a significant portion of the company since the
1920s. Humble was completely incorporated into Jersey Standard in 1972
Known as Imperial Oil Company and owned by Jersey Standard (now using the Esso trademark)
Known as Standard Oil Company (Indiana) or Stanolind. Later known as Amoco Corporation and merged with BP in
1999. Indiana Standard also incorporated companies such as American Oil Company (1954) and Pan American
Petroleum & Transport Company (1925). See BP
Known as Irving Oil Company
Previously known as Standard Oil Company (New Jersey) or Esso and renamed Exxon Corporation in 1972. Merged
with New York Standard in 1999 to form ExxonMobil Corporation
Known as Standard Oil Company (Kentucky) or Kyso and acquired by California Standard in 1961
Known as the Kerr-McGee Corporation, purchased Deep Rock Oil Corporation in 1955 and used the Deep Rock trade
mark. Acquired by Anadarko Petroleum Corporation in 1996
Known as the Leonard Refining Company and acquired by Total in 1971
Known as Standard Oil Company (Louisiana) or Stanola and completely acquired by Jersey Standard in around 1943
Formerly the Ohio Oil Company and then renamed Marathon Oil Corporation in 1962, merging with Ashland in 1998
becoming Marathon-Ashland Petroleum
Known as McColl-Frontenac Oil Company, used the Red Indian and Marathon trademarks and acquired by Texaco in
1941
See New York Standard
Known as the Murphy Oil Corporation
Known as Standard Oil Company (Nebraska) and acquired by Indiana Standard in 1939
Known as Standard Oil Company (New York) or Socony and merged with Vacuum Oil Company in 1931, becoming
Socony-Vacuum Oil Company and then changed name to Socony-Mobil Oil Company in 1955 and Mobil Oil Company
as of 1966. Mobil merged with Exxon in 1999 to become ExxonMobil Corporation
Known as Standard Oil Company (Ohio) or Sohio. Acquired completely by BP in 1987
Known as Petroléos de México, the Mexican national oil company
Known as Standard Oil Company (Pennsylvania) or Sopa. Acquired by Jersey Standard in the 1930s
Known as Pennzoil Company, merged with Quaker State in 1998 and acquired by Shell in 2002
Known as Phillips Petroleum Company and merged with Conoco in 2002 becoming Conoco-Phillips Corporation
Known as The Powerine Company, originally Denver Powerine Company (not to be confused with the Powerine Oil
Company of California) and purchased by Jersey Standard in 1945.
Known as Pure Oil Company, merging with Union in 1965
Known as Quaker State Oil Company and merged with Pennzoil in 1998
Known as Refiners Oil Company and sold to Ohio Standard in 1930
Known as Richfield Company, merged with Atlantic in 1966 to become Arco and acquired by BP in 2000
(Continued on next page)
Organometallic Additives
19
Table 1. The oil companies discussed in this article that sold leaded gasoline, their former names and their present owner (Continued)
Company
Shell (UK/NETH)
Sinclair
Skelly
Socony
Sohio
Spears & Riddle
Sterling
Sun
Supertest (CAN)
Texaco
Tide Water
Total (FR)
Union
Vacuum
Walburn
Description
Known as Royal Dutch Shell or the Shell Oil Company in the US
Known as Sinclair Oil Corporation, acquired by Arco in 1969 and spun off on its own in 1976
Known as Skelly Oil Company, merged with Getty in 1977, but gasoline production ceased in 1958
See New York Standard
See Ohio Standard
Known as Spears & Riddle Company of West Virginia, used the Fleet-Wing brand name and acquired by Ohio Standard
in 1928
Known as Sterling Oil Company and acquired by Quaker State in 1931. The Sterling brand continued until the 1960s
Known as Sun Oil Company and later renamed Sunoco
Known as Supertest Petroleum Corporation and acquired by BP in 1971
Known as The Texas Company and merged with Chevron in 2001
Known as Tide Water Oil Company and later acquired by Getty. Also see Associated
Formerly known as French Petroleum Company of Canada, but renamed Total Petroleum (North America) and originally
known as Compagnie Française des Pétroles or CFP and now Total-Elf-Fina. In 1997, Total sold its filling station
system to Ultramar Diamond Shamrock, who was purchased soon thereafter by Valero Energy Corporation
Known as Union Oil Company of California and acquired by Chevron in 2005
Known as Vacuum Oil Company and merged with New York Standard in 1931 becoming Socony-Vacuum Oil Company.
In 1966, the company took the name Mobil. See New York Standard
Known as Walburn Petroleum Corporation and acquired by Richfield in 1929. Walburn was the first company to offer a
leaded grade of gasoline in the New England region.
Data from: Giddens (1955); Beaton (1957); Spence (1962); Dixon (1967); Scott (1968); Larson et al. (1971); Jones (1972); Johnson (1983); Dedmon
(1984); Wall (1988); and Bamberg (1994). All companies are based out of the United States (US) unless otherwise noted; AUS, Australia; CAN,
Canada; FR, France; MX, Mexico; NETH, The Netherlands; UK, United Kingdom
telluride and selenium (plus iodine, ethanol and aniline); TEL
proved to be the most cost-effective (Seyferth, 2003). A patent
was applied for TEL in 1922 and approved in 1926 (Boyd, 1957;
Robert, 1983). In 1922, GM contracted DuPont to manufacture
TEL (Midgley, 1937).
GM assumed that TEL would be a temporary fix for gasoline (Kettering, 1945). Because it was believed that petroleum
supplies would be exhausted in the near future, the consensus
was that alcohol would become the automotive fuel of the future
(Anonymous, 1925; Kovarik, 2005).
In 1923, DuPont commenced research on efficient manufacture of TEL and began construction of a 1,300-lb-per-day plant
in Deepwater, New Jersey (Needleman, 2000) (Table 2). While
DuPont developed its production techniques, Jersey Standard
was looking at alternatives. An optimal technique, funded by
Jersey Standard, was developed by chemists at Clark University
in Massachusetts (Gibb and Knowlton, 1956). In 1924, Jersey
Standard and GM joined forces to form Ethyl Gasoline Corporation (Ethyl). Ethyl marketed the Ethyl Fluid (an additive
package containing TEL), while DuPont produced it (Robert,
1983).
Beginnings of Leaded Gasoline
Leaded gasoline was first sold at a Refiners Oil Company filling
station in Dayton, OH, on February 1, 1923 (Midgley, 2001). A
second station was added a few days later, and, in a few weeks,
leaded gasoline was being sold at filling stations in both Dayton
and Cincinnati (OH) (Young, 1961).
TEL was initially added to gasoline at the refinery (Gibbs,
1990). In 1921, GM considered equipping cars with one tank
containing TEL and a second with unblended gasoline. Later
in 1923, blending proceeded at filling-station dispensers with a
device known as an Ethylizer. This Ethylizer was a glass and
metal container with measuring equipment attached to deliver
the proper quantity of TEL required for the amount of gasoline
(Midgley, 2001). Between February 1 and August 1, 1923, Refiners Oil Company operated approximately 30 Ethylizers. From
September 1923 to February 1924, Refiners, Indiana Standard,
and Spears and Riddle operated approximately 500 Ethylizers
in the Midwest. From February to May 1924, approximately
12,000 Ethylizers were in use by Indiana Standard, Refiners
Oil Company, Jersey Standard, Gulf, Louisiana Standard, and
Spears and Riddle (Surgeon General of the US, 1925). Safety
precautions prompted a change in procedures later in 1924,
and TEL was added only at restricted blending facilities (Kovarik, 2005). Other refiners that reportedly used TEL in 1924
included Sinclair, Sun, and Gulf (Anonymous, 1924a; Farber,
2005).
The Spread of Tetraethyl Lead Across The United States
In September 1923, Indiana Standard obtained the first 5-year
contract from Ethyl for the Midwestern states; its leaded grade
became known as Red Crown Ethyl and the first station to offer
the grade was in Richmond, IN (Anonymous, 1923; Giddens,
1955). By July 1924, Indiana Standard’s leaded gasoline was
being sold as far west as North Dakota (Anonymous, 1924b).
Indiana Standard’s leaded grade in the 1920s could also be
known as Orange-American Gas (which was dyed orange) or
American Strate. Indiana Standard was the first oil company
to offer leaded gasoline on a wide scale. Their leaded grade
20
Oudijk
Table 2. Lead anti-knock manufacturing facilities of the world1
Company
GM Chemical
Jersey Standard
DuPont
Ethyl
IG Farben5
Sloi7
Octel/Innospec8
Oblaider Co. Ltd
PPG/Houston Chemical
Nalco
Mexican Government
Tetraétilo de Mexico13
OAO Sintez14
TDS Chemical
Japanese Government15
1 Based
Location
Duration of production
Dayton, Ohio
Linden (Bayway), New Jersey
Deepwater, New Jersey3
Antioch, California
Maitland, Ontario
Baton Rouge, Louisiana
Pasadena, Texas
Orangeburg, South Carolina
Sarnia, Ontario
Pittsburg, California
Tokyo, Japan
Thessaloniki, Greece
Gatel, Germany
Frose, Germany
St. Nazaire, France
Trento, Italy
Port Ellesmere, England
Paimboeuf, France9
Port de Bouc, France
Bussi, Italy10
Doberitz, Germany
Beibesheim, Germany11
Doberitz, Germany12
Beaumont, Texas
Beaumont, Texas
Freeport, Texas
Mexico City, Mexico
Coatzacoalcos, Mexico
Mexico City, Mexico
Dzerzhinsk, Belarus
Usol’e Sibirskoe, Russia
Jiang Su, China
Koriyama, Japan
1923–1925
1924–1925
1924–1991
1955–1981
?–1985
1938–1985
1952–1980
1953 – ?
1957–1994
1958–?
1971–19714
1967–?
1936–1945
1939–1945
1940–1944
1934–1978
1936–Present
?–1996
?–?
? –1997
1996–2002
?–1996
?–1996
1961–1983
1961–?
1963–1985
1940– ∼1955
1960–1997
1955–?
1949–2003
1949–
?–Present
1941–1945
Estimated capacity2
Small
Small
100
(NA)
NA
230
NA
(now closed) NA
15
(now closed) NA
0
(now closed) NA
NA
NA
306
NA
NA
NA
(now closed) NA
NA
small
24
small
120
(now closed) NA
55
NA
26
(now closed) NA
8
(now closed) NA
NA
NA
on Robert (1983), Wakim et al. (1990) and the websites for the individual manufacturers.
millions of pounds except as noted.
3 Tetramethyl lead (TML) manufacturing occurred at the Deepwater plant from about 1960 to 1984 (Wakim et al., 1990).
4 The plant was constructed through a joint venture between Ethyl and Japan’s Toyo Soda Co. and Mitsui & Co. Because of the
impending lead phase-out in Japan, the plant was dismantled before it ever produced tetraethyl lead (TEL) (Anonymous, 1971d).
5 It is believed that the German plants shut down in late 1944 or early 1945 when invading troops arrived. I. G. Farben obtained
its TEL manufacturing technology through a joint venture with Jersey Standard before World War II (Anonymous, 1945).
6 In thousands of metric tons.
7 Sloi is the Societa Lavorazioni Organiche Inorganiche (Anonymous, 1961b). This plant is just east of Rome; Octel’s Italian plant
was located between Venice and Milan.
8 Until 1961, Associated Octel was known as the Associated Ethyl Corporation and previously, as the Ethyl Export Corporation
(before 1938) (Robert, 1983). As of 2006, Octel is known as Innospec (available at: www.innospecinc.com).
9 Octel’s Paimboeuf facility in France may be the same plant where I. G. Farben produced TEL during World War II. It was known
after the war as Société Octel–Kuhlmann SA. It produced both TEL and TML. Much of the information concerning the European
plants is from Wakim et al. (1990) and Aftalion (2005).
10 Known as Societa Italiana Additivi per Carburanti SpA–SIAC. Produced both TEL and TML (Ruzzenenti, 2008)
11 Known as AK Chemie GmbH & Co. KG. Produced both TEL and TML (Wakim et al., 1990).
12 Octel purchased the Doberitz plant from the Oblaider Company Ltd. In 1996. Oboadler controlled three operating companies
that manufactured and sold lead antiknock compounds: Alcor Chemie AG, Alcor Chemie Vertriebs AG and Novoktan GmbH.
13 Originally a joint venture between Petroléos de México (Pemex) and DuPont and its plant was located close to Mexico City
(Robert, 1983).
14 It is possible that additional unknown TEL manufacturing facilities existed in the Soviet Union during World War II and possibly
afterwards.
15 TEL manufacturing was undertaken by an unknown company (possibly the Japanese military) in Koriyama, Japan (approximately130 miles north of Tokyo) during World War II. It is understood that there were significant difficulties associated with the
manufacturing process and numerous workers were killed. The plant was shut down after the war (Robert, 1983).
2 In
was later known as Solite Gasoline with Ethyl. Later in 1924,
Jersey Standard offered a leaded grade along the East Coast and
some southern states (Gibb and Knowlton, 1956). By June of
1924, Jersey Standard’s sales of leaded gasoline had reached
South Carolina (Anonymous, 1924c). In 1924 and 1925, Ethyl
Gasoline was sold in 25 states including New England, most of
the East Coast and the Midwest (Robert, 1983).
Within a few years, the trade name Ethyl Gasoline became
synonymous in the US with premium-grade. By the 1930s, most
filling stations offered two grades: Ethyl and Regular, while
some offered a third lower-octane unleaded gasoline known as
3rd Grade. The Regular was unleaded until at least 1933.
In May 1925, the Surgeon General suspended leadedgasoline sales throughout the US. The suspension was brought
about by the death of several TEL-manufacturing workers in
October 1924 at Jersey Standard‘s Bayway plant in Linden,
NJ. However, sales had already been suspended in New York
City, Philadelphia (PA), and New Jersey by local authorities
in October 1924. At Jersey Standard’s plant, seven men died
and 33 were hospitalized. At the DuPont plant at Deepwater,
NJ, 10 died. At GM’s plant in Moraine City, OH, at least two
more died and 40 were hospitalized (Kovarik, 2005). More than
80% of the TEL workers at these plants either died or survived
severely poisoned by exposure to TEL (Rosner and Markowitz,
1985). It was well known at the time that the manufacturing
of TEL was dangerous. In fact, workers at the Bayway plant
called the TEL “loony gas” because it inflicted hallucinations
and delusions of persecution (Kovarik, 1994). Furthermore, its
employees nicknamed DuPont’s TEL plant as the “House of
Butterflies” (Kovarik, 1994, p. 7).
The US Public Health Service (US PHS) and the US Bureau
of Mines subsequently investigated the health impacts of leaded
gasoline usage in a series of basic tests. They chiefly investigated
the acute impacts, not the chronic or “long-term” effects. The
US PHS decided that leaded gasoline was not a public-health
threat. The legitimacy of such studies would come into question
several decades later (Needleman, 1998, 2000; Kovarik, 2005).
However, the US PHS did acknowledge potential problems with
its studies stating that,
It remains possible that if the use of leaded gasoline becomes
widespread, conditions may arise very different from those studied by us which would render its use more of a hazard (US PHS,
1926, p. 5).
After the Surgeon General’s Approval
Sales of Ethyl Gasoline resumed in May 1926, but the Surgeon General recommended that the gasoline be dyed red,
warning signs be posted and maximum lead concentrations
in the gasoline not exceed 3.17 g/gal1 (Anonymous, 1926a).
This concentration was only a suggestion and not a legal
limit; however, it is believed that no refiners ever knowingly
1
1 g/gal, the normal unit of measure for organic lead in gasoline in
the US, is equal to 0.26 g/L.
21
Figure 1. An advertisement by the Atlantic Refining Company in the August 17, 1926. Bridgeport Telegram of Bridgeport, Connecticut promoting
the introduction of its new leaded gasoline (“Atlantic Ethyl”) (Anonymous,
1926c).
exceeded this concentration (Barusch et al., 1974). In 1926,
Jersey Standard’s and GM’s TEL plants were closed, and TEL
was produced only at DuPont’s Deepwater facility (Kovarik,
2005).
In mid-1926, leaded gasoline was sold in New England by
Beacon, whereas in Pennsylvania, it was offered by Atlantic,
Pennzoil, and Sterling (Anonymous, 1926b, 1926c, 1926d,
1926e; Robert, 1983) (Figure 1). In the Midwest, Indiana Standard, Refiners Oil Company, and Nebraska Standard offered
leaded gasoline (Anonymous, 1926f; Giddens, 1955; Midgley,
2001). In the South, leaded gasoline was sold at filling stations owned by Humble, Kentucky Standard and Fleet-Wing (a
trademark of Spears and Riddle) (Anonymous, 1926g, 1926h,
1926i; Gibb and Knowlton, 1956); in the Rocky Mountains only
Conoco offered a leaded grade (Anonymous, 1926j; Banham,
2000).
Sinclair, Sun, and Gulf, who had contracted with Ethyl prior
to the Bayway deaths, did not immediately return to Ethyl Gasoline after the Surgeon General’s approval. Sinclair and Gulf
renewed sales of leaded gasoline in the early 1930s, whereas
Sun did not return for another two decades.
22
Oudijk
Jersey Standard offered a leaded grade called Standard Ethyl
Gasoline in early 1924. It was rescinded in 1925 because of the
Bayway deaths and not reinstated in May 1926 because of safety
concerns. Instead, a high-octane grade blended with benzol, a
petroleum product containing mostly benzene, was introduced
in April 1926 under the trade name Esso. In late 1926, Jersey
Standard began selling leaded gasoline in the Carolinas, but in
no other states. However, in 1927, TEL usage resumed in Jersey
Standard’s gasoline throughout the East and South (Gibb and
Knowlton, 1956).
The ban on leaded gasoline was not lifted in New York City
until 1928. The first three oil companies to resume leadedgasoline sales within the city were Tide Water, Beacon, and
Walburn (Anonymous, 1928a).
In 1928, approximately 500 million gallons of leaded gasoline was sold in the US (Robert, 1983; Chamberlain, 1991).
By 1929, this figure had almost doubled, but was still only
approximately 10% of the total gasoline sold, although in
New England, as much as 60% was leaded (Anonymous,
1929).
Leaded grades did not reach the west coast until late 1926:
Union and Associated introduced a leaded grade in November 1926, whereas Richfield began sales in late 1928 (Anonymous, 1926k, 1928b). In 1926, Union’s sales of Ethyl Gasoline
were limited to California, Oregon, Washington, and Nevada. In
early 1927, Union began sales in Arizona and British Columbia
(Anonymous, 1927). California Standard introduced its leaded
grade in 1929 (Anonymous, 1929).
In 1928, Enarco introduced a leaded grade in the Midwest known as White Rose Ethyl. At about the same time,
Ohio Standard introduced its leaded grade, known initially
as Red Crown Ethyl, but renamed soon thereafter as Sohio
Ethyl (Anonymous, 1928c, 1928d; 1932). Until 1929, New York
Standard marketed a high-octane grade, known as Socony Special, to compete with Ethyl Gasoline. However, by late 1929,
Ethyl had contracts with companies, such as New York Standard
(Socony Special, SO Ethyl or Mobilgas Ethyl), Phillips (Phillips
66 Ethyl) and California Standard (Red Crown Ethyl or Standard Ethyl) (Anonymous, 1929). In 1930, Ethyl contracted with
Texaco, which had the most filling stations nationwide (Anonymous, 1930a). Based on Texaco’s advertisements, their leaded
gasoline was called Texaco Ethyl, but in 1932, the name was
changed to Fire-Chief Ethyl.
Some companies, at first, resisted the use of Ethyl Fluid
because of competition with the manufacturers. For example,
Shell began to offer a high-octane unleaded grade known as
Super-Shell in 1930. However, it could not compete with its
competitors and a leaded grade was introduced in January 1931
(Table 3). By 1932, Shell was operating lead-blending facilities along the west coast (Beaton, 1957). In the mid- to late1920s, Gulf, Texaco, and Sinclair also offered high-octane unleaded grades. For example, Gulf offered No-Nox, while Sinclair
offered a grade known as H-C Gasoline. However, neither
could successfully compete with Ethyl Gasoline (Giddens,
1955).
The Spread of Tetraethyl Lead Worldwide
Organolead usage in Canada was begun in 1926 by Imperial
(Anonymous, 1926l; 1931a). Between 1926 and 1929, Imperial had a semi-exclusive right to use TEL in Canada. Health
concerns and high costs caused a slow rate of adoption of
leaded gasoline compared with the US (MacDowell and Radforth, 2006); however, by 1932, leaded gasoline was offered
in Canada by eight oil companies: British American (Peerless
Ethyl or Pratts Ethyl), Canadian (Canadian Ethyl), Home (Home
Ethyl), Imperial (Imperial Ethyl), McColl-Frontenac (Cyclo
Ethyl), Redline-Glico (Glico Ethyl), Regal (Regal Ethyl), Shell
(Super-Shell Ethyl) and Sinclair (Sinclair HC w/Ethyl) (Anonymous, 1932). By 1934, Cities Service (Koolmotor), Irving (Irving Premium), and Supertest were also offering leaded grades
(Chantler, 1935).
Sales of leaded gasoline began in Mexico in 1937 (Robert,
1983). However, these sales were generally limited to the Mexico
City area. In 1940, the Mexican government rescinded Ethyl’s
patents and Ethyl discontinued its sales (Anonymous, 1940a).
The Mexican government constructed a TEL plant near Mexico
City in 1940, but TEL production was fraught with problems
(Brown and Knight, 1992). TEL usage in Mexico remained light
until the construction of a facility near Mexico City (possibly the
same location as the government plant) through a joint venture
between DuPont and Pemex sometime around 1955 (Robert,
1983). A second TEL plant was constructed in Coatzacoalcos
sometime around 1960 (Soto-Jimenez et al., 2006). In Cuba,
Sinclair and Cuba Standard first offered leaded gasoline sometime before 1932 (Anonymous, 1932).
The United Kingdom (UK) began sales of leaded gasoline
(then known as Pratts Ethyl) in 1928 through Anglo-American
(Anonymous, 1928e). In 1930, Ethyl organized a subsidiary in
the UK known as the Ethyl Export Corporation; it became Associated Ethyl Company in 1938 and Associated Octel Company in
1961. Associated Ethyl was owned by Anglo-American, AngloPersian, New York Standard, Texaco, and California Standard.
Anglo-Persian first introduced a leaded grade in the UK, known
as BP Plus, in April 1931. The trade name changed to BP Ethyl
in August 1933 (Bamberg, 1994).
Leaded gasoline was introduced in Australia in 1932 by Commonwealth. This leaded grade was known as COR Plus, probably similar in composition to BP Plus, and dyed blue. Atlantic
Union, a joint venture between the American oil companies: Atlantic and Union, introduced a leaded grade in around September
1934. One month later, Vacuum also introduced a leaded grade
(Cook and Gale, 2005).
Leaded automotive gasoline was introduced in Japan in 1927.
In Italy, leaded gasoline was first seen in 1935 (Robert, 1983)
and in France in 1939 (LaPerche, 2004). Irish sales of leaded
gasoline began sometime before 1932 (Anonymous, 1932).
In 1936, Ethyl built TEL-manufacturing plants in Europe, the
first one in Germany and the second in France (1938). A plant
was built in the UK in 1940 and a second German plant was built
in 1939, but without Ethyl’s knowledge. Germany had begun to
23
Table 3. Lifetimes of leaded and unleaded gasoline in the United States
Leaded
grade
introduced
Unleaded
grade
introduced
Leaded
premium grade
phased out
Unleaded
premium
introduced
Leaded grade
completely
phased out
Ashland Oil & Refining Company
1933
≤ 1974
≤ 1982
∼ 1981
∼ 1989
Atlantic Refining Company (later Arco)
1926
1970
1978
1980
1989
British Petroleum (BP)
1958a
1970
1980
NA
≤ 1994
1932 –1936
1971
1974
NA
∼ 1989
Clark Oil & Refining Company
Continental Oil Company (Conoco)
1932
1926
1970
1974
1974
1980
1970
NA
∼ 1989
1995b
Getty Oil Company
1926c
1974
1984
1982
1984
Gulf Oil Company
1931d
1974
1980
1980
—
Hess Corporation
1961e
<1974
1981
<1981
1989
Humble Oil & Refining Company
1924
1974
—
—
—
Kerr-McGee Corporation (Deep Rock)
1930
≤ 1974
≤ 1982
NA
∼ 1989
Marathon Oil Company
1930
1970
1979
1980
∼ 1989
Murphy Oil Corporation
Phillips Petroleum Company
1956e
1929
1970
1970
<1982
1980
1970
NA
∼ 1989
≤ 1994
Pure Oil Company
Richfield Oil Company (later Arco)
1930
1928
—
1970
—
1978
—
1980
—
1989
Royal Dutch-Shell Group (Shell)
1931
1970
1978
1977
<1994
≤ 1931d
1970
1978
NA
≤ 1994
Skelly Oil Company
Standard Oil (California) (Chevron)
1930
1929
—
1970∗
—
1981
—
1981
—
1995b
Standard Oil (Indiana) (Amoco)
1924
Always
1978
≤ 1970
1986
Standard Oil (Kentucky) (Kyso)
1924
—
—
—
—
Company
Cities Service Company (Citgo)
Sinclair Oil Company
Source
Scott (1968); Anonymous
(1974g); Anonymous
(1980e)
Anonymous (1926c);
Anonymous (1970j);
Potts and Atlas (1980);
Brady et al. (2002)
Anonymous (1980g);
Bamberg (1994)
Anonymous (1971c);
Hodge (1974a)
Broadway (1974)
Anonymous (1926j);
Anonymous (1974h);
Blauvelt (1975); Potts
and Atlas (1980);
Anonymous (1995c);
Banham (2000)
Anonymous (1926k); Knox
(1981a); Morris (1983)
Anonymous (1931c);
Thompson (1951); Potts
and Atlas (1980);
Anonymous (1980f)
Hodge (1974a); Knox
(1981b); Sauer (1989)
Gibb et al. (1956); Larsen
et al. (1971)
Anonymous (1930b); Ezell
(1979)
Spence (1962); Anonymous
(1970i); Anonymous
(1980c)
Anonymous (1970g)
Anonymous (1929); Potts
and Atlas (1980); Wertz
(1983); Wallis (1988)
Anonymous (1930c)
Anonymous (1928b);
Anonymous (1970h);
Anonymous (1970j);
Jones (1972); Potts and
Atlas (1980); Brady et al.
(2002
Beaton (1957); Forbes and
O’Beirne (1957); van
Dyke (1970); Roche
(1978); Potts and Atlas
(1980)
Anonymous (1931b);
Spence (1966)
Ironside (1970)
Anonymous (1929);
Anonymous (1970f);
Anonymous (1980d); US
EPA (1995)
Giddens (1955); Potts and
Atlas (1980); Dedmon
(1984); Obel (1986)
Anonymous (1926g)
(Continued on next page)
24
Oudijk
Table 3. Lifetimes of leaded and unleaded gasoline in the United States (Continued)
Leaded
grade
introduced
Unleaded
grade
introduced
Leaded
premium grade
phased out
Unleaded
premium
introduced
Leaded grade
completely
phased out
Standard Oil (New Jersey) (Exxon)
1924
1974
1981
1980
1995f
Standard Oil (New York) (Mobil)
1929
1971
1978
1978
1989
Standard Oil (Ohio) (Sohio)
1928
1970
1980
≥ 1979
—
Standard Oil (Pennsylvania) (Sopa)
Sun Oil Company (Sunoco)
1930
1950
—
1972g
—
1980
—
1983
—
1989
The Texas Company (Texaco)
1930
1970h
1980
1979
≤ 1994
Union Oil Company (Union 76)
1926
1974
1986
>1986
<1994
Company
Source
Gibb et al. (1956); Larsen
et al. (1971); Anonymous
(1980a); Wall (1988);
Anonymous (1995c)
Anonymous (1929); Roche
(1978); Potts and Atlas
(1980); Sauer (1989)
Spencer (1962);
Anonymous (1970i);
Anonymous (1980g)
Gibbs et al. (1956)
Anonymous (1980a);
Johnson (1983); Sauer
(1989)
Anonymous (1930a); James
(1953); Anonymous
(1970e); Potts and Atlas
(1980)
Anonymous (1926b);
Waddell and Niven
(1976); Obel and
Williams, 1986
introduced leaded gasoline in the UK in 1931, but did not enter the US market until 1958.
grades were offered only along the West Coast at this date.
c The name Getty Oil Company was first used in 1956. Getty’s predecessor, the Associated Oil Company, first introduced leaded gasoline in 1926.
d Reportedly used tetraethyl lead (TEL) in 1924. TEL usage was discontinued by these companies in 1925 as per the Surgeon General’s instructions. TEL was
not reinstated in 1926 by these companies.
e Date that the company first began selling gasoline commercially. It is assumed that leaded gasoline was sold at the time of their founding.
f In the Northeast, Exxon phased out leaded gasoline in 1987.
g Marketed only on a test basis. Full-scale sales did not begin until 1974.
h Unleaded was offered for a limited time only on the west coast.
—Company was no longer in existence or had been purchased by another company at time of conversion.
Always, Indiana Standard had always offered a high-octane unleaded grade. This unleaded grade (known as Amoco-Gas and later Amoco Super Premium) was
originally produced by the American Oil Company, who became affiliated with Indiana Standard in 1922 (Dedmon, 1984).
a BP
b Leaded
import Ethyl Fluid (known as Fluidin by the Germans) directly
from the US in 1934: 12 tons in 1934, 104 tons in 1935 and 4.65
tons in 1936 (Robert, 1983). Imports stopped following startup
of the German TEL plant. The imported TEL had been used
primarily for aviation gasoline. The use of TEL in automotive
gasoline in Germany began in 1939 (DuPuis, 2004).
Before World War II, TEL usage in continental Europe was
predominantly for aviation gasoline. In the pre-war years, there
was significant competition among anti-knock agents utilizing
ethanol, methanol and benzol, and many of these agents came
from Germany and France (Robert, 1983). Benzol, derived
from coal gasification, was often mixed with gasoline in France
and the result was known as binaire. In some cases, gasoline
was mixed with benzol and alcohol and known as ternaire
(Nowell, 1994).
