ENVIRONMENTAL CONTAMINANTS ENCYCLOPEDIA

FUEL OIL, GENERAL ENTRY

July 1, 1997

COMPILERS/EDITORS: 

ROY J. IRWIN, NATIONAL PARK SERVICE

WITH ASSISTANCE FROM COLORADO STATE UNIVERSITY

STUDENT ASSISTANT CONTAMINANTS SPECIALISTS:

MARK VAN MOUWERIK

LYNETTE STEVENS

MARION DUBLER SEESE

WENDY BASHAM

NATIONAL PARK SERVICE 

WATER RESOURCES DIVISIONS, WATER OPERATIONS BRANCH

1201 Oakridge Drive, Suite 250

FORT COLLINS, COLORADO 80525 
WARNING/DISCLAIMERS: 

Where specific products, books, or laboratories are

mentioned, no official U.S. government endorsement is

implied. 

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This document was put together by human beings, mostly by

compiling or summarizing what other human beings have

written. Therefore, it most likely contains some

mistakes and/or potential misinterpretations and should

be used primarily as a way to search quickly for basic

information and information sources. It should not be

viewed as an exhaustive, "last-word" source for critical

applications (such as those requiring legally defensible

information). For critical applications (such as

litigation applications), it is best to use this document

to find sources, and then to obtain the original

documents and/or talk to the authors before depending too

heavily on a particular piece of information.

Like a library or most large databases (such as EPA's

national STORET water quality database), this document

contains information of variable quality from very

diverse sources. In compiling this document, mistakes

were found in peer reviewed journal articles, as well as

in databases with relatively elaborate quality control

mechanisms [366,649,940]. A few of these were caught

and marked with a "[sic]" notation, but undoubtedly

others slipped through. The [sic] notation was inserted

by the editors to indicate information or spelling that

seemed wrong or misleading, but which was nevertheless

cited verbatim rather than arbitrarily changing what the

author said. Most likely additional transcription errors and typos

have been added in some of our efforts. Furthermore,

with such complex subject matter, it is not always easy

to determine what is correct and what is incorrect,

especially with the "experts" often disagreeing. It is

not uncommon in scientific research for two different

researchers to come up with different results which lead

them to different conclusions. In compiling the

Encyclopedia, the editors did not try to resolve such

conflicts, but rather simply reported it all.
It should be kept in mind that data comparability is a

major problem in environmental toxicology since

laboratory and field methods are constantly changing and

since there are so many different "standard methods"

published by EPA, other federal agencies, state agencies,

and various private groups. What some laboratory and

field investigators actually do for standard operating

practice is often a unique combination of various

standard protocols and impromptu "improvements." In

fact, the interagency task force on water methods

concluded that [1014]:

It is the exception rather than the rule that

water-quality monitoring data from different

programs or time periods can be compared on a

scientifically sound basis, and that...

No nationally accepted standard definitions exist

for water quality parameters. The different

organizations may collect data using identical or

standard methods, but identify them by different

names, or use the same names for data collected by

different methods [1014].

Differences in field and laboratory methods are also

major issues related to (the lack of) data comparability

from media other than water: soil, sediments, tissues,

and air. 

In spite of numerous problems and complexities, knowledge

is often power in decisions related to chemical

contamination. It is therefore often helpful to be aware

of a broad universe of conflicting results or conflicting

expert opinions rather than having a portion of this

information arbitrarily censored by someone else.

Frequently one wants to know of the existence of

information, even if one later decides not to use it for

a particular application. Many would like to see a high

percentage of the information available and decide for

themselves what to throw out, partly because they don't

want to seem uniformed or be caught by surprise by

potentially important information. They are in a better

position if they can say: "I knew about that data,

assessed it based on the following quality assurance

criteria, and decided not to use it for this

application." This is especially true for users near the

end of long decision processes, such as hazardous site

cleanups, lengthy ecological risk assessments, or complex

natural resource damage assessments.

For some categories, the editors found no information and

inserted the phrase "no information found." This does

not necessarily mean that no information exists; it
simply means that during our efforts, the editors found

none. For many topics, there is probably information

"out there" that is not in the Encyclopedia. The more

time that passes without encyclopedia updates (none are

planned at the moment), the more true this statement will

become. Still, the Encyclopedia is unique in that it

contains broad ecotoxicology information from more

sources than many other reference documents. No updates

of this document are currently planned. However, it is

hoped that most of the information in the encyclopedia

will be useful for some time to come even with out

updates, just as one can still find information in the

1972 EPA Blue Book [12] that does not seem well

summarized anywhere else. 

Although the editors of this document have done their

best in the limited time available to insure accuracy of

quotes or summaries as being "what the original author

said," the proposed interagency funding of a bigger

project with more elaborate peer review and quality

control steps never materialized. 

The bottom line: The editors hope users find this

document useful, but don't expect or depend on

perfection herein. Neither the U.S. Government nor

the National Park Service make any claims that this

document is free of mistakes.

The following is one chemical topic entry (one file among

118). Before utilizing this entry, the reader is

strongly encouraged to read the README file (in this

subdirectory) for an introduction, an explanation of how

to use this document in general, an explanation of how to

search for power key section headings, an explanation of

the organization of each entry, an information quality

discussion, a discussion of copyