;'-'-909
LISTING WASTE OIL AS A HAZARDOUS WASTE
Report to Congress
This report (SW-909) was prepared by the
Office of Solid Waste as required by section 8(2)
of the Used Oil Recycling Act of 1980 (Public Law 96-463)
and was delivered to Congress on January 16, 1981
US. Ervi'omeptai PiCt2cl:on Agency.
Rep/.on V. Libr.ry
230 C-X'l^ Duller- Street
Chicago, Illinois 60604
U.S. ENVIRONMENTAL PROTECTION AGENCY
1981
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'-909
LISTING WASTE OIL AS A HAZARDOUS WASTE
Report to Congress
This report (SW-909) was prepared by the
Office of Solid Waste as required by section 8(2)
of the Used Oil Recycling Act of 1980 (Public Law 96-463)
and was delivered to Congress on January 16, 1981
U.S. Environmental Protection Agency.
Region V. Library
230 S.'X't'i Dcaiborn Street ^
Chicago, Illinois 60604
U.S. ENVIRONMENTAL PROTECTION AGENCY
1981
-------
US. Enwfoonments! Protection Agency
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. DC 20460
JAN 1 6 1981
THE A
Honorable Walter F. Mondale
President of the Senate
Washington, D.C. 20510
Dear Mr. President:
I am pleased to transmit the Report to Congress "Listing
of Waste Oil as a Hazardous Waste" pursuant to Section (8)(2)
of the Used Oil Recycling Act of 1980, Public Law 96-463.
The Report presents the Agency's basis for determining
that certain waste oils are hazardous wastes according to the
criteria promulgated under subsections (a) and (b) of Section
3001 of the Solid Waste Disposal Act, as amended by the Resource
Conservation and Recovery Act (RCRA) of 1976. The information
presented here will be used later this year to support the
proposed listing of these waste oils as hazardous wastes under
Section 3001 of RCRA. At that time, the Agency will also pro-
mulgate proposed rules under Sections 3002 through 3004 and
3012 of RCRA for the transportation, treatment, storage, dis-
posal, and recycling of waste oils determined to be hazardous
wastes.
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3 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
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CONTENTS
INTRODUCTION 1
DEFINITION OF WASTE OIL 2
SUMMARY OF LISTING DETERMINATIONS 3
UNUSED WASTE OIL 5
I. Chemical compos It Ion 5
A. Crude Oil 5
B. Refined oil products 6
II. Sources and Management Pract ices 9
A. Spills 9
B. Vessel Operat ions 14
C. Inadequate Handling or Formulation 15
III. Basis for Listing 16
A. Adverse effects of crude and refined oil
products: 16
1. Aquatic environment 16
2. Human health 21
3. Drinking water 33
0. Hazards posed by mismanagement 35
USED OIL 42
I. Constituents and Management Practices 42
A. Automotive 42
B. Industr ial 52
1. Lube Oils 53
a. Metalworking 53
b. Railroad and Marine 57
2. Non-lube Oils 58
a - Hydraui ic Oils 58
b. Transformer Oils 59
c. Turbine Oils 60
d. Quenching Oils 61
II. Basis for Listing 63
A. Adverse effects of contaminants in used oil 63
B. Hazards posed by mismanagement 71
References 79
Appendices 87
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INTRODUCTION
This document presents the Administrator's basis for list-
ing waste oil as a hazardous waste. Under Section 3001 of the
Resource Conservation and Recovery Act (RCRA), the listing of a
solid waste as a hazardous waste brings it under the control of
a comprehensive management system which regulates the transport-
ation, treatment, storage, and disposal of hazardous wastes.
Section 3001 of RCRA directs EPA to identify those solid
wastes Which should be subject to the hazardous waste regulations
prescribed under Sections 3002 through 3004 of RCRA. In addition,
recognizing the significant threat to human health and the envi-
ronment posed when used oil* is improperly managed, the Congress
passed the Used Oil Recycling Act (P.L. 96-463). Section 8 of this
Act requires, no later than January 13, 1981, for the Administrator
to: (1) determine whether used oil is a hazardous waste, as defined
in Section 3001 of RCRA? and (2) report to the Congress the basis
for this determination. The Act also directs EPA, no later than
October I"), 1931, to promulgate regulations which protect human
health and the environment from the hazards associated with
recycled used oil.
The purpose of this document is to present the Admiristrator' s
basis for listing certain waste oils (including certain used oils)
as hazardous wastes. Later this year, the Agency plans to issue
'proposed rules to (1) list, these oils as hazardous wastes and (2)
* As explained below, used oils are a subset of waste oils.
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establish regulations for their transportation, treatment, stor-
age, disposal, and recycling.
DEFINITION OF WASTE OIL
This section desci'ibes the universe of waste oil covered i.n
this document. First, this document addresses only pet.coieum-
darived oil. Oils derived from vegetable or aninal fats are not
included because they are generally not toxic to humans or aquatic
life.1 Additionally, the Used Oil Recycling Act limits the
statutory definition of "used oil" to oil derived from petroleum
and, thus, it is appropriate for EPA to similarly restrict the
regulatory definition of "waste oil".
Second, EPA is defining petroleum-derived oils as those which
meet the following three characteristics:
(1) lack a defined chemical structure;
(2) contain mixtures of isomers*; and
(3) contain three or more members of an homologous
series which differ by a fixed carbon-containing
increment.**
Petroleum-derived wastes meeting the above criteria are defined as
waste oils; petroleum-derived wastes not meeting these criteria are
* An isomer is a molecule having the same number and kind of
atoms as another molecule, but differing from it in respect to
atomic arrangement or configuration.
** An homologous series is a series of organic compounds in
which each successive member differs by a fixed increment in
certain constituents from the proceeding member. For example,
CH3H (methanoi), C2H50H (ethanol), and C3H7OH (butanol) form
an homologous series.
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- 3 -
candidates for designation as "other hazardous wastes"*. This
method of distinguishing waste oils from other petroleum-derived
hazardous wastes is the same as that used by EPA to implement
regulations for oil vs. other hazardous materials under Section
311 of the Clean Water Act (CWA).**2
Finally, this document addresses both unused and used waste
oil. Unused oil generally becomes a waste oil when it is spilled,
when it mixes with other wastes (e.g., a ship's ballast water),
or when it fails specifications for its intended use and is dis-
carded (e.g., ASTM D396 specifications for fuel oils). Used oil
becomes a waste oil when it is contaminated with physical or
chemical impurities resulting from use, such that, the oil cannot
be reused for its original purpose without, first removing these
impurit ies.
SUMMARY OF LISTING DETERMINATIONS
In regulations prescribed pursuant to Section 3001 of RCRA,
solid wastes are listed as toxic hazardous wastes if they contain
* Thus, using this approach, waste automotive crankcase oil is
deemed to be a waste oil rather than an "other hazardous waste"
because it (I) lacks a definite chemical structure, (2) contains
multiples of isomers, and (3) contains members of an homologous
series in which each successive member has one more CfH group
in its molecule than the next preceeding member. By contrast,
petroleum-derived, waste PCBs are regulated as "other hazardous
wastes" rather than as waste oils because the members of the
homologous series that they contain do not. differ by a carbon-
containing increment. The homologous series increment, instead
of containing carbon, is made up of a chlorine atom.
** It is important that the regulated community be able to dif-
ferent iate between waste oils and other petroleum-derived wastes
because there will be different requirements under RCRA for these
two types of wastes.
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- 4 -
any of a number-of desigated constituents* unless, after con-
sideration of multiple factors, EPA concludes that the waste
does not pose a substantial present or potential threat to human
health and the environment when improperly treated, stored, trans-
ported, disposed of, or otherwise managed. These multiple factors
include the type of toxic threat posed; the concentrations of the
toxic constituents in the waste; the migration potential, persist-
ance and degradation potent.ial of the toxic constituents; the
degree to which the toxic constituent.s bioaccumulate in ecosystems;
the plausible types of improper management to which the waste
could be subjected; the quantities of waste generated; damage
incidents involving wastes containing the toxic constituents; and
actions taken by other governmental agencies with respect to the
waste or its toxic constituents.3
Using these criteria, the Administrator has determined that
r
the following waste oils are hazardous wastes, and thus should
be subject to the regulations prescribed under Sections 3002
through 3004 of RCRA:
1. Oil spilled to land, and oily debris generated from
cleaning-up spills to land or surface water;
2. Used automotive oils; and
3. Used industrial oils.
The exception to this are any of the above waste oils whose pet-
roleum base is white oil.
* These constituents are ones which have been shown in reputable
scientific studi.es to have toxic, carcinogenic, mutagenic, or
teratogenic effects on humans or other life forms.
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- 5 -
UNUSED WASTE OIL
This chapter first discusses the chemical composition of
unused oil. The sources and quantities generated of several
categories of unused waste oil, and the management practices
typically used to store, treat, recycle, or dispose of it are
presented next. This is followed by the Agency's rationale for
listing certain unused waste oils as hazardous wastes, including
a description of the potential human health and environmental
hazards posed by improper management of these waste oils.
I. Chemical composition
The chemical composition of crude oil and refined oil pro-
ducts are described below. As explained later in this chapter,
certain constituents in the oil-component of wastes containing
unused oil pose a potential threat to human health and the
environment when these wastes are improperly managed.
A. Crude oil
Crude oil is not a chemically well-defined substance, but a
complex mixture containing literally thousands of compounds,
including hydrocarbons, sulfur- oxygen- and nitrogen-containing
compounds, and metallo-organic compounds. Although oils from
various parts of the world differ widely in their content of
the above substances, they are generally divided into three main
groups on the basis of their predominant hydrocarbon structure:
paraffinic, naphthenic, and aromatic.
Paraffinic (alTcanic) crude oils contain mostly saturated
straight and branch-chained carbon compounds, along with lesser
amounts of cycloaikanes and aromatics. Naphthenic crudes contain
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- 6 -
appreciable quantities of compounds with at least one saturated
ring structure (cycloakanes). Aromatic crude oils contain a
large concentration of unsaturated benzene ring structures. The
varying proportion of these three classes of compounds (alkanes,
cycioalkanes, and aromatic hydrocarbons) determine the physical,
as well as the chemical properties of crude oils.
Although the relative quantities of these compounds differ in
t
crude oils, an average of the gross compositional data on all
world crude yields the following approximate composition for the
"average" crude oil:4
paraffin hydrocarbons (alkanes) 30%
naphthene hydrocarbons (cycloalkanes) 50%
aromatic hydrocarbons 15%
nitrogen, sulfur and oxygen- 5%
containing compounds
Although any specific crude may differ appreciably from these
average values, it can be assumed that all crude oils contain
some of all three types of hydrocarbons identified above.
B. Refined oil products
Refined oil products (e.g., lubricating oils) also lack
constant chemical compositions. The two factors responsible for
this variation are crude oil source and the process used to refine
the oil. The first factor was described above; the second is dis-
cussed below.
A complex combination of inter-dependent processes form the
basis of refinery operations. These may include fractionation,
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- 7 -
cracking, polymerization, and hydrotreating. The particular
combination of processes used at a refinery determines the com-
position of the final product. For example, catalytic cracking
and related conversion processes favor the formation of olefins,*
aromatics, and branched paraffins at the expense of other types
of hydrocarbons. Solvent treating, on the other hand, removes
aromatics, cycloparaffins and olefins.5 The processes used at a
refinery are chosen based on the type (e.g., fuel oil, lubricating
oil) and characteristics (e.g., high octane, low freezing point)
of the products that are desired.
Despite the fact that the composition of refined products is
highly variable, the following general characterizations can be *
made. The compounds in refined products are similar to those found
in crude oils with the addition of (1) the olefin class of hydro-
carbons, and (2) chemical additives** designed to make the product
perform more efficiently. Table 1 presents "average" values for
the percentage of hydrocarbon compounds found in various refined
products.
As noted earlier, a refinery's products may vary significantly
from these values, depending on the source of crude oil and the
methods used to refine it. And, because the categories in Table 1
* Olefins are straight or branched-chained aliphatic hydrocarbons
with at least one double bond. They are used as feedstocks in
certain refinery processes (e.g., alkylation and polymerization)
to yield high octane blending components for motor gasoline and
some jet fuels.
** The additive package differs depending on how the oil is to be
used. For example, chemicals added to automotive engine oil to
decrease engine knock differ from those added to an oil to lower
its freezing point.
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- 8 -
TABLE 1
Relative Percentages of Hydrocarbons
in "Average" Refined Oil Products
Petroleum Product
Motor Gasoline
Jet
Kerosene
Distillate Fuel Oils
Residual Fuel Oils*
Naphtha, Petroleum Solvents
Lubricating Oils and Greases
Paraffins
40-50
35
40
30
15
20-35
20-40
Naphthenes
30-40
50
45
45
45
30-45
30-55
Aromatics
10-35
15
15
25-40
25
20-50
15-45
* includes 15% non-hydrocarbon compounds containing oxygen,
nitrogen or sulfur
NOTE: Olefins are often not measured, although they are present
in most products to some degree
Source: reference 4, p. 86
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- 9 -
are quite broad, there are instances where the "average" values
for a particular category do not reflect the composition of certain
groups of hydrocarbons within a category*. However, the table is
useful because it illustrates that, like crude oils, most refined
products contain significant quantities of all three classes of
hydrocarbons (i.e., alkanes, cycloalkanes, and aromatic).
II. Sources arid Management Practices
Most unused waste oil fits into three general categories:
(1) spilled oil, (2) oily wast.e from tank-cleaning and deballasting
operations, and (3) oil unfit for its intended use because it has
been improperly handled or fails to meets specifications. These
three sources of unused waste oil are discussed below.
A. Spills
Surface Water; About 10,000 oil spills totalling 10 to 20 million
gallons of oil enter the territorial waters of the United States
every year.6 Through the provisions of the National Oil and
Hazardous Substances Pollution Contingency Plan**, the National
Response Team*** ensures that appropriate cleanup operations of
this spilled oil are undertaken by the discharger or by federal,
state, or local authorities. Removal of the spilled oil from
* E.g., white oils, which are a subset of the "lubricating
oils and greases" category, are refined such that they contain
essentially no aromatic hydrocarbons. Therefore, the "average"
value of 15 to 45 percent aromatics is inaccurate for white oils.
** This plan is designed to guide federal spill response actions
under Section 311 of the CWA.
*** The National Response Team is a multi-agency organization
responsible for oil spill contingency planning at the national
level.
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- 10 -
surface waters results In the creation of an oily debris which
must be disposed of. Currently there are no federal regulations
controlling the treatment, storage, or disposal of the oily
debris resulting from these cleanup operations.
Efforts by emergency response teams to locate adequate sites
to manage (i.e., store, treat, or dispose) oily debris are often
frustrated. Local residents are always anxious to have the debris
removed from sight, but frequently are unwilling to allow it to
be disposed of in their sanitary landfills. Citizen opposition
is even worse when neighboring communities are asked to accept
another's debris, regardless of whether their landfill is better
able to contain it.
Because of the intense emotional atmosphere associated with oil
spill cleanup, the resulting oily debris must often be temporairily
stored until an appropriate site is found. Sometimes, either
because of citizen pressure or the absence of a suitable nearby
site, the debris is disposed of in a landfill which is inadequate
to contain it.*^
Land; The Coast Guard and EPA. receive notification of only oil
spills that:
cause a film or sheen upon or discoloration of the
surface of the water or adjoining shorelines or
cause a sludge or emulsion to be deposited beneath
the surface of the water or upon adjoining shorelines.
(40 CFR Part 110). -
* There is growing recognition among local officials that the
time to identify appropriate sites to dispose of oily debris Ls
before rather than after an oil spill occurs. To encourage this
type of advance planning, EPA has prepared a detailed, how-to-
do-it manual (EPA-600/7-80-016) and an accompanying film for oil
spill debris disposal for state and local officials.
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- 11 -
Oil spills also occur to land. They are typically caused
by tank failures, pipeline ruptures or leaks, spillage during
transfer from one container to another, and indiscriminate dumping,
Because the Agency has no reporting requirements for tJiese spills,
it is difficult to estimate the quantity of waste oil generated
from them. However, several states require persons to file re-
ports on oil spills to the land as well as water. The following
is a summary of data collected in these reports.
MAINE: Nearly 90,000 gallons of oil were spilled in Maine in
1979. Table 2 illustrates the environmental media (i.e., surface
water, ground water, or land) affected by these spills. Although
the majority of the spills entered surface water, a significant
number occurred on land. Note also that several of the spills
resulted in ground-water contamination.®
MICHIGAN: During 1976, approximately 500 spills to ground water
were reported to the Michigan Department of Natural Resources.
The largest of these was a spill of 360,000 gallons of fuel oil.9
NEW HAMPSHIRE: Table 3 summarizes the reported oil spills that
occurred in New Hampshire over the past six years. Note that of
the 219,368 gallons of oil spilled during that, period, nearly
half of the oil spilled on land.10
NEW YORK: 4,287 oil spills totaling over 9 million gallons were
reported to New York's Department of Conservation from January,
1976 to September, 1979. Approximately 25% of these spills
occurred on land, involving over 1.5 million gallons. New York's
records indicate that 238,983 gallons of the oil spilled on the
ground was not cleaned up.H
While not comprehensive, data from these few states indicate
that the amount of oil generated from spills to land is signifi-
cant and, therefore, should not be overlooked'when assessing the
magnitude of the potential environmental threat posed by unused
waste oil.
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- 12 -
TABLE 2
State of Maine
Environmental Media Affected by Spills in 1979
Medium Affected Number of Spills
Land 95
Surface Water 153
Land to Surface Water 66
Ground Water 6
Ground Water to Surface Water 17
Land to Ground Water 4
Total Spills 341
Source: reference 3.
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TABLE 3
State of New Hampshire
Oil Spill Summary for 1975-1980
Year
'75
'76
'77
'78
'79
'80**
# Spills
Reported
45
53
52
59
79
52
* Spills
12
17
13
11
27
23
TO LAND
Gallons
Spilled
19632
23441
6210
8855
27985
15816
(*)*
(2)
(4)
(4)
(2)
(10)
(7)
# Spills
33
36
39
48
52
29
TO WATER
Gallons
Spilled
22335
19430
6687
30323
29692
8962
(f)*
(12)
(21)
(23)
(21)
(33)
(17)
Total
101939
117429
*(#) Indicates number of spills with an unestimated amount
of spilled oil
** Through November, 1980
Source: reference 10.
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Unlike oil spilled to surface water, oil spilled to land is
not subject to federal regulation (unless it ultimately reaches
surface water) and, therefore, its cleanup is not supervised by
a federal organization comparable to the National Response Team.
In fact, there is no federal law which even requires oil spilled
to land to be removed from the ground.
Some states send officials to oversee cleanup operations of
large oil spills to land. But, in most cases, the treatment,
storage, arid disposal of oily debris resulting from this type of
spill is not. subject to control.
B. Vessel Operations
Ships arid vessels generate two types of wastewaters which
contain unused waste oil: ballast water* and tank cleaning water**
The discharge to surface water of ballast and tank-cleaning
water is subject to regulations (33 CFR Part 157) administered by
the Coast Guard. If oily water is brought ashore (as is often
done during deballasting operations), it is usually first pumped
to on-shore storage tanks, and ultimately released to refinery
wastewater treatment plants. Oil recovered onboard from tank-
cleaning water is generally used as a feedstock at oil refineries
* Ballast water; After crude oil or petroleum products are off-
loaded from a tanker, water or seawater is pumped into the vessel's
storage tank to maintain stability. Oil adhering to the tank's
wall mixes with the water as a result of ship motion, thus creating
an oily wastewater.
** Tank-cleaning water: Before a change in fuel oil cargo is made,
cargo tanks are washed. Oily wastewaters generated by tank cleaning
are either added to a ship's ballast water or processed through an
oil-water separator. In the latter case, water which has passed
through a separator is discharged at sea, whereas the oil component
is retained on-board and is eventually brought ashore.
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when it is brought ashore.^
Of the unused waste oil generated onboard vessels, nearly
300 thousand metric tons of it are discharged to surface waters
each year.13 The Agency has no data on the quantity of waste oil
brought ashore in ballast and tank-cleaning waters.
C. Inadequate Handling or Formulation
Unused oil may become unsuitable for its intended use and,
thereby, a waste oil when it is improperly handled. An example
of this occurred in North Carolina in 1978 when several barrels of
the federal government's automotive lubricating oil could not be
used in its military vehicles because the oil had been stored
for longer than its recommended shelf life.*^-^
Unused oil may also become waste oil if it is formulated in
a way that does not meet specifications for its intended use.
Oil purchased by the government, for example, must meet certain
specifications. These specifications differ depending on how
the oil Is to be used (e.g., the requirements for fuel oil differ
from those for lubricating oil). If oil is 'off-spec1, it is
generally returned to the seller. The oil can then either be
re-formulated, sold for another use, or disposed of.
The Agency has no data on how much of these types of unused
waste oil are generated, nor on how they are ultimately reused or
disposed of.
* The oil was ultimately given to a state-operated re-refinery
to be used as a feedstock for lubricating oil.
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III. Basts for Listing
A. Adverse effects of crude oils and refined products
Crude or refined oils are the major component of the unused
waste oils described earlier. In this section, the toxic effects
of these components are discussed, first with respect to aquatic
organisms and, second, with respect to humans. This is followed by
a brief description of the organoleptic (taste and odor) properties
of oil-tainted ground water.
1. Aquatic Environment
EPA has already established that oil discharged to surface
water poses a significant threat to the environment. In response
to a court challenge in 1974, EPA successfully defended its posit-
ion that an oil spill sufficient to produce a film or sheen* on
the surface of the water is large enough to cause harm to the
environment.15 in its deposition (see Appendix 1), EPA documented
that oil produces a harmful effect on aquatic organisms not only
by physically coating them, but also by causing adverse chemical
changes within the organism.
Appendix 4(a) of this deposition includes descriptions of the
following types of damage to aquatic organisms caused by floating
oily layers: inability of ducks to swim or dive for food in the
presence of oil films; loss of insulating ability of feathers con-
taminated with oil and subsequent loss of normal body temperature
and death; reduced viability of duck eggs due to oil-soaked plum-
* An oil layer at. least 150 nanometers thick (1 nanometer = 1
biiltoneth of a meter), or 39.37 billioneths of an inch, is
required to produce such a sheen.
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- 17 -
age; and pneumonia and gastro-tntesttnal irritations in waterfowl
following preening of oil-coated feathers.
Appendices 4(b), 5 and 6 of the deposition document some of
the adverse physiological changes to aquatic organisms resulting
from small spills of oil to surface water. Harmful effects cited
in these appendices include: inhibition of marsh grasses to
reproduce; blocked chemoreception in fish lax-vae; increased
susceptibility of seagrasses to parasites; abnormal development
of herring larvae; and the killing of various organisms including
copepods, shrimp, and white mullet.
The deposition's claim that oil poses a significant threat to
the environment when discharged to surface water is supported
by information presented in Tables 4 and 5. Table 4 is a compil-
ation of data on the lethal toxicity of various oils to aquatic
organisms. 1-6 The table is presented here for two reasons. First,
to confirm that low concentrations of oil can be lethal. And
second, to point out that, in nearly all cases, oil's water soluble
hydrocarbons (aromatic) are toxic at lower concentrations than the
other components or types of oil listed in the table.
Table 5 summarizes the sublethal effects of crude oil and re-
fined oil products on aquatic organisms.17 The purpose of including
the table in this document is to re-emphasize that the sublethal
effects of oil are significant (e.g., disruption of feeding, breed-
ing, and locomotive behavior; interference with thermoregulatLon;
etc.), and that the concentrations necessary to bring about these
effects are often very small.
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- 18 -
TABLE 4
(a thorough
Summary of
discussion of
lethal toxicities of various petroleum product* to aquatic organism*
duration and test condition* is found in Moore, Dwyer, and Katz, 1973)
, Type
orfuisa
Marine Fioni
Finfish
Larvae and
Eces ..
Pelagic
Crustacea ....
Benthjc
Cr-us'-acet —
Soluble
H-autor?