Ethyl Gasoline Up To and Through World War II
Use of Ethyl Gasoline increased steadily in the US until 1931,
then usage decreased more than 28% probably because of the
depressed economy (Anonymous, 1933a) and sales of leaded
gasoline continued to decline until 1937 (Edgar, 1939). Meanwhile, Ethyl had secured contracts from 36 companies worldwide by 1928 and from 103 companies worldwide by 1932
(Anonymous, 1928f; 1932) (Table 4). In 1936, Ethyl reported
that 72% of US gasoline was leaded (Anonymous, 1936a); by
1940, this reached 88% and TEL was blended into all but one
major brand (Anonymous, 1940b). Sun, the sole brand, used
catalytic cracking (then known as the Houdry Process) to produce a high-octane unleaded grade (then dyed blue). Sun did
not offer a leaded grade until 1950 (Johnson, 1983).
Before 1933, TEL was found only in premium grades in
the US (Beall et al., 2002). However, in June 1933, Ethyl
began marketing TEL for regular grades to small refiners, and
Ashland was the first (Anonymous, 1933a). Ashland’s regular
leaded grade was dyed green and was then known as Green
Pepper (Scott, 1968).
This regular-grade leaded gasoline was known by Ethyl as
Q-Fluid (also known as Q Brand or just Q), and Ethyl required
that licensees neither advertise the grade as leaded nor dye it red
and provide only a limited octane rating (Anonymous, 1933b).
However, Imperial had already introduced a leaded regular grade
25
Table 4. Oil companies offering leaded gasoline worldwide in 1932
Company
Trade name
Aetna Oil Service
Allegheny-Arrow Oil Co.
American Oil Co.
Anglo-American Oil Co. (UK)
Anglo-Persian Oil Co. (UK)
Ashland Refining Co.
Associated Oil Co.
Atlantic Refining Co.
Barnsdall Corp.
British American Oil Co. (Canada)
Canadian Oil Co. (Canada)
Canfield Oil Co.
Champlin Refining Co.
Colonial Beacon Oil Co.
Col-Tex Refining Co.
Continental Oil Co.
Continental Refining Co.
Crystal Oil Refining Corp.
Deep Rock Oil Corp.
Eason Oil Co.
Elk Refining Co.
Fleet-Wing Oil Corp.
Freedom Oil Works Co.
Garber Refinery, Inc.
General Petroleum Corp.
Glasgow Oil & Refining
Globe Oil & Refining Co.
Gulf Refining Co.
Hickok Oil Corp.
Home Oil Distributors (Canada)
Humble Oil & Refining Co.
Imperial Oil (Canada)
Indian Refining Co.
Irish-American Oil Co. (Ireland)
Johnson Oil Refining Co.
Kanotex Refining Co.
Kendall Refining Co.
Latonia Refining Corp.
Aetna Ethyl
Arrow Ethyl
American Ethyl
Pratts-Ethyl Petrol
B.P. Plus
Red Pepper Ethyl
Associated Ethyl
Atlantic Ethyl
Super-Gas Ethyl
Peerless Ethyl
Canadian Ethyl
Canfield Ethyl
Champlin Ethyl
Esso (with Ethyl)
Col-Tex Ethyl
Conoco Ethyl
Coreco Ethyl
Crystal Ethyl
Kant Nock Ethyl
Eason Ethyl
Elk Ethyl
Fleet-Wing Ethyl
Freedom Ethyl
Omar Ethyl
General Ethyl
Glyco Ethyl
Globe Ethyl
No-Nox Ethyl
Hi-Speed Ethyl
Home Ethyl
Esso (with Ethyl)
Imperial Ethyl
Texaco Ethyl
Pratts Ethyl
Johnson Ethyl
Kanotex Ethyl
Kendall Ethyl
Sohio Ethyl & Fleet-Wing Ethyl
Lincoln Oil Refining Co.
Lion Oil Refining Co.
Louisiana Oil Refining Corp.
Lubrite Refining Corp.
Magnolia Petroleum Corp.
McColl-Frontenac Oil Co. (Canada)
Mexican Petroleum Corp.
Mid-Continent Petroleum Corp.
Midwest Refining Co.
A. D. Miller & Sons
National Refining Co. (Enarco)
Ohio Oil Co.
Oil Creek Refining Co.
Pan American Petroleum Corp.
Pasotex Petroleum Co.
Linco Ethyl
Lion Ethyl
Loreco Ethyl
Mobilgas Ethyl
Magnolia Ethyl
Cyclo Ethyl
Pan-Am Ethyl
Nevr-Nox Ethyl
Midwest Ethyl
Miller’s Ethyl
White Rose Ethyl
Marathon Ethyl
Oil Creek Ethyl
Pan-Am Ethyl
Red Crown Ethyl
Company
Pennsylvania Oil Products Refining
Pennsylvania Refining Co.
Pennzoil Co.
Phillips Petroleum Co.
Producers & Refiners Corp.
Pure Oil Co.
Redline-Glico, Ltd. (Canada)
Refiners, Inc.
Regal Petroleum (Canada)
Richfield Oil Co. (Calif.)
Richfield Oil Co. (NY)
Rio Grande Oil Co.
Root Refining Co.
Shell Co. (Canada)
Shell Eastern Petroleum Products
Shell Petroleum Corp.
Sinclair Cuba Oil Co.
Sinclair Refining Co.
Sinclair Refining Co. (Canada)
Skelly Oil Co.
Solar Refining Co.
Spartan Refining Co.
Standard Oil (Calif.)
Standard Oil (Cuba)
Standard Oil (Indiana)
Standard Oil (Kentucky)
Standard Oil (Louisiana)
Standard Oil (Nebraska)
Standard Oil (New Jersey)
Standard Oil (New York)
Standard Oil (Ohio)
Standard Oil (Pennsylvania)
Sterling Oil Co.
Stoll Oil Refining Co.
Texas Company
Texas Pacific Coal & Oil Co.
Tidal Refining Co.
Tidewater Oil Co.
Tri-State Refining Co.
Union Oil Co. (Calif.)
United Refining Co.
Utah Refining Co.
Vacuum Oil Co.
Wadhams Oil Corp.
Waverly Oil Works Corp.
White Eagle Oil Corp.
White Star Refining Co.
H. F. Wilcox Oil & Gas Co.
Wirt Franklin Petroleum Corp.
Wolverine-Empire Refining Co.
Trade name
Eldred Ethyl
Penn-Drake Ethyl
Pennzoil Ethyl
Phillips ‘66’ Ethyl
Parco Ethyl
Purol Ethyl
Glico Ethyl
Refiners Ethyl
Regal Ethyl
Richfield Ethyl
Richfield Ethyl
Rio Grande Ethyl
Root Ethyl
Super-Shell Ethyl
Super-Shell Ethyl
Super-Shell Ethyl
Sinclair HC w/Ethyl
Sinclair HC w/Ethyl
Sinclair HC w/Ethyl
Skelly Aromax Ethyl
Solar Ethyl
Sparcolene Ethyl
Standard Ethyl
Esso (with Ethyl)
Red Crown Ethyl
Crown Ethyl
Standard Ethyl or
Esso (with Ethyl)
Red Crown Ethyl
Standard Ethyl &
Esso (with Ethyl)
Socony Special
Sohio Ethyl
Standard Ethyl &
Esso (with Ethyl)
Sterling Ethyl
Stoll Ethyl
Texaco Ethyl
T-P Ethyl
Tydol Ethyl
Tydol Ethyl
Tri-State Ethyl
Union Ethyl
Keystone Ethyl
Pep ‘88’ Ethyl
Mobilgas Ethyl
Wadhams Ethyl
Waverly Ethyl
White Eagle Ethyl
White Star Ethyl
Wilcox Ethyl
Palacine Ethyl
Empire Ethyl
Data from Anonymous (1932).
in Canada in 1931 under the trade name Three Star (Anonymous, 1931a). Jersey Standard’s leaded regular was known as
Essolene, whereas Richfield called its brand Golden (Gibb and
Knowlton, 1956; Jones, 1972). In 1936, the maximum octane
rating for these regular-grade gasolines (Q) rose from 70 to 73
RON (Anonymous, 1936b).
In 1940, Ethyl lost an antitrust case that stemmed from its
licensing of refiners and jobbers (Robert, 1983). Prior to 1940,
Ethyl curtailed the number of sellers of leaded gasoline. Afterwards, Ethyl could not restrict customers and all brands could
contain TEL (Anonymous, 1940a). At this point, many more oil
companies joined the wave.
26
Oudijk
To compete with GM, which partially owned Ethyl, the Ford
Motor Company began to market in 1940 a benzol-based gasoline as an alternative to leaded gasoline known as Benzol Gas.
Ford’s efforts were accomplished through the use of independent
marketers using a franchise program predominantly in Michigan. Ford continued this practice until at least the mid-1950s
(Banham, 2002). Ford’s Benzol Gas did not contain organoleads.
During World War II, lead concentrations and octane ratings of automotive gasoline decreased because of the war. TEL
was needed for aviation gasoline to run military planes. In
1943, premium-grade octane ratings decreased from 80 to 76
RON (Anonymous, 1944). Regular-grade, then known as house
brand, stayed at 72 RON, but its volatility decreased. In 1944,
premium-grade gasoline sales were discontinued until the war’s
end (Robert, 1983). Immediately after the war, a lead shortage
occurred. Indiana Standard, for example, could produce gasoline
with octane ratings of only 78.5 and 75 RON for their premium
and regular grades, respectively. Before to the war, Indiana Standard’s ratings had been 80 and 75, respectively, and during the
war, they had been as low as 76 and 70 RON (Anonymous, 1946).
Post-war octane ratings increased and it was not uncommon
to find them exceeding 100 in the 1950s. The 100+ octane
gasolines were commonly known as aviation grade (or superpremium grade). Leonard was the first refiner to offer a 96octane super-premium grade (in 1953) and by 1957, they were
producing a 105-octane grade. Some of the refiners offering
a super-premium grade in the 1950s included: Conoco, Humble, Jersey Standard, Shell, Sinclair, Sohio, and Sun (Carmical,
1956). However, companies such as Sun and Indiana Standard
also offered unleaded or low-lead grades (<0.50 g/gal) in the
1950s (Johnson, 1983).
In 1949, Ethyl required that all refiners meet a minimum
octane rating of 86 RON for all grades sold under the Ethyl
trademark. In the Rocky Mountain region, the minimum was
83 RON (Anonymous, 1949). In 1949, more than 85% of all
gasoline sold in the US contained TEL (Beatty and Lovell,
1949); by 1960, the percentage exceeded 90% (Nriagu, 1990)
and by 1963, it reached 98% (Seyferth, 2003).
By the 1940s, leaded gasoline had become such an integral
part of the US economy that the Federal government protected it
from criticism in the marketplace. Rayner-Canham and Overton
(2006) reported that:
Though evidence of the toxicity of lead accumulated through the
1930s and 1940s, TEL was safe from criticism. Responding to a
complaint from Ethyl Gasoline Corporation, manufacturer of TEL
(and owned by General Motors and Standard Oil of New Jersey),
the Federal Trade Commission (FTC) issued a restraining order
preventing competitors from criticizing leaded gasoline in the marketplace. Ethyl gasoline, the FTC order read, “is entirely safe to the
health of motorists and the public” (p. 311).
Leaded Gasoline Up to the Phase-Out
By 1969, 97.5% of gasoline worldwide contained lead additives. In the late 1960s, lead concentrations as high as 4.5 g/gal
could be found in Bolivia, Mexico, Paraguay, and Venezuela,
while the average concentration worldwide was approximately
2.5 g/gal (In this article, the term “average” is intended to specify
the arithmetic mean). However, in countries such as Japan and
Austria, unleaded grades had already been introduced (Aronov,
1970).
In 1959, the US Surgeon General increased the recommended
lead concentration limit to 4.39 g/gal (or 4.86 g/gal in aviation
gasoline) (E. I. DuPont, 1961; Hamilton, 2004); the Surgeon
General believed that this would not cause health problems
(Dauvergne, 2008). However, automotive gasolines never contained this extreme concentration. The highest concentration
was in a premium grade, which reached 4.04 g/gal (Hamilton,
2004). In the Mid-Atlantic region of the US, this value was
reached in 1979 (Shelton, 1980).
Average lead concentrations commonly increased during
summer compared to winter (Shelton et al., 1982). Higher octane is needed where high atmospheric pressure and elevated
temperature prevail and concentrations commonly increase in
coastal areas (Hamilton and Falkiner, 2003). Seasonal differences in lead content ranged from as little as 1% to more than
40%, although in 1950 and 1951, average winter values exceeded summer values, reflecting restrictions of the Korean War
(Anonymous, 1951).
Average total lead concentrations in gasoline nationwide
were approximately 1.1 g/gal and 1.5 g/gal for regular- and
premium-grade in the late 1940s, respectively (Figures 2 and 3).
These increased through the early 1950s reaching approximately
2 g/gal for regular and approximately 2.5 g/gal for premium. Average concentrations in both grades dropped approximately 0.5
g/gal in 1956, but then rebounded through the late 1950s. Premium grade continued to increase until about 1973, peaking
at just less than 3 g/gal. After 1973, average concentrations declined, despite a few interruptions, until the complete phase-out.
Lead Contents of United States Gasolines
After 1935, the US Department of Energy (US DOE) National
Institute of Petroleum and Energy Research (NIPER) (located
in Bartlesville, Oklahoma) issued periodic reports on gasoline
composition, including lead content in various regions (Figure
2). The national average lead contents of regular- and premiumgrade gasolines from 1950 to 1990 are shown (Figure 3) (Shelton
et al., 1982; Dickson et al. (1987); Gibbs, 1990; Kaplan, 2003).
Not all gasoline contained the cited concentrations; reported
values are averages of highly varied lead content in sampled
gasoline. Standard deviations surrounding the values can also be
significant. Concentrations varied depending on: refiner; original crude-oil composition, and refining equipment used. Furthermore, the addition of TEL affected octane ratings of various
gasolines differently (Hebl et al., 1933).
Examples of average organic lead contents of regular-,
premium- and super-premium-grade gasolines from 1946 to
1990 in the Mid-Atlantic region of the US (Connecticut,
27
Figure 2. An example of semi-annual data on leaded regular and premium grades in the Northern New England and northern New York region (winter
1979) collected by the United States Department of Energy (US DOE) National Institute of Petroleum and Energy Research (NIPER). Data from Shelton
(1980).
Delaware, Maryland, New Jersey, central and southern New
York, eastern Pennsylvania, and Virginia) are presented in Figures 4–6. These graphs also include the range in values and
sample-set size. Similar data are available for the entire mainland US. They show that significant variation in the average
concentrations, even those from year to year.
For regular grade, the highest average concentrations in this
region were in the late 1950s (approximately 2.75 g/gal), although the highest concentration in a single sample was in 1980
(>3.5 g/gal). For premium grade, the highest average concentration in this region was in 1968 (approximately 2.9 g/gal),
although the highest concentration in a single sample was also
in 1979 (slightly more than 4 g/gal). Graphs depicting threepoint moving averages for the Mid-Atlantic region are provided
for the regular- and premium-grades (Figures 7 and 8). These
graphs depict a smooth progression of temporal changes in lead
content; however, the lead content in regular-grade was more
varied compared to premium.
Figure 3. Graph of the average lead concentration in premium and regular grades of automotive gasoline from 1950–1989 in the United States. Solid
line is premium grade; dashed line is regular grade. Data from Shelton et al. (1982); Dickson et al. (1987), Gibbs (1990) and Kaplan (2003).
28
Oudijk
Figure 4. Graph of the average organic lead concentration in regular-grade gasoline of the Mid-Atlantic region of the United States from 1946 to 1990
showing the range and sample-set size. Data from the National Institute of Petroleum and Energy Research (NIPER), Bartlesville, OK.
Tetraethyl Lead Manufacturers
Between 1924 and 1938, DuPont was the sole manufacturer of
TEL in North America. In 1938, Ethyl built a TEL manufacturing plant in Baton Rouge, LA, because DuPont’s Deepwater
plant could not keep up with the demand. However, DuPont
ran operations at the Louisiana plant (Nickerson, 1954; Robert,
1983).
When GM’s and Jersey Standard’s TEL patents expired in
1948, DuPont withdrew from the partnership and marketed TEL
alone (Larsen et al., 1971). Prior to 1948, Ethyl’s share of the
North American market had been 100%; however, by 1960, it
had declined to 55% (Robert, 1983).
In 1963, four US firms were producing organoleads for gasoline blending: DuPont (38.4%), Ethyl (33.5%), Pittsburgh Plate
Glass Industries (PPG) (16.2%) and National Aluminate Corporation (Nalco) (11.8%) (market share in 1975 in parentheses)
(Federal Trade Commission [FTC], 1983) (Tables 5a and 5b).
PPG, whose TEL division was formerly known as the Houston Chemical Company, entered the market in August 1961,
whereas Nalco began as a tetramethyl lead (TML) manufacturer
in 1963. PPG marketed under the Houston Chemical name until
1978, but until 1963, Houston Chemical was a subsidiary of the
Chatham Chemical Corporation and owned by Philadelphia and
Reading Corporation (Anonymous, 1960).
Houston Chemical operated two plants in Beaumont, Texas
for TEL and TML production. Nalco had a plant in Freeport,
TX, and began producing 15,000 tons of TML yearly in late
1963. DuPont had TEL plants in Deepwater, NJ, and Antioch,
CA (built in 1955), Maitland, Ontario, plus a blending facility
in Beaumont, TX. Ethyl had plants in Baton Rouge, LA (1938);
Pasadena, TX (1952); Orangeburg, SC (1953), Sarnia, Ontario
(1956), and Pittsburg, CA (1958) (Robert, 1983) (Table 2).
In 1962, GM and Jersey Standard sold Ethyl to Albemarle
Paper Manufacturing Company, which continued the business
under the Ethyl name (Robert, 1983). Based on its website (available at: www.ethyl.com), Ethyl changed its name to NewMarket
Corporation in 2004. NewMarket Corporation is now the parent company of Afton Chemical Corporation and Ethyl. Afton
manufactures anti-knock additives, whereas Ethyl produces specialty chemicals.
From 1921 to the present, TEL was manufactured at approximately 30 locations worldwide (Table 2). In 2009, two active
TEL manufacturing facilities exist: one in the UK and a second
in China.
Transport of Tetraethyl Lead
Prior to 1930, transport of TEL to refineries and blending facilities was by truck: either tanker trucks or drums loaded onto
29
Figure 5. Average organic lead concentration in premium-grade gasoline of the Mid-Atlantic region of the United States from 1946 to 1981 showing the
range and sample-set size. Data from the National Institute of Petroleum and Energy Research (NIPER), Bartlesville, OK.
Figure 6. Graph of the average organic lead concentration in super-premium-grade gasoline of the Mid-Atlantic region of the United States from
1956–1963 showing the range and sample-set size. Data from the National Institute of Petroleum and Energy Research (NIPER), Bartlesville, OK.
30
Oudijk
Figure 7. Graph of the three-point moving average of average organic lead concentration in regular-grade gasoline of the Mid-Atlantic region of the
United States from 1946–1990. Points represent the National Institute of Petroleum and Energy Research (NIPER) data, whereas the line represents the
moving average. Data from NIPER, Bartlesville, OK.
trucks. Because of the toxic nature of TEL, shipping could
be difficult and dangerous. Beginning in 1930, Ethyl began to
deliver TEL through a specialized railcar, commonly 6,000 gallons in capacity. These railcars were branded with the acronym
“EBAX” or Ethyl Branded Antiknock. These tanker trucks and
railcars were dedicated to TEL transport. In 1960, Ethyl also
developed a special ship for TEL deliveries overseas (Robert,
1983).
DuPont’s shipping methods ranged from a 1-litre can to a
9,600-gallon railcar. TEL in cans or drums could be obtained
only from its Deepwater, New Jersey plant. TEL in tanker trucks
or railcars was available from the Deepwater plant as well as
plants in Antioch, California and Beaumont, Texas (E. I. DuPont,
1961).
Lead Scavengers
Chemistry of the Scavengers
A drawback of TEL usage was damage to valves, spark plugs and
combustion chambers by lead-oxide deposition, formed during
leaded-gasoline combustion. Bromine and chlorine are corrective agents (Robert, 1983) and anti-knock fluids were changed
to include scavengers such as brominated and chlorinated organics. These compounds converted lead oxides to volatile halide
salts that exited with exhausts (Nriagu, 1990).
The lead scavengers: ethylene dibromide (EDB) and ethylene
dichloride (EDC), are common contaminants in the environment
(Falta et al., 2005). Despite being phased out almost 20 years ago
in the US, they are still common in the environment. Because
these compounds are toxic and resistant to degradation, they
Table 5. Composition in percent of some of Ethyl’s antiknock
packages prior to 19571
Package
By weight:
TEL
EDB
EDC
Other2
By volume:
TEL
EDB
EDC
Other
Figure 8. Graph of the three-point moving average of average organic lead
concentration in premium-grade gasoline of the Mid-Atlantic region of the
United States from 1946–1981. Points represent the National Institute of
Petroleum and Energy Research (NIPER) data, whereas the line represents
the moving average. Data from NIPER, Bartlesville, OK.
Motor Plus (%)
Motor (%)
Aviation (%)
59.79
20.84
18.30
1.07
61.48
17.86
18.81
1.85
61.41
35.68
None
2.91
58.3%
15.4
23.6
2.1
59.2%
13.0
23.9
3.9
64.8%
28.5
None
6.7
Data from Ethyl Corp. (1957). EDB, ethylene dibromide; EDC, ethylene dichloride; TEL, tetraethyl lead.
1 Prior to 1960, DuPont offered similar products known as Motor Mix,
Motor Mix A, and Aviation Mix. In 1957, these three products cost US
$37.5, US $37.07 and US $40.84 per pound, respectively (Anonymous,
1957).
2 Other = Dye and solvent.
Table 6. Typical use of scavengers for tetraethyl lead (TEL) in motor
gasoline in the United States
Ethyl trade name
Years
Bromine (theories) Chlorine (theories)
3-J Mix
1926–1928
B Mix
1928–1929
Aviation Mix
1929C Mix
1930–1933
C Mix A
1933–1934
44 Mix
1934–1943
Motor Mix (62 M 1942–19601
1.5
1.15
1.0
0.85
0.75
0.7
0.5
0.1
0.1
0.0
0.3
0.4
0.45
1.0
Data from Oliver and Rowling (1965); Barusch et al. (1974).
1 The amount of bromine and chlorine (or ethylene dibromide [EDB] and ethylene dichloride [EDC]) remained constant until the lead phase-out in the late
1980s (Beall et al., 2002).
are often involved in litigation and, therefore, their history is
important to investigators.
The first leaded gasoline sold in February 1923 contained
the following lead scavengers: triethylbromide at 6.93 g/gal and
carbon tetrachloride at 1.5 g/gal. In March 1923, the formulation changed to 3 parts TEL and 2 parts carbon tetrachloride
(Thomas et al., 1997). In September 1923, carbon tetrachloride
was replaced by trichloroethylene (TCE). During much of 1924,
ethylene chlorobromide was also used and possibly tribromoaniline (DeLong, 1926). In 1925, the formulation was 35.7 weight
percent (wt%) EDB, 61.4% TEL, and 2.9% chloronaphthalene.
Compounds known as TEL stabilizers, such as lecithin and tertbutyl phenol, were also added to these packages to prevent
TEL oxidation during storage (Graham et al., 1956). In 1942,
EDB was partially replaced by the less efficient EDC to save
costs (Robert, 1983). Chlorine is less expensive than bromine;
however, the use of only a chlorine-based scavenger can cause
exhaust valve problems (Gibbs, 1990).
The quantity of EDB and/or EDC in a package is based on
its organolead content and expressed as “theory units”. One
theory unit (T) is defined as the theoretical amount of bromine
or chlorine required to convert all lead in the gasoline to the
corresponding lead halide (Gibbs, 1990). Ethyl’s final mixture
had 0.5 T of bromine and 1.0 T of chlorine, corresponding to
an EDC:EDB:Pb molar ratio of 1:2:1, and containing 61.48
wt% TEL, 17.86 wt% EDB, 18.81wt% EDC and 1.92 wt%
dye (Thomas et al., 1997). The mixture was patented by Ethyl in
1943 and called Motor Package. The package also contained 0.1
wt% or less of p-oxydiphenyl amine and was commonly dyed
red, yellow or blue (Ethyl Corp., 1957). This formulation was
used until the 1990s phase-out (Beall et al., 2002). In 1955, Ethyl
offered a second package, known as Motor Plus, containing
59.79 wt% TEL, 20.84 wt% EDB, 18.30 wt% EDC, plus 1.07
wt% dye (Ethyl Corp., 1957) (Table 6 and 7).
Other lead scavengers used in US gasoline on a limited basis
were: acetylene tetrabromide; hexachloropropylene; mono- and
poly-halopropanes, -butanes and -pentanes, and polyhaloalkylbenzenes (Yust and Barnes, 1958). Propylene dibromide was
reportedly used in some packages overseas (Ganguli, 1998).
In European packages, 1.0 T of bromine was used as of 1961.
Small amounts of tricresyl phosphate and trimethyl phosphate
were sometimes added to European blends as well (Oliver and
Rowling, 1965). In 1992, Germany banned halogenated scavengers because of possible dioxin formation in the exhausts
(Sakai and Fiedler, 2004). German studies showed that, below
an organic lead concentration of 0.58 g/gal, no adverse effects
occurred despite the lack of a scavenger (Thomas et al., 1997).
Table 7a. Standard antiknock compounds manufactured by DuPont and Ethyl
Type of Mix
Name of Mix
Ethyl
Standard antiknock packages
Straight fluids
Aviation mix dyed
Reacted mixes1
TEL Motor Mix
TML Motor Mix
Aviation Mix
MLA 250 Mix
MLA 500 Mix
MLA 750 Mix
TELMEL 102
TELMEL 25
TELMEL 50
TELMEL 75
TEL Motor
Special#1
TEL Motor
MLA 500 Special#1
Tetramix 50 S-1
TELMEL 10
Physical mixes1
Special packages
Straight fluids
Reacted mixes
Physical mixes
31
DuPont
TEL Motor Antiknock
TML Motor Antiknock
TEL Aviation Antiknock
Tetramix 25 Antiknock
PM-10
PM-25
PM-50
PM-75
TEL Motor
Special Antiknock S-1
Special #1 Yellow3
Tetramix 25 S-1
—
PM-10
Data from FTC (1983). MLA, mixed lead alkyls; TEL, tetraethyl lead; TML, tetramethyl lead.
1 For each company, the numerals in the name of the mix show the proportion of the antiknock compound in
the fluid is TML. Thus, MLA 250 is 25% TML and 75% TEL and PM-10 is 10% TML and 90% TEL.
2 Ethyl’s TELMEL 10 is identical in composition to DuPont’s PM-10 and PPG’s MAF Motor Mix 10P (Table
6b).
3 TEL Motor Special #1 Yellow is TEL Motor Special #1 with an orange dye added.
32
Oudijk
Table 7b. Standard antiknock compounds manufactured by PPG and Nalco
Type of Mix
Standard antiknock packages
PPG
Straight fluids
Reacted mixes1
Physical mixes1
Special packages
Straight fluids
Reacted mixes
Physical mixes
TEF Motor Mix
TMF Motor Mix
Aviation Mix
Aviation Mix Dyed
MAF Motor Mix 25R
MAF Motor Mix 50R
MAF Motor Mix 75R
MAF Motor Mix 10P
MAF Motor Mix 25P
MAF Motor Mix 50P
MAF Motor Mix 75P
TEL Motor Mix C+
MAF Motor Mix 50R-C+
MAF Motor Mix 10P
Nalco
Nalkyl E-1
Nalkyl M-1
TEL Aviation Antiknock
—
Nalkyl ME 25
Nalkyl ME 50
Nalkyl ME 75
—
—
—
—
—
—
—
Data from FTC (1983). TEL, tetraethyl lead.1 For each company, the numerals in the name of the mix represent
how much of the antiknock compound in the fluid is tetramethyl lead (TML). Thus, mixed lead alkyls (MLA) 250
is 25% TML and 75% TEL and PM-10 is 10% TML and 90% TEL.
Manufacturers of Scavengers
With the introduction of Q Fluid, EDB demand increased and
thus more bromine was needed. There ensued a mad scramble
by Ethyl to obtain bromine sources. In the 1920s, bromine was
extracted from brine wells near Midland, MI, owned by Dow
Chemical Company (Doyle, 2004). This supply was insufficient
and Dow began to process seawater to produce EDB (Boyd,
1957). Plants were built in Ocean City, MD, and Cape Fear, NC,
in the late 1920s as part of a joint venture known as the DowEthyl Chemical Company (Anonymous, 1936c; Spitz, 1988).
Plants were also constructed at Kure Beach, NC, and Freeport,
TX (Nickerson, 1954). Dow’s Freeport plant became operational
in the late 1930s and it produced EDB for approximately 50
years (Doyle, 2004). By 1955, annual production rates for EDB
and EDC each exceeded 100 million pounds (Gibson, 1956).
Because of EDB shortages, EDC usage was common during
World War II, but because of corrosion problems, it was not used
in aviation gasoline (Robert, 1983). Chlorinated compounds,
such as TCE, carbon tetrachloride or chloronaphthalene, were
then also used (Thomas et al., 1997). EDB was also produced at
a plant in Tornesch, Germany (near Hamburg) until about 1945;
Octel (now Innospec Corporation) presently operates a plant in
Almwych, Wales. A second British plant was located at Hayle
in Cornwall (Robert, 1983).
In 1952, the Freeport plant expanded and the North Carolina
plant closed down (Robert, 1983). The Freeport upgrades promoted annual EDB and EDC production rates of 28.5 million
pounds and 15 million pounds, respectively (Spitz, 1988). Those
rates increased throughout the 1950s. In 1969, Ethyl extracted
bromine from wells in Arkansas, in a joint venture with the
Great Lakes Chemical Company. The Arkansas plant continued
to produce until the late 1990s (Robert, 1983; Doyle, 2004). By
the 1970s, four EDB manufacturers were active in the US: Dow,
Ethyl, PPG, and Great Lakes. By the mid-1980s, Ethyl and PPG
no longer manufactured EDB in the US. The EDB section of
Dow’s Freeport plant closed in 1987 (Doyle, 2004).
Tetraethyl Lead Extenders
In the late 1950s, several companies augmented TEL with some
amines, phenols, monocarboxylic acids, and alcohols, known as
TEL extenders, in order to increase octane ratings. Extenders
also interfered with agglomeration and prolonged the shelf life
of anti-knocks (Richardson et al., 1961a). Chevron added acetic
acid at 1 wt% to gasoline containing 6 mL of anti-knock fluid per
gallon to increase octane by approximately 6 points (Richardson
et al., 1961a). The ratio of acetic acid to TEL was 15 to 1.