10 ppm»--
650 ppm»'
5 ppms'-
50 oprfl**
0.1 ppm5*"-
1 ppm*"
1 ppm1*'-
10 ppm**'
1 ppm1*"-
10 ppro**'
Dujpe~*anu
1_2 ppm»-
313 mg/1
[ppmpi
1 pprr">
10,000 mg/I
[ppw]"
1 ppns**-
42 ppm"
5 ppm**-
100 ppm"
2 ppm»-
100 ppms
*2 Fuel oil/
Kerosene
<100 ul/1
tppm]"
550 ug/ml
[ppm]"
0.1 ul/l[ppm}"
4 ug/ml
[ppm?1
5 porrw>-
50 ppmw
5 ppm""-
50 ppm*"
Fresh
crude
Toxic to man;
salt marsh
planu."
88 mg/1
[ppm)"
If ml/1
[xlO> o/oo]
0.1 ul/l[ppm)»
100 ppm" »
0.1 ml/1
[XJO> ppm]»
40 ppt
[X10> ppni}»
0.56 mg/1
IppmJ"
Guofaae
91 ppm»
D>Ml
fud
204-420 ppm»
Refioen
eff)uenu
WaiK
oil
10 ppm"
1.700 ppm"
l->25 ppm"
15- >» ppm"
Lubrieuu
Boiauab
2,000-10,000
n«/Hppm)»
No eff«*
reported"
> 10.000 ppm"
Wothend
crude
Coating more
HCniTieaat
than lethal
toxieity."
G-wpod,....
Bivalves
Other Benthk
Invertebrate
Freshwater
Finfish
^
Flora
Mammals i
Birds
10 ppm2*'-
5 ppro2*-
100 pprr-3*' ! 2.000 pprr35
5 ppm3"-
SOC ppa*
1 ppm**'-
10 ppm»-
5.6 ppm11-
4,924 ppm*
0.5 ppm2*-
100 pDm»
5 ppro»-
100,000 ppm*
10 ppm3'
200 DDm31
«*^w yp*"
50 ppm*1"-
500 pom""
30-40 ml/1
(xlO3 ppm}3'
5 ppm2**-
50 ppm"'
1,000-150,000
mg/lfppm}30
Toxicity re-
ported for
several
species, but
- concentra-
tion given *
1 ml/1
[xlO3 ppmpi
10s pprn»
100 ppn>-
6,100 ppm™
0.3 mg/1
[ppm]" '
500 mg/1
tppmp°
40 mg/1
[ppmp»
180 mg/1
[ppmP'
160-4.000
mg/Uppmp1
160-1.000
mg/Uppmp'
-39 ppm"
3,000-180,000
mg/UppmP'
No effect
reported. is
Incorpon.
tion.™
1352-2,417
mg/Uppmp1
Most lethal (or sublethal) effects are caused b> phvsica) coating, entanglement.
ingestion of &TJC oil dropleu, or incorporation of hydrocarbons through food chains
Note: (1) Numbers in brackets represent reported values (volume to volume or weight to (5) The manner in which the above values are reported is only an attempt to exemplify
volu roe basis) c««rt«5 to ppm. the ranges in threshold tetnal toxicities, based on some'of the existing published '
(2) Superscript numbers refer to references, data, and should therefore not be regarded as absolute limits of toxicity for a givei
(3) Asterisks indict* values estimsted by Moore, Dwyer, and Kali, 1973. (However, category of toxicant or test organism. It must be understood that there exist
estimates are supported by examples given therein). numerous additional published data that fall within the ranges suggested above,
(4) In some cases, the above values have been taken from summary type presentations md possiblv data that may suggest further widening these ranges. It is not the
(for example: Moore, Dwyer, and Katz, 1973), the corresponding reference numbers author's intention u> herein summarize all of the uxieity valuw reported thus far
therefore do no: necessarily refer to the original publication. for petroleum and petroleum product*.
-------
TABLE 5
—Summary of some sublethai effect* of petroleum .product* on nurine lite—Continued
Typ* oTfwimr.
Fish
Crustaceans'
,
Si««s '• K*f«rcnot
Bamacit lanae
(Exaanus bQWninQts}. . .Mirono',. 19*0
Crab larvae \
( f'Qch 1/7^12 pflUf \
Chinook si'mon t
(Oneorhynchus j
Baiiey. 1973"
Atlantic siiversides
1973
Lobster (Homarus
11973
Polhnpcf
pcitvmcrus Straughan. 197]
Lobster (H '
cnmcnuf) (Atema & Steir., 1972
Pachycr-cvhus i
crc&sipes Kittredge. 1971"
i
Uca puoncn ; Krebs. 1973 •'•
i
TT» pcvoMtiir. pnduei
-or
Benzene
Crode (whole fractions)
(water soluble!
(water insoluble)
Crude, kerosene
Crude-Santa Barbara
La Rosa crude
Crude
No. 2 fue! oil
ConontntMB
1C-- IOC' ul'l ipprr.i
10-100 ul/1 (ppm)
5,10 ppm
140 ppm (v/v)
12 ppm estimated
5SS ppm (v/v)
10 ppm
Field studv
after blowout
Extracts
Dilutions of diethyl
ether extracts (1.100)
Field observations
after W. FaJmouth spill
SuUtUii, rttfaatt
Abnormt development
Initial increase
in respiratior,
Initial increase
in respiration
rustoiogical damage
to chemoreceptors
Effects on chemo-
reception. feeding times.
stress behavior,
aggression
Apparent decrease in
aaull breeding; no
recruitment in oiled
areas
Delay in feeding
Inhibition of
feeding
Adverse effects
on sexual behavior
Molluscs'
Other benthic
invertebrates
Mussel (Myttiu!
edulis)
I
Snail (.Vcusanuf
&6so/^rw^)
Snail (Xasscnus
titSOtftlLb)
C;am (Mya
crenuna) . ..
Oyster (Crasf-
oftrva virginica]
littona)
Ch-ster (Crass-
ostrea virgiitifc)
Mussel (Mytiliu
edulis)
Polychaeta
(Ccpitelic capuala.)
Gilfi'lan. 1973-'
Blumer e* al.
1973
J&cobson & Box ian
1973
Bam' & Yevich 1974
Mackin & Hopkins,
1961
Perkins, 1970"
Menzel. 194S; in
Nelson-Smith, 1973
Biumer, et al
1971"
Bellan, et al.
1972'
Crude
Kerosene
No 2 fuel oil
Bleedwaler
BP 1002
"Oil"
No. 2 fuel oil
Detergent
1 ppm
Saturated* extract
diluted 10">
Collected from field
30 ppm
0.01 ppm
Collected from
field after spill
0.01-10 ppm
Reduction in carbon
budge* (1171^0 cc jn
respi^'- ;_se
in feeding)
chemotactic perception
of food
Gonadal tumors
Reduced grou-th and
glycogen content
iignificanl infiib- — -
ition to growth
Marked taintine
Inhibition in devel-
opment of gonads
Decrease in
survival, fecundity
Note- '1 Uktn from NtUouJ Acaotmy of Seienea, 1VTI
•2 uk«n from Moore, Dw>cr an
-------
TABLE 5 (Cont'd)
—Summary of some gublethal effect* of petroleum product* on marine life
Type MT*niur.
Marine fiors.
Lar\ae and eggs:
Sptcw
Fnywi'iar.ivlon
(Chwrclic vaiganf). . . . .
Phytoplankton
(duiiiims and
dmofiaoilicicf')
Phytoplankton
(Aslenanclm
taponica )
Phytoplankton
(Phaecdaetylum
tncomutum)
Phytoplankton
(Moncchrysif
\vihcri)
Phytoplankton
(Phatttdaelyi-un,
tricornu'um,
Ske'ClcmeTT^a
costatum. Cfiivrflla
ST>.. Ouamy-
Phvtopiankton . .
iKelp (.\facrirjifiif
anpusliful in
Lichen (Lichen
pyQInceC )
Pink salmon fry
( Oncark yr.chus
gwlnu-chc)
Black Sea turbot
(Rnjcmiras maeoticuf)..
Plaice larvae
(PifruTuntcies
platessa)
Cod fish larvae
(Gccus morhuc)
Lobster larvae
[Homaruf
amcricanus)
Sea Urchin larvae
StrvnffylGcentrotus
purp-uratus)
Relerenet
Knauss. ei a!. 197?
Mironcn. 1970'1-1
Aubert, et al. 1969"'
Lacaze, 1967"
Strand, et al. 1971*'
Kuzzi 1973' >
Gordon and Prouse,
1973' '
Wither I'-GS'2
Brown 197°*'
Rice 1^73
Mironov, 1967
Wilson 1970"
Kuhnhold 1970*
Wells 1972'
Allen 1971*
Trpe pcWbieui* product
Crude Naptnalene
"Oil'
Kerosene
Kuwait crude
Kuwait crude;
cispersant
emulsion:
Extracts of outboard
motor oils. No. 6
fuel oil, No. 2 fuel oil
Venezuelan crude.
No. 2 and 6
fuel oils
BPioo!
"02"
BP 1002
Extracts of Bunker C
Conceits* tior.
1 ppm
3 ppm
1C'1
10"* ppm
38 ppm
Ml ppm"
20-100 ppm
10-300 mg/Kppm)
0.01 ppm
from 103 ppm, 104
ppm
nil nnm
Subttui* mponM
Suppi-esf pro»th;
reduction of
bcarixinau uptake
Inhibition or delay-
in cellular division
Depression of
growth rate
Depression of
growth rate
Inhibition of growth;
reduction of bicarbonate
uptake at 50 ppm
Stimulation of photo-
synthesis at 1&-30
mg/1; decrease in phoU
synthesis at 100-200
ug'l No. 2 fuel oil
i57c reduction in
photosynthesis within
5*6 hours
1 ppm emulsifier
decrease; total C*
fixation
Avoidance effects; cou
have effect on
migration behavior
Irregularity and delay
in hatching; resulting
lar\'ae deformed and
inactive
Disruption of
feeding behavior
Adverse effect on
Dehavior, leading to
death
fertilized egg
development
-------
2. Human Health
Thera are several substances listed in Appendix VIII of
40 CFR Part 261 that, are present in oil's aromatic or water
soluble fraction. These include naphthalene, phenols, benzene,
benz(a)anthracene, and benzo(a)pyrene. The last three have been
identified by EPA's Carcinogen Assessment Group as exhibiting
substantial evidence of carcinogenicity. Detailed discussion of
the toxic and carcinogenic effects of these substances are con-
tained in the Agency's water quality criteria document.s prepared
under Section 304(a)(l) of the CWA.18
The substances listed in Appendix VIII have been shown to have
toxic, carcinogenic, mutagenic or teratogenic effects on humans or
other life forms. The presence of any of these constituents in a
solid waste is presumed to be sufficient to the list the waste as
a hazardous waste unless, after consideration of designated mul-
tiple factors, EPA concludes the waste is not hazardous.19 These
multiple factors were described earlier (see page 4).
Table 6 presents the relative concentration of some of these
substances in both crude oils and certain refined oil products.
The authors of the table found that benzene, naphthalene and
phenols accounted for about 90% by weight of the identified
organics in the water soluble fraction of samples of crude and
#2 fuel oil. For bunker C fuel oil, phenols and naphthalenes
were among the most abundant class of compound found, with each
present at a concentration of about 1 m
-------
- 22 -
TABLE 6
Water Soluble Components of
Crude, and Refined Oils
Compound C^ass
Crude
(4 samples)
#2 Fuel
(5 samples)
Bunker C
(1 sample)
* Benzene
Indans
* Naphthalenes
Tetraliris
Biphenyls
Anilines
Quinolines
Indoies
Benzothiophes
* Phenols
Phthalides
Benzaldehydes
Aromat ic Ketones
44-
4-44
44
4
44 i-
44
++4
44
+
44
+4
4-4-+
4+4- = High relative concentration
44 = Low relative concentration
4 = Trace amounts
= Not detected
* = Substances listed in Appendix VIII of 40 CFR Part 261
NOTE: Although no absolute concentrations (i.e., ppm) for most of
these substances were given, the levels for phenols and naphtha-
lenes in Bunker C fuel oil were reported to both be about 1 ppm.
Thus, it seems likely that substances with relative concentrations
of (444) have absolute concentrations in the ppm, as opposed to
the ppb range.
Source: reference 20.
-------
- 23 -
The fact that carcinogens are found in oil is especially
important in determining whether oil-containing solid wastes are
hazardous wastes. EPA has in the past employed the assumption
that "carcinogenlcity is a non-threshold phenomenom. As such,
"safe1 or "no effect" levels for carcinogens cannot be estab-
lished because even extremely small doses will elicit a finite
increase in the Incidence of cancer. Accordingly, the water
quality criteria promulgated under Section 304(a)(l) of the CWA
state that, for maximum protection of human health, the ambient
water concentrations for carcinogens should be zero.*21
Similarly, under RCRA, the fact that a solid waste contains
known or proven carcinogens generally is sufficient cause to list
the waste as hazardous, unless there is strong indication that the
waste's constituents will not migrate and persist if the waste is
improperly managed.22
Of the carcinogens present in oil, benzo(a)pyrene or BaP is a
highly potent carcinogen. It has been reported to be present in
crude oil an! refined oil products.23 Because the BaP molecule
is hydrophobic, it will partition preferentially into lipids,
where it is subject to both bioaccumulat ion and biomagriif icat ion
effects.24 Samples of crude oil from the Persian Gulf, Libya,
and Venezuela have been found to contain 400, 1,320, and 1,600
* However, because zero concentration may not attainable at the
present time, the criteria specify ranges for carcinogens associ-
ated with incremental cancer risks. Cancer risk levels provide
an estimate of the additional incidence of cancer that may be
expected in an exposed population. A risk of 10~5 for example,
indicates a probability of one additional case of cancer for every
100,000 people exposed; a risk of 10~6 indicates one additional
case of cancer for every million people exposed, and so forth.
-------
- 24 -
ug/kg respectively of BaP.*25
Data on other levels of carcinogens found in crude oils
(e.g., benz(a)anthracene) are scarce. It has been estimated,
however, that the carcinogenic hydrocarbon content of crude oils
generally falls within the 100 to 1,000 ug/kg range.26
Data on the carcinogenic hydrocarbon content of refined oils
is also limited. However, unless an oil product has been refined
with processes that remove aromatic hydrocarbons (e.g./ solvent.
washing), it can be assumed that the product will contain cctrcin-
ogens similar to those found in the parent crude. In fact, since
most refining processes enrich rather than diminish the aromatic
content of refined products relative to the crude oils from which
they are derived, it is likely that the carcinogenic hydrocarbon
content of most refined products is at least, as high as that of
crude oils. For example/ the level of benzene found in motor
gasolines generally exceeds 10,000 ppm.**27
The above substances are harmful whether- ingested from surface
water or ground water, and thus aquatic organisms as well as humans
could be adversely affected by consuming oil-tainted surface water
* At the 10~6 cancer risk level, the ambient water quality cri-
teria for protection of human health from chronic exposure are
2.8 ng/1 (parts per trillion) for both benzo(a)pyrene and benz(a)
anthracene.
** Benzene is known to cause leukemia and other adverse effects
in humans at concentrations of 25-100 ppm (see Industrial Union
Dept., AFL-CIO v. American Petroleum Institute, __ U.S. _ , _
fJuiy^1980)(slip op. at 7, 20-21, reviewing regulations of the
Occupational Safety and Health Administration).
At the 10~6 cancer risk level, the ambient water quality cri-
teria for protection of human health from chronic exposure is .66
ug/1 (parts per billion) for benzene.
-------
- 25 -
or gix>und water. However, because the previous section already
documented the harmful effects that oil in surface water has on
aquatic organisms, the following discussion will focus on the
potent, ial threat to human health posed by ingest ion of these
substances in oil-contaminated ground water.
Two factors play a significant role in determining the toxic
effects of oil in ground water: the types of hydrocarbons the
oil contains, and the solubility of these hydrocarbons in water.
To begin with, the more reactive a compound, the more likely
it will be to interfere with biological functions. The probable
mechanism whereby hydrocarbons exert this interference is through
cell membrane disruption and incorporation.^ The relative
reactivity and, hence, toxicity of the classes of hydrocarbons
found in oil increases from paraffins to naphthenes to olefins to
aromatics.29 oils containing a predominance of aromatic compounds
are generally more toxic than those containing mostly paraffinic
or naphthenic hydrocarbons.30f31 Note that the Appendix VIII
substances described earlier are all aromatic hydrocarbons.
As discussed in more detail below, the solubility of the hydro-
carbons in oil is also a significant factor in determining the
effects of oil in ground water. Unless these hydrocarbons are water
soluble, they may either never reach ground water or will not mix
with it sufficiently to pose a threat to humans that use it. The
water solubility of hydrocarbons also increases from paraffins, to
naphthenes, to aromatics.32 Benzene, for example, has a saturation
solubility of 1,800 ppm in distilled water, as compared to about
-------
- 26 -
10 ppm for the alkane of equivalent, molecular weight.*33 Thus,
the aromatic portion of oil tends not only to be the most toxic,
but is also the most likely to migrate to ground water.
Toxtclogicai data on oil ingest.ton by humans and other non-
aquatic organisms is scarce. The Agency is unaware of any studies
on the effects of crude oils on terrestiai organisms. Research
on the effects of refined oil products is also scant. However,
the small amount of research that, has been conducted on refined
oils offers some insight into the potential adverse effects of
all oils on terrestiai organisms, including humans.
Toxicity Studies
This discussion deals with three types of refined oil: middle
distillate fuels, lubricating oils, and white oils. The middle
distillate category includes kerosene, diesel fuel, and fuel oils
No. 1 arid 2. The general hydrocarbon composition of this category
of oil is shown in Table 7.
Table 8 summarizes the general hydrocarbon composition of
)
lubricating oil stocks. Like the middle distillat.es, lube oils
generally contain all three types of hydrocarbons. However, be-
cause aromatic hydrocarbons produce poor viscosity characteristics
and are unstable towards oxidation, some or all of these aromatics
are often removed from lube oil stocks. The degree to which the
aromatics are removed depends upon the use to which the oil is to
* Solubility is also a function of molecular weight (i.e.,
solubility increases as molecular weight decreases). This is why
compounds of similar molecular weights are compared when assessing
the effect of hydrocarbon type on. solubility.
-------
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-------
- 28 -
TABLE 8
Hydrocarbon Composition of
Lubricating Oil Stocks
n Type Percent
(by we ight)
Alkane 45-76
Cycioalkane 13-45
Aromatic 19-30
TABLE 9
Hydrocarbon Composition of
White Mineral Oils
Hydrocarbon Type Percent
(6 samples)
Straight and branched alkaries 26.8
Cyclic aikanes
noncondensed (1 ring) 26.8
condensed
2 rings 22.1
3 rings 13.6
4 rings 6.7
5 rings 2.9
6 rings 0.9
Aromat ic hydrocarbons 0
Sources: reference 5, pg. 20 for Table 8:
reference 5, pg. 23 for Table 9
-------
- 29 -
be put. Lube oils from which all aromatic hydrocarbons are re-
moved are called whits oils. White oils are transparent, color-
less and odorless and tasteless when cold. They are used for
medicinal purposes, as food additives, as finishing oils, and
other uses requiring a very pure lubricant. Table 9 provides the
general composition of white oils.
The point to remember about the chemical composition of these
oils is that white oils contain no aromatics, whereas the middle
distillates and lube oils do. The toxic effects on terrestial
organisms to each of these three types of oil is discussed below.
The majority of the literature on oil toxicity to terrestial
organisms stems from a concern for workers exposed to oil while
performing their jobs. Workers are usually exposed to oil
either when it splashes from machinery onto their bodies, when
they lean against oil-coated machines, or when they inhale oil
mists (generated when oil contacts hot pieces of machinery).
Studies conducted on humans and test animals therefore, tend to
focus on dermal or aerosol exposure to oil. Few occupations call
for the oral ingestion of oil and, consequently, little data has
been collected on this mode of exposure. The exception to this
is data collected on white oils. Because white oils are used as
laxatives, their biomedical effects when ingested by humans and
test animals have been studied.
Data on human toxicity to the three types of oil will be pre-
sented first.*
* All damage incidents taken from reference 5.
-------
- 30 -
Middle distillates
Acute skin contact with kerosene soaked clothing caused severe
epidermal riecrolysis in a 12-year old boy. Extensive erythema
and detachment of epidermal tissue overlying a purulent exudate
occurred. Skin patch tests with kerosene for 24 hours caused skin
irritations of varying degree in humans; a highly aromatic middle
distillate fuel produced the strongest skin irritation.
A worker who swallowed fuel oil during a siphoning procedure
developed acute gastritis with hematomesis. Gastric mucosai
lesions, observed on X-ray, healed in about 1.5 months. Intense
gastrointestinal irritation has been noted after kerosene
swallowing.
Diesel fuel ingestion by young children often causes pneumonia,
due to entry of the fuel into the lungs (i.e., aspiration
pneumonitis). Cough, dyspnea and a blood-tinged frothy discharge
have been noted in these cases.
Extensive bilateral pulmonary necrosis and gangrene occurred
a 44-year old man who aspirated diesel fuel.
in
Folliculitis, furuncles, pyoderma, abscesses and papular erupt-
ions have been reported due to repeated exposures to diesel fuel.
Lubr ic at ing oils;
Squamous cell carcinoma of the hands, face, and groin after
chronic oil exposure in industry has an occurrence which parallels
the degree of refining an oil underwent prior to use. The poly-
cyclic aromatic hydrocarbons present in all but white oils are
believed to be responsible for their carcinogenicity.34
Cases of skin cancer due to petroleum oil used in industries
such as cotton mule spinning and metalworking reached a peak in
1928 and declined slowly by 1945. This is due to the introduction
of concentrated suifuric acid washing in the 1930's and later on,
solvent extraction, which removes polycylcic aromatics from lub-
ricating oils.*
* The degree of washing (either acidic or solvent) determines
the amount of aromatics remaining in the oil.
-------
- 31 -
The following are data collected from two studies on lube
oil-induced skin cancer:
In Great Britain, skin cancer studies have revealed that over 86%
of skin cancer cases that could be traced have been found to occur
in association with oil exposure, although the type of oil was
not related to incidence.
In France, in a study conducted on 5,000 workers exposed to
lubricating oils and oil aerosols, it was found that the scrotal
skin cancer rate for these workers was 36 times higher than that
of the general unexposed population.
White oils;
Ingest ion of white mineral oil, as a laxative, causes lub-
rication of the rectal sigmoid. The oil prevents absorption of
fat soluble vitamins A, D, E, and K, with resultant problems
related to deficiencies of these vitamins (alteration of calcium
arid phosphorous metabolism through interference with vitamin D
absorption; hypoprothrombinemia due to interference with vitamin K
absorption). It also coats particles of food in the intestine,
interfering with absorption, and sometimes contributing to severe
weight loss.35
Nonetheless, the Food and Drug Administration allows the use
of mineral oil in food, subject to stringent quality and quantity
standards.*
* These standards include provisions which regulate:
1. the quality and quantity of white mineral oils added to food
for human consumption.
2. the use of mineral oil as a component of non-food articles
which come in contact with food for human consumption (21 CFR
Part 178). These standards restrict oils that can be used for
this purpose to white oils. The quality and quantity limit-
ations prescribed in Part 172 for white oils are incorporated
by reference in these rules for non-food articles.
3. the addition of mineral oil to animal feed. Quality and
quantity specifications are prescribed for using white oils
for this and other animal-related purposes (CFR Part 573).
-------
- 32 -
Bronchial inflammation, distortion, and plugging with oil has
been observed in persons who have aspirated white mineral oil. The
symptoms of oil pneumonia are non-specific, but include dyspnea,
cough, wheezing, and chest pain.
Data on animal toxicity to these three types of oils are more
extensive. However, again the literature is heavily weighted
towards descriptions of aerosol and dermal, rather than oral ex-
posure to oil. Appendix 2 contains the results of aerosol and
dermal studies conducted on animals. These studies indicate
that both aromat ic and non-aromatic oils can be harmful to ani-
mals either when they ingest it through their lungs, or when it is
applied to their skin. The data suggests that hemorraghic lungs
and various blood ailments are the cause of illness (and sometimes
death) in animals exposed to aerosols containing aromatic oils.
Exposure to non-aromatic aerosols, on the other hand, usually re-
sults in oil accumulations in the lungs. The differential response
to the two types of oil mirrors that described earlier on human
toxicity to aromatic and non-aromatic containing aerosols.
The data on dermal exposure of animals to oils is also similar
to that on humans. The effects of exposing animals to aromatic-
containing oils (e.g., hair loss, blood abnormalities, severe skin
ailments) appears to be generally more severe than to oils contain-
ing no aromatic hydrocarbons. In the latter case, only minor skin
irritations developed.
Animal studies conducted on oral ingestion of oil are perhaps
more pertinent when assessing the hazards of oil-tainted ground
-------
- 33 -
water. This is because it is by this means of exposure that oily
ground water poses its chief potential threat. Table 3 in Appen-
dix 2 summarizes available data on the toxic effects of orally
administei • oil to test animals. Again, the data seems to
suggest tl both aromatic and non-aromatic oils can be harmful
to terrestial organisms. However, unlike the data on aerosol and
dermal toxicity, the studies on ingestion of aromatic and non-
aromatic oils do not lend themselves easily to comparison. This
is because the types of animals tested and the oil dosages adminis-
tered are less similar for the aromatic and non-aromatic oils than
is the case with the aerosol and dermal studies. Also, there are
fewer studies on oral toxicity from which to make generalizations.
However, the data in Table 3 are useful for the purposes of this
document because they illustrate that oral ingestion of oil can
pose serious health hazards to terrestial organisms.
3. Drinking Water
Aside from the toxic effects that oil can have on consumers
of oil-tainted ground water, the contamination of drinking water
with oil is also of ^reat concern because of oil's organoieptic
propert ies.
The previous discussion described, in qualitative terms, the
toxic effects of oil to humans and other terrestial organisms.
Mo quantitative toxicity value for oil was provided because oil's
toxicity varies with its chemical composition. Quantitative
values have been reported, however, for the concentration at
which oil renders water objectionable to drink.
-------
- 34 -
Human taste is very sensitive to oil and, depending on the
individual, a concentration between 0.005 and 0.5 pounds in
100,000 gallons of water will produce water which will be
described as having a bad taste.36 Oil also has a strong odor
which, for many people, makes oil-contaminated water unpleasant
to drink. For these reasons, mismanaged waste oil poses a sig-
nificant potential threat to ground water supplies of drinking
water.
Ground water is, of course, an essential environmental re-
source; at least half the population of the United States depends
on it for their drinking water.3? Congress expressed special
concern for protection of ground water in the legislative history
of RCRA. The Agency views the potential contamination of large
portions of ground water as posing a "substantial" hazard to human
health and the environment, within the meaning of Section 3004 of
RCRA, even if the contamination results not in a direct threat to
human health, but rather to the destruction of ground-water
resources.
It has been suggested that because petroleum is organo-
leptically objectionable at very low concentrations, it is
unlikely that oil-polluted drinking water will pose a toxic
threat to humans. This, however, has never been scientifically
determined to be true. Nonetheless, regardless of whether oil
produces an adverse organoieptic or toxic threat to consumers
of ground water, either threat is significant and detrimental
to humans.
-------
- 35 -
B. Hazards posed by mismanagement
f;' As stated earlier, there are three principal sources of
unused waste oil: spills, vessel operations, and inadequate
storage and formulation. This section explains why unused
waste oil derived from spills poses a significant threat to
human health and the environment, while that derived from the
other two sources poses a minimal threat.
Existing regulations and management practices ensure that
waste oil derived from vessel operations does not pose a
sufficient environmental threat to warrant its listing as a
hazardous waste under RCRA. The first section of this document
described how unused waste oil brought ashore* from vessels is
normally processed at oil refineries. In the case of oily
wastewaters (e.g., ballast water), the wastewater is stored in
tanks for a short time until it is released to a refinery's
wastewater treatment system.** In the case of oil separated
from wastewater (e.g., tank-cleaning water) on board a vessel,
the oil is typically used as a feedstock at oil refineries
when brought ashore. Thus, in both cases, the unused waste oil
is managed in a manner which maximizes its recovery.
Additionally, EPA believes that economic considerations
will minimize the threat of improper management of waste oil
resulting from inadequate storage and formulation. Because oil
* Unused waste oil discharged to surface water is subject to
regulations administered by the Coast Guard (33 CFR Part 157).
** These treatment systems are designed to recover oil from
various wastewater streams.
-------
- 36 -
is becoming px-ogressiveiy more expensive, the Agency be-
lieves that less and less waste oil will be generated from
poor handling practices (e.g., letting oil exceed its shelf
life) other than spills. That is, as the cost of oil rises,
handling practices should improve. For this same reason, the
Agency believes that negligible quantities of waste oil will
be generated when unused oil flunks certain specifications.
Off-spec oil will either be reblended to meet specifications,
or will be used for lower quality uses.* Thus, because the
quantity of unused oil that becomes a waste due to inadequate
handling or formulation practices is small, the environmental
threat posed by this oil should also be small.
Unused waste oil derived from spills does, however, pose a
potential significant threat to the environment.** The follow-
ing discussion will focus on the environmental hazards posed by
(1) oil spilled to land, and (2) oily debris generated from
cleaning-up spills to land and surface water.
As indicated earlier, the aromatic component of oil is toxic,
and contains several substances (including three carcinogens)
listed in Appendix VIII of Part 261. If unused oil is spilled
or otherwise improperly managed on land overlying an aquifer,
its aromatic component may migrate to ground water. The degree
* E.g., 'off-spec' oil destined for use in military vehicles
could be sold to retail stores as low cost motor oil.
** Oil spilled to surface water In sufficient quantities to
create a sheen has been shown to be harmful to the environment.
While in the water, such oil is subject to regulations {40 CFR
Part 110) pursuant to Section 311 of the CWA and, thus, no
further regulatory control under RCRA is warranted.
-------
- 37 -
to which oil and its components are transferred to ground
water is governed by several processes which include:
1. the extraction of soluble components from the oil
into residual water in the soil;
2. the transport of dissolved components to the ground-
water body, for example by rain water; and
3. the adsorption of oil components on the soil.
The influence of each of these processes depends on the
amount and composition of the oil, on the nature of the soil,
on the rate of rainfall, and on the gx'ound-water level and its
grade.38 Figures 1 and 2 illustrate the effect of several of
these factors on oil migration to ground water.39 As can be
seen, oil released into soil tends to flow downward, with some
lateral spreading. As oil moves down through the soil, some of
its components become trapped between individual soil particles
and remain behind the main body of oil. Other components con-
tinue to travel through the soil, and may eventually reach
ground water.40
In order to study the behavior of oil spilled to land, soil
core samples were taken at the sites of several known oil spills
in Alberta, Canada.41 in general, the total concentration of oil
declined with depth, with the total concentration of the aromatic
fraction appearing to increase relative to the other two fractions
(i.e., naphthenic and parrafinic). Oil was detected in the ground
water below several of these sites. These findings are significant
for two reasons. First, they document that oil can migrate to
ground water. Second, they lend support to the commonly held,
-------
- 38 -
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- 40 -
theory that, oil traveling through soil becomes enriched in
aromatic hydrocarbons relative to the source of the oil spill.
Contamination of ground water supplies by oil has been
reported in all Canadian provinces, in the United States, and
in Europe.42 jn 1968, for example, a major ground watar re-
source in southern California was contaminated with hundreds
of thousands of gallons of gasoline.*43
In addition to oil spills, another significant potential
source of ground-water contamination is oily debris generated
from cleaning-up oil spills to land or surface water. Oily
debris is typically disposed of at landfills, landfarms, or
incinerators. The facilities used to manage this debris are
not always adequate for this purpose. In at least one instance,
oil spill debris has been washed from a landfill by fiooclwaters
simply because the disposal site was located in a known flood-
plain.44 In another case, oil was detected in soil samples 7
meters (20 feet) below a iandfarm disposing of oily debris. Oil
was also found in the ground water below the site.""
Oil that has either migrated through soil or has reached
ground water is subject only to anaerobic degradation. It has
been estimated that anaerobic degradation of oil takes on the
order of 100 years.46,47 Thus, damage to water resources from
oil can be very long-lived.
* Gasoline meets the definition of petroleum-derived oil
described earlier and, thus, would be considered to be a waste
oil when spilled.
-------
- 41 -
Summary
Oil spilled to land, and oily debris generated from
cleaning-up spills to land or surface water, pose a significant
threat to ground water supplies. Substantial quantities of both
of these types of unused waste oils are generated each year.
Past, management practices suggest a risk of improper management.
The oils have been known to enter ground water when improperly
managed. The aromatic component of these oils is not. only the
most likely to migrate to ground water, but also is the most
toxic. Oil is organoleptically objectionable to humans at very
low concentrations. Oil that reaches ground water does not
readily degrade.
The Agency believes that all of these considerations support
the proposed listing as a hazardous waste of (1) oil spilled to
land, and (2) oily debris generated from cleaning-up spills to
land or surface water. The exception to this is unused waste
oil that, has essentially no aromatic hydrocarbons (i.e., white
oils). Because these oils are used for medicinal purposes, arid
are allowed to be used in food, the Agency believes it would be
inappropriate to list either- of the above two types of unused
waste oils as hazardous wastes if their petroleum base is
white oil.
-------
- 42 -
USED OIL
Used oil is generally categorized as automotive, industrial,
or aviation oil.* Used oil is similar to unused oil in that it
contains an oil component that poses a potential threat to human
health and the environment when improperly managed. Thus, for the
same reasons given earlier for unused oil, the Agency believes that
used oil should be listed as a toxic (T) hazardous waste. In add-
ition, many used oils contain contaminants which cause them to be
hazardous for reasons other than their oil component. The identi-
fication of these contaminants and the additional hazards posed by
them are the focus of this chapter.
The first part of this chapter describes the quantities gen-
erated, typical hazardous contaminants, and the practices commonly
used to manage used automotive and industrial oils. This is
followed by the Agency's rationale for listing used automotive and
industrial oils as hazardous wastes.
I. Constituents and Management Practices
A. Automotive
The Bureau of the Census1 most recent (1977) compilation pro-
vides the following breakdown of U.S. sales of lubricating oil:48
* Used aviation oils are not. addressed in this document for two
reasons. First, aviation oils make up less than one percent of
total oil sales and, thus, relatively little used oil is generated
from this source compared to automotive and industrial oils.
Second, because of centralized servicing areas, most used aviation
oils are collected, segregated, and treated, or — in the case of
synthetic jet fuels — returned to the manufacturer for reclaiming.
The Agency believes that because relatively little used aviation oil
is generated, and because that which is generated is usually managed
in an environmentally sound manner, it is not imperative that this
oil be subject to the hazardous waste management rules at this time.
-------
- 43 -
Billion of gallons
automotive 1.29
aviation .02
industrial
lube 1.03
other _ .53
2.86
According to this source, automotive lube oil sales made up about
45% of the total market in 1977. The Bureau of Census includes
the following types of oils in the automotive lube oil category:
engine oil, gear lubes, hydraulic oils, and transmission fluids.
1. Const ituents
At present, additives comprise greater than 15% by volume of
automotive oils.49 Table 10 presents the chemical composition
and functions of these additives. During service, the additives
are chemically changed or consumed., and the oil itself becomes
contaminated from both internal* or external** sources.^0
Table 11 is a comparison of the properties and components of
used automotive oils with that of various virgin oils. The table
is divided by dotted lines into 3 sections. The first section
presents some of the physical properties and chemical components
of used automotive oils. The second section shows other physical
and chemical properties and components which reflect the additive
* The primary source of internal contamination is breakdown of
the additive package and subsequent interaction among its
chemical components. These components may be oxidized during
combustion, forming corrosive acids.
** Examples of external sources of contamination include soot and
lead compounds from engine blowby, dirt and dust; engine wear
metal particles; rust; gasoline from incomplete combustion;
coolant from imperfect engine seals; water from blowby vapor.
-------
- 44 -
TABLE 10
Lube Oil Additives, Automotive and Industrial Oil
ADDITIVE
Antiwear/Extreme Pressure
Zinc Dithiophosphate
Organic phosphates
Organic sulfur &
chlorine compounds
Lead compounds
Amines
Corrosion & Rust Inhibitors
Zinc dithiophosphates
Basic sulfates
Metal phenolates
Fatty acids and amines
Alkenyl-succinic acids
Detergents/Dispersants
Barium, calcium & mag-
nesium phenolates
Organic phosphates &
sulfates
Polymeric alkyl thio-
phosphates
Alkyl succinimides
Friction Modifiers
Yatty acids and amines
Lard oil
Organic phosphorous
Phosphoric acid esters
Molybdenum disulfi.de
Antioxidants
Zinc dithiophosphate
Aromatic amines
Hindered and sulfurized
phenols
Nitrogen & sulfur compounds
Metal Deactivators
Weak organic acids
Organic complexes of
amines, sulfides,
phosphates
FUNCTION
Forms protective film,
reduces wear
Prevents corrosion by
forming protective film
or by neutralizing acids
Disperses insoluble con-
taminants by keeping them
suspended in the oil
Used in automatic trans-
missions and limited
slip differentials
Reduces foam in cx'ankcase
Reduces oxidation and pre-
vents rust and corrosion
by forming a protective
film on metal surfaces
-------
- 45 -
TABLE 10 (Cont'd)
Lube Oil Additives, Automotive and Industrial Oils
ADDITIVE
Pour Point Depressants
Polymethacrylates
Alkylated naphthalenes
Chlorinated paraffins
Phenolic polymers
Viscosity Index Improvers
Methacrylate polymers
Butadiene
Olefins
Alkylated styrene
Emuisifiers (industrial
lubes only)
Sulfonates
Surfactants
Naphthenates
Fatty acid soaps
Biocides/Fungicides
(industrial lubes only)
FUNCTION
Lowers freezing point, thus
allowing free flow at low
temperatures
Minimizes viscosity changes
as temperature fluctuates
Holds oil-water mixtures in
suspension
Kills bacteria and fungus
which cause odor problems
* Sources: References 55; 49, Table 2-2;
and 51, Table 2.
-------
- 46 -
TABLE 11
Properties and Components of Used Automotive Oil
Compared with Selected Virgin Oils
Property/Component
Used Automotive
Oil - Range
Virgin Distillate
Range
Virgin Residua;
Range
Bottom Settlings &
Water (BS&W) %
Water %
Fuel Dilution %
Flash Point °F
Chlorine ppm
Br ppm
Carbon Residue %
Ash %
N ppm
S ppm
Ba ppm
Ca
Mg
Na
P
Zn
Ai
Cr
Cu
Fe
K
Mn
Ni
Pb
Si
Sn
Cd
0
.2 -
.4 -
175
1700
1000
1.82
.03
530
2100
10
700
10
16
500
300
.0
8
5
50
5
5
3
800
10
5
- 22
33.8 **
9.7 **
- 415
- 4700***
- 3000 ***
- 4.43**
- 3.78
- 1770**
- 6500**
- 2000
- 3000
- 1108
- 300
- 2000
- 3000
- 800
- 50
- 348
- 2000
- 79
- 10
- 30
- 11,200
- 875
- 112
4
0 - 1.5 0
0
0
126 - 204 150
.002 - .005 0
200 - 5900 3000
.7
.4
• 1
.5
13
10.5
3
1.7
8.2
mm
0
0
-
-
0
-
-
-
0
0
-
-
*
-
0
0
-
-
-
0
0
3
270
.5
4000
95
27.9
480
219
14
5
230
118
4.1
164
NOTE: The term "distillate" in column 3 refers to middle distillate
oils (e.g. Nos. 1 and 2 fuel oils); the term "residual" in column 4
refers to heavier fuel oils (e.g., Nos. 4 and 5 fuel oils).
* Source: Unless otherwise indicated,
data are taken from reference 134.
** Data from reference 53, Tables 2, 3, and 4.
*** Data from reference 49, Table 3.
-------
- 47 -
content of the oils. The third section shows the metal content of
the oilsr the first six elements (Ba, Ca, Mg, Na, P, and Zn) are
associated with additive compounds; the remainder are wear and
contaminant metals. This table offers an overall picture of the
make-up of used automotive oil, and highlights the general differ-
ences between these and virgin oils. The remainder of this
discussion will focus on the specific toxic components of used
automotive oil which provide support (in addition to that provided
for unused oil) for its listing as a hazardous waste.
Polynuclear aromatic hydrocarbons (PNA's or PAH's);
As stated above in the discussion of unused oil, PNA's as
a class ax-e toxic, and many are potent carcinogens as well.
Already found in virgin oils, PNA's are "known to concentrate
in used automotive lubricating oils, apparently coming from
the gasoline or diesel fuel and their combustion products."51
The National Bureau of Standards (NBS) uses benzo(a)pyrene
(BaP), as an indicator of total PNA content. According to
NBS analyses as summarized in a RECON report,52 the BaP levels
in used motor oils may be as much as 900 times greater than
those found in unused motor oil basestocks (see Table 12)*.
In absolute terms, a 1975 BERJ (Bartlesv ^e " ier~ • Research
Center) analysis of ten used automotive oils found the concen-
tration ranges for three specific PNA's to be: phenanthrerie
40-110 ppm; pyrene 30-100 ppm; and 1,2-benzanthracene
3-30 ppm.53
* Note, however, that the BaP content of used diesel oil is
less than .15ug/g. This is considerably lower than the levels
measured in used gas engine oils.
-------
- 48 -
TABLE 12
Benzo(a)pyrene Concentrations as
Measure of PNA Content In Used and Virgin Oils
Oil BaP in ug/g
#2 virgin (distillate) .03 - .6
#6 virgin (residual) 2.9 - 44
virgin motor oil basestocks .03 - .28
used motor & waste oils 3.2 - 28
used diesel motor oil < .15
used industrial oil 5.9
Source: reference 50, Table 14.
-------
- 49 -
Trace metals;
Trace metals of concern in used automotive oil derive
from several different sources. The extremely high lead
content (800-11,200 ppm; see Table 11) is attributed chiefly
to piston blowby in engines using leaded gasoline*. Lead
compounds may also be a minor component of some antiwear/
extreme pressure additives (see Table 10).
Barium, which like lead is absent from automotive lube"
oil stocks, is generally found in used automotive oil in
the range of 10-2000 ppm (see Table 11)**. Barium derives
from detergent/dispersant additives (see Table 10), which
make up 6.8% by volume of SE quality multigrade motor oil.55
According to Table 11, the chromium concentration of
used automotive oil ranges from 8 to 50 ppm; cadmium was
measured at 4 ppm. The presence of both these trace metals
in used automotive oil derives from engine wear.
Nitrosamines;
Nitrosamines are formed when secondary amines react with
the following nitrogen compounds: nitrites, nitrates, and
nitrogen oxides. A report to the National Science Foundation
indicates that, since both nitrogen and amine compounds are
found in used automotive oils, the formation of nitrosamines
is possible.56 Furthermore, various nitrosamines have been
patented for use as anti-oxidants in fuels and as a lube
* However, because diesel fuel is unleaded, the lead content
of used diesel lube oil is negligible.
**
NBS analyses have reported barium levels as high as
3906 ppm in some crankcase oils.54
-------
- 50 -
oil additive.5"7 Other precursors to nitrosamine formation
are currently used as lube oil additives. These include
various aryl and aikyl amines which serve as anti-oxidants,
and morpholine which is a corrosion inhibitor.58 These
"precursors" react with nitrogen compounds in the used oil,
in the environment, or in the human body, to form nitros-
amines.59
Chlorinated hydrocarbons*: '
Petroleum is composed of a mixture of hydrocarbons,
including benzene and naphthalene. When these and other
hydrocarbons are exposed to the significant levels of halo-
gens introduced during automotive use (see chlorine and
bromine concentrations, Table 11), halogenated hydrocarbons
(e.g., chlorinated benzene and chlorinated naphthalene)
may be formed. The halogen content of used automotive oil
derives from two sources: additive package breakdown (see
Table 10); and addition of chlorine and bromine, as lead
scavengers, to leaded gas.
* Until the early 1970's, small amounts of poiychiorinated
biphenyls (PCS) were added to certain automobile transmission
fluids to enhance controlled swelling of rubber seals. Trans-
mission fluids from older automobiles thus may be a source of
low level PCS contamination of some used automotive oils ,,60
EPA's regulations under the Toxic Substances Control Act
(TSCA) presume that all used oil is contaminated with PCBs.^l
Although information from an independent testing laboratory
specializing in used automotive oil analysis indicates that
used automotive oil samples are, for the most part, free of
PCB contamination, the common collection practice is to mix
used oils taken from various sources.^2 jn this way, used
automotive oil may be contaminated through contact with PCB-
laden hydraulic or transformer oil collected from industrial
sources (see section on industrial oils).
-------
- 51 -
2. Management Practices
In 1978, an estimated 50-65% of the motor oil sold for
passenger car use was sold to people who change their own oil.6-*
These people are "known in the industry as "do-it-yourselfers"
(DIYs). Within the next 5 years, this group is expected to comprise
75-80% of such sales.6^ Currently, most used oil generated from
DIYs (over 200 million gallons) is dumped on the ground or into
streams or sewers, or is placed in containers and put out for trash
collection.65'66
Service stations and automobile dealerships collect waste oil
on their premises in 500-1000 gallon tanks*. The oil collected at
service stations is derived from both on-site maintenance of auto-
mobiles and DIYs who bring their used oil to these stations. No
attempt is made at either service stations or automobile dealer-
ships to segregate used oil from engines using unleaded fuel from
that of engines using leaded gasoline.
Used oil tanks at service stations and automobile dealerships
are emptied by independent collectors. The collector's trucks
generally hold between 2000-6000 gallons. Used oil from several
service stations or dealerships is usually placed in the same
truck. The collectors normally sell the oil for use as a fuel,
a dust control agent, a pesticide/ herbicide carrier, or as a
* In addition to used oil, brake and transmission fluids, gas-
oline, kerosene, antifreeze (ethylene glycol), and such solvents
as benzene, trichlorethane, and perchloroethylene are often placed
in used oil tanks at service stations and automobile dealerships.
The low flash points, toxicity, and possible carcinogenicity of
many of these substances further increase the hazards posed by
the used oil.
-------
- 52 -
feedstock to rereflners.* Other uses which claim small amounts
of used oil are asphalt mixes, and use as a herbicide.
Used lube oil from diesel engines generated by large commercial
trucking fleets may remain segregated from other used automotive
oil in the collection process. Much of this oil goes to rerefiners,
with the exception of that produced by the mining and construct-
ion industry (about 20% of all diesel vehicles). The practice in
these industries is to change the oil in the field, where it
is simply flumped on the ground. 6? Some trucking fleets also mix
low levels (2-6.5%) of used diesei lube oil with diesel fuel and
burn the resulting blend in their engines.*>8
B. Industrial
The Bureau of Census data cited earlier (see page 43) indicate
that industrial oil sales made up about 55% of the total lube oil
market in 1977. The industrial category is subdivided into two
groups: lube oil, including metalworking oils and oil used in
railroad and marine diesel engines; and non-lube oils, including
hydraulic, transformer, turbine, and quenching oils.^9/70
In general, industrial oils contain an additive package similar
to that of automotive oil (see Table 10). Table 13 shows some of
the physical properties and chemical components of used industrial
oils. Table 12 compares the PNA level of used industrial oil to
that of various other used and virgin oils.
* Some collectors treat the oil before selling it, to remove water
and solids, and small amounts of oxidation products. Although such
"reclaiming" before sale and reuse may produce a cleaner and more
marketable oil, the properties and components of concern discussed
in this document are not removed or mitigated.