A second extender was tert-butyl acetate, which decomposed
to form acetic acid and iso-butene (Richardson et al., 1961b).
In 1959, Texaco added tert-butyl acetate (known as ‘TLA’ or
Texaco Lead Appreciator) (Anonymous, 1959).
Although not exactly TEL extenders, boron and silicon compounds were added to leaded gasoline resulting in an octane
increase. These compounds removed lead deposits in the combustion chamber (Hughes et al., 1951). They also increased
compression ratio and caused knocking. Some boron additives
include: ethyl borate, iso-butyl borate, n-butylborine and tertbutylborine. From the 1950s until about 1980, Sohio marketed a
gasoline known as Boron containing these compounds (Richardson et al., 1961b). Richfield also offered a grade with boron
additives in the 1960s (Anonymous, 1961a).
In 1953, Shell began to add tricresyl phosphate (TCP) to
its premium-grade gasolines as a combustion-chamber-deposit
modifier (Gibbs, 1990). A premium-grade with 3.17 g/gal of
lead would contain approximately 380 ppm of TCP. At about
the same time, Conoco began to add TCP to its gasoline as
well (Anonymous, 1954). Eventually, cresyl diphenyl phosphate was used more frequently. Other phosphorus-containing
additives included (with their trade names in parentheses):
methyl diphenyl phosphate, tris chloropropyl thionophosphate
(Ethyl ICC 1), mixed methyl phenyl phosphate (Ethyl ICC 3),
trimethyl phosphate (Ethyl ICC 4) and tris chloroethyl phosphate (Enjay Paradyne 101) (Barusch et al., 1974).
Air-pollution regulations ended the use of phosphates in unleaded gasoline in 1974 (Gibbs, 1990). Their use in leaded
gasoline probably ended not long afterward.
Like the halogens that are added to gasoline on a “theory”
basis, the concentration of phosphorus is also spoken of in theory
units. “One theory of phosphorus” is defined as the amount of
phosphorus needed to convert all of lead in gasoline to lead
orthophosphate (Pb3 (PO4 )2 ). Phosphorous was normally added
at a concentration of 0.2 to 0.5 theories (Barusch et al., 1974).
In 1964, Sinclair proceeded to add nickel isodecycloorthophosphate as a combustion- chamber-deposit modifier
at a concentration of 2 to 3 ppm. In 1968, the additive was
changed to zinc isodecycloorthophosphate because of the potential toxicity of nickel. In 1971, its use was discontinued (Gibbs,
1990).
Mixed Lead Additives
Introduction of Alternative Organolead Anti-Knocks
In the 1950s, several oil companies, as well as DuPont and
Ethyl, researched TEL alternatives. After approximately 35
years of TEL usage, a second organolead, TML, was found
to have advantages and was introduced (Stormant, 1960). These
advantages were greater in European gasoline and TML usage commanded a greater market share overseas (Oliver and
Rowling, 1965).
The 1950s brought the “muscle car,” compression ratios increased and higher octane was needed; from 1952 to 1958 the
average compression ratio increased from 7.2 to 9.5 (Gibbs,
1990). By 1960, average octane ratings (RON) for premium and
regular were 99.3 and 92.4, respectively (Anonymous, 1960).
Reforming and catalytic cracking became common refining
methods and the aromatic and olefin content of gasoline increased. Back in 1930, approximately 30% of gasoline had been
produced through thermal cracking, less than 10% had been
thermally reformed and the remainder had been straight run. By
1960, thermally cracked gasoline accounted for approximately
10% of the total, whereas catalytically cracked and catalytically
reformed gasolines each accounted for approximately 35%. In
1960, straight-run gasoline accounted for only 10% (Perry et al.,
1960). As gasoline changed and engines became more powerful,
TEL began imparting various octane ratings based on RON and
MON methods (Graiff, 1966). At low speeds, TEL was not distributing evenly around the cylinders, lowering the octane (Korn
and Moss, 1960). However, TML is more volatile and increased
volatility helped its distribution. Based on Ethyl’s studies:
! TML was more effective in gasoline with a higher reformate
content (more aromatics) (Pastell and Morris, 1960; Morris,
1962);
33
! TML was more efficient with the MON method compared to
the RON method (at lower speeds) (Hesselberg and Howard,
1961);
! In comparison to TEL, TML’s effectiveness did not diminish
as quickly at higher concentrations (Korn and Moss, 1960);
and
! TML worked better at lower sulfur concentrations (Oliver and
Rowling, 1965).
Composition of the Mixes
In 1960, California Standard and New York Standard began
to use an additive package that included physical and reaction
mixtures of TEL and TML (Shapiro and Frey, 1968). Ethyl was
the first manufacturer of TML in the US (Robert, 1983) and their
package was known under the trade name Mixed Lead Alkyls or
“MLA” (Barusch et al., 1974).
California Standard’s trade name for the gasoline that used
this package was Methyl (Barusch et al., 1974). In California
Standard’s gasolines of 1960, TML completely replaced TEL in
selected grades (normally premium grade), although both TEL
and TML were typically used in regular and super-premium
grades (Stormant, 1960). Later in 1960, DuPont also began to
offer packages containing both TEL and TML. These mixedlead packages offered by DuPont were known as Tetramix (Bart,
1960). Later in the 1960s, Nalco and PPG also offered similar
packages known as Nalkyl ME and MAF, respectively (Galperin
and Kaplan, 2008).
Two types of mixed-lead packages were offered to refiners:
a physical mix that consisted solely of different percentages of
TEL and TML, or a reactive mix that contained the byproducts
of a catalyzed reaction (also known as a redistribution reaction)
between TEL and TML. In general, studies showed that reactive
mixes gave slightly better engine performance than physical
mixes, but they were more expensive (Morris, 1962).
In 1960, California Standard and New York Standard introduced several different lead packages in their gasolines, containing various concentrations of TEL, TML, and their reaction
byproducts: trimethylethyl lead (TMEL), diethyldimethyl lead
(DEDML), and methyltriethyl lead (MTEL) (Stormant, 1960)
(Tables 8). The reaction byproducts were obtained through the
catalytic reaction (Shapiro and Frey, 1968) and they required a
catalyst, even after prolonged heating (Calingaert and Beatty,
1939). However, Wood (1965) noted that these reaction byproducts could form if the Ethyl Fluid were stored for more than
200 days. Wood (1965) also found that some additives, such
as trimethyl phosphate, accelerated the reaction, but manganese
additives, such as methyl cyclopentadienyl manganese tricarbonyl (MMT), decelerated it.
A physical mixture contained 20%, 50%, or 80% of either
TEL or TML (PM20, PM50 and PM80), but the initial mixture
used for the redistribution reaction contained 25%, 50%, or 75%
of TML, which produced different proportions of the reaction
products: TMEL, DEDML and MTEL. Boiling points for the
reaction products are between those of TEL and TML (Tables 9
34
Oudijk
Table 8. Characteristics of the methyl and ethyl organoleads (“the mixes”), methyl cyclopentadienyl manganese tricarbonyl (MMT) and
the organic-iron additives
Name
Formula
TEL
MTEL
DEDML
TMEL
TML
MMT
Ferrocene
Iron carbonyl
(C2H5)4Pb
CH3(C2H5)3Pb
(CH3)2(C2H5)2Pb
(CH3)3(C2H5)Pb
(CH3)4Pb
C9H7MnO3
Fe(C5H5)2
Fe(CO)5
Molecular
weight
(g/mol)
Boiling
point
(◦ C)
Melting
point
(◦ C)
Vapor
pressure
(torr 20◦ C)
Density
(d20
4 )
Aqueous
solubility
(mg/l/L)
Flash
point
(◦ C)
323.44
309.41
295.38
281.36
267.33
218.10
186.04
195
200
70
51
27
109
231.67
249
103
−133
−30
NA
NA
−30.2
2.22
173
−20
0.26
0.75
2.2
7.3
22.5
7
NA
35
1.66
1.71
1.79
1.88
2.00
1.39
1.49
1.45
0.25
1.9
4.6
7.65
15
29
NA
NA
85
NA
NA
NA
38
96
NA
−15
Odor
Fruity
NA
NA
NA
Odorless
Herbaceous
Camphor
Odorless
Data from Hesselberg and Howard (1961); Lansdown and Yule (1986); Gangolli (1999); Craig (2002); Commonwealth of Australia (2003); Howe
o
et al. (2004); Elvers (2007); Patolka (2008). d20
4 , density at 20 C; mg/L; DEDML, diethyldimethyl lead; methyl cyclopentadienyl manganese
tricarbonyl; MTEL, methyltriethyl lead; TEL, tetraethyl lead; TMEL, trimethylethyl lead; TML, tetramethyl lead.
and 10). DuPont may also have offered a package containing
only TML and scavengers (E. I. DuPont, 1961). The different
packages sold by one manufacturer resemble those of the same
type of other manufacturers. Less than 1% of the sales from
all four were non-standard mixes. The non-standard mixes were
generally the same as the standard ones, but contained only EDC
as scavenger (FTC, 1983).
With regard to the different packages offered on the market,
Barusch et al. (1977) reported that,
Redistribution reaction products [the reactive mixes] are marketed
under the trade name Mixed Lead Alkyls (MLA) by the Ethyl Corporation and Tetramix (TMEL) by DuPont. Houston Chemical and
Nalco also market these materials. Ethyl’s MLA 250 is identical
to DuPont’s TMEL 25 and is the redistribution product obtained
from a mixture of 25% TML and 75% TEL. Similarly, MLA 500
is identical to TMEL 50 and is manufactured from an equimolar
mixture of TML and TEL (p. 20).
Kerosene was commonly added to standardize the strength
of the anti-knock package. To handle TML safely during manufacturing, toluene was used as a diluent. Toluene was also used
as a standardizing agent for the TML and Tetramix antiknocks.
DuPont’s mixtures could be obtained with 13 types of dye rangTable 9. Approximate weight percentage of total lead in
individual organoleads for commercial reacted mixes
ing in concentration from 0.29 to 1.18 g/100 US gallons (E. I.
DuPont, 1961).
Market Share of the Mixes
In 1976, Ethyl estimated that mixes constituted 20% of the lead
market. Nalco’s sales were essentially all TML and made up
approximately 46% of the total 1978 TML market. In 1977,
PPG stopped producing TML and began purchases from Nalco
(FTC, 1983).
The type of lead package used depended on the refiner’s needs
and on economics. According to Stout et al. (2002), mixing of
different lead packages did not occur in the same gasoline.
However, different packages could be added to different grades.
The same lead scavenger concentrations: 0.5T bromine and 1.0T
chlorine, were used with the mixes both in the US and Europe
(Oliver and Rowling, 1965) (Table 10).
Usage Time Frame of the Mixed Leads
The mixes “caught on” with many companies, especially smaller
refiners with less modern equipment. Use of mixes had begun
in 1960 (Stormant, 1960), but popularity in the US did not
spread quickly (Wakim et al., 1990). In 1960, TML production
Table 10. Approximate weight percentage of total lead in individual
organoleads for commercial physical mixes
Reacted mixes (RM)
Organolead
TEL
MTEL
DEDML
TMEL
TML
Physical Mixes
RM25 (%)
RM50 (%)
RM75 (%)
28.80
49.51
18.60
2.99
0.10
4.83
25.59
42.40
23.40
3.79
0.09
3.61
20.51
49.60
26.19
Data from DuPont (1961). DEDML, diethyldimethyl lead; MTEL,
methyltriethyl lead; TEL, tetraethyl lead; TMEL, trimethylethyl
lead; TML, tetramethyl lead.
Organoleads
TEL
MTEL
DEDML
TMEL
TML
PM10 (%)
PM25 (%)
PM50 (%)
PM75 (%)
90.0
0.00
0.00
0.00
10.0
75.0
0.00
0.00
0.00
25.0
50.0
0.00
0.00
0.00
50.0
25.0
0.00
0.00
0.00
75.0
Data from DuPont (1961). DEDML, diethyldimethyl lead; MTEL, methyltriethyl lead; TEL, tetraethyl lead; TMEL, trimethylethyl lead; TML,
tetramethyl lead.
Table 11. United States (US) production of tetraethyl
lead (TEL) and tetramethyl lead (TML), 1962–1985,
in millions of US pounds
Year
TEL
TML
%TEL
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
494
—
587
549
543
555
485
371
325
281
302
353
464
315
364
327
328
412
325
275
224
—
—
—
18
—
—
138
109
299
460
506
504
—
670
763
455
353
—
553
463
433
192
132
130
106
107
27
96.0
—
—
80.0
83.2
65.2
51.3
42.0
39.2
—
31.1
31.6
50.4
47.2
—
37.2
41.5
48.8
62.8
67.5
63.2
—
—
—
Data from Wakim et al. (1990); Davenport et al. (2002).
—, quantity is not reported.
was 5 million pounds (Shapiro and Frey, 1968). In 1962, TEL
production was 494 million pounds versus 18 million pounds
for TML (Wakim et al., 1990). California Standard and Socony
began usage in 1960 (Stormant, 1960); however, the introduction
dates for other refiners are not known. Later in the 1960s, TML
production remained approximately 50% that of TEL (Rhue et
al., 1992), although Ethyl stated that mixes accounted for only
20% of the market in the 1970s (FTC, 1983). Contradictory data
provided by Wakim et al. (1990) show that TML became more
popular than TEL by 1969, and in the early 1970s, close to 70%
of the US organolead usage was TML (Table 11). This suggests
that most US refiners were using TML by the early 1970s.
The growing use of TML in the late 1960s presumably reflected Nalco’s late entry into the market. Nalco, in partnership
with Indiana Standard, invented a new electrolytic process for
manufacturing TML and began sales in late 1963 as a TML-only
producer (Barusch et al., 1974; Wakim et al., 1990).
Use of mixes declined after 1980. Some suggest that mixes
were not used at all after 1980 (Hurst, 1996; Stout et al., 1998;
Morrison, 2000b). Others state that use continued until approximately 1985, and possibly later (Kaplan et al., 1997). According
to Wakim et al. (1990), TML constituted close to 70% of production during the early 1970s (TML used exclusively as an
anti-knock agent) (Table 11). However, in 1980, this percentage
declined. The reduction probably was caused by costs, lack of
manufacturers and the impending phase-out of leaded gasoline.
The mixed-lead packages were more expensive than TEL-only
35
packages (Shapiro and Frey, 1968) and the quantity of leaded
gasoline was declining. By the end of 1982, only 47% of the
market was leaded (Chamberlain, 1991) and most of it was regular grade (Gibbs, 1990). TEL-only packages constituted 93%
of the market in 1985 (Wakim et al., 1990). After 1980, TEL
was the predominant organolead and after 1985, presumably
mixes were no longer used or received minimal use. Furthermore, Nalco, which produced approximately 50% of the TML,
had significantly reduced its production by late 1982 (Anonymous, 1982a). The loss of Nalco’s TML meant that 5% or less
of the market was attributable to mixes by the end of 1982. In
1983, DuPont was the sole US manufacturer of TML (Kuney
and Mullican, 1983). Nalco totally closed its TML facility in
Freeport, TX, in September 1985 and DuPont’s TML manufacturing in Deepwater, NJ, ended in 1984 (Wakim et al., 1990).
Consequently, TML production in the US ceased after 1985.
Towards the end, small refineries, which presumably could
not meet octane requirements without lead additives, clung to
the mixes. By 1981, leaded premium essentially disappeared.
After 1981, Getty was the sole manufacturer of leaded premium
on the East Coast and it stopped production in 1984 (Morris,
1983). Because mixes were commonly used in premium grades,
but not always (Wakim et al., 1990), this is evidence that they
were used less frequently in the US after 1981.
The Mixes Worldwide
Mixes were used in the UK, Japan (Tokunaga and Uthiumi,
1997), Puerto Rico (Oudijk, 2005), Brazil (Schifer et al., 2005)
and continental Europe as early as 1961 (van Rysselberge and
Leysen, 1961). TML was more popular in Europe than in the
US because of the local popularity of manual transmissions
(Harwood, 1963; Robert, 1983). Stormant (1960) indicates that
patents had been obtained for TML in Europe in 1960, whereas
in the US, they had only recently been applied for. Mixes were
used in Brazil until the phase-out in the early 1980s (Schifer
et al., 2005).
Usage in Europe lasted longer than it did in the US; mixes
were used in Spain as late as 2000 (Encinar et al., 2001). In
Canada, mixes held on until the phase-out in 1990. Patriarche
and Campbell (1999) report that in the last two years of Canada’s
lead usage, TML accounted for approximately 39% of the total. The actual percentage likely is higher because it included
aviation gasoline, which reportedly does not contain TML in
Canada.
The Lead Phase-Out
At this point, a few terms should be defined:
! phase-down is the lowering, but not complete removal, of lead
! phase-out is the complete removal, or banning, of organic
concentrations in gasoline by regulations;
lead in gasoline; and
36
Oudijk
! roll-back schedule is the progressive lowering of lead concen- The United States Government’s Phase-Down of
trations with time with known concentration ranges at specific
years.
Why Organolead Anti-Knocks were Phased Out
Between the 1970s and the present, leaded-gasoline usage
was phased out in the US and most of the developed world
because:
! medical evidence showed that adverse health impacts linked
!
!
!
!
!
to lead occur at low exposure levels. The most severe impacts
affect children (Needleman, 2000);
catalytic converters introduced in response to growing air
pollution require the use of unleaded gasoline; organoleads
inactivate the catalysts (typically palladium and platinum) in
these devices (Otto and Montreuil, 1976);
modern refining methods were developed, enabling octane
ratings to increase without lead additives (Colucci, 2004);
the recent use of high-grade hardened metal parts eliminated
the need for special lubrication of engine valve seats, which
was provided by the organolead additives (Lovei, 1998);
lead scavengers increased corrosion of exhaust system components, particularly mufflers and tailpipes (Faust and Sterba,
1970), and
the life of sparkplugs would be increased significantly with
the use of unleaded gasoline (Colucci, 2004)
Dr. Clair Patterson, a geochemist at the California Institute
of Technology (“Cal Tech”) (Pasadena, CA), spearheaded the
lead phase-out. Patterson (1965) found anomalously high lead
concentrations in the atmosphere, in Greenland’s ice caps and in
human blood and all were attributable to car exhausts (Patterson,
1965; Nriagu, 1998). He concluded that this lead was subjecting
people to “severe chronic lead insult.” After he presented his
findings to Congress, the US government began to remove lead
from gasoline. Dr. Herbert Needleman, a psychiatrist at the
University of Pittsburgh, made chemical analyses of teeth and
discovered the deleterious effects of gasoline-lead exposure on
children (Rosner and Markowitz, 2005). Needleman went on to
document the negative impact of leaded-gasoline exhausts on
children’s health and he then advocated a lead phase-out.
The problem with introducing unleaded grades was the need
for high octane ratings. The compression ratios of automobiles
of this era were high. In the 1960s and early 1970s, oil companies
such as Jersey Standard and Texaco offered leaded grades with
octane ratings of 99 (Esso Extra) and 100 (Texaco Sky Chief),
respectively (Schulz, 1971). Accordingly, removing organoleads
from gasoline would cause a corresponding lowering of the
octane rating, unless more advanced refining techniques were
employed. Therefore, to prevent knocking, engines with lower
compression ratios would be needed. Because older cars can
still be used, the phase-out could not be immediate and there
would need to be concurrence with the automakers.
Organoleads
The first US legislation dealing directly with leaded gasoline
was passed in 1967 when Congress required that all gasoline
additives be registered. In 1970, because of numerous and frequent smog problems, Congress passed the Clean Air Act.
In 1970, President Nixon asked refiners to remove lead from
gasoline by 1971 (Johnson, 1983). Nixon indicated that if this
were not done voluntarily, law would mandate it. Union, Atlantic, Phillips, and Gulf indicated that they would offer an unleaded grade (Kentworthy, 1970). However, Union and Phillips
ended up only offering low-lead grades in California in 1970. In
late 1970, Union offered a 93.5-octane grade with an 80% lead
reduction in California and Nevada (Rosenblatt, 1970). Amoco
had already offered an unleaded grade, which was available in
25 states, Shell began offering an unleaded grade and Sun and
Humble made available a low-lead grade (Johnson, 1983). As of
1970, the lead content of Murphy’s premium grade was reduced
by 25% to 75%. The lead content of Murphy’s 100-octane grade
remained unchanged (Anonymous, 1970g).
However, other refiners ignored Nixon’s request. Many offered only low-lead grades or no unleaded grades until forced to
do so. Prime examples included: Conoco, Jersey Standard, and
Sun (Anonymous, 1973: Johnson, 1983). The lack of response
by the oil companies led to more legislation.
Shell’s unleaded grade (91-octane), known as Shell of the
Future, was introduced in October 1970, but withdrawn in August 1972 because of poor sales (Anonymous, 1972a, 1972b). It
had been marketed throughout Shell’s marketing territory as of
November 1970. Shell reintroduced a lead-free grade in 1974
(Mateja, 1974).
Sun offered a 90-octane grade in the summer of 1970 with
0.5 g/gal of lead, whereas Amoco offered a lead-free 91-octane
grade in the spring of 1970 (Johnson, 1983; Dedmon, 1984).
Gulf also offered a low-lead grade in 1970 (Morrison, 2000b).
Arco began to offer an unleaded, 91-octane grade, known as
ARCOClear in Los Angeles, Chicago, Philadelphia, Detroit,
and Washington, DC in June 1970. Most Atlantic stations (part
of Arco) were carrying an unleaded grade by the end of 1971,
while Richfield stations (also part of Arco) had unleaded grades
by the end of 1972. In 1971, the average lead content nationwide
of regular-grade dropped from 2.42 g/gal to 2.23 g/gal, and
in premium-grade, it dropped from 2.81 g/gal to 2.65 g/gal.
However, a significant amount of lead was still being used. The
year 1970 is considered to be the peak in US lead usage, although
some records show 1969 as the peak (Johnson, 1983; Shelton
et al., 1982). US EPA records show that the maximum usage
of automotive-gasoline lead occurred in 1970 at 232 kilotons
(Caldwell, 1992).
In 1971, market share of unleaded or low-lead fuel being
sold was only 3% (Anonymous, 1971a) (Table 12). Despite
the availability of unleaded grades, sales were sub-par because
prices were typically US $0.01 to US $0.04 higher per gallon
than they were for leaded grades. Economic analyses revealed
Table 12. Oil companies that had introduced unleaded or
low-lead grades of gasoline by September 1970 in the United
States
Oil
company
Low
lead
Unleaded
Octane
rating
Lead
Concentration (g/gal)
Amoco1
—
—
X
—
X
X
X
X
X
—
X
X
—
X
—
X
X
X
—
X
X2
—
—
—
—
X
—
—
X2
—
X2
—
91
100
91
91
91
94
91
96–97
91
91
93.5
91.5
91
91
91
93.5
0
0
NA
0
0
0.5
0.5
0.5
NA
0
<0.5
NA
0
0.5
0
0.5
Ashland
Arco
Chevron
Gulf
Humble
Mobil
Murphy
Phillips
Powerine
Shell
Sun
Texaco
Union
Data from van Dyke (1970); Anonymous (1970c).
1 Amoco had previously offered an unleaded grade of gasoline in the
eastern and southern states. 2 Available only in western states. X =
being offered as of September 1970. — = not being offered as of
September 1970.
that the lack of price incentives caused the phase-out to last four
years longer (Borenstein, 1993).
In 1972, the US Bureau of Mines made a study of the average
octane ratings of gasoline throughout the US. It found that although organolead concentrations had declined, octane ratings
had been maintained. The Bureau attributed the steady octane
levels to improved refining and blending practices (Anonymous,
1972c).
Despite the fact that it was the first refiner to offer an unleaded
grade in 1970 (except for Indiana Standard), Texaco confined
its unleaded sales (known as Lead-Free Texaco) to California
and offered only a low-lead grade for the rest of the country
(Anonymous, 1970a). Union actually had some success with
its low-lead gasoline. In 1971, sales of Union’s low-lead grade
exceeded 39% of its total gasoline sales (Anonymous, 1971b).
Lead concentrations in regular-grade gasoline declined from
an average of approximately 2.5 g/gal in 1971 to less than 1.6
g/gal in 1979 (Figure 3) (Shelton et al., 1982). The US EPA mandated that major retailers offer at least one grade of 91 RON unleaded by July 1, 1974, at all stations exceeding sales of 200,000
gallons annually (US EPA, 1973; Anonymous, 1974a). The US
EPA’s regulation was issued at the end of 1972 and required that
the unleaded gasoline have a lead concentration of less than 0.05
g/gal and a phosphorous concentration of less than 0.005 g/gal
(Anonymous, 1972d). The US EPA also required that companies with six or more stations offer unleaded gasoline at least
60% of their locations. The US EPA allowed RON adjustments
for elevations exceeding 2,000 feet, with reduction of 1 unit for
each 1,000 feet above sea level and up to 3 units at 5,000 feet
(Anonymous, 1972e). These regulations affected 50% of the
37
220,000 existing stations. Despite the regulations, 38% of the
affected stations were not offering unleaded gasoline at the time
of the deadline (Anonymous, 1974b). Stations selling 150,000
to 200,000 gallons annually were given until October 1974 to
meet the requirements (Anonymous, 1974c).
In 1971, New York City passed regulations differing from
federal ones, requiring a more rapid phase-out (Johnson, 1983).
Five oil companies: Mobil, Sun, Getty, Shell, Humble, Gulf, Texaco, Chevron, and Cities Service, unsuccessfully sought an injunction against this regulation (Bird, 1973; Schoenbrod, 2006).
The US EPA mandated that refiners implement a rollback
schedule to an average lead content of 1.7 g/gal by January
1, 1976, and 0.5 g/gal by January 1979 (Anonymous, 1975a).
The US EPA was sued by the National Petroleum Refiners Association (plus four refiners) and the mandate was reversed in
January 1975 (Anonymous, 1975b; Anonymous, 1976). The
mandate was reinstated by appeal in March 1976 (Anonymous,
1976). The court considered the Clean Air Act to be precautionary and did not require proof of actual harm for the regulations
to be appropriate (Kovarik, 2005).
In January 1978, the US EPA ordered that lead contents must
be lowered to 0.8 g/gal at large refineries and to 2.65 g/gal at
small refineries. Therefore, from 1978 to 1982, average lead
contents could range from 0.8 g/gal to 2.65 g/gal. However,
most refineries were large and the 0.8 g/gal limit would have
prevailed. A small refinery produces less than 50,000 barrels
per day, has operated or was under construction since October
1976, and was not owned by a company with a total capacity of
70,000 barrels per day or more (Needleman, 2000).
By 1981, for the first time since the 1920s, more unleaded
than leaded gasoline was sold in the US. However, the US EPA
subsequently reversed course and changed its rollback schedule,
requiring average lead concentrations of 1.1 g/gal by November
1982, 0.5 g/gal by July 1985, and 0.1 g/gal by January 1, 1986
(Kaplan, 2003). In California, the limit was changed to 1 g/gal
in October 1984 for premium grade (92 octane or higher) and
0.8 g/gal for regular grade (less than 92 octane) (California Air
Resources Board, 1984). The federal regulation was changed
in July 1983 to a maximum leaded pool limit of 1.1 g/gal for
all refineries, allowing some refineries to market some brands
with lead higher than 1.1 g/gal and some lower (Kaplan, 2003).
In 1984, Chicago completely banned sales of leaded gasoline
(Anonymous, 1984).
The End of Leaded Premium
By 1981, leaded premium grades were almost nonexistent
(Gibbs, 1996a, 1996b). By April 1980, Texaco, Conoco, and
Phillips stopped selling leaded premium in most of the country.
Texaco discontinued their leaded, premium-grade (Sky Chief)
in 1980 and replaced it with Super Lead-Free Sky Chief. Shell,
Arco, Amoco, Mobil, and Gulf took similar steps in 1978 (Potts
and Atlas, 1980). Clark, a Midwest refiner, had discontinued its
leaded premium grade as early as 1974 (Broadway, 1974). Sun
discontinued leaded premium along the East Coast in late 1980
38
Oudijk
(Johnson, 1983) and Exxon discontinued its leaded premium in
the Eastern and Southern states in 1981. Other companies, such
as Chevron, continued production of leaded premium in the East
for approximately one more year. However, BP, Citgo, Phillips,
Hess, and Union discontinued leaded premium in some regions
as early as 1974 (Hodge, 1974a, 1974b).
In 1974, filling stations on New Jersey’s Turnpike and Garden
State Parkway stopped selling leaded premium (Anonymous,
1974d). In Washington, DC, leaded premium was difficult to
find by early 1978 (Anonymous, 1978a). In 1974, 10% of filling
stations in the country did not offer leaded premium (Anonymous, 1974e). The abandonment of premium grade was caused
by poor sales (Anonymous, 1980a).
In 1970, the percentage of leaded premium was 42% of the
total gasoline sold, but by 1980, it was less than 5%. The only
holdout in the East for leaded premium was Getty. In 1970,
Getty began to offer only one grade of gasoline: leaded premium
(Anonymous, 1970b). In 1974, it changed its marketing philosophy and offered both regular and premium grades. In 1983, it
began to replace its leaded grades with unleaded (Morris, 1983).
By 1984, Getty no longer sold leaded gasoline and was the first
company to quit completely.
Union continued to sell a premium leaded grade until 1986,
but only in the Far West, and it did not introduce an unleaded
premium until sometime after 1986 (Obel and Williams, 1986).
In 1970, Amoco distributed a premium-grade unleaded gasoline
in the eastern and southern states. This grade accounted for 20%
of Amoco’s sales at that time (Smith, 1970).
In Europe, leaded regular was phased out first. Leaded regular
was phased out in the 1980s, whereas leaded premium continued selling until 2000, although sales of leaded were minimal
compared to unleaded at this late date.
The Introduction of Unleaded Premium
In the late 1970s, many oil companies introduced an unleaded
premium grade. For example, Arco and Marathon first offered unleaded premium sometime around Christmas of 1980,
whereas Mobil had already begun to do so in November
1978 (Roche, 1978; Anonymous, 1980b; Anonymous, 1980c).