-------
- 53 -
TABLE 13
Properties and Components of Used Industrial Oil
Property/Component
Water %
Plash Point °F
Cl ppm
S ppm
Pb ppm
Ba ppm
Cr ppm
Cd ppm
Range
25.7 - 26.2
315 - 355
1000 - 8300
5400 - 10,030
Mean
Max imum
125
59.7
7,9
2.7
2000
550
45
21
Source for data on first four properties/components
reference 51, Table 3.
Soui'ce for data on last four components:
reference 141, Table 3-7.
-------
- 54 -
The data contained in these tables must be treated, however,
as only a rough sketch of the contaminants that may be found in
used industrial oils. The used industrial oil category is much
riore diverse than that of used automotive oil because industrial
oils perform a wider variety of functions compared to automotive
oils. The contaminants in industrial oils vary with each function*,
as does the type of additive package used. The components of these
additive packages are less predictable than those in automotive
oils because users of industrial oils frequently have their add-
itive packages custom-blended for their particular needs. Thus,
unlike used automotive oil, it is impossible to identify a set of
contaminants that can be expected to be present in used industrial
oil per se.
The Agency has limited data on contaminants found in some of
the larger sub-categories of used industrial oil. This data will
be presented next, along with a description of how these types of
industrial oil are currently being disposed of or reused. The
section is divided into two parts: lube and non-lube oils.
1. Lube Oils
Metalworking oils:
Metalworking oils are lube oils used for catting, grinding,
drilling, and machining metals. They range from 100% oil (neat
oil) to low concentrations of oil in water emulsions (soluble
oils).
* E.g., the trace metals in used metalworking oils vary with the
type of metal that is being cut, ground, drilled, etc.
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a. Constituents:
Chlorinated hydrocarbons*:
The chlorine content of used metaiworking oils is high, which
can lead to significant chlorinated hydrocarbon emissions when
the oil is burned. In the neat metaiworking oils, the chlorine
is derived from the additive package. Metaiworking oils require
enhanced extreme pressure additives which may contain as much
as 18% active chlorine.73
Used soluble metaiworking oils are also likely to have a
high chlorine content. When the oil is recovered from the oil-
water emulsion, the recovery process typically includes breaking
the emulsion with hydrochloric acid. Chlorine from the acid may
react with the oil's hydrocarbons to form chlorohydrocarbons.
Nitrosamines;
Recent studies indicate that "soluble cutting oils may contain
nitrosamines, either as contaminants in amines, or as products
from reactions between amines and nitrites".74 The nitrosamine
content of metaiworking oils is attributed to the additive
package, specifically to the antiwear/extreme pressure, cor-
rosion and rust inhibitors; friction modifiers; antioxidants;
and metal deactivator additives (see Table 10).
* PCBs can enter metaiworking oil through "tramp oil" accu-
mulations. Tramp oil is oil (usually hydraulic oil) from other
parts of the machine which leaks or drips into metaiworking oil.
Hydraulic oil is likely to be contaminated with PCBs (as explained
later in the discussion on hydraulic oil), and it can accumulate
in metaiworking oil in sufficient amounts to raise a 5% oil/water
emulsion to 10% oil.71 In addition, PCB additives were used in
industrial lube oils prior to 1973.72 These could still be con-
tributing to the PCB contamination of used metaiworking oils.
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- 56 -
Use of synthetic lubricants in metalworking oils is
increasing, 77 anfl concentrations of nitrosamines in synthetic
cutting oils have been measured at 1-1000 ppm.78
Trace metals:
Used metaiworking oils are heavily contaminated by fine wear-
metal particles (see Table 13), and with barium from detergent/
dispersant additives.
b. Management Practices:
Over 64 million gallons of metaiworking oils were sold in
1978.79 Because the typical metalworking operation does not con-
sume oil, about 60 million gallons of used oil are generated and
must, be disposed of or reused annually.
The neat oils have an extremely high metal content, the soluble
oils have a high water content — both pose problems for rerefining,
The high chlorine arid sulfur content of the neat oils, and of the
acidified and recovered soluble oils, makes burning undesirable.
As a result, only a small amount of these oils -- about 20% or 12.8
million gallons -- is being collected for reuse.80 ^he remainder,
is being disposed of by dumping, uncontrolled burning, ox- by land
applicat ion.
* Defined as a product made by chemically reacting lower molecu-
lar weight materials to produce a fluid of higher molecular weight
with planned and predictable properties.7^ The princj_pie types are
esters, silicones, flouro- and chlorocarbons, and polyoxyalkanes .
In 1980, synthetics made up 2% of the total lube (automotive and
industrial) market. This figure may be up to 10% by 1985.76
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- 57 -
Railroad and marine oils:
a. Constituents:
Because railroad and marine use of engine lube oils parallels
that of automotive applications, ^1 the trace metal content, of used
railroad and marine diesel engine lube oils should be similar to
that of used automotive oil (see Table 11), with the exception of
lead. Diesel fuel is unleaded, so there should be little or no
lead in any used diesei engine lube oil.
The additive package required by railroads consists of deter-
gents, 10.5% by volume.^2 This may result in significant, barium
concentrations in used railroad diesel engine lube oil (see
Table 10).
Marine diesel engine lube oils* also require an alkaline det-
ergent additive, up to 15% by volume in the crankcase oils.
This too may lead to high barium levels in used marine oil (see
Table 10).
b. Management Practices:
About 80% of railroad oil is consumed in use, leaving about
10.3 million gallons to be disposed of or reused. The vast major-
ity (greater than 95%) of this amount is collected, rerefined, and
returned to the railroads for reuse.^3 Like automotive diesel
fleets, the railroads also mix their used lube oil with virgin
diesel fuel, at very low blend ratios.
In 1978, about 35.5 million gallons of marine cylinder arid
crankcase lube oils were sold. Much of the cylinder oil is con-
* All information on marine oils is taken from reference 55,
pp. 48-52.
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sumed in use; the remainder is drained out of the engine into
the bilge tank. Crankcase oil, when changed, is also placed in
the bilge tank. In the past, these bilge oils have been dumped
at sea. Now, naval and some commercial shipyards collect these
used oils.
About 60% of all marine oils are consumed in use. Of the re-
mainder, 16% is collected for reuse as fuel (marine facilities
also blend low levels of used lube oils with virgin diesel fuel)
or for rerefining. The remaining twenty-four percent (or 8.5
million gallons) is dumped at sea or on the land.
2. Non-Lube Oils:
Hydraulic oils:
Hydraulic oils are widely used in industry, primarily in dies-
casting, steel foundry operations, automobile production, and
mining.
a. Constituents:
Chlorinated hydrocarbons;
Until 1972, PCB-based hydraulic fluids were commonly used.
When manufacture of these fluids was discontinued, it was
not recommended that hydraulic systems be drained, flushed, or
refilled*. Rather, the public was advised to merely replace
these fluids (without PCBs) as leaks and spills occurred.. As
a result, PCB levels in hydraulic systems range from 60 to
500,000 ppm.84
* The extreme complexity of hydraulic systems makes it very
difficult to eradicate all PCB contamination from these systems
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Nitrosamines:
Nitrosamine precurors may be present in the form of
nitrogen and amine compounds, deriving from the anti-rust,
anti-oxidant, and anti-wear additives found in hydraulic
oils.85
b. Management Practice:
In 1978, 234 million gallons of hydraulic oils were sold.
Small quantities of this oil were consumed in use or lost
through leakage and spills.
Large industrial facilities recover much of their used
hydraulic oil, which may be sold to collectors, burned as a
fuel supplement in the plant itself, or used as a dust control
agent on plant site roads arid parking lots. At construction
sites and mining operations, however, hydraulic oils are not
recovered. It is estimated that 40% of these hydraulic oils,
or about. 94 million gallons, are disposed of annually. ^
Transformer Oil;
a. Constituents:
Chlorinated hydrocarbons;
Transformer oils, used in electrical transformers as a
heat transfer medium, are straight mineral oils with no add-
itives.^"7 However, until 1977, PCBs were widely used as a
dielectric fluid in transformers and other electrical equip-
ment. These PCBs still remain in many transfox-mer systems,
contaminating transformer oil.
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- 60 -
The preamble to EPA's PCB regulations states that as
many as 38% of the 35 million transformers using mineral oil
contain between 50 and 500 ppm PCBs.^8 &n independent test-
ing laboratory estimates that about 50% of all transformer
oils show greater than 50 ppm PCB contamination. This occurs
because, even if transformers are drained and cleaned out,
they have "long memories", and PCBs are likely to remain in
the system.89
In addition to PCBs, transformer oils have also been found
to contain trichiorobenzene, a persistent toxic substance.-'0
b. Management Practice:
About 98 million gallons of transformer oils were sold in
1978. This unusually high figure reflects an increased demand
to replace PCB-contaminated oil.
Transformer oils do not make a good rerefinery feedstock
because of their low viscosity. EPA's PCB regulations strictly
control the disposal and reuse options of PCB-contaminated oils.
At present, most used oil collectors are refusing all trans-
former oil, thus putting the burden of proper disposal on the
generators.91
Turbine oil*;
a. Constituents:
Turbine oils are used in steam, natural gas, or dual cycle
turbines that generate electricity or run compressors. The oils
require a high temperature oxidation inhibitor, about 2% by volume.
* All information on turbine oils is taken from reference 55,
pp. 61-62.
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- 61 -
Because ashless additives such as aromatic amines or hindered
phenols are preferred, nitrosamine precursors may be present in
the turbine oils as a result of the additive package.
b. Management Practice:
Eighty-four million gallons of turbine oil were sold in 1978.
Turbine oils may be changed as often as once a year, or may be
treated and reused for up to 20 years.
Most turbine oil is used in large industrial plants, which
tend to collect their used oil. It is estimated that about 50.4
million gallons of used turbine oil is recovered and either
disposed of or reused.
Quench ing oil;
a. Constituents:
Quenching oils act as a cooling medium for hot metals. These
oils contain numerous additives, including barium sulfonate, z iric
compounds, sodium nitrate, and antimony trioxide.^2
b. Management Practice:
About 50% of the 7.5 million gallons of quenching oils sold in
1978 were collected from metalworking shops. At shops which place
used quenching arid metalworking oils in the same container, the
quenching oils become tainted with the contaminants found in used
metalworking oils.
*****
On the whole, mixing of used industrial oils from different
sources does not. occur to the extent it does with automotive oils.
Many users of industrial oil find it more cost-effective to burn
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their used oil as a fuel or otherwise manage it (e.g., by
using the oil as a dust suppressant on unpaved roads or parking
lots on their property), rather than give or sell it to used oil
collectors. This is not to say that mixing of different types of
used industrial oils does not occur within industrial plants. For
financial and space constraints often operate against providing
separate storage facilities for, say, neat metalworking oils and
soluble oil-water emulsions.93 Nonetheless, the opportunity to
segregate oils with different contaminants is greater when gen-
erators reuse their oil on-site rather than give it to used oil
collectors.
Some used industrial oil is, however, consigned to used oil
collectors. The collectors usually transport different types of
used oil in the same compartment of their trucks, so that the
various contaminants in the individual waste streams become mixed
throughout the composite tfaste oil.
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- 63 -
II. Basis for Listing
A. Adverse effects of contaminants in used oil
This section briefly describes the toxic effects of the var-
ious contaminants found in certain used oils*. In addition, for
each contaminant, the discussion notes if substances containing
these contaminants are subject to controls under regulatory pro-
grams other than those concerned with solid waste management.
Polynuclear aromatic hydrocarbons (PNAs);
The toxic and carcinogenic effects of PNAs were described
earlier in the chapter on unused oil. SC>2, which is present in
the vapor produced when used oil is burned, is considered to have
a synergistic effect on PNA-induced carcinogenesis. ^4
Halogentaed Hydrocarbons;
1. Polychlorinated biphenyls (PCBs):
a. Health Effects: PCBs have been identified by EPA's Car-
cinogen Assessment Group as exhibiting substantial evidence of
care inogenicity. 95 PCBS are also highly toxic. They are absorbed
through the lungs, the skin, and the gastrointestinal tract; then
are circulated throughout the body in the blood, and are stored
in the liver, kidneys, lungs, adrenal glands, brain, heart, and
sk in.96
Yusho disease (human PCB poisoning) affected at least 1000
people who ate rice bran oil contaminated with PCBs. These
* Detailed discussions of the adverse environmental effects of
many of these contaminants are contained in the criteria docu-
ments prepared under Section 304(a)(l) of the CWA. See 45 PR
79318 (November 28, 1^80).
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- 64-
victims also evidenced an abnormally high cancer rate of the
stomach and liver. It is estimated that the Yusho victims in-
gested PCBs at a rate as low as 67 ug/kg of body weight per day
for 3 months.97
Skin lesions have developed among workers exposed to air
containing PCBs at levels as low as .1 mg/m3.^^
b. Ecological Effects: PCBs are inert and persistent, having
a tendency to accumulate in waterways and to bioaccumulate in
fish. PCB levels of 1 ppb may adversely affect aquatic insects
and crustaceans. Concentrations as low as .1 ppb have been shown
to depress photosynthesis in phytoplarikton and to retard their
rate of cell growth arid division. ^9
c. Other Regulations: EPA has designated PCBs as a toxic
pollutant arid has set effluent standards prohibiting any discharge
of PCBs into navigable waters by PCB manufacturers, electrical
capacitor manufacturers and electrical transformer manufacturers.
The ambient water criterion for PCBs is .001 ug/l.100 There
are no ambient air quality standards for PCBs. However, disposal
of PCB-contaminated wastes is governed under TSCA by 40 CFR Part
761. Wastes (specifically used oil) containing less than 50 ppm
PCBs may be rerefLned or burned without controls, but may not be
used as a road oil, dust suppressant, or sealing and coating agent.
Used oil with 50-500 ppm PCBs must be burned in a high-efficiency
boiler or approved incinerator, where the destruction efficiency
is 99.9%; it may also be disposed of in approved chemical landfills
Used oil with greater than 500 ppm PCBs must be disposed of only
by high temperature incineration.
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- 65 -
PCBs are listed a hazardous constituent in Appendix VIII,
40 CFR Part 261; thus raising the presumption that any wastes
containing these substances are hazardous wastes.
The National Institute of Occupational Health and Safety has
determined that levels in the workplace for two types of PCB
compounds must not exceed 1 mg/m^ (Arochlor 1242) and .5 mg/m^
(Arochlor 1254).101
2. Other halogenated hydrocarbons:
a. Health Effects: Chlorinated benzenes and chlorinated
naphthalenes, among other halogenated hydrocarbons, may be found
in used oil. Both of these compounds are toxic when ingested or
inhaled. Chlorinated naphthalenes are also toxic when applied to
the skin, and may produce skin lesions, as well as acute liver
atrophy.!02
These compounds emit toxic fumes when heated to decomposition;
they may react with oxidizing materials.103
Nitrosamines:
a. Health Effects: Nitrosamines are suspected human, and
known animal carcinogens. Evidence of a causal relationship of
nitrosamines to human cancer is supported by the following facts:
all mammals studied are susceptible to carcinoma induction by at
least one nitrosamine; nitrosamines are effective carcinogens by
inhalation, ingest ion, and dermal contact; nitrosamines can be
formed in vivo in mammals through the interaction of nitrosamine
precursors, (specifically, injested secondary amines and nitrites)
Nitrosamines are carcinogenic and mutagenic in a wide range of
animal species, with tumors affecting all vital organs.
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- 66 -
b. Ecological Effects*: Plants are capable of assimilating
nitrosamines and their precursor compounds from the soil and from
water cultures, and can form nitrosamines by metabolic activity.
The presence of nitrosamines in plants appears to have no detri-
mental effect on the plant itself, but may pose a hazard to
animals ingesting these plants.
c. Other Regulations: Nitrosamines and their precursors are
widely distributed in the environment. Currently available data
do not provide sufficient information to estimate total or relative
human exposure via ingestion or inhalation, nor are they sufficient
to set criteria for maximum exposure. However, nitrosamines are
listed as hazardous constituents in Appendix VIII, 40 CFR Part. 261,
thus raising t.he presumption that any waste containing these sub-
stances is hazardous.
As to nitrosamine precursors, the national primary drinking
water standard (NPDWS) for nitrate nitrogen is 10 mg/1.106 The
national primary ambient air quality standard for nitrogen dioxide
is 100 ug/m^ (.05 ppm), annual arithmetic mean.107
Trace Met.als
1. Lead :
a. Health Effects: When ingested or inhaled, lead and its
compounds are highly toxic.108 Lead is a cumulative poison, and
can attack the liver and kidneys, the brain and nervous system,
as well as the blood vessels and other tissues. Lead poisoning
can be fatal.
* Information on the ecological effects of nitrosamines is
taken from reference 105.
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- 67 -
It is believed that the human intake rate at which lead
accumulation begins to exceed excretion is about 1 mg/day.109
However, chronic ingest ion of .1 mg/day over several years has
been reported to cause lead poisoning.
b. Ecological Effects: Lead is rarely taken up by plant
roots, but can contaminate vegetation exposed to airborne parti-
cles of the metal. If such plants are used for forage or fodder,
their lead content may enter the food chain.11^ Lead has also
been shown to be toxic to aquatic organisms, with the degree of
toxicity depending on such variables as water temperature and
alkalinity. 11:L
c. Other Regulations: EPA has set .05 mg/1 as the NPDWS for
lead. 5 mg/1 (or 100 times the NPDWS) is the threshold concen-
tration for lead, above which the extract from any lead-containing
waste meets the characteristic of "EP Toxicity" pursuant to 40 CFR
Part 261.
The ambient air quality standard for lead is 1.5 ug/m3,
averaged over 3 months. The OSHA standard is 50 ug/m3, based on
an 8-hour workday. H2
2. Barium
a. Health Effects: Ingestion of soluble barium compounds
results in severe gastrointestinal distress and muscular paralysis.
Inhalation of barium compounds can lead to baritosis, a benign
respiratory affliction.113
Fatalities from inhalation of barium oxide,114 and from
ingest ion of barium carbonate11^ have occurred. The fatal dose
of barium for humans is reported to be 550-600 mg.11^
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- 68 -
b. Ecological Effects: The existence of soluble barium
compounds toxic to aquatic species is unlikely under normal
marine and freshwater conditions.H?
c. CH-her Regulations: The NPDWS for barium is 1 mg/1. 100
mg/1 is the threshold concentration for barium, above which the
extract from any barium-containing waste meets the characteristic
of "EP Toxicity" under 40 CFR Part 261.
The OSHA criterion for soluble barium compounds is .5 mg/m^.
3. Chromium*
a. Health Effects: Hexavalent chromium compounds are highly
toxic when ingested/ inhaled, or applied to the skin.H8 Control-
led experiments with animals indicate that hexavalent chromium
compounds are toxic and possibly fatal to animals, with the skin,
mucosa, lungs, and kidneys being affected.H9 Chromium is also
a suspected cause of lung cancer.120
b. Ecological Effects:
Low levels of hexavalent chromium (.03-64 ppm) inhibit algae
•growth. Sigrnficant adverse effects on fish have been observed
at .2 mg/1 of hexavalent chromium.121
Chromium is taken up through plant roots. Although natural
soil contains some chromium (40 ppm, mean), additions of even
small amounts (5-50 ppm) have been shown to damage vegetation.122
c. Other Regulations: The NPDWS for chromium is .05 mg/1.
The waste extract concentration for chromium triggering the
* When incinerated- chromium oxidizes to hexavalent chromium,
thus rendering potentially hazardous all chromium-containing
wastes that are burned.
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- 69 -
"EP Toxicity" characteristic for hazardous wastes under 40 CFR
Part 261 is 5 mg/1*.
OSHA standards are I mg/m^ for the metal and its insoluble
salts, and .5 mg/m^ for its soluble chromium salts.
4. Cadmium
a. Health Effects: Cadmium compounds are extremely toxic and
may be fatal when ingested or inhaled.1^3 when ingested, little
absorption is likely to occur because of rapid elimination by
vomiting. When inhaled, cadmium accumulates in the kidneys,
liver, pancreas, and thyroid, and is retained in the body for
many years. ^4
The estimated fatal dose of inhaled cadmium to humans is
about 50 mg/m^ for one hour.125
b. Ecological Effects: Cadmium is taken up from the soil
by plant roots. If present in the air as a dust contaminant, it
can also enter plants via precipitation.126 such cadmium uptake
can result in decreased crop yields.127 Furthermore, foods grown
in cadmium-contaminated soils irrigated with cadmium-polluted
water can accumulate sufficient quantities of the metal to pose
a human health hazard.128
Cadmium levels of less than 1 ug/1 can have adverse effects
on certain fish species.129
c. Other Regulations: The NPDWS for cadmium is .01 mg/1.
The waste extract concentration for cadmium triggering the
* On October 30, 1980, EPA proposed to amend the "EP toxicity"
characteristic for chromium to apply to hexavalent chromium
instead of total chromium, (see 45 FR 72029-34).
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- 70 -
"EP Toxictty" characteristic for hazardous wastes under 40 CFR
Part 261 is 1 mg/1. Application of wastes containing cadmium
to food chain crops is controlled under 40 CFR 257.3-5 and
40 CFR 265.276.
OSHA sets its cadmium standard at 2 mg/m^.
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B. Hazards posed by mismanagement
Accurate data on the quantity of used oil generated and the
management practices currently used to reuse or dispose of it
are difficult to obtain because there are so many sources of used
oil and no national reporting requirements for the oil's generation
or management. Estimates vary considerably as to how much used
oil is generated each year, with a recent EPA draft report placing
the amount at 464 million gallons for used automotive oils and
380 million gallons for used industrial oiis.-^O
The four most frequently cited methods for managing used oil
are: burning it as a fuel; applying it to road surfaces or other
land areas as a dust suppressant or road oil; re-refining it to
produce lube oil basestocks; and disposing of it either in land-
fills or by indiscriminately dumping it into sewers or on the
ground. Again, there is considerable disagreement in the liter-
ature as to how much oil is managed by each of these methods.
The following breakdown (by percentage) is consistent with most
reports on this subject:
Burned as a fuel 55%
Used as a road oil, dust 15%
suppressant or other land
application use
Re-refined to a lube oil 10%
basestock
Disposed of in landfills, 20%
or indiscriminately dumped
There are potential hazards associated with many of these manage-
ment oractices.
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Land application:
When used oil is applied to the land (either as a road oil,
dust supressant, or when indiscriminately dumped), the oil and
its contaminants can migrate by flotation (precipitation-induced
runoff), by percolation through the soil, by direct runoff (if
the application is excessive), by volatilization, and by dust
transport.131 The quantities of oil and contaminants transported
by these various mechanisms varies greatly, depending on terrain,
soil porosity, wind and rain conditions, temperature, traffic
volume, and rate of application. Nonetheless, the potential for
environmental contamination is significant.
The chapter on unused oil described the hazards posed when oil
migrates to surface water and ground water. Trace metals in used
oil may also pose a threat to human health and the environment
because they may be taken up by plant roots from oil-contaminated
soil. Volatilization of the oiled surface can produce toxic
metal-laden dust particles, which can enter vegetation via pre-
cipitation .132 Such dust can also coat vegetation, which may be
used as food for wild or domestic animals. Thus, toxic metals in
used oil may enter the food chain.
The toxic effects of other used oil contaminants (specifically
halogented hydrocarbons, including PCBs, and nitrsoamines) were
described in the previous section of this document. These con-
taminants may migrate to surface and ground waters if used oils
containing them are improperly applied to land surfaces.
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Landfill ing:
When used oil is disposed of in an insecure landfill, the
potential for contamination of ground water supplies is the same
as that described earlier for unused oil. The potential harm is
*
of course greater for used oil than with unused oil because the
former contains hazardous contaminants which may migrate to ground
water along with the oil component.
Burn Lng:
When used oil is burned, either as a fuel or for the purpose
of thermal disposal, its contaminants may enter the atmosphere.