Chevron began offering an unleaded premium grade in early
1981 (Anonymous, 1980d), while Exxon began selling unleaded
premium in 1978 in Canada, but not until 1980 in the US
(Anonymous, 1978b; Anonymous, 1986). As noted earlier, Indiana Standard had always offered an unleaded premium grade
and they were the first oil company to offer both a regular and
premium unleaded grade throughout their marketing territory
(Pratt, 2000).
Use of Pool Averages
The organic lead concentrations in gasoline mandated by the
US EPA were for pool averages. A pool is the gasoline of a certain grade that was manufactured by a refinery during a certain
quarter. Therefore, some batches could have a lead concentration
exceeding the mandate. In the early parts of the phase-out (the
mid- to late-1970s), the pool was considered all the gasoline
(leaded and unleaded) manufactured by a refinery. Towards the
end of the phase-out (early-1980s to the end of the 1980s), the
pool was considered to be only the leaded gasoline.
Before 1982, many blenders could produce gasoline with a
lead concentration of up to 2.65 g/gal (Hershey, 1982); however, the US EPA changed its regulation to include blenders in
1982 (Anonymous, 1982b). As of 1982, 74 facilities qualified
as “small refiners,” accounting for 3.5% of domestic gasoline
production and 9.6% of lead usage (Anonymous, 1982c).
Gasoline imports, which were a small fraction of the nation’s
supply, were not subject to the US EPA’s lead-concentration mandates (Hershey, 1982). During the first quarter of 1985, imported
gasoline contained an average lead concentration of 0.8 g/gal,
whereas the US refinery average was 0.32 g/gal (Anonymous,
1985; Dickson et al., 1987). Imports accounted for approximately 4.4% of the leaded gasoline used at this time.
Lead Credits and Banking
To ease the phase-out process, the US EPA allowed trading in
lead credits among refiners and importers beginning in November 1982. Refiners and importers who reduced their average
lead contents in their pools below the US EPA’s limit generated
credits that could be sold to those exceeding the limit. Credits
generated in any quarter had to be used in that quarter. In 1985,
the US EPA allowed refiners to bank credits until the end of
1987. Refiners and importers were required to report quarterly
all trades, banking deposits, withdrawals and volumes (US EPA,
1995).
Participants performing trades increased from 165 in the third
quarter of 1983 to 537 in the third quarter of 1985. The number
of depositors peaked at 416 in the second quarter of 1985 and
those making withdrawals peaked at 213 in the second quarter of
1986. Significant trading and selling took place during this time
and lead concentrations could have been significantly variable,
depending on the refiner or blender (US EPA, 1995) (Figures 4
and 5). Accordingly, the legal mandate of 0.1 g/gal was probably
not reached until 1988 (Kaplan, 2003).
The Final United States Phase-Out
The final “nail in the coffin” for leaded gasoline was neither
its adverse impacts on human health nor its effect on air pollution (through the inactivation of catalytic converters). The US
government was finally convinced to phase out leaded gasoline because the US EPA found that the use of unleaded gasoline would be less expensive in the long-term (Schwartz et al.,
1985). Schwartz and his colleagues showed a striking correlation between sales of leaded gasoline and lead concentrations
in children’s blood. A cost-benefit analysis was then performed
and it was shown that costs associated with these impacts to
children were greater than the price for converting to unleaded
fuels.
The oil companies discontinued sales of leaded gasoline at
different times in different regions of the US. For example,
Exxon ended sales along the East Coast in late 1986 (Anonymous, 1986), whereas Shell discontinued sales east of the Rocky
Mountains only by 1989 (Musick, 1989). Chevron discontinued
leaded in Florida (except in the Panhandle) and southeast Georgia in 1987 (Anonymous, 1987). By early 1989, Mobil, Sun,
Amoco, and Arco were no longer selling leaded in the New
York area; however, Hess offered leaded until sometime in late
1989 (Sauer, 1989). After October 1989, only Chevron offered
a leaded grade along the East Coast (Musick, 1989).
Zitomer (1993) reported that in 1980 approximately 53% of
US refinery output of motor gasoline was leaded. By 1985, the
output was less than 36% and by 1990, less than 5.2%. In 1992,
the output was 3%. In 1987, most oil companies began offering
three unleaded grades: regular (87 octane), mid-grade (89) and
premium (92 or higher). Accordingly, many companies were
eager to use up their lead credits. Use of the credits caused lead
concentrations in 1986 to frequently exceed US EPA mandates
(Obel, 1986).
After 1988, leaded gasoline was scarce in the eastern US
(Schmidt, 1989). In January 1988, all banking and credits were
exhausted (US EPA, 1995). In places such as New Jersey or
New York, leaded grade was sold only at particular stations or
could be purchased as a supplement.
The lack of leaded gasoline was particularly problematic for
farmers. Farm equipment, which during this time ran exclusively
on leaded gasoline, may last for many years to decades. It was
exempt from the US EPA’s ban. However, leaded gasoline often
was not available for farming equipment (Anonymous, 1989).
Leaded gasoline was completely banned in California in 1992
and in the entire country (the 50 states) in 1996. The ban was
originally set for 1988, but it was delayed because of lobbying by
western states where cars can last longer (Schwartz et al., 1985).
The maximum allowable lead concentration in unleaded in 2009
is 0.05 g/gal in the US and European Union (EU) (CONCAWE,
1992).
The Pacific Northwest completed the phase-out last. Because
of the milder climate, roads are commonly not salted and old
cars are not uncommon. When the ban took effect on January
1, 1996, many stations in Oregon and Washington waited to the
last minute to change over (Anonymous, 1995a).
Significant lead usage occurred in New Mexico in the 1990s.
For example, Chevron halted sales east of the Rocky Mountains in the late 1980s, but in 1993, leaded sales in New
Mexico were still approximately 10%. In 1993, Total’s leaded
sales in New Mexico were still approximately 5% (Rothenberg,
1993).
By 1995, only Chevron was producing leaded grades (US
EPA, 1996). Chevron stations in western Washington and western Oregon replaced their leaded grade in May 1995 with an
unleaded mid-grade known as Chevron Plus Unleaded. Stations in northern Idaho made the change in the summer of 1995
(Anonymous, 1995b). Exxon and Conoco stations in the Northwest (presumably obtaining their leaded grade from Chevron
39
through supply agreements) also discontinued their leaded grade
in the summer of 1995 (Anonymous, 1995c).
Use of leaded motor gasoline continued in some US territories after the ban. For example, leaded grades could be found
in the US Virgin Islands and Puerto Rico in 1998 and 1999,
respectively. However, at this late date unleaded was by far the
predominant automotive fuel in these US territories (J. Negron,
personal [oral] communication, 2007 [Geo-Envirotech Corporation, San Juan, PR]).
Exemptions from the United States Phase-Out
Vehicles and activities exempt from the organolead ban in the
US are: auto and boat racing, aviation, farming, lawn equipment, and airport vehicles (US EPA, 1996). Aviation gasoline is
solely for propeller-driven aircraft and this exemption appears
to be worldwide. As of 2009, National Association of Stock
Car Auto Racing (NASCAR) events in the US are significant
users of leaded gasoline. However, as of 2009, it is reported
through several websites that NASCAR has eliminated or lessened the use of leaded gasoline in their events. Innospec in the
UK produces TEL for the gasoline used in these racing vehicles
(available at: http://www.innospecinc.com) and refiners such as
Citgo, Shell, Sun, and Conoco-Phillips (under the Union 76
trademark) produce the fuel. An exemption for racing gasoline
also exists in at least Canada and Australia. Vehicles such as
jet-skis, snowmobiles, farm tractors and lawnmowers are also
exempt from the ban; however, finding leaded gasoline for these
vehicles may be very difficult.
Worldwide Lead Phase-Out
The first country to completely switch to unleaded gasoline
was Japan in 1988, followed by Brazil in 1990 (Nriagu, 1990)
(Table 13). In Canada, it took several years for unleaded gasoline
to be commonplace. In 1974, unleaded sales were merely 2% of
the total and many of them were from US tourists (Anonymous,
1974f). Most of the unleaded sales in Canada during the early
1970s were by Shell. However, Canada completed its phase-out
in 1990, 6 years ahead of the US.
In the UK, the maximum lead content in gasoline was set in
November 1974 at 2.12 g/gal. The previous limit had been 2.46
g/gal (Barry, 1975). In 1976, it was lowered to 1.9 g/gal and
then in 1978 to 1.73 g/gal (Berwick, 1987). After 1981, the UK
followed the EU standards.
In the EU, the maximum organic lead concentrations in premium and regular grades were set in 1978 at 1.54 g/gal and
0.58 g/gal, respectively (Yerkey, 1983). However, these concentrations were merely recommended and responses of the various countries differed. The Federal Republic of Germany (West
Germany [FRG]), Italy, and the UK responded quickly to the
recommendations; France was one of the slowest. In 1987, EU
countries were permitted to produce and use unleaded gasoline
(Hagner, 2000).
Organoleads were phased out completely in the EU in 2000.
Many individual countries had imposed stricter limits and had
40
Oudijk
Table 13. History of leaded gasoline usage in selected countries
Country
Leaded introduced
Unleaded introduced
Phasedown begins
Total ban
References
1933
1932
1939
<1980
1986
<1969
NA
1987
1971
1997
2002
1993
1931
1941
1926
NA
<1932
1928
1939
1934
NA
NA
1935
1985
<1953
1970
1997
NA
<1969
1989
1982
1995
1991
<1989
1979
1975
1973
1997
NA
1971
1989
1972
1994
1984
1992
2000
1991
1990
2000
>1998
19931
2000
1996
1998
>2007
2000
Japan
Korea (South)
Malaysia
Mexico
1927
NA
NA
1937
<1968
1987
1991
1991
1970
1987
1985
1986
19884
1994
1998
1997
Netherlands
New Zealand
Soviet Union5
1933
1939
∼ 1938
1985
<1995
1956
1978
1987
1956
2000
1996
2003
1945
1947
NA
1928
1923
1985
1985
1991
1987
19707
1970
1962
1984
1973
1970
1995
2000
1995
1999
19968
Wirth (1985); Lovei (1998)
Nriagu (1990); Cook and Gale (2005)
Aronov (1970); Robert (1983); Nriagu (1990)
Thomas et al. (1997)
de Vleeschouwer et al. (2004); Nriagu (1990)
Wirth (1985); Lovei (1998)
Anonymous (1926k); Nriagu (1990)
Luo et al. (2003)
Anonymous (1932); Lovei (1998)
Hagner (2000)
Hagner (2000); LaPerche et al. (2004)
Robert (1983); von Storch et al. (2003)
Thomas and Kwong (2001)
Foner (1992); Faiz et al. (1996)
Robert (1983); Thomas et al. (1997); Hagner
(2000)
Aronov (1970); Robert (1983); Nriagu (1990)
Faiz et al. (1996)
Lovei (1998)
Robert (1983); Driscoll et al. (1992); Kojima
and Lovei (2001)
Thomas et al. (1997); Hagner (2000)
Edgar (1939); Thomas et. (1997)
Thomas and Orlova (2001); Anonymous
(2003); Edelstein et al. (2007)
Sörme et al. (2001); Thomas et al. (1997)
Mosimann et al. (2000); Breu et al. (2003)
Sayeg (1998)
Berwick (1987); Thomas et al. (1999)
Kaplan (2003)
Argentina
Australia
Austria
Belgium
Brazil
Canada
China
Cuba
European Union
France
Germany2
India
Israel3
Italy
Sweden
Switzerland6
Thailand
United Kingdom
United States
NA, not available.
1 The official date for the ban in the European Union (EU) was 2000, although several countries completed the ban earlier. Portugal, Spain, and Greece were
given a 1-year ban extension to 2001.
2 West Germany (FRG) was the first country in Europe to restrict lead content in gasoline; however, the German army was exempt from these restrictions because
other NATO countries were not subject (Hagner, 2000). As of January 1, 1972, German automotive gasoline could contain no more than approximately 1.54
g/gal of lead. As of January 1, 1976, the value could not exceed approximately 0.60 g/gal. After 1976, Germany followed European Union guidelines with the
total ban in 2000 (Hagner, 2000).
3 Includes the Palestinian territories and the “>2007” date is based on this writer’s travels.
4 Leaded gasoline was essentially removed from the market in Japan in 1980. Between 1980 and 1988, leaded gasoline was quite difficult to find in Japan.
5 Also includes Russia after the breakup of the Soviet Union. In 1956, the Soviet Union banned leaded gasoline in large cities, such as Moscow, Leningrad, Baku,
Odessa, Kiev and tourist areas of the Caucasus and Crimea (Thomas, 1995; Thomas and Orlova, 2001). Lead content in Soviet regular grade was 0.65 g/gal,
whereas in premium grade, it was 1.42 g/gal (Thomas and Orlova, 2001).
6 Switzerland banned leaded gasoline in 1925 and it is unlikely that any leaded gasoline was sold that year. The ban was rescinded in 1947 (Breu et al., 2003).
7 Unleaded grades (regular and premium) were available either through Indiana Standard filling stations in the Eastern and Southern states or possibly by other
refiners as a low-octane and inexpensive grade known as 3rd Grade. As a new grade of gasoline, unleaded was introduced by select refiners in 1970 and, at first,
predominantly in the Western states.
8 In California, the final ban was implemented in 1992.
completed the phase-out earlier, as indicated below and on Table
13; however, Greece, Italy, Portugal, and Spain were granted a
one-year extension to implement the phase-out (Reitze, 2001).
The FRG was probably the most proactive country in Europe
to phase-out leaded gasoline. In August 1971, the FRG Parliament passed the Gasoline Lead Content Regulations (Hagner,
2000). As of January 1972, gasoline with an organolead content exceeding 1.54 g/gal could not be produced in, or imported
to, the FRG. After January 1976, this figure shrank to 0.58
g/gal. After 1978, the FRG followed the EU standards; however, in 1995, Germany required that a super unleaded grade
(95 octane) and a 92 octane unleaded grade be offered with a
maximum organolead content of 0.05 g/gal (Hagner, 2000).
In Brazil, the phase-out was completed in 1990. The phaseout came fast because it is the largest sugar-cane producer in the
world and its ethanol supplies are plentiful. Ethanol has been
used as an octane enhancer in its gasoline since the 1940s. Then,
in the 1980s, the government had begun programs to increase the
use of ethanol as an automotive fuel. Today, most Brazilian cars
are built or have been modified to use either gasoline or ethanol
(Lovei, 1998). Moreover, all gasoline in Brazil now contains at
least 24% ethanol.
Mexico introduced unleaded gasoline, known as Magna Sin,
in 1991. Between 1986 and 1992, the organolead content of
Mexican gasoline, known as Nova, declined from 3.77 g/gal
to 0.27 g/gal. Leaded gasoline was completely phased out in
1998 and Mexico’s last TEL plant (Tetraétilo de México in
Coatzacoalcos, Vera Cruz State) closed in 1997 (Flores and
Albert, 2004).
Many countries completed the phase-out of leaded gasoline
before the US did. These countries include Antigua and Barbuda (1991), Austria (1993), Bermuda (1990), Bolivia (1995),
Canada (1990), Colombia (1991), Denmark (1994), Finland
(1995), Guatemala (1991), Slovak Republic (1994), South Korea
(1994), Surinam (1993), Sweden (1994), and Thailand (1995)
(Faiz et al., 1996; Onursal and Gautam, 1997).