Anywhere from 20 to 100% of the lead in used oil entering a
steam boiler can be expected to be emitted from the stack. Most
of the remainder is deposited on tubes and elsewhere in the com-
bustion furnace. Furnace deposits may be emitted during soot-
blowing, where this is practiced, or they may eventually be
removed during furnace and boiler cleaning.^33
Seventy-six to 79% of the lead and 3 to 51% of the barium in
used oil burned as fuel are emitted in particles less than a micron
in size.134 These submicron size emissions remain suspended in the
atmosphere longer and, therefore, may have a wider dispersion range
than larger part icles. 135 Compared to large particles, submicron-
size particles tend to penetrate more deeply into the respiratory
tract, and are retained there longer.136
Other trace metals in used oil may be expected to behave sim-
ilarly to lead with regard to stack emissions, but very limited
data are available.
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- 74 -
Stack burning tests measuring PNA emissions from boilers
burning used oil indicate that PNA emissions are similar to those
resulting from burning virgin oils
Damage Cases
Used oil serving as a mask for dangerous substances has been
implicated in a number of damage incidents, as have many of the
contaminants discussed above.* These incidents show empirically
the potential for substantial harm if used oil is managed
improperly.
In Missouri in 1971, about 5000 gallons of waste oil con-
taining 300 ppm dioxin were sprayed on the floor of a horse
arena. Sixty-three horses died; many other horses, dogs, cats
and birds became ill after exposure to the arena. One child
who played in the area developed epistaxis, gastrointestinal
disorders, and severe hemorrhagic cystitis. Ten other persons
were afflicted with diarrhea, headaches, nausea, and persistent
skin lesions.
In Nebraska in 1958, an explosion attributed to burning used
oil with a low flash point (possibly resulting from gasoline
dilution) occurred in a meat packing plant. As a consequence,
the State enacted legislation establishing a minimum flash
point for used oil burned as a
In 1978, 33,000 gallons of transformer oil contaminated with
PCBs wer-e dumped along 210 miles of secondary roads in North
Carolina. The North Carolina Agriculture Commissioner caut-
ioned against any direct or indirect human consumption of
crops grown within 100 yards of the spill. Nearby residents
reported nausea, dizziness and cramps. 140
In Texas in 1978, used oil serving as a "mask" for toxic
wastes was applied to roads as a dust suppressant. Nearby
residents suffered headaches and nausea; livestock died.
The used oil was found to contain nitrobenzene and cyanide.
* Unless otherwise indicated, all information on damage cases
is taken from reference 138. Many other damage incidents from
improper management of used oil are contained in EPA's collect-
ion of incidents from individual states.
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Summary
When used oil is improperly managed, its oil component poses
the same potential threat to ground and surface waters as does
that of unused oil. In addition to the arguments made earlier
for listing certain waste unused oils as hazardous wastes, the
Agency believes that the following points lend further support
for deeming some used oils to be hazardous wastes:
1. Most used automotive oils, and certain industrial oils,
have been shown to contain significant concentrations of
some or all of the following contaminants:
a. polynuclear aromatic hydrocarbons such as benzo(a)-
pyrerie, phenanthrene, and 1,2-benzanthracene, which
are potent carcinogens;
b. polychlorinated biphenyls (PCB's), which are carcino-
genic, and other halogenated hydrocarbons, which are
persistent toxics;
c. nitrosamines, or their precursors, which are potent
carcinogens;
d. trace metals, such as lead, barium, chromium, and
cadmium, which are toxic as elements and in compounds.*
2. Typical used oil storage, collection and transportation
practices often result in related wastes, such as anti-
freeze and solvents, being mixed in with used oil. Further-
more, used oil is sometimes deliberately contaminated, thus
serving as a "mask" for such toxic substances as dioxin,
nitrobenzene, and cyanide.
3. Over 800 million gallons of used oil are generated in
the United States each year.
* The levels of these metals in used automotive oils, other
than used diesel lube oil, exceed that which triggers the
"EP toxicity" characteristic for hazardous waste under 40 CFR
Part 261 (see Table 11). Used diesel oil contains negligible
quantities of lead and, thus, would meet the characteristic of
"EP toxicity" for only barium, chromium, and cadmium.
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In Kansas, 56 cattle died and 112 more had to be slaughtered
when used oil laden with PCBs was used on back-rubbers on a
farm.
In Minnesota, used oil, grease, various other hydrocarbons,
and phenols were disposed of in an unlined basin. Soil and
ground water were found to be contaminated with PNAs up to
1400 feet from the basin.
In Massachusetts, one million gallons of solvents, used oil,
toxic metals, and halogenated hydrocarbons leached from an
abandoned disposal site. Rainwater runoff resulted in
contamination of the Concord River's aquatic environment.
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- 77 -
4. Used otl applied to the land (e.g., as a road oil, dust
suppressant, or when indiscriminately dumped) poses an
environmental hazard resulting from the direct release of
the oil onto the land, and through percolation and run-off
into ground and surface waters.
5. Used oir~"disposed of in insecure landfills may also leach
through the bottom of such landfills, and subsequently
contaminate ground water supplies.
6. Because of the presence of contaminants, uncontrolled
burning of certain used oils, either as a fuel or for the
purpose of thermal disposal, may result in significant levels
of hazardous emissions to the environment. This, in turn,
may expose humans, wildlife, and vegetation in the area to
these harmful substances.
7. Many of the contaminants in used oil are persistent,
bioaccumuiative, or have potential for increased penetration
of the respiratory tract, thus magnifying the possibility of
exposure and harm.
3. Improper management of waste oil has caused many actual
damage incident s.
The Agency believes that ail of these considerations support
the listing of used automotive and industrial oils as toxic (T)
hazardous wastes.
Used, automotive oils will be listed as hazardous wastes based
on the following constituents : polynuclear aromatic hydrocarbons
(including benzo(a)pyrene and benz(a)anthracene); chlorinated
napthaiene; chlorinated benzenes; nitrosamines; lead; barium;
chromium and cadmium. Though certain types of used automotive
oils may not contain one or more of these substances (e.g., used
diesel lube oil does not contain lead), the fact that different
types of automotive oils are typically stored and transported in
the same container argues for the Agency's presumption that most
used automotive oil will eventually become contaminated with most
of the hazardous substances specified above.
-------
- 78 -
Significant quantities of used industrial oils are source-
segregated and managed on-site (e.g., burned as a fuel, used as
a dust suppressant). Therefore, unlike used automotive oils, it
would be inappropriate to generalize that all industrial oils
will eventually become contaminated with hazardous substances
found in individual types of used oils. For this reason, a
common set of contaminants has not been specified as the basis
for listing used industrial oil per se as a hazardous waste.
Instead, all used industrial oil will be listed as a hazardous
waste based on its aromatic oil component*. This is the same as
was done for unused oil. In addition, where the Agency has suf-
ficient data on the hazardous contaminants of particular types of
industrial oils, these substances will be listed as additional
reasons for deeming the oil to be hazardous. For now, the follow-
ing types of used industrial oils will be deemed to be hazardous
wastes based on the following hazardous constituents in addition
to aromatic hydrocarbons:
Metaiworking: nitrosamines; barium
Railroad and marine: barium
Hydraulic: PCBs**; nitrosamines
Transformer: PCBs
Turbine: nitrosamines
* The exception to this are used industrial oils that have no
aromatic oil component (e.g., finishing oils made with white oil
basestocks).
** Even though used oils containing greater than 50 ppm PCBs are
deemed to be hazardous wastes under RCRA, EPA intends to subject
these oils to the management standards under TSCA (40 CFR Part
761) rather than RCRA.
-------
- 79 -
References
1. EPA, Quality Criteria for Water, July, 1976, p. 113.
2. Crump-Wiesner, Hans J. and Allen L. Jennings, "Properties
and Effects of Nonpetroleum Oils," Proceedings of Joint
Conference on Prevention and Control of Oil Pollution,
Washington, D.C., American Petroleum Institute, 1975,
pp. 31-32.
3. Federal Register, Vol. 45, May 19, 1980, p. 33107.
4. EPA, Washington State Refineries: Petroleum, Petroleum
Derivatives, and Wastewater Effluent Characteristics
(EPA 600/7-78-040), March 1978, p. 38.
5. OSHA, Occupational Health and Safety Aspects of Fog Oils
SGF No. 1 and SGF No. 2 and Smoke Screens Generated From Them
TDAMD-17-77-C-7020), April 1978, p. 14.
6. EPA, A Small Oil Spill at West Falmouth (EPA 600/9-79-007),
March 1979, p. 5.
7. EPA, Oil Spill Debris - Where to Put the Waste (EPA 600/7-
80-016), January 1980, pp. 2-3.
8. State of Maine, Department of Environmental Protection,
Statewide Oil Spill Statistical Report for 1979, p. 9.
9. Dennis, David M. "Effectively Recovering Oil Spills to
Groundwater," Proceedings of Joint Conference on Prevention
and Control of Oil Pollution, Washington, D.C., American
Petroleum Institute, 1977, p. 255.
10. Written correspondence from Thomas R. Beauiieu, State of
New Hampshire, Water Supply and Pollution Control Commission,
Nov. 24, 1980.
11. Written correspondence from Frank Estabrooks, State of
New York, Department of Environmental Control, Nov. 1980.
12. Telephone conversation, Arline M. Sheehan, EPA, OSW, HIWD,
with Fritz Ybenga, USCG, Office of Merchant Marine Safety,
Cargo and Hazardous Materials Division, Dec. 9, 1980.
13. EPA 600/9-79-007, p. 5.
14. Telephone conversation, Arline M. Sheehan with Gil Holland,
North Carolina Department of Corrections, Nov. 25, 1980.
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- 80 -
15. Biglane, Kenneth, Affadavit supporting EPA's "Sheen Test",
May 1974.
16. EPA, Quality Criteria for Water, pp. 114-115.
17. Ibid, pp.116-120.
18. see 45 FR 79318 (November 28, 1980).
19. 45 FR 33107 (May 19, 1980).
20. Winters, Kenneth and Patrick L. Parker, "Water Soluble
Components of Crude Oils, Fuel Oils, and Used Oil Crankcase
Oils," Proceedings of Joint Conference on Prevention and
Control of Oil Pollution, Washington, D.C., American
Petroleum Institute, 1977, pp. 579-580.
21. see 45 FR 79318 (November 28, 1980).
22. 45 FR 33113 (May 19, 1980).
23. Payne, Jerry. F. and Robert Maloney, "Are Petroleum Hydro-
carbons an Important Source of Mutagens in the Marine
Environment?" Proceedings of Joint Conference on Prevention
and Control of Oil Pollution, Washington, B.C., American
Petroleum Institute, 1979, pp. 533-535.
24. EPA, A Study on the Environmental Benefits of Proposed
BAETA and NSPS Effluent Limitations for the Offshore
Segment of the Oil and Gas Extraction Point Category
(EPA 440/1-77-011), May 1977, pp. 188.
25. ZoBell, Claude E., "Sources and Biodegradation of Carcino-
genic Hydrocarbons," Proceedings of Joint Conference on
Prevention and Control of Oil Pollution, Washington,D.C.,
1971, p. 442.
26. Ibid, p. 448.
27. DOE, Motor Gasolines, Winter 1979-80 (DOE/BETC/PPS-80/3),
Bartlesville Energy Technology Center, Bartlesvilie, Oklahoma,
July 1980.
28. Hutchinson, Thomas C., e_t al. , "Relationship of Hydrocarbon
Solubility to Toxicity in Algae and Cellular Membrane Effects,"
Proceedings of Joint Conference on Prevention and Control of
Oil Pollution, Washington, D.C., American Petroleum Institute,
1979, p. 541.
29. EPA 600/7-73-040, p. 85.
30. EPA 440/1-77-011, pp. 37, 156.
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- 81 -
31. Hutchinson, p. 541.
32. EPA 600/7-78-040, p. 47.
33. EPA 440/1-77-011, p. 345.
34. Ibid, p. 111.
35. Ibid, p. 45.
36. Clean Environment Commission, Canada, "Preliminary Report
on Contamination of Underground Water Sources by Refined
Oil Products," Ground Water, Vol. 44, Jan./Feb. 1976,
p. 37.
37. EPA, Report to Congress, Waste Disposal Practices and
Their Effects on Ground Water, January 1977, p. ii.
38. Van Der Waarden, M., et al., "Transport of Mineral Oil
Components to Groundwater - I," Water Research, Vol. 5,
1971, p. 213.
39. American Petroleum Institute, Underground Spill Cleanup
Manual, API Publication 1628, June 1980, pp. 5, 8.
40. Ibid, p. 4.
41. Duffy, J.J., and M.F. Montadi, "Subsurface Persistence of
Crude Oil Spilled on Land and Its Transport in Groundwater,"
Proceedings of Joint Conference on Prevention and Control
of Oil Pollution, Washington, D.C., American Petroleum
Institute, 1977, p. 475.
42. Clean Environment Commission, Canada, p. 38.
43. McKee, Jack E., et al., "Gasoline in Groundwater," Journal
of Water Pollution Control Federation, Vol. 44, February
1972.
44. EPA, Oil Spill Debris: Decisions for Debris Disposal,
(EPA 600/2-77-153b), August 1977, p. 40.
45. Ibid, p. 58.
46. Duffy, p. 477.
47. EPA 600/2-77-l53b, p. 41.
48. Bureau of the Census, "Sales of Lubricating and Industrial
Oils and Greases," Current Industrial Reports, 1977.
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- 82 -
49. Mascetti, G.J. and H.M. V/hlte, Utilization of Used Oil,
prepared for DOE by the Aerospace Corporation, August 1978,
p. 2-5.
50. Ibid. , pp. 2-7, 2-8.
51. Becker, D.A. and J.J. Comeford, Recycled Oil Program;
Phase I - Test. Procedures for Recycled Oil Used as Burner
Fuel, report to the Federal Trade Commission by the National
Bureau of Standards, October 1978, p. 39.
52. Recon Systems, Inc. and ETA Engineering, Inc., Used Oil
Burned As A Fuel, draft report prepared for EPA, November
1980, pp."7-28, 7-29, 7-30.
53. Whisman, M.L., et al., Waste Lubricating Oil Research:
Characterization of Basestocks From Used Lubricating Oils;,
Part I, Bartlesvilie Energy Research Center, Bartlesville,
OK, June 1975, p. 18.
54. Becker and Corneford, p. 12.
55. Richard J. Bigda and Associates, Review of All Lubricants
Used in the U.S. and Their Re-refining Potential, prepared
for DOE, June 1980, p. 25. ~
56. Fine, David 'and R.Y. Fan, Report to the National Science
Foundation, September 16, 1976, as referenced in EPA,
Assessment of Industrial Hazardous Waste Management,
Petroleum Re-refining Industry, 1977, p. 14.
57. EPA, Scientific and Technical Assessment Report on Nitre-
samines, November 1976, pp. 9, 163.
58. Ibid., pp. 171, 173.
59. Ibad. , p. 13.
60. Versar, Inc., Microeconomic Impacts of the Draft "PCS
Ban Regulations", Final Task Report submitted to EPA,
March 1979, p. 5.
61. Federal Register, Vol. 44, No. 106, Thursday, May 31, 1979,
p. 31525.
62. Telephone conversation, Jane Castner, EPA student assistant
with William Welbes, Chemical Analyst, Twin Cities Testing
Service, St. Paul, MN, July 7, 1980.
63. Richard J. Bigda and Associat.es, p. 26.
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- 83 -
64. National Petroleum Rerefiners Association, "1978 Report
on U.S. Lubricating Oil Sales," 1978.
65. Richard J. Bigda and Associates, p. 27.
66. National Petroleum Rerefiners Association.
67. Richard J. Bigda and Associates, p. 37.
68. Teknekron, Inc., Technical, Economic, and Environmental
Assessment of Waste Oil Recovery and Disposal, Volume I,
prepared for the Ontario^ Ministry of Transportation and
Communications, March 1976, pp. 168-169.
69. Bureau of the Census.
70. Mascettl and White, p. 3-1.
71. Richard J. Bigda and Associates, p. 66.
72. Versar, Inc., PCB Manufacturing, Processing, Distribution
in Commerce, and Use Ban Regulation; Economic Impact
Analyses, Final Report submitted to EPA, March 1979,
p. 115.
73. Richard J. Bigda and Associates, p. 63.
74. Fishbein, Lawrence, Potential Industrial Carcinogens and
Mutagens, prepared for EPA, May 1977, p. 226.
75. Mascetti and White, p. 2-4.
76. Richard J. Bigda and Associates, p. 9.
77. Ibid, pp. 9-10.
78. Fishbein, p. 226.
79. Richard J. Bigda and Associates, p. 66.
80. Ibid, p. 66.
81. Mascetti and White, p. 3-7.
82. Richard J. Bigda and Associates, p. 47.
83. Ibid, pp. 46-47.
84. Versar, Inc., 1979, p. 87.
85. Richard J. Bigda and Associates, p. 56.
-------
- 84 -
86. Ibid, p. 59.
87. Ibid, p. 71.
88. Federal Register, Vol. 44, No. 106, Thursday, May 31, 1979,
p. 31517.
89. Telephone conversation, Castner and Welbes.
90. EPA Report to Congress, Waste Oil Study, April 1974, p. 20.
91. Richard J. Bigda and Associates, p. 72.
92. Wapora, Inc., Assessment of Industrial Hazardous Waste
Practices - Special Machinery Manufacturing Industries,
prepared for EPA, March 1977, p. 83.
93. Yates, John J. et al., Oil Audit and Reuse Manual for the
Industrial Plant, prepared by ETA Engineering, Inc. for
the Illinois Institute of Natural Resources, Chicago, IL,
November 1978, p. 19.
94. Teknekron, Inc., p. 174.
95. 45 FR 79339 (November 28, 1980).
96. EPA, Support Document/Voluntary Environmental Impact
Statement for PCBs, April 1979, p. 9.
97. Ibid, p. 17.
98. Ibid, p. 17.
99. Ibid, p. 19.
100. 40 CFR 129, Subpart A.
101. DHEW, National Institute for Occupational Health and Safety,
Registry of Toxic Effects of Chemical Substances, Herbert E.
Christensen, ed., June 1976, p. 944.
102. Sax Irving R., Dangerous Properties of Industrial Materials,
3rd ed., New York: Van Nostrand Reinhold Company, 1968,
p. 552.
103. Ibid., p. 552.
104. EPA, Nitrosamines, p. 44.
105. Ibid., pp. 47-49.
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- 85 -
106. 40 CFR 141, Subpart B.
107. 40 CFR 50, Subchater C, §11.
108. Sax, pp. 865-866.
109. Teknekrori, Inc., p. 160.
110. Ibid, p. 160.
111. EPA, Quality Criteria for Water, pp. 84-85.
112. Federal Register, Vol. 43, No. 220, Tuesday, November 14,
1978, p. 52963.
113. Browning, Ethel, Toxicity of Industrial Metals, 2nd ed.,
New York: Appleton-Century-Crofts, 1969, p. 62-63.
114. Sax, p. 448.
115. Browning, pp. 63.
116. EPA, Quality Criteria for Water, p. 19.
117. Ibid, p. 20.
118. Sax, p. 572.
119. National Academy of Sciences, Medical and Biologic Effects
of Environmental Pollutants; Chromium, 1974, p. 82.
120. Browning, p, 126.
121. EPA, Quality Criteria for Water, p. 40.
122. National Academy of Sciences, pp. 84-85.
123. Sax, pp. 516, 517.
124. Browning, p. 99.
125. Ibid., p. 102.
126. Lagerwerff, J.V. and A.W. Specht, "Contamination of Roadside
Soil and Vegetation with Cadmium, Nickel, Lead, and Zinc,"
Environmental Science and Technology, Vol. 4, 1970,
p. 585.
127. EPA, Quality Criteria for Water, pp. 30-31.
-------
- 86 -
128. Ibid, p. 31.
129. Ibid, pp. 29-30.
130. Recon Inc., p. 2-2.
131. Teknetron, Inc., p. 155.
132. Lagerwerff and Specht, p. 583-586.
133. Recon, Inc./ p. 4-3.
134. Chansky, Steven, et al. , Waste Automotive Lubricating
Oil Reuse as a Fuel, prepared for EPA, September 1974,
p. 81.
135. Teknekron, Inc., p. 141.
136. Ibid., p. 141.
137. Recon, p. 4-6.
138. EPA, Damages and Threats Caused by Hazardous Material
Sites, May 1980.
139. Statement by Duane Ekedahl, Executive Director,
Association of Petroleum Rerefiners, to EPA on proposed
hazardous waste guidelines and regulations as announced
in the 5/2/77 Federal Register, July 1, 1977, p. 8.
140. Leepson, Marc, "The Waste That Wouldn't Go Away",
Environmental Action, October 7, 1978, p. 67.
141. Yates, John J., et_ al. , Used Oil Recycling in Illinois;
Data Book, prepared by ETA Engineering, Inc. for the
Illinois Institute of Natural Resources, Chicago, IL,
October 1978.
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APPENDIX 1
AFFADAVIT SUPPORTING EPA'S "SHEEN TEST"
-------
AFFIDAVIT
DISTRICT OF )
)
COLUMBIA ) SS
)
KENNETH BIGLANE, being duly sworn, deposes and says:
I am the Director of the Division of Oil and Special
Materials Control, Office of Water Program Operations, of the
United States Environmental Protection Agency. It is my
official duty to formulate and to direct national programs to re-
spond to discharges of oil and hazardous materials and to prevent
such discharges, pursuant to section 311 of the Federal Water >
Pollution Control Act, as amended, P. L. 92-500, 86 Stat. , 816
et seq. , 33 USC 1251 (FWPCA). I held the position equivalent to
my present one within the Federal Water Pollution Control Admin-
istration of the Department of the Interior when the regulations
concerning discharges of oil, now codified at 40 CFR 110, were
originally promulgated in September 1970 (Appendix I).
-------
I hold a Bachelor of Science degree and a Master of Science
degree in Zoology from Louisiana State University. My graduate
studies were in fisheries physiology, parasitology, histology,
and fish toxicology.
From 1952 to 1956, I served as an Aquatic biologist with the
Louisiana Wildlife and Fisheries Commission. Louisiana then
had approximately 20, 000 oil and gas wells, and during that
period I investigated and assessed the environmental impact of
several hundred oil spills ranging in size from amounts barely
sufficient to cause a sheen on the surface of the water to those
of thousands of barrels. During this same period, I conducted
a study of the environmental effects of oil and oil field brines
which included field observations, chemical and biological
laboratory analyses, and toxicity bioassays.
From 1956 to 1962, I served as both the Chief of the Division
of Water Pollution Control of the Wildlife and Fisheries Com-
mission a.nd as Executive Secretary of the Louisiana Stream
Control Commission. My experience with oil pollution during
this period included administering the State investigative and
regulatory program which included the production, refining, and
transportation of petroleum products.
During the period 1962 to 1966, I served as Headquarters
Biologist and Operations Officer of the United States Public
Health Service in Washington, D. C., and in 1966 I began service
with the Federal Water Pollution Control Administration of the
-------
Department of the Interior. As a part of my duties with the
Federal Water Pollution Control Administration and subse-
quently with the U. S. Environmental Protection Agency (EPA),
I personally investigated and evaluated more than 20 oil dis-
charges, some examples are shown in Appendix 2(a). These
field investigations of oil discharges included: evaluation and
survey of biological effects of oil discharges, review of methods
and procedures employed in the oil removal operations and
countermeasures to mitigate damage to the environment, and
critique of oil spill response contingency planning including,
organizational structure and notification and coordination of Fed-
eral, State and local authorities.
In addition to the personal field investigations previously
noted, I have, in my capacity as Director of the Oil and Special
Materials Control Division, participated in a supervisory and
advisory capacity with respect to thousands of oil spills nation-
ally and internationally. My activities included advice on
countermeasures and oil spill clean-up methods and procedures
for minute spills in environmentally sensitive locations and large
spills in similar areas, including the open sea.
In addition to my experience in the field and national program
office supervision and guidance, I have participated in numerous
international activities related to biological effects of oil in the
environment and oil spill contingency planning, prevention and
control. I served as a U.S. representative to the International
Conference on Oil Pollution of the Sea, Rome, Italy, October 1968.
-------
Upon my return from this Conference, I once again visited the
beaches and coasts of Brittany and Cornwall to re-evaluate the
effects of cleanup efforts and the environmental impact of the
Torrey Canyon oil spill of 1967.
I served as a U.S. Delegate to the International Conference on
Marine Pollution Damage, Brussels, 1969. The results of this
Conference produced two Conventions (1) the International Con-
vention Relating to Intervention on the High Seas in Cases of Oil
Pollution Damage; and (2) the International Convention on Civil
Liability for Oil Pollution Damage.
In June 1971, I was invited by the Australian Government to
testify and gave extensive testimony at Brisbane, Australia, before
the Royal Commission on the Great Barrier Reef with respect to
the environmental impact of offshore oil drilling and production
operations.
In December 1971, I received the EPA Gold Medal for Exceptional
Service for activities "in developing a national program responsive
to the need for controlling spills of oil and hazardous materials."
I was a member of an Interagency Task Force chaired by the
Department of State to develop the Great Lakes Water Quality
Agreement with the Canadian Government which was jointly signed
on April 15, 1972. This International Agreement, which includes
oil pollution standards for the Great Lakes, marked the first time
two Heads of State committed their Governments to cooperate in
the cleanup and preservation of such a large, shared natural resource.
-------
I served as a consultant to the Smithsonian Institute with respect
to coastal zone oil pollution in Indonesia and attended a symposium
hosted by the Indonesian Government in Jakarta, Indonesia, in August
1973.
Since 1968, I have also served as a member of the United States
National Committee on Prevention of Marine Pollution which advises
The United States Department of State in the formulation of U.S. Policy
on international oil pollution.
I have published articles in scientific and other journals and have
presented papers before technical and other groups. A list of over
30 such articles, ranging from aquatic biology and the environmental
effects of oil and other pollutants to oil spill prevention and regu-
lation, is attached as Appendix 2(b).
# * *
Section 311(b)(3) of the FWPCA prohibits discharges of oil in harm-
ful quantities. 40 CFR Section 110 defines "harmful quantity of oil" as
a quantity sufficient to "cause a film or sheen upon or discoloration of
the surface of the water or adjoining shorelines or cause a sludge or
emulsion to be deposited beneath the surface of the water or upon
adjoining shorelines. "
Each year the U.S. Coast Guard and EPA receive notification,
pursuant to the reporting requirements of Section 311(b)(5) of the
FWPCA, of approximately 10, 000 spills of oil into or upon the nav-
igable waters of the United States. The number of unreported spills
of oil is not known, but I believe that the number of oil spills
5
-------
occurring annually substantially exceeds 10,000. Eighty percent
of the reported spills are of 10 barrels or less (one barrel is
42 gallons at 60 degrees Fahrenheit). Such smaller spills have
a seriously degrading effect on the environment. This is parti-
cularly true of spills occuring on inland waters, in estuarine
areas, and near the coastline, which generally are habitats for
birds and other wildlife. Estuarine and coastline areas are the
productive zones for sea life, and are particularly important and
sensitive to oil discharges.
A recent report, The Appearance and Visibility of Thin Oil
Films on Water (EPA-R2-72-039)(Appendix 3) prepared by EPA's
Edison Water Quality Research Laboratory, demonstrates that
there is a quantitative relationship between the appearance of an
oily layer on water and its thickness. This report states that an
oily layer of at least approximately 150 nanometers (nm) thick
(1 nanometer = 1 billionth of a meter or 39. 37 billionths of an
inch is required in order to produce a sheen as defined in
40 CFR 110. Specific colors in an oily layer denote specific
thicknesses in the range of 300 - 900 nm. With thicknesses
greater than 900 nm, colors become dull and grade into light and
dark bands with little color. These inherent appearances of oil were
found to be a function of thickness and not a function of oil type or of
water type. The results of this study are confirmed by the study of the
American Petroleum Institute and the General Research Corporation.
6
-------
This same report (Appendix 3) demonstrates a direct correlation
between thickness of an oily layer measured in nanometers and sur-
face concentration measured in milligrams per square meter.
Thus, for example, an oily layer of 150 nanometers thickness, which
would produce a sheen as defined in 40 CFR 110, contains a surface
concentration of 150 milligrams per square meter.
Surface concentration may be mathematically converted to
concentration in the water column for any given depth to which the
oil could be mixed. If an oily layer of 150 nanometers were to be
mixed into the top 1 centimeter of water, the resultant concen-
tration would be 15 parts per million (ppm):
150 mg X 103cc = 150 X 10"1 mg = 15 mg/liter or 15 ppm
104 liter liter
If the same amount of oil were mixed into the upper 10 centimeters
of water, the resultant concentration would be 1. 5 ppm.
Although surface concentration can be mathematically con-
verted into concentrations in the water column, the physical and
chemical properties of oil make uniform distribution extremely
unlikely. Oil is a complex mixture of various components with
differing physical and chemical properties. All oil discharges
contain components which float on the surface and components
which dissolve in the water. Depending upon factors such as the
wave action, the amount of suspended solids in the receiving
waters and the weather, floating oily layers may also result in
oily water emulsions and oily sludge. Since oil discharges may
produce these various conditions in the aquatic environment, the
i
harmful effects of oil in the water cannot be measured by
7
-------
reference to concentrations of dissolved oil components alone.
The harmful effects of floating oil, oily emulsions and oily sludge
are widespread, obvious, and long-term.
The attached Appendix 4(a) is an annotated bibliography, pre-
pared under my direction, of scientific works documenting some
aspects of the ecological damage that is caused by floating oily
layers. The devastating damage caused to waterfowl by floating oil
needs no documentation. In the presence of an oil film, ducks are
imperiled when swimming or diving for food. As a result of the
loss of insulating ability of feathers contaminated by oil, oil soaked
ducks cannot maintain a normal body temperature and die from
exposure. The viability of duck eggs becomes greatly reduced as a
result of contamination from oil-soaked plumage. While preening to
cleanse their feathers of oil, waterfowl ingest oil and, as a result,
become susceptible to pneumonia and gastro-intestinal irritation.
Amounts as small as a one-inch circle on the belly of one species
of waterfowl (murre) is sufficient to destroy the insulating air
pocket and cause death from exposure.
The scientific publications in Appendix 4(b) also show that small
amounts of crude oil have damaging effects on other organisms as
well: reproduction in marsh grasses is inhibited, chemoreception
of fish larvae is blocked, susceptibility of seagrass to parasites is
increased, mangrove seedlings are killed, herring larvae develop
abnormally.
8
-------
Appendix 5 is a report summarizing recent research carried
out by an interdisciplinary team of scientists under the direction
of Dr. L. R. Brown of Mississippi State University to determine
the environmental effects of crude oil in Gulf Coast estuaries.
Dr. Brown is a Professor of Microbiology and Associate Dean of •
the College of Arts and Sciences of Mississippi State University.
He.holds B. S., M.S., and Ph. D. degrees in Bacteriology from
Louisiana State University. He has published more than 50 articles
in scientific journals on biological and microbiological topics.
Since 1958, he has been engaged in petroleum related microbiology.
Examination of the interim results of this ongoing research reveals
the following salient points as submitted by Dr. Brown:
"1. The sensitivity of selected estuarine organisms to
oil pollution varies between organisms and with
time of year.
"2. Exposure of shrimp, Penaeus sp. , to as little as
0.1 ml of oil in 130 liters of water will elicit
anomalous behavior. A 2 ppm oil in water mixture
results in demonstrable oil uptake and 15 ppm is
sufficient to produce a total kill in most instances.
"3. While mullet, Mugil cephalus, and oysters,
Crassostrea virginica, can withstand the addition
of a large volume of oil applied at one time,
fatalities are noted when small (calculated to pro-
duce a 1 ppm mixture of oil in water), intermittent
-------
applications are used. Exposure to a single
application (producing a 75 ppm oil in water
mixture) causes significant alterations in the
normal metabolic processes of these organisms.
"4. The addition of 1. 5 liters of crude oil per square
meter causes a significant decrease in marsh
productivity.
"5. Additions to experimental aquariums of emulsi-
fied crude oil calculated to produce concen-
trations of 0. 5-6. 0 ppm but analyzed to be
0. 25-3. 0 ppm are sufficient to kill 50 percent
of the copepods [microscopic animals important
in the fish food chain], Acartia sp. , present.
"6. Oysters exposed to a 300 ppm mixture of crude
oil in water for 96 hours still demonstrate an
"oily" taste after 3 months in clean water."
Also attached as Appendix 6, is a copy of an extract from the
Report of the National Technical Advisory Committee on Water
Quality Criteria, dated April 1, 1968 (U.S. Government Printing
Office). This appendix contains a list of the scientists who pre-
pared the Report. The Report shows scientific evidence of the
harmful effects of floating oily layers, oily emulsions, and oily
sludge on fresh water organisms; marine and estuarine organisms;
and wildlife such as waterbirds, muskrats and otters.
10
-------
The Committee recommended that, to protect marine life,
oil should not be deposited into estuarine or coastal waters in
sufficient quantities (1) to be detected as a visible film or sheen,
or by odor; (2) to cause tainting of fish and/or edible invertebrates;
(3) to form an oil-sludge deposit on the shores or bottom of the re-
ceiving water; or (4) to become effective toxicants according to the
criteria recommended in the "Toxicity" section of the Report.
The environmental damage caused by discharges of oil in
quantities sufficient to produce a sheen on the surface of the water
has been widely recognized. Moreover, effective enforcement of any oil
spill proscription requires that the spill of a prohibited quantity be
readily determinable. Under the "sheen" provision of 40 CFR 110,
it is a simple matter for a responsible person to know which spills
are prohibited. On the other hand, a spill limitation based on quanti-
ties measured by volume (e.g., quarts, gallons, barrels) or weight
(e.g., Ibs. ), would be virtually impossible to enforce. First, only the
spiller has any possible way of determining the quantity of the spill.
Second, it has been my experience in investigating oil spills that
persons at the scene and responsible for the spill are frequently
unaware of how much oil has been discharged and its effect on the
environment, even within very broad limits. As a result, the "sheen"
test is well suited to define a discharge which damages the environ-
ment and to provide a regulatory mechanism which will work. This
combination of environmental harm and enforcement workability has
led other nations and international organizations to adopt a visible
oil standard to abate oil pollution.
11
-------
Recent amendments of the 1954 International Convention for the
Prevention of the Pollution of the Sea by Oil, to which mere than 70
nations were parties, confirmed the 1954 Convention's permission of
vessel ballast discharges which "would produce no visible traces of
oil on the surface of the water." This same standard was adopted
by Congress in the Oil Pollution Act Amendments of 1973 designed
to implement the Convention.
The Agreement between Canada and the United States of
America on Great Lakes Water Quality, signed by the President
and Prime Minister Trudeau at Ottawa on April 15, 1972, defined
"harmful quantity of oil" to mean:
"any quantity of oil that, if discharged
into receiving waters, would produce
a film or sheen upon, or discoloration
of, the surface of the water or adjoining
shoreline or that would cause a sludge
or emulsion to be deposited beneath the
surface of the water or upon the adjoin-
ing shoreline"
This definition of "harmful quantity of oil" is identical to the defini-
tion at issue in this proceeding.
12
-------
Section 311(b)(4) of the FWPCA provides that a quantity of oil
which:
"at such times, locations, circumstances,
and conditions, will be harmful to the public
health or welfare of the United States,
including, but not limited to, fish, shellfish,
wildlife, and public and private property,
shorelines, and beaches except that in the
case of the discharge of oil into or upon the
waters of the contiguous zone, only those
discharges which threaten the fishery
resources of the contiguous zone or threaten
to pollute or contribute to the pollution of the
territory or the territorial sea of the
United States may be determined to
be harmful."
Based on the foregoing and my experience in evaluating the
environmental effects of oil spills, it is my opinion that an oil
spill sufficient to produce a film or sheen on the surface of the
water is large enough to cause harm to the environment.
Subscribed and sworn to before me,
A Notary Public, in and for the
District of Columbia, This
3rd day of May, 1974.
My Commission expires
POLLY P. ANDERSON
.-.- 3o
13
-------
ONLY APPENDICES 4 THROUGH 6 OF THE AFFADAVIT ARE PRESENTED IN
THIS DOCUMENT BECAUSE THE AFFADAVIT'S OTHER APPENDICES DO NOT
DEAL DIRECTLY WITH OIL'S TOXIC EFFECTS ON AQUATIC ORGANISMS.
-------
APPENDIX 4 a
DOCUMENTED HARMFUL EFFECTS OF
SMALL QUANTITIES OF CRUDE OIL ON LIVING ORGANISMS
1. Baker, J. M. 1971. Seasonal effects. In The Ecological Effects
of Oil Pollution on Littoral Communities, Ed. Cowell, E. B.
Institute of Petroleum, London. •*-•• *
Oiling of marsh plants during the early stages of flowering has
drastic effects as a result of damage to buds or primordia. Oiling of
open flowers frustrates the formation of seed.
2. Blumer, M. 1973. Interaction between marine organisms and
oil pollution. Environmental Protection Agency Report number
EPA-R3-73-042, May 1973.
Hydrocarbons are remarkably stable in marine sediments and
in the fatty tissues of marine organisms. Even chemically reactive
hydrocarbons can move unaltered through several levels in the marine
food web.
3. FWQA - 1969. Report of the National Technical Advisory
Subcommittee on Water Quality Criteria for Fish and Other Aquatic
Life and Wildlife.
British investigators have attributed the disappearance of eel
grass (Zostera sp.) to minute quantities of oil. Oil weakens the plant
and makes it susceptible to attack by the parasitic protozoa Labyrinthula.
-------
4. Gardner, G. R. 1972. Chemically induced lesions in estuarine
or marine teleosts (fish). Proceedings, Symposium on Fish Pathology.,
Armed Forces Institute of Pathology, Washington, D. C.
Deterioration of the chemoreceptor structures of (silverside
fish) Menidia menidia was found after exposure to both soluble and
insoluble components of Texas-Louisiana crude oil for 168 hours.
5. . Glynn, P. W. et al. 1971. Fundamental analysis for deter-
mining the effects of oil pollution on the ecology of a tropical shore.
Report, Smithsonian Tropical Research Institute.
Mangrove communmities are highly sensitive to crude oil
contamination. Major elements of the fauna have not returned after
33 months.
6. Keinhold, W. W. 1970. The influence of crude oils on fish
fry. FAO Technical. Conference on Marine Pollution, Dec. 9-18,
1970, Rome, Italy. 10 pp.
Toxic components are dissolved from oil films injuring herring
larvae and younger stages of floating eggs. Herring larvae were
unable to avoid oil contaminated water because chemoreceptors are
blocked very quickly upon contact with oil components.
7. Mackin, J. G. 1950. A comparison of the effects of the
application of crude petroleum to marsh plants and to oysters. Texas
A&M Research Foundation. As reported in IMCO Study VI, Appendix 3.
Seedlings of the mangrove Avicennia were killed by application.
of 25 ml of crude oil per square foot of water area.
-------
8. Mironov, O. G. 1967. The effects of low concentrations of
oil and petroleum products on the development of eggs of Black Sea
turbot. Vop. Ikhtiol. 7: pp 577-580.
Black Sea flatfish larvae were killed by exposure to 100 ppm
fresh crude oil in 24 hours. .At 0.01 ppm mortality was delayed and
23-40 percent of the larvae developed abnormally.
f.
9. Smith, J. E. ed. 1968. "Tbrrey Canyon" pollution and marine
life. Mar. Biol. Assoc. U.K. Cambridge Univ. Press.
An indirect effect of oil pollution accounted for the death of
intertidal crustaceans. As a result of biodegradation of oil, dissolved
oxygen was depleted and small crustaceans which had"sheltered under
stones were suffocated.
10. Tuck, L. M. 1960. The Murres. Dep. Northern and Natl.
Resources, Natl. Parks Branch, Canadian Wildlife Service, Ser. 1.
A patch of oil, one inch in diameter, on the belly of a murre
(waterfowl) was sufficient to destroy the insulating air pocket and
cause death from exposure.
-------
APPENDIX 4 b
DOCUMENTED HARMFUL EFFECTS OF OILY LAYERS. '
OILY EMULSIONS AND OILY SLUDGES ON LIVING ORGANISMS
a) ; Effects of free oil on waterfowl
1. Clark, R. "Oil Pollution and the Conservation of Seabirds, "
International Conference on Oil Pollution of the Sea, Rome (1969), found
that oiled bird feathers become matted together destroying the water
repellant property and allowing water to replace the air normally
trapped in them.
2. Erickson, R. "Oil Pollution and Migratory Birds, " Atlantic
Naturalist, IS (1) 5-14, 1963, found that bird plummage becomes oil-
soaked and water-logged such that birds loose bouyancy and their
ability to fly. - •" ...
3. Chubb, J. "Observations on Oiled Birds, 1951-53, " Northwest
Nature, (. S.) 2: 460-461, 1954, showed that in the presence of an oil
film diving ducks were unable to dive for food.
4. Hartung, R. "Energy Metabolism in Oil Covered Ducks, "
J. Wildlife Management, 31 (4): 798-804, 1967, showed that as a result
of the loss of insulating air in the feathers (ref. 1 above) oil-soaked
ducks lost more than twice the heat of unsoaked ducks.
5. Tuck, L. "The Murrs, " Department of Northern Affairs and
Natural Resources, National Parks Branch, Canadian Wildlife Service,
Ser. 1, 1960, documented that a patch of oil one inch in diameter is
-------
sufficient to destroy the insulating air pocket and cause death from
exposure to the chilling effect of the sea.
6. Hartung, R. and Hunt, G. "Toxicity of Some Oil to Waterfowl, "
J. Wildlife Management 31 (4) 798-804, 1966, in laboratory experiments
found that various industrial oils caused lipid pneumonia, gastro-
intestinal irritation, fatty livers and adreno-cortical hyperplasia when
,»:
fed to ducks in doses which were regarded to be less than that which
would be ingested during preening of oil plumages.
7. Hartung, R. "Some Effects of Oiling on Reproduction of Ducks, "
J. Wildlife Management 29 (4) 872-874, 1965, showed that the viability
of embryos is greatly reduced when the eggshell becomes smeared with
oil from the contaminated plumage of the female.
8. Rittinghaus. "On the Indirect Distribution of the Oil Pest in
a Sea Bird Sanctuary, " Onithol Mitteil, 8 (3), 1956, found that oiled
tern eggs did not hatch.
b) Effects of free oil on water living organisms
1. McKee and Wolf. W?ter Quality Criteria: State of California
Water Quality Control Board, 2nd Ed., 1963, reported studies showing
that free oil inay act by direct contact on the epithelial surfaces; of fish
and interfere with respiration, may coat and destroy algae and other
plankton and.may interfere with the natural processes of aeration and
photosynthesis.
2. Dr. Clarence Tarzwell, Director of the National Marine Water
Quality Laboratory, in his testimony before the Senate Subcommittee on
-------
On Oceans and International Environment, 1971, stated that surface oil
may blanket the surface of the water and prevent the uptake of oxygen
and may act as a contact toxicant for surface organisms or organisms
that come to the surface may get it into their gills. He also reported
on studies with 300 plankton which showed growth inhibition-resulting
from surface oil concentrations of 0. 8 gallons per acre-foot of water.
Based on studies at the Edison Water Quality Laboratory and by the
American Petroleum Institute this represents a quantity of oil causing
a rainbow discoloration of the surface of-the water and a film only
. 00008 cm in thickness.
3. Straughan, D. ".Oil Pollution and the Environment," 1970
Evangeline Section Regional Meeting of the Societ}' of Petroleum
Engineers, 1970, reported barnacles (c_. fissus) smothered by free oil.
4. Kenyon (personal communication) found that sheens of surface
diesel oil were sufficient to coat the fur of two sea otters and cause
death due to exposure in Alaskan environments.
5. Massachusetts Institute of Technology, 1970, Man's Impact on
the Global Environment: Report of the Study of Critital Environmental
Problems noted that chlorinated hydrocarbons are much more easily
dissolved in floating films of oil than in water and can then be carried
into the water column upon dispersal of the film. One study was reported
which showed the concentration of chlorinated hydrocarbon (DDT) to be
10, 000 times higher in an oil film than in the underlying water column.
6. Kunhold, W. "The Influence of Crude Oils on the Fish
Fry: FAO, " Technical Conference on Marine Pollution, Dec. 9-18,
-------
1970, Rome, Italy, reported that toxic components dissolved from
floating oil films injured larvae and young stages of floating eggs.
Likewise harmful effects from emulsified oils are found:
1. Mass. Institute of Technology "Man's Impact on the Global
Environment: Report of the Study of Critical Environmental-Problems, "
1970, stated that toxic effects of emulsified oils to fishes can result
from direct contact coating of fins and asphixiation.
2. McKee and Wolf Water Quality Criteria: State of California
Water Quality Control Board, 2nd Ed., reported studies indicating that
emulsified oils act by direct contact on epithelial surfaces of fish to
interfere with respiration'and may coat and destroy algae and other
plankton.
3. Clendenning, K. and North, W. "Effects of Wastes on the Giant
Kelp, Macrocystis pyufere, " Waste Disposal in the Marine Environment,
Proc. 1st Itn. Conf. Pergamon Press, N. Y., 1960, reported that
emulsions of diesel oil in sea water caused the death of sea urchins.
4. Tarzwell, C. - testimony referenced above, stated that when
emulsified oil gets into the gills of gill-breathing organisms it can be
toxic. They can also be ingested directly when the droplets are small.
The ingested hydrocarbons in addition to direct toxic effect can be
incorporated into the flesh and passed up the food chain similar to the
persistant chlorinated hydrocarbons.
-------
Finally, the harmful effects of sludged oils include:
1. Zo Bell, C. "The Occurrance, Effects and Fate of Oil
Polluting the Sea, " Int. Conf. Water Pollution Research, 1962, oil
is readily adsorbed by clay and silt and after burial almost no • •
bacterial decomposition occurs.
2. Blumer, M., Souza, and Sass, J., "Hydrocarbon Pollution
of Edible Shellfish by An Oil Spill"., .Int. Jour, on Life in Oceans
Coastal Waters, Vol. 5, No. 3, March 1970, describes widespread
and long-term damage to bottom living organisms as a result of persis-
tent sedimented diesel oil resulting from a barge spill.
3. Tarzwell, C. - testimony cited above, states that oil going
to the bottom and can blanket the bottom and kill through direct contact.
When broken up it can be ingested and passed up the food chain.
4. Erickson, R. "Effects of Oil Polluiton and Migratory Birds, "
Biological Problems in Water Pollution, 3rd Seminar (1962), R. A.
Taft San. Eng. Center, Cincinnati, Ohio, 1965, noted that migratory
birds are indirectly affected by deposits of oil on the bottom in shallow
water or along the shore that reduce the available food supply of both
plant and animal matter. Various elements in food chains are eliminated
by chemical or physical properties of the oil, or items in the diet of
waterfowl may become unavailable by being overlaid or imbedded in tarry
materials.
5. Battelle Memorial Institute Oil Spillage Study Literature Search
and Critical Evaluation for Selection of Promising Techniques to Control
-------
and Prevent Damage, 1967, points out that the accumulation of
petroleum sludge on the bottom may prevent germination and growth
of plants and the production of invertebrates important as food, either
by smothering or by toxic effects.
6. Water Quality Criteria, National Technical'Advisory Committee,
1968, states that settleable oily substances may coat the bottom, destroy
benthic organisms, and interfere with spawning areas. Oil may be
absorbed quickly by suspended matter, such as clay, and then due to
wind action be transported over wide areas and deposited on the bottom
far from the source.
7. North, \V., etal. "Successive Biological Changes Observed
in a Marine Cove Exposed to a Large Spillage of Mineral Oil in
Pollutions Marines par les Microorganismes et les Produits Petroliers, "
Symposium de Monaco, 1964, documented long-term damage to bottom
fauna resulting from a spill of crude oil in 1957. Populations of several
species.had not recovered four years after the incident.