Most of the world now runs on unleaded gasoline, but some
exceptions persist, such as Algeria, Bhutan, Cambodia, Israel,
Kazakhstan, Laos, Mongolia, Myanmar, North Korea, Palestine,
Tajikistan, Turkmenistan, and Uzbekistan (as of 2009). Leaded
gasoline is also used in countries occupied by the US military such as Afghanistan and Iraq (Dauvergne, 2008). In many
countries, leaded gasoline was phased out late and/or high lead
concentrations were used well into the 1990s and 2000s. For
example, as of 2002, Pakistan continued to use only leaded
gasoline and, as of 1991, lead contents there were as high as 7.7
g/gal (Parekh et al., 2002).
Leaded gasoline is available in the countries cited above,
but in Israel for example, most gasoline is unleaded. It is believed that Innospec in the UK produces all or the majority the
organolead additives used in these countries. Ethyl closed its last
TEL plant in 1994, but continues to supply customers through
an agreement with Octel (and now Innospec). As of 2009, TEL
plants only exist in Port Ellesmere, UK, and China.
The Outcome of the Phase-Out
From an environmental viewpoint, the worldwide phase-out of
leaded gasoline was a success. In the US alone, seven million
tons of lead (1.4 × 1010 lbs or 6.3 × 1010 kg) were released into
the environment between the 1920s and the phase-out (Steinberg, 2002). Approximately 5.2 × 1012 gallons of leaded gasoline were produced worldwide during this period (Nriagu, 1990).
In 1947, researchers investigated the lead content of street dusts
in New York City from 1924 to 1934 and their findings revealed
an average 50% increase in lead content in that short period (LinFu, 1991). In 1980, the National Academy of Sciences reported
that each year approximately 600,000 tons of lead were released
to the environment and automobile emissions accounted for approximately 90% of the total (National Research Council, 1980).
One study found that exposure to vehicle exhausts running on
leaded gasoline caused a 4- to 5-point drop in the intelligence
quotient (IQ) of children in African cities (Dauvergne, 2008).
This lead has had a significant impact on the environment
and on human health, especially in children. Direct correlation
was found between reductions in atmospheric lead concentrations, the phase-out, and blood lead concentrations in children
41
(Eisenreich et al., 1986; Falk, 2003). In the US, a 90% reduction
in the lead concentration in human blood was observed after the
phase-out. Similar declines have been documented in several
other countries (Landrigan, 2002).
Other Organometallic Anti-Knock Agents
Many alternatives to TEL and TML were developed. Important
organometallics used as anti-knocks, and the year they were
introduced, include (Table 8):
! iron pentacarbonyl, also known as iron carbonyl (1926);
! dicyclopentadienyl iron, also known as ferrocene (1951);
! methyl cyclopentadienyl manganese tricarbonyl, also known
! cyclopentadienyl manganese tricarbonyl, also known as cyas MMT (1959), and
mantrene (developed in the 1950s, usage began in the 1990s).
Iron Carbonyl
Germany was second only to the US in conducting research
into anti-knock agents and alternative petroleum products in the
1920s and 1930s, because of its lack of petroleum reserves and
its growing future military ambitions (Sampson, 1975). The
German company, I. G. Farben, introduced iron carbonyl, an
antiknock additive, in 1926.
Iron carbonyl saw some usage in Germany and Italy in the
1920s and 1930s at a concentration of 0.5% or less, and was
marketed under the names Motolin and Monopolin (Kovarik,
2003; Hamilton, 2004). An alternative package known as Motyl
contained 50% iron carbonyl in kerosene. The gasoline containing this package was known as Motaline (Barusch et al., 1974).
In the 1930s, it quickly lost market share to other octane boosters, such as methanol, ethanol, benzol and TEL and was phased
out shortly thereafter.
Ethyl studied the use of iron carbonyl for several years. Precipitation of iron oxides within the combustion chamber caused
it to foul the spark plugs. Ethyl’s research focused primarily on
appropriate scavengers to alleviate the iron-oxide precipitation,
but an effective mixture was never found (Robert, 1983). Iron
carbonyl was never used in the US.
Reportedly, nickel carbonyl, a similar antiknock agent, has
seen some usage outside of the US (Hamilton and Falkiner,
2003).
Ferrocene
Researchers at DuPont discovered ferrocene to be an antiknock
agent in 1951 and patented it in 1952. However, it caused engine
wear and never saw usage in the US, although it saw some use in
Europe (Schroeder and Pederson, 1988). As of 2007, ferrocene
is used in China, in South Africa and possibly in other African
countries. It is typically added at a concentration of 0.06 g/gal
to 0.12 g/gal (available at: www.china-additives.com). It has
been added to both gasoline and diesel fuel and may be mixed
42
Oudijk
with tert-butyl acetate. As of 2007, several companies in China
manufacture ferrocene (www.china-additives.com).
Methyl Cyclopentadienyl Manganese Tricarbonyl
MMT was initially marketed in 1959 by Ethyl as a supplement or
replacement for TEL; it was added to both leaded and unleaded
gasoline (Gibbs, 1990). At times, MMT has been known as
CI-2 (an abbreviation for “combustion improver-2”). It did not
become popular as an octane enhancer until approximately 1974,
when the lead phase-down was beginning. As organoleads were
reduced, MMT became more prevalent as it offset octane loss.
However, because of its greater cost compared to TEL or TML,
MMT was not ordinarily used as the primary antiknock agent
(Barusch et al., 1974).
MMT has a density of 1.39 g/cm2 (at 20◦ C), a boiling point
of approximately 233◦ C, a freezing point of 1.5◦ C to 2◦ C, and is
essentially insoluble in water, but highly soluble in hydrocarbons
(Brown and Lovell, 1958) (Table 8). When mixed with TEL, it
was known by Ethyl as Motor Mix 33 or AK-33X (57.5 wt%
TEL, 17.6 wt% EDC, 16.7 wt% EDB, 6.97 wt% MMT and 1.2
wt% dye) (Nriagu, 1990). Ethyl also recommended the use of
an organophosphorus additive in conjunction with Motor Mix
33 to prevent excessive engine wear (Barusch et al., 1974). As
of 1994, the MMT-containing anti-knock package marketed by
Ethyl was called HiTEC 3000 (Ethyl Corporation, 1994). In the
1980s, Ethyl also offered a package known as HiTEC 1000,
consisting of gasoline containing 0.1 g/gal of TEL and 0.1 g/gal
of MMT (Brown, 1987).
MMT was found to be more effective as an octane enhancer
when mixed with TEL. MMT is also more effective in fuels with
low aromatic content (or higher alkylate) (Brown and Lovell,
1958). Ethyl’s studies showed that, in unleaded fuels, MMT was
twice as effective as TEL in raising the RON rating, but about
the same for the MON. MMT was used in many “low-lead”
gasolines offered in the US during the mid- to late-1970s and
early 1980s (Owen and Coley, 1995). DuPuis and Hill (1979)
found a concentration of 6 mg manganese per gallon of gasoline
(mg Mn/gal) in an unleaded US gasoline in 1978.
By 1976, MMT was widespread in the US at a concentration of 12 mg Mn/gal (Stout et al., 2006), it was added to
approximately 40% of US gasoline (at more than 50 refineries) and its percentage was increasing (Stevens, 1977; O’Toole,
1977). Refiners adding MMT as of 1977 included at least Exxon,
Gulf, Chevron, Amoco, and Arco (O’Toole, 1977). MMT usage
reportedly began in Canada in 1976 (Bhuie, 1997), although
Hamilton and Falkiner (2003) claim that usage began in 1972.
MMT interfered with the use of catalytic converters, a problem similar to that resulting from the use of organoleads. In some
instances, use of MMT doubled the hydrocarbon concentration
entering converters (Stevens, 1977); although MMT concentrations below 6 mg Mn/gal reportedly alleviated such problems
(Uden et al., 1978). In July 1977, the California Air Resources
Board banned MMT in unleaded gasolines in California because
it plugged converters and fouled spark plugs after driving less
than 5,000 miles of use. Both Ford and GM confirmed these
findings (Anderson, 1977).
MMT was banned in the US for use in unleaded gasoline in
October 1978, although a special waiver could be obtained from
the US EPA (Colucci, 2004). In early 1978, MMT had been used
in 50% of US unleaded gasolines at an average concentration of
4 mg Mn/gal (Uden et al., 1978). GM was strongly against MMT
usage and Ford and Chrysler concurred (Stevens, 1977). Further studies were conducted in 1978 and 1979, funded by GM,
Ford, Chrysler, Exxon, Union, Ethyl, Amoco, Chevron, Arco,
Mobil, Gulf, and Sohio, and these confirmed the earlier results
(Tolchin, 1979). However, Ethyl claimed that no problems existed. Furthermore, the EPA had found that significant MMT
usage would increase the manganese content of ambient air,
especially in the fine-particle fraction (Wallace and Slonecker,
1997), causing air-quality problems.
MMT usage continued in leaded gasoline, but was permitted
in unleaded only from June to October 1979, during the oil
embargo, to increase unleaded production (Tolchin, 1979). The
ban for such unleaded was reinstated as of October 1, 1980
(Holusha, 1979; Blumberg and Walsh, 2004).
In 1990, Ethyl requested a waiver from the US EPA for MMT
usage, but the waiver was denied in 1992. Ethyl appealed in 1993
and the federal court ordered the US EPA to reconsider. In 1995,
MMT was permitted in unleaded gasoline at concentration of
12 mg Mn/gal; however, its use in the US is rare and it is banned
in California (Blumberg and Walsh, 2004).
In 1996, the following refiners indicated that they do not
use MMT: Amoco, Arco, BP, Chevron, Conoco, Exxon, Hess,
Marathon, Mobil, Pennzoil, Phillips, Shell, Sun, and Texaco
(Halpert, 1996). MMT is not permitted in reformulated gasoline
(Davis, 1998; Blumberg and Walsh, 2004). According to Kaplan
(2003), as of 2003 MMT is added to US gasolines only at a few
small refineries in the southern Rocky Mountains, accounting
for only approximately 0.02% of all US gasoline use as of 1998
(Hamilton and Falkiner, 2003). Still, since 1976, more than
70 million pounds of MMT had been sold in the US (Davis,
1998).
MMT is presently manufactured by Afton Chemical Corporation, a division of NewMarket (available at:
www.aftonchemical.com). According to Afton’s 2009 website,
MMT is being used by more than 150 refiners in 45 countries
in Europe, Africa, Asia, and Central and South America, as
well as the United States and Canada. Furthermore, Afton states
that MMT is permitted in gasolines of the EU at a maximum
concentration of 6 mg Mn/L.
Blumberg and Walsh (2004) report that MMT has seen much
use in Canada where it is added at a maximum concentration
of 6.8 mg Mn/L. After Canada’s lead phase-out in 1990, MMT
was in approximately 90% of Canadian gasoline. Canada banned
MMT in 1995, but Ethyl sued the Canadian government in 1998
and the ban was rescinded (Markell and Knox, 2003; Blumberg
and Walsh, 2004). More recently, refiners voluntarily ceased
usage of MMT and, as of 2004, 95% of Canadian gasoline is
MMT-free.
In Australia, MMT is used, not as an octane enhancer, but as
an anti-valve seat recession additive. The three Australian suppliers of MMT are: Ethyl Asia Pacific Company, Wynn’s Australia Pty Ltd., and Nulon Products Australia Pty Ltd. MMT is
not manufactured in Australia, but is imported and blended into
packages. Ethyl Asia offers two types of packages: 1) HiTEC
3062, containing 62% MMT in a mixed aromatic and aliphatic
solvent, and 2) HiTEC 3000, containing neat MMT (similar to
the US version also known as HiTEC 3000). Wynn’s and Nulon
offer packages that contain either <5% or <10% MMT mixed
in a petroleum distillate (Commonwealth of Australia, 2003).
The recommended concentration in gasoline is approximately
18 g Mn/L.
43
Secondly, leaded gasoline changed the history, the landscape
and the social structure of the world. It helped bring about
the expansion of the automobile industry, the advent of the
superhighway, the introduction of the shopping mall and the
arrival of the drive-through fast-food restaurant, with all its
resulting influences. It had an impact on the food we eat, how
and where we live, how we work, our health, and the wars we
fight. Before TEL, the automobile was not an important factor
in the lives of most Americans. After leaded gasoline arrived, it
became an integral element in the US and world economy. Future
forensic scientists studying the role of TEL in history may have
to decipher problems much more complex than environmental
contamination.
Acknowledgements
Cymantrene
With the production of many new cars in China and India and the
lack of sufficient petroleum supplies, the manufacture of new
or alternative anti-knock additives in the Far East is increasing. A recent anti-knock additive is cymantrene, also known as
cyclopentadienyl manganese tricarbonyl (CMT), a compound
similar in composition to MMT. Cymantrene has seen use in
China at a concentration of 18 mg Mn/L. Craig (2002) reports
that cymantrene has also been used in Canada. Although its antiknock properties have been known for a few decades, it has only
recently been marketed. As of 2007, several Chinese websites
(such as http://www.china-additives.com) were advertising the
sale of cymantrene. A review of these websites in 2009 suggests
that sales of cymantrene are no longer active in China.
Conclusions
Today, organolead additives are no longer used in most western
nations, although they may linger in some Asian and African
countries. Currently used antiknock agents are predominantly
employed with a view to environmental and health considerations. Oxygenates, which also suppress knock, are used to
increase the oxygen content of the gasoline, thereby reducing atmospheric emissions. These oxygenates include methyltert-butyl ether (MTBE), ethanol and tert-butyl alcohol (TBA),
among numerous others. However, different environmental and
health problems have recently arisen with some of these oxygenates.
Why is all this important? First, the history of organometallic
additives often plays a significant part in unraveling the environmental liability behind gasoline releases. This article provides
an overview of these additives, but each refinery or blending
facility may have used different techniques to produce its gasoline on close to a daily basis. The information provided herein
can help to fingerprint the composition of a gasoline in an environmental investigation. Furthermore, this information could
be used to help age date these releases. However, site-, refinery-,
or company-specific information about a target gasoline, if obtainable, is always preferred.
I obtained significant assistance and access to hard-to-find references from Dr. Yakov Galperin of Environmental Geochemistry
Consulting (Moor Park, CA) and Dr. Michael Wade of Wade
Research (Hollyfield, MA). Dr. Hans von Storch of the GKSS
Research Center in Germany reviewed the section on the European phase-out. Ms. Cheryl Dickson of NIPER in Bartlesville,
OK, and Dr. Nicolaj Walveren of the University of Utrecht
in The Netherlands were also helpful and provided needed information on US and European gasoline. Mr. Juan Negron of
Geo-Envirotech Corporation in San Juan, Puerto Rico provided
information on gasoline usage in the Caribbean area. Mr. Irving ‘Butch’ Grossman of the New Jersey Geological Survey
(Trenton, NJ) reviewed the manuscript and significantly improved it. Several unnamed librarians at the Library of Congress
(Washington, DC) and Rutgers University (New Brunswick, NJ)
were extremely helpful. Ms. Julia Ryan of Triassic (Hopewell,
NJ) drew the graphs. ISEF provided three anonymous reviewers
and their help is greatly appreciated. All these people helped to
improve the article, but responsibility for any errors remains my
own.
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44
Oudijk
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The Rise And Fall Of Organometallic Additives In Automotive Gasoline

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