-------
REPORT
to
DIVISION OF OIL AND SPECIAL MATERIALS CONTROL
•
of the
ENVIRONMENTAL PROTECTION AGENCY
on
EPA Contract No. 68-01-0745
Lewis R. Brown
Program Director
Mississippi State University
26 April 1974
-------
INTRODUCTION
On June 30, 1972, Mississippi State University was awarded
a three-year contract by the Environmental Protection Agency to
study "The Fate and Effect of Oil in the Aquatic Environment-Gulf
Coast Region." This contract (EPA Contract No. 68-01-0745) is an
interdisciplinary, multiinstitutional effort involving senior
scientists from Mississippi State University, the University of
•
Southern Mississippi and the Gulf Coast Research Laboratory. In
addition to being responsible for the microbiological aspects of
the program, I serve as the Program Director. The major effort
in this program is directed toward investigating the chronic
effects of subacute levels of oil on the ecosystem and it should be
emphasized that trie investigations include not only well replicated
laboratory bioassay experiments but also field studies. To date
all experiments have been conducted with Empire Mix crude oil
and salinities in the range of 12-18 ppt. This report is a synopsis
of some of the more salient results to date; specifics can be
found in Progress Reports 1-6, the Interim Report and the forth-
coming Seventh Quarterly Report.
RESULTS
_*
Crude oil has only limited solubility in water, albeit there
are some water soluble components present. The total oil present
-------
in the water column can be increased significantly by emulsifica-
tion but a majority of the oil will become attached to particulate
matter, evaporate and/or rise to the surface. Under these condi-
tions, the use of the phraseology "oil concentration in the water.
column" is of questionable value in-most bioassay tests even for
f.
tests of short duration. Uptake o'tf oil by biological specimens is
dependent not only upon the concentration of oil in the water and the
method of application but also on the total time of exposure and thus
to the total amount of oil to which the organism has been exposed.
For example, our results have shown that the greater the amount
of oil in the water column, the greater the uptake by shrimp when
dosages of emulsified oil calculated to yield 2, 4 and 8 ppnn oil were
added to test aquaria (29 gal) in the laboratory. Significant uptake by
the shrimp was demonstrated 12 hours after the addition of oil (the
first sampling after the oil was added). It is noteworthy to point ou~
that these data are based on analyses conducted using a liquid chrom-
atographic technique which determines aromatic compounds rather
than aliphatic compounds since in many instances gas chromatograpihic
analyses failed to indicate oil uptake. As expected the average oil con-
centration in dead organisms was considerably greater than in organisms
surviving, thus suggesting differences between individual organisms.
Another point of considerable significance is the fact that the TL5Q
(»
value varies seasonally and thus extrapolation from laboratory data
to the field must take this factor into account. In the presence of
-------
emulsified oil (15 ppm) the shrimp exhibit a "spiraling phenomenon"
which should make them far more susceptible to predation. Upon
removal from the oily water, the shrimp revert to normal behavior.
Erratic behavior by shrimp'has been observed in the laboratory
with the addition of as little as 1 drop of oil in a 29 gallon aquarium.
In an experiment involving the spillage of oil into a brackish
water pond, it was noted that menhaden which exhibited erratic
behavior at the surface were quickly devoured by other fish, once
again illustrating the potential problem of oil altering normal be-
havior patterns required for survival.
Both mullet and oysters can survive high doses (350 ppm or
greater) of emulsified oil in short term experiments but signifi-
cant changes in enzyme levels can be attributed to the presence
of oil in tests employing 75 ppm oil added to the system. The true
significance of these findings in regard to long term survival,
reproduction, etc, are not clear at this time, but suffice to say,
exposure to oil does alter the normal metabolic activity of the
organisms. In more recent studies it has been found that the
addition of small amounts (1 ppm) of oil daily for 11 days, followed
by 11 days with no oil additions, 11 more days of oil additions, etc.,
drastically alters the results. Under these conditions oysters
began to die during the second oil addition period and mullet began
to die during the third oil addition period. Additional tests are
being conducted but the results to date seem to imply that the
-------
sequential addition of oil is far more toxic to mullet and oysters
than is the addition of a large amount of oil at one time.
Some histological abnormalities have been found in organisms
exposed to oil, but on the basis of the results to date it cannot be
said with certainty that they were caused by oil.
There seems to be a lot of controversy over the length of
•t.
time required for oysters to cleanse themselves of the "oily taste"
after exposure to oil. Our studies have shown that after exposure
of oysters to 300 ppm emulsified oil (rdose) for 96 hours, the
"oily taste" is still detectable even after 3 months'of depuration
in clean water. It should be pointed out that the exact length of
time for depuration in the environment is dependent upon season,
salinity, and other facts.
Crude oil has been shown to cause significant decreases in
marsh grass productivity in in situ experiments.
Particularly germane to the present report are the results
of recent tests just conducted on Acartia (found in brackish and
high salinity water). Cultures obtained from ths ecosystem ponds
to be employed in the field studies yielded TLcgvalues (96 hr)
of 0. 5-2. 0 ppm (1. 25 ppm, average) for emulsified oil; cultures
obtained from the Gulf yielded TLgQ values (96 hr) of 1. 0-2. 0
ppm (1. 50 ppm, average) for the emulsified oil; and laboratory
cultures yielded TI^Q values (96 hr) of 2.0-6.0 ppm (4. 0 ppm,
average) for the emulsified oil. The TL,QOvalues (96 hr) for the
above cultures were 6-10 ppm, 6-10 ppm, and 10 ppm respectively.
-------
These values are based on the quantities of oil added to the system
and actual analyses of the water revealed oil concentrations of 50%
of the values reported above.
. ' SUMMARY ' " -
In summation, and within the experimental procedures outlined
in the progress reports prepared for this contract, the following
points are submitted.
1. The sensitivity of selected estuarine organisms to
oil pollution varies between organisms and with time
of year.
2. Exposure of shrimp, Penaeus sp., to as little as 0.1 ml
of oil in 130 liters of water will elicit anomalous behavior.
A 2 ppm oil in water mixture results in demonstrable
oil uptake and 15 ppm is sufficient to produce a total kill
in most instances.
3. While mullet, Mugil cephalus, and oysters,
Crassostrea virginica, can withstand the addition of a
large volume of oil applied at one time, fatalaties are
noted when small (calculated to produce a 1 ppm mixtura
of oil in water), intermittent applications are used.
Exposure to a single application (producing a 75 ppm oil
in water mixture) causes significant alterations in the
normal metabolic processes of these organisms.
-------
4. The addition of 1. 5 liters of crude oil per square
meter causes a significant decrease in marsh
productivity.
5. Additions to experimental aquariums of emulsified
crude oil calculated to produce concentrations
of 0. 5-6. 0 ppm but anal/zed to be 0. 25-3. 0 ppm
are sufficient to kill 50 percent of the copepods,
Acartia sp., present.
6. Oysters exposed to a 300 ppm mixture of crude
oil in'water for 96 hours still demonstrate an
"oily" taste after 3 months in clean water.
-------
ter Quality Criteria
Report of the
National Technical Advisory Committee
to the
Secretary of the Interior
APRIL 1, 1968
WASHINGTON, D.C.
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
-------
• .3*- CLASEXCS M. TARZ\VELL, Chairman, Diree-
;-. • tor. Nation al Marine Water Quality Laboratory,
" '-~ federal V/ater Pollution Control Admiaistra-
. '_" • ikrz, U.S. Department of the Interior, West
;r KL-gston, R.L -.-'.-..., -,- ..".*.'••. .. . -.
- MR. VVTAUTAS ADOMAITIS, Research Chemist,
-.. Bureau cf Sport Fisheries and WDdlife, North
:,-;' ?^*z Wildlife Res-arch Center, U.S. Depart-
. .J' Eient of the Interior, Janaestovra, N.Dak.
^ DR. BERTTL G. ANDERSON, Professor cf Zoology,
'.* . Los Sciences BuDding, The Pennsylvania State
. x •'• Ush-ershj-, University park, Pa. • • '• •- ' ' .
-,\^*R- GEORCH E. -BURDICK, SupervisiDg Aquatic'
**'•• BwJogjst (PoUution Research), New York Con- -
Department, S^te Campus, Albany,
x. PK.T.I? A. BUTLER, Laboratory Director,JBu-
^- reau of Conur.ercial Fisheries Biological Labo-
• " rstory, U.S. Dssartment of the Interior, Gulf
* '
.
D?_ ROBERT J. CONOVER, Atlantic Occinogrsphic
« Group, Fisheries Research Board, of Canada,
".-• Dssnnouth, Nova Scotia. ; -••••••:..-.-•.;•..• ..;'•
D?- OLIVER B. CO^E, Director, Rsh-Pesticids Re-.;-
Sisrch LaboraJory, Bureau of Sport Fisieries '
erd Wildiifa, U.S. Department of the Interior, - -
Cchisbia, Mo. - . :* •.-:-.--.*•-..... ••-. '-:
D?w }L'CHA?.JD F. FOSTER, >v'azager,' Earth Sciences
. SKZQZ, Envircsrsenal and Radiological Sci-
t, PaciSc Northwest Labo- ":
riciis Memorial Institute, RichJand, :
: Wash. -.- .:.,.•....-,•.-. .-;:-'- - .• •.:.-„;• '-.: r ;. ..;
Ds. F. E. J. F?.Y, Professor of Zoology, Depart- '"•
. 'nent of Zoojosy, Unf\-ersity of Toronto, To- ..•
Depar
Ds. PiUL S. GAL-SO?F, Conrjltaat, Woods Hole, '"
...
Da. AJU3SS R_ GAUHN, Professor of Zoology, D*- .-
parsnect of Zcclogy asd EnxmoJo^j', Univer-
•-• ' sty of Utah, Salt Lake Gty,. Utah. • •• -.-"'.: ... ' ' •
Ms. Vv ILUAM F. GUSEV, Assistant Chief, Division .
of Wildlife Services, Bureau of. Sport Fisheries
- asd Wildlife, U.S. Department of the Interior, '
" : Washiagtoa, D-.C. • 4 . • -' .-. -^ •.-:-- -% -•; - ^
I>7."Vv'iLiUii J. HASGIS, JR., Director, Vbpnis In-''''
siisi^ of Marine Science, College of WHD'aza
p~tf Mar}' acd .University of Virginia, G!ou- -'
crsrr ?oi=t, Va. -.-,..,.' •• •/ -.. --•...,.•' ::
MX. E!_:GES'E p. HAVDU, Water Resources and -
Management, -Weyerhaeuser Co., Pulp and ."
Paperboard Divisica, Longview, Wash. !;• • ••'":
Ms. CKOS^VELL HENDERSON, Fishery Bio'.oaist,
-• Bureau of Sport Fubcries and Wjidlife, U.S. De-
pim^ent of the Interior, Colorado S^iti Uni-
versity, Fort Collins, Co'o. . '••'.'
MR. EOCENE T. JENSEN, Chief, OSes of Es'tunrbs
Sr-JdJiS, Federal V/ater Pollua'on Control Ad- .
=-J=i'--2t'cn, U.S.. Department of the Interior, '
Dx. J. M, LAWREKCE, Aubum Unxversitv, A
bum,Ala. •- •• . • '"••.. .. • - . **
Da. VICTOR L. LOOSAKOFT, Professor of M^las
Marine Biological Laboratory, Uni-
of -ihe Pacific, Dillon Eeach, Cali
Ds. DONALD I. MOX.-NT, National Water Quality
Laboratory, Federal Water Poliirtioa. Control
Adrainistradcn,. Deparnrrent of-ihe 3!n^rio^"
Duliith, Mian, ; •--..-'
DR. RUTH PATRICK, Cura^r and.Chzinna.2 of -as
Limnology Department, Academy of Naniral
- Sciences of Philadelphia, Philadelphia, ra. •
Da. BENJAMLS H. PMNGLE, Supervisory Chemist/
' Northeast Marbs Heali Sciences LabDrai3r>-
. PubUc. Health Service, U.S.. ' Departssnt cf
Health, Education, and Welfare, Narragznsts,
•• R.L .::--. ., '. - • . . -• • ":
DR. D. I. RASMUSSEN, Dh^ctor, Division of W3d- .
. life ManajeEen^ Forest Service, U.S. Depart-
- "• cent of Agricdtsre, Washington, D.C
DR. THEODORE R. RICE, Director, Radiobioiosicaf
Laboratory, Bureau cf Commercial Fishe"nis, '
U^: Department of the Interior, Beaufoit, N.C. ;
MR, JOHN L.' SLVCOCK, Chief, Section of Wetland
_ Ecology, -Pat^eat Wildlife Research .Ctzlir/
Bureau of Sport Fisheries and Wildlife, f~*"r~L
Md... , -.-;.- . ...... *...%-.'. . . •_--
Da. WiLLiAi^ A. SPOOR, Professor of Zooloey, De-
partment cf Bioiogicai Sciences, Univzrs-ry of
• Cbc'rcujy CincinnatJ, Ohio. -- _- - .
MR: Zuczs'E W. SCRSSR, Commission of G--^.
• aoc Inland Fisheries, Erownto wn, Va. -.. • .
Ms. WILLIAM E. WEBB, Watrr Quality Bioioist, -
. " "rho- Fish and GSJT.S ' I>eptrrtmen£. Boise.
-- ". . - ^^^
MR. ARTHUR N. WOCDALL, Assistzia Chid; Dhi-
. rloQ of Fishery Research, Bcrcau of S^ort Flsi—
eries and Wildlife, U^. Departaent of -die In-
terior, Washington, D.C, • .-. -•-:• • -
DR. Ri.ROLDB=^csos, fechrlccl Execu±,-s Secrz.
zry, Federal Water Pollution Control .
tfadon, U.S. D=
ect of the Interior, Wash-
-------
•0.
Oil slicks am barely visible at a concentration of
about 25 gaj/sq mi (Ainer. Petroleum Inst. 1949).
At 50 gal/sq mi, an oil film is 3.0 x 10-* inches
thick and is visible as a silvery sheen on the sur-
". fsct. Sources of oil pollution are bilge and ballast
.. waters from ships, oil refinery wastes, industrial
plant wastes such as oil, grease, and fats from the
lubrication of machinery, reduction works, plants
cacufscturing hydrogenated glycerides, free fatty
acids, and glycerine, rolling mills, county drains,
storm-water oversows, gasoline filling stations, and
bulk stations.
Wiebe (1935) showed that direct contact by fish
(bass and bream) with crude oil resulted in death
caused by a Sim over the gill-filaments. He also
demonstrated that crude oil contains a water-solu-
b'e fraction that is very toxic to fish. GaltsofT, et al.
(1935) showed that crude oil contains substances
soluble in sea water that produce an anaesthetic
erTect on the ciliated epithelium of the gills of
oysters. Fjee oil and__emulsions may act on the
epithelial surfaces of fish gills and interfere with
respiration." They may coat _and destroy algae and
other piankton'.jHereby removing a source of fish
food, and _whta ingested by fish they rhay^tajnt\
.their fi«h.
\ Settsable oily substances may coat the bottom,
4; destroy benthic organisms, and interfere with
'spawning areas. Oil may be absorbed quickly by
' suspended matter, such as clay, and then due to
wind action or strong currents may be transports
over wide areas asd deposited on the bottom f<
from the source. Even when deposited on the bo
torn, oil coniiauo-Jsly yields water-soluble sut
stances that are to.xJc to aquatic life.
Films of oil on the surface may interfere wit
reaeration and photosynthesis and prevent th
respiration of aquatic insects such as water boat
men, backswimiaers, the larvae and adults c
many species of aquatic beetles, and some specie
of aquatic Dipiera (fiies). These insects surfao
and carry oxygen bubbles beneath the surface b;
means of special setae which can be adversely af
fected by oil. Berry (1951) reported that oQ film.
dai'the lower Detroit River are a constant threat t<
waterfowl. Oil is detrimental to waterfowl by de>
stroying the natural buoyancy and insulation o:
their feathers.
A number of observations made by various
authors in this country and abroad record the con-
centrations of oO in fresh water which are dele-
terious to different species. For instance, penetra-
tion of motor oil into a fresh water reservoir
used for holding crayfish in Germany caused the
death of about ~20rCOO animals (Seydell, 1913).
It was established experimentally that crayfish
weighing from 35 to 38 g die in concentrations of
5 to 50 mg/1 wiuiin 1S to 60 hours. Tests with two
species of fresh water fish, ruff (small European
perch), and whiteisn (fam. Coregonidae) showed
that concentrations of 4 to 16 mg/1 are lethal to
these species in 1S to 60 hours.
The toxicity of crude oil from various oil fields
in Russia varies depending on its chemical ecu-
position. The oil used by Veselov (1948) in the
studies of the pollution of Belaya River (a tribu-
tary in the Kama in European Prussia) belongs TO a
group of raethaao-aroiaatic oils with a high con-
tent of asphalt, tar compounds, and sulfur. It
contains little paraSa and considerable amo\ints
of benzene-ligroln. Small crucian carp (Carcsslus
carassius) 7-9 era long were used as the bioassay
test animal This is considered to be a hardy fish
that easily withstands adverse conditions. The
water soluble fraction of oil was extracted by
shaking 15 ml cf cO in I liter of water for 15
minutes. The oO film was removed by filtration.
Dissolved oxygen was controlled. A total of 154
tests were performed using 242 fishes. The average
survival time was 17 cays at the concentration of
0.4 ml/1 of oil but only 3 days at the concentration
of 4 ml/1. Further increase in concentration had no
appreciable effect on fish mortality.
Seydel! (1913) stated that the toxicity of Rus-
sian oil is due to nsphlhenic acids, small quantities
of phenol, and volatile acids (Veselov, 194S).
-------
Cidrss (1957; reports the following 96-hour TLa
values of naphrienic acid for bluegill sun5sh
(Lgpomis macrockirus)—5.6 mg/1; pulmor.ate
snail (P'nysa heterostropha)—6.1 to 7.5 rng/1 (in
soil water), and diatom (speciss not identified)—
41.8 to 43.4 mg/1 in soft water and 28.2 to 79.8
ng/1 in hard water. Naphthenic acid (cyclohexane
oirboxyJic acid) is. extracted from petroleum and
is LLScd in the manufacture of insecticides, paper,
• and rubber. ...
Chipman and Galtsoff (1949) report that crude
oil ia concentrations as low. as 0.3 rag/1 is ex-
tremely toxic to fresh water fish. Dorris, Gould,
and Jenkins (1960) made an intensive study f>l the
toxicity of oil refinery effluents to fathead-minnows
in Oklahoma. By standard bioassay procedures,
they found that mortality varied between 3.1 per-
cent to 21.5 percent after 48 hours of exposure to
untreated effluents. They concluded that toxicity
jathsr than oxygen demand is the most important
.effect of ofl refinery efiuents on receiving streams.
Pickering and Henderson (I966b) reported the
results of acute toxicity studies of several impor-
tant petrochemicals to fathead minnows, bluegilis,
goldfish, and gxippies in both soft water and hard
•watsr. Standard bioassay methods were used. Be-
caios several of the compounds tested have low
solubility in water, stock solutions were prepared
by blending the calculated concentrations into 500
ml of water before addition to the test container.
"Where necessary, pure oxygen was supplied by
bubbling at a slow rate. The petrochemicals tested
•were benzene, chlorobenzene, 0-chlorophenol, 3-
chloropropene, 0-cresol, cyclohexane, ethyl ben-
zene, isoprene, methyl methacrylate, phenol, 0-
ph'Jialic anhydride, styrene, toluene, \inyl acetate,
and xylene. These petrochemicals are similar in
ihsir toxicities to fish, vvith 96-hour TL^ values
ranging from 12 to 368 mg/1. Except for isoprens
ar.d methyl methacrylate, which are less toxic,
values for all four species of fish for the other
petrochemicals ranged from 12 to 97 mg/1, a rela-
tively small variation. In general, 0-chlorophenol
and "O-cresol are the most toxic and methyl metii-
acrvlate and isoprene are the least toxic.
Rr«>mm*ndaric,n: In view of available data, it is cca-
c!:oieti iha: to provide suitable conditions for aqua'Jc
L::'e, oil and petrochemicals should not be addsd in
%ueh quantities to the receiving watere that tbsy v-Hl:
(i) prccuce a visible cofor fiim on the surface, (2)
impart aa oily odor to water or an oily lasts to fish
^:*l edfoie Invsr.ebrates, (3) coat the backs and bot-
van o£ tlw water course or taint any of the asiociated
'ctoia, or (4) become effective toxicants according to
ih« criteria recommended in the 'Toxicity" section.
-------
EsW
.ar«
' i
Crude oil and petroleum products
The discharge of crude oD and petroleum prod-
ucts into esruarine and coastal waters presents spe-
cial problems in water pollution abatement. Oils
from diferent sources have highly diverse proper-
ties and chemistry. Oils are relatively insoluble in
sea and brackish waters and surface action spreads
the oQ in thin surface films of variable thickness,
depending on the'amount of oil present. Oil, when
adsorbed on day and other particles suspended in
the water, forms large, heavy aggregates that sink
to the bottom. Additional complications arise
from the formation of emulsions in water, leach-
ing of water soluble fractions, and coating and
tainting cf sedentary animals, rocks, and tidal
flats.
Principal sources of oil pollutioa'are numerous.
Listed in order of their dsstructiveness to ecosys-
tems, the}' are:
(1) Sadden and uncontrolled discharge-from
wells towards the end of drilling operation.
(2) Escape from wrecked and submerged 01!
talkers.
(3) Spillage of oil during loading and unload-
ing operations, leaky barges, and accidents
during transport.
(4) Discharge of oil-contarninated ballast and
bilge water into coastnl areas and on ths
high seas.
(5) C^-ing and flushing of oil tanks at sea.
On the average, a ship's content of such
wastes is estimated to contain 2 to 3 per-
cent oH in 1,000 to 2,000 tons of waste.
(d) Spillage from various shore installations,
refineries, railroads, city dumps, garages,
and various industrial plants.
Spillage From Wrecked Oil Tankers
Even though wrecks of oil tankers along the
Atlantic coast and subsequent spillage of oil into
the sea ha%-e been reported several times, no thor-
-------
ouch examination has been made of the effect of
03~pollution on local marine life, except for frc-
c'jcnt references to the destruction of waterfowl.
One of these disasters attracted the general atten-
tion of the public and members of lie Audubon
- Society of New England. One night in 1952, two
rankers, the Fort Mercer and the Pendleton, went
srround on the shoal oi Monomu> r'oint, Cape
Cod. Large amounts of oil spilled from the broken
vessels, spread long distances ^loug the shore, and
vers responsible for high mortality of ducks (scot-
ers and eiders). Many thousands of oil-smeared
dying birds were seen along the coast. Attempts to
save some of the birds by removing the oil with
various solvents failed. No published records are
fouzd en the effect of this massive spillage on
aquatic life. According to the records of the Mas-
sachusetts Audubon Society, serious ofl spreads
threatening fish and bird life have occurred at least
six rimes since 1923 along the beaches of Cape
Cc
-------
According to data published by 'he American
Petroleum Institute (1949), the first trace of color
that may be observed as a surface film on the sea
is formed by 100 gallons of oil spread over 1
square mDe. Films of much darker colors may
indicate 1,332 gallons of oil per square mile. Ex-
periments conducted by the Conrnirteef oa the
Prevention of Pollution of the Seas U953) sLowcd
that 15 tons of oil covered an area of 8 square
miles. In 8 days, it hnd drilled about 20 relies
from the point of discharge. The same comnrir.ee
(1953) indicated another source of oil pollution
that should not bz neglected. It has beec f:-_i:id ur_.
unburned fuel oil escaping through the funnels^'
oD-burniag ships may comprise 1 to 2 percent of
the total oil consumed and it may be deposited 'on
the sea surface. British investigators attributed the
disappearance of eel grass (Zos/era) to minute
quantities cf oil. Oil weakens the plant ?jid makes
it susceptible to attacks ^ a parasitic protozc^a
(Labyrinthula*). Observations made several years
ago at Woods Hole showed that youcg Zosiera
that began to reappear in local bays after several
years of absence were already infected by this
microorganism even though they aooeared to be
healthy.
Adsorption of Oil by Sand, Clay, Silt, and
Dtnsr Suspended Particles
Oil of surface films is easily adsorbed en clay
particles and other suspended r^...crials, fomirg
large and relatively heavy aggregates that s:Jik to
the bottom. The surface of u.e water may appeir
free from pollution, until the sediment is c.:L~ed by
wave actioa and the -leased oil iloats up again.
During World War II, a product >_nown L
"carbonized sand" was manufactured for the U.S.
Navy and used for the primary purpose of rapidly
removing oil spilled or leaked from ships Car-'on-
ized sand was used principally as a rapid me'.hod
to prevent and stop fires. Sand and oil aggr.-rales.
being much heavier than * :~ water, sank •'.ery
rapidly and remained on the bottom. "Experuzr-:-?'
work has shown that the toxic effect of oils Is not
diminished by this method (Chipman and Gais-
off, 1949). Since the end of World War H, a num-
ber of preparations to be used as solvents, emu!si-
fters, and dispersing agents of oil slicks in harbor
waters appeared in New Zealand, Western Europe,
and the United States. These preparations are be-
ing offered under various trade names and their
chemical composition is not always staled. It is
often claimed that such compounds remo'.e oil
slicks more efficiently than mopping with straw or
coarse canvas fabric (sk/uu), a method exten-
sively used in Auckland Harbor (Chitry, 1943).
It is hov>r ; Generally recognized that various
detergents and emulsifiers are toxic to aquatic life
and therefore compound the danger of oil pollu-
tion. Mechanical means such as preventing the
spread of a slick by surrounding it with floating
barriers ^pia^tic booms), spreading' sawdust and
removing an oH aggregate by scooping or raking,
and erecting grass or str?w barriers along the
beaches are probably more effective ^at present
than the chemical methods of dispersing or dis-
solving oil. Even anchoring oil by ccmbiobg it
with reUL,;iy heavy carbonized sand setms to be
preferable to chemical methods.
Tcxicity of Cruos Oi! and Petroleum Products
Oil may in JUT; aquatic life by direct contact
with the organism, by poisoning with various water
soluble substances that may be leached from oil,
or by emulsions of oil which may sraear the gills or
be swallowed with water and food. A heavy oil
aim o- the water surface may interfere with the
exchange of gases and respiration.
A number cf ch stations have been recorded
of the concentradons of oil in sea water which are
deleterious -> '•arieus species. Experimental data,
however, are scarce and consequently the toxicol-
ogy of oil to rr.ance organisms is not well under-
stood.
NelsT. (1925) observed marine mollusks (A--;'S
arenana) behg destroyed by oil on tidal flats of
Staten I:'.^i, N Y. Tne Pacific coast sea urchin,
Slrongylocer.troius purpura:us, dies in abc-t 1
hour in a 0.1 percent emulsion of diesel oil. After
20 to 40 minutes b '-his conc-.ntration the auircols
fail to clins to the bottom and may be washed
away (North, et a!., 1964).
Crude c'.i absorbed by carbonized sand does not
lose its toxicity. This has been shown by laboratory
experiments r-rducted at Woods Hole (Chiprzaa
and Galtsoff, 1949). Tne amount of oil used was
limited to th: 7-^:^7 held in the sand, hence no
free oil was present in the water. The oil-sand
aggregates were placed in containers rilled with sea
water but never came into contact with the test
animals. Four species were bioassayed: the very
hardy toad fish (Opsar.us ten') in the yolk sac
stase, the modenteiy tolerant barnacle (Balanus
balanoides'). and oyster (Crc.ssostrea virgin'tca),
and the extremely sensitive hydrozoan, (Tubularia
crocca).
The sup.-ival of toadnsh embryos was indirectly
proportional to the concentration of oil in water.
-------
In 3 conccr.rr.ion of 0.5 percent, the embryos sur-
' VTVCO" for 13 cays (end of test); in 1.25 percent,
Sj cays; in 2.5 percent, 6 days; and in 5 percent,
4J dcys. Earr.ades suffered 80 to 90-percent
nonaiiry with::: 70 hours in 2.0-percent mixtures
• of oil in sea. \vater. They became inactive in 23
hours in concentrations of 2 percent and above.
Tub-ulzriz sufered 90 to 100-percent mortality
• within 24 hours after being placed in water con-
tairiinc a 1:200 oil-carbonized sand aggregate.
Water extracts of crude oil were-lethal within 24
hours at concentrations of 500 rag/1 and greater.
.' • Experiments with oysters consisted primarily of
determining the effect of oil adsorbed on carbon-
ized sand on the number of hours trie oysters re-
main open and feeding and on the rate of water
'_ transport, across the gills. A paste-lite, aggregate of
02 in caibc'niied sand (50 ml crude oil to 127 g
sand) was prepared, wiped clean of excess oil, and
diced in the mixing chamber. Sea ^ater was de-
livered through this chamber to the recording ap-
paratus at a rats slightly in excess of the rate of
water transport by oyster gills (Galtsoff, 1964;
Chipman and Galtsofi, 1949). There was a notice-
able decrease in the cumber of hours the test
oysters remained open and in the daily water trans-
port rats through the gills. The time open was re-
• duced from 95 to 100 percent during the first 4
days of testing to only 19-8 percent on the 14th
day. The total amount of water transported per
day, and presumably used for feeding and respira-
tion, was reduced from 207 to 310 liters during the
first 6 da\s to orJy 2.9 to 1 liter per day during
the period between the eighth and 14th day of
conrirrjous testing. These tests indicate that oil
incorporated ir.io the sediments near oyster beds
continues to leach water-soluble substances which
depress the normal functions of the mobusk.
Critical observations are lacking on the effect of
oil os pelagic larvae of marine invertebrates, but
there is good reason to assume that crude oil and
petroleum products are highly toxic to free-swira-
—Ho larvae of oysters. Spee*- (1928) considers
that they are killed by contact with surface oil film.
Laboratory experience of Galtsoff (unpublished
records) shows that oyster larvae from 5 to 6 days
old were Killed when minor quantities of fuel oil
were spilled by ships in the Woods Hole harbor
and the contaminated water penetrated into the
laboratory sea water supply.
The tests described above, leave no doubt that
water-soluble substances are leached from oil
spilled into water and adversely afTect marine life.
It is reasonable to assume that the water soluble '
materials of ol' may contain various hydrocarbons,
phenols, suISces, and other substances toxic to
aquatic life. The water-soluble fraction leached
from crude oil is easily oTJdizcd by aeration zuad
loses its toxicity (Chiprnan and Galtsoff, 1949).
Carcinogenic Substances From
Oil-Polluted Waters
Presence of hjdrocarboas similar to beczo-
pyrece in oil-polluted coastal waters and sediments
of France in the Mediterranean was reported by
Mallet (1965) and Mallet and Sardou- (1965).
The eSuents from the industrial establishments on
the shores at Villefranche Bay comprise tar sub-
stances, which contain benzopyrsnes, benzo-8,
9-fiuoranthene, dibenzanthracenes, chrysene, 10-
methyl anthracene, and nitrogenous derivatives
such as dimethylbenzacridine. These substances
are carried out into the bay water and settle on the
bottom. The pollution is augmented by incom-
pletely burned oiis discharged by turbine ships.
The content of benzcpyrene in bottom sediments
ranges from 500 micrograms b. 100 g sample col-
lected at the depth of 8 to 13 crn to 1.6 micro-
grams at 200 cm Similar contamination is cf im-
portance in the Gulf of Fos. Etang de Berne, and
in the delta of the Rhone River.
Carcinogenic hydrocarbons were found to be
stored in plankton of the ba\ cf Villefranchs, in
concentrations van ing from 2.5 to 40 rnicrograrns
per 100 g. Fixation of benzopyrenes was found
also in the bodies of holothurians (Lalou, IS65)
in a bay near Antibes. The reported concentration
in the visceral mass of holothurian was sli:;htly
higher than that in the bottom sediment
Observations on storage of carcinogenic com-
pounds found in oil-polluted water are biologically
significant. The important question cf biological
magrlScation as these compounds are ingested by
plankton feeders remains unanswered and needs
to be investigated.
Sampling of Oii-Foiiutsd Sea Water
The question of the minimal concentration of oil
and petroleum products consistent with unin-
hibited growth and reproduction of aquatic species
is more difficult to answer than it is in the case of
other contaminants. As has been shown above, oil
is found in water in four distinct phases: (1) sur-
face oil film, (2) emulsion in sea water, (3) ex-
tract of water soluble substances, and (4) semi-
solid aggregate of oil and sediment covering the
bottom. Obviously, no single sample could include
all four phases and the method of sampling should
-------
vary accordingly. Collection of samples of a heavy
oil slick near the origin of spillage presents no par-
ticular difficulty because an adequate quantity may
be scooped easily and placed in a proper container.
Serious difficulty arises, however, in case of zn
irridescent film of oil approaching the thickness of
a monomolecular layer. Garrett (1964), made a
special study of slick-forming materials naturally
occurring OQ sea surfaces, and demonstrated their
.highly complex composition. The. collection of
very thin layers of'surface water was mads by
means of a specially constructed plastic screen.
The entrapped compounds were washed ofrinto
a large container (Garten, 1962). He found'sur-
face-acting substances in all areas where jhe' -sea
surface was altered by monomolecular films, and
concluded that "a chemical potential-' exists
whereby such surface alterations can occur when
conditions are suitable for the adsorption and
compression of the surface-active molecules at
the air/water boundary." The oil film at the
air/water boundary may be composed of several
interacting organic compounds. This complexity
must be kept in mind in studies of oil pollution in
sea water.
If a relatively thick layer of contaminated water
is needed, the sample may be scooped or sucked
from an area of sea surface enclosed by a floating
frame. Interference due to wave ripples is mini-
mized in this way.
For analysis of an oil emulsion in sea water, a
sample of a desired volume may be collected by
pump or by any type of self-closing water bottle
lowered within the surf area.
For obtaining water soluble substances leached
from oil sludge, sampling should be mads by
pumping or by using a water sampler lowered as
close as possible to the oil-covered bottom.
Samples of oil adsorbed on sediments can be
obtained by using bottom samplers designed to
take quantitative samples.
Contamination of beaches by floating tar ballast
and cleaning water discharged by ships sailing
along our coast is of such common occurrence that
at present it is almost impossible to find a public
beach free from this nuisance. Cakes of solidified
oil tar can be picked by hand from the tidal zone
of any beach along the Atlantic and Gulf coasts.
Recommendation: Until IT. ore information on the
chemistry and toxicology of oil in sea water becomes
available, the following requirements are recommended
for the protection of marine life. No oil or petroleum
products should be discharged into estuarins or C02s:il
waters in quantities that (1) can be detected as a
visible film or sheen, or by odor, (2) cause tainting
of fish and/or edible invertebrates, (3) form ar» oil-
sludjs deposit on the shores or bottom of the receiving
-------
Oil
Waterblrds, musk rats, otters, and many other
wildlife species require water that is free of surface
oil. Studies by Hartung (1965) demonstrated that
egg laying was inhibited \vhen ma'.lards ingested
small quantities of oil. Whsr. oil from the plumage
was coated on mallard eggs, it reduced hatching
from SO.to 21 percent. The full significance of this
Of dzinage to wildlife populate-as is unknown.
Dr£32dc losses of watarbirds (ducks, geese,
'""coot, •sv-'ass, gaanets, rnurres, and others) result
!; frota contamination of the plum age by oil from the
' sszizsz of the water. Once the bird's plumage is
. soaked vo:h oil, the bird loses its rarcrEl insula-
• tion to tie cold and dies. Many hundreds of thou-
pgn^t of birds have died fxoa oil pollution in
.••soas \rars in North A men can waters.
'.. Oii that sertlss to the bottom of aquaas habitats
can bJazi'et large areas and destroy the plants eud
anisaJs of value to waterfowl. Reportedly, some
oD sSudges oa the bottoms of aqusdc habitats tend
to concentrate pesticides, thus creating a double
hazard to waterfowl that would pick up these con-
sts in their normal feeding process.
-------
APPENDIX 2
ANIMAL TOXICITY STUDIES
-------
TABLE 1
Animal Toxicity Resulting from
Aerosol Exposure to Oil
Animal
Experimental Data
Results
1. Middle Distillates
6 albino
rats
25 rats
rats
rats
rats
rats
37 rats
9600 mg/m3 aerosol of
deodorized kerosene;
6 hr/day for 4
consecutive days
9600 mg/m3 aerosol of
deodorized kerosene;
6 hr/day, 5 days/wk
for 13 weeks
14,400 mg/m vapors of
(?9~C-10 aromatic dis-
tillate for 7 hours
3200-5200 mg/m3 vapors
of Cg-C^Q aromatic dis-
tillate; 18 hr/day;
up to 2,424 hours of
exposure
260-1000 mg/m3 vapors
of Cg-C^g aromatic dis-
tillate; 8 hr/day; 5
days/wk; 700 hr. total
4600 mg/m vapors of
C^]_-C^2 aromatic dis-
tillate for 7 hours
3200 mg/m3 vapors of
C^^-C^2 aromatic dis-
tillate; 18 hr/day;
up to 1,683 hours of
exposure
loss of coordination;
sluggishness; dermatitis;
normal weight gain
2 died after 16 and 30
days; bronchopneumonia;
elevated urine pH;
erythrocytopenia; no
progressive effects
acute LC
50
decreased rate of weight
gain; neutrophilia; lympho-
cytopenia; decreased total
leukocyte count; bilateral
cataracts; hemorraghic
lungs, liver, kidneys,
spleen; increased myelotic
precursors in bone marrow
no adverse effects
acute LC
50
50% died after 18 hr; de-
creased rate of weight gain;
hemorraghic lungs, liver;
splenic dystrophy; decreased
total leukocyte count; neutro-
philia; lymphocytopenia; watery
bone marrow; dermatitis
-------
TABLE 1 (Cont'd)
Animal Toxicity Resulting from
Aerosol Exposure to Oils
Animal
mice
mice
mice
3 rhesus
monk ays
3 rhesus
monkeys
4 rhesus
monkeys
beagles
beagles
4 cats
Experimental data
6900 mg/m3 deoderized
kerosene aerosol (dur-
ation not specified)
9700 mg/m3 vapors of
C9~C10 aromatic dis-
tillate; 3.75 hr.
exposure
3400 mg/m vapors of
Cn-Ci2 aromatic dis-
tillate; 3.75 hr.
exposure
1000 mg/m3 vapors of
C9~C10 aromatic dis-
tillate; 7 hr/day; 5
days/wk; 90 exposures
260 mg/m3 of vapors of
C9~C10 aromatic dis-
tillate; 7 hr/day; 5
days/wk; 90 exposures
300 or 1280 mg/m3 vapors
of Cn~Ci2 of aromatic
distillate; 7 hr/day; 5
days/wk; 90 exposures
100 mg/m3 deodorized
kerosene aerosol;
6 hr/day; 5 days/wk
for 13 weeks
20 mg/m3 given as above
6400 mg/m3 deodorized
kerosene aerosol; 6
hours/day for 14 days
Results
slight depression in
breathing rate; no
respiratory tract
irritation
Acute LC
50
Acute LC
50
hair loss; dry skin;
sedation; tremor; leuko-
cytopenia; neutrophilia;
lymphocytopenia; decreased
erythrocytic and myelocytic
precursors in bone marrow
elevated hematocrit;
leukocytopenia; neutro-
philia; lymphocytopenia
eye and skin irritation;
diarrhea; neutrophilia;
lymphocytopenia; increased
erythrocytic and decreased
myelocytic precursors in
bone marrow
no adverse effects
mean weight increase
no adverse effects
-------
TABLE 1 (Cont'd)
Animal Toxicity Resulting from
Aerosol Exposure to Oils
Animal
Experimental Data
Results
2. Lubricating Oils
Acute exposure
6 albino
mice
7 albino
mice
6 albino
mice
13 albino
mice
4330 mg/m3 aerosol
of S.A-E. 10 motor
oil? 2 hr exposure
4330 mg/m3 aerosol
of S.A.E. 10 motor
oil; 92 hr exposure
total (intermittent
schedule)
4500 mg/m^ aerosol
of S.A.E. 10 motor
oil; 2 hr exposure
4500 mg/m^ aerosol
of S.A.E. 10 motor
oil; 90 hr exposure
total (intermittent
schedule)
oil retention in terminal
bronchioles and alveolar
ducts; vigorous oil
phagocytosis
one death; heavy oil reten-
tion in all divisions of
respiratory tree; pneumonia;
coalescence of oil into giant
droplets (>_ 30 diameter)
2 deaths; oil retention in
terminal bronchioles and
alveolar ducts; vigorous
oil phagocytosis
increased macrophage'S and
foam ceils in alveolar lumina
and septae; oil deposition
in 2 weeks; decreaecl ATP
activity of macrophages;
focal oil granulomas and
pneumonia in 3 weeks
Chronic exposure
6 rhesus
monkeys
80 white
mice
132 mg/m3 aerosol
of S.A.E. 10 motor
oil; 100 days;
schedule of 30 min
aerosol alternating
with 30 min air room
same as for monkeys
3 deaths; oil accumulation in
lungs followed by gradual
clearing over one year; pneu-
monia; bronchiolitis; pulmona
fibres is; pulmonary edema;
weight loss; atrophic stomach
fur loss
gradual accumulation in lung
macrophages in peripheral
and subpleural alveoli; no
free oil; oil macrophages in
tracheobronchial lymph nodes;
minimal toxicity
-------
TABLE 1 (Cont'd)
Animal Toxicity Resulting from
Aerosol Exposure to Oils
Animal
Experimental Data
Results
120 mice
160. rats
30 rats
45 rats
5 or 100 mg/m3 aerosol
of lubricating oil;
6 hr/day; 5 days/wk;
12 months
same as for mice
13, 30, or 60 mg/m3
aerosols of industrial
lubricating oils
(without additives);
5 hr/day for 6 months
same as above
lung oil macrophages
scattered randomly; no
major lung response; no
other adverse effects
pulmonary tissue damage
indicated by elevated lung
alkaline phosphatenes;
progressive interstitial
pneumonia only with
higher concentration
serum neuraminic acid levels
increased progressively;
decrease of serum albumin
and leukocyte phagocytic
activity; increased serum
globulins
leukopenia; increased para-
sympathetic tone; decrease in
weight gain rate; decreased
respiratory rate; increased
neuromuscular excitability
threshold; pulmonary infil-
tration and inflammation;
liver, kidney, heart and
adrenal degeneration
3. White Oils
20 rats
Acute exposure
30,000 mg/m3 aerosol
of mineral oil 6 hr/
day for 3 weeks
increased macrophages and
foam cells in alveolar lumina
and septae; oil deposition
in 2 weeks; decreased ATP
activity of macrophages;
focal oil granulomas and
pneumonia in 3 weeks
-------
TABLE 1 (Cont'd)
Animal Toxicity Resulting from
Aerosol Exposure to Oils
Animal
Experimental Data
Results
Chronic Exposure
218 hamsters
46 rabbits
18 dogs
5 or 100 mg/m3 aerosol
of mineral oil;
5 days/wk; 6 hr/day;
26 months
same as above
same as above
no major lung tissue
response; presence of oil
macrophages in alveoli;
no other pathological
findings
no adverse effects
pulmonary tissue damage
indicated by elevated lung
alkaline phosphatenes;
scattering and coalescence
of oil droplets in lungs;
granuiomas with intra-
cellular oil droplets
-------
TABLE 2
Animal Toxicity Resulting from
Dermal Exposure to Oil
Animal
Expermental Data
Results
1. Middle Distillates
Wistar rats
5 albino
guinea pigs
albino guinea
pigs
20 guinea pigs
10 white
Belgian
rabbits
79 mice
100 mice
undiluted diesel fuel
applied to tail skin
6 hr/day for 10 days
diesel fuel applied
to intracapular skin
5 times/wk for 19 days
various petroleum fuel
distillates applied to
skin every other day;
4 applications total
Landsteiner and Jacobs
skin sens itization
method with diesel fuel
Draize method with
diesei fuel
0.10-0.15 g/animal of
C$-Ci2 aromatic dis-
tillate applied to
skin 3 times/wk; 150
applications total
intrascapular skin;
daily application of
light grade diesel
fuels
dermatitis; hair loss;
decreased hemoglobin;
erythrocytpotenia
reticulocytosis;
leukocytosis; neutro-
philia; lymphocytopenia
erythema; desquamation;
hair loss; ulceration;
and crusting
hyperplasia; hyper-
keratosis; hair loss;
aromatic fuels more toxic
than paraffinic fuels
no skin sensitization
mild pimary irritant to
skin and conjunctiva
dry, thick, scaly skin;
hyperkeratosis; epidermal
atrophy; dermatitis;
ulcerat ion
dermatitis
-------
Animal Toxicity Resulting from
Dermal Exposure to Oil
Animal
Experimental Data
Result
2. Lubricating Oils
albino guinea
pigs
0.6 ml/animal of yellow
lubricating oil
desquamation and
hyperkeratos Ls
3 . White Oils
two Holstein
Friesian
calves
albino guinea
pigs
0.13 ml/kg of body-
weight/day of white
lubricating oil for
8 weeks applied to
skin
0.6 ml/animal of white
lubricating oil applied
to skin every other day
for 4 days
no gross skin
pathology
slight erythema
and desquamation
,.c
6°504
-------
TABLE 3
Animal Toxicity Resulting from
Oral Adminstration of Oils
Animal
Experimental Data
Results
1. Middle Distillates
Wistar rats
138 Wistar
rats
5 Wistar
rats
10 rabbits
cow
ewe
20-25 ml/kg of body-
weight/day diesel oil
by gastric intubation
for 14 days
16.0 ml/kg of body-
weight diesel oil by
gastric intubation
6.9 ml/kg of body-
weight/day diesel oil
by gastric intubation
for approx. 3 weeks
1.0 ml/kg of body-
weight of fuel oil
orally
approx. 7 liters of
diesel fuel ingested
accidently
ingestion of diesel
fuel-soaked grass
hemoglobinemia; reticulo-
cytosis; neutrophilia;
lymphocytopenia; thrombo-
cytopenia; elevated serum
raalate dehydrogenase,
apartate and alanine
aminotransferase
acute oral LD5Q
subacute LD5Q
23% drop in blood sugar
in 5-7 hr; return to
normal levels by 12 hr.
low grade fever; diarrhea;
constipation; lowered milk
production; stiff uncertain
gait; swelling of hind fet-
locks; recovery in 8 days
weakness; weight loss;
nodular lesions on inner
rumen wall; complete loss
of fleece; neutrophilia;
2. Lubricating Oils
mice
chronic ingestion of
spindle oil for 20-
90 weeks (dose not
specified)
fatty infiltration and
degeneration of liver,
spleen, overy and
adrenals
-------
TABLE 3 (Cont'd)
Animal Toxicity Resulting from
Oral Adminstration of Oils
Animal
Experimental Data
Results
3. White oils
mice
rats
1 monkey
1 monkey
20 mi/kg of body-
weight/day of white
mineral oil ingested
with diet
5 ml/kg of body-
weight/day of white
mineral oil ingested
with diet
2.2 ml/kg of body-
weight/day of white
mineral oil in diet;
total consumption
96 ml
1.1 ml/kg of body-
weight/day of white
mineral oil in duct;
total consumption
36 ml
rough, dry skin; pilo-
erection; restlessness;
weight loss in 5 days;
all died by 7 days; fatty
degeneration of liver;
proliferation of reticulo-
endothelial cells of spleen;
epidermal hyperkeratosis;
renal tubular degeneration
same as above in mice
weight loss; diarrhea;
death in 3 weeks; hepatic
and renal congestion;
ulceration and inflammation
of colon, heart, lung and
spleen
diarrhea; weight loss;
death in 11 days; same
pathological findings
as above
1 monkey
1.1 ml/kg of body-
weight/day of white
mineral oil in duct;
total consumption
195 ml in 3 months
no adverse effects;
slight hepatic and renal
congestion
-------
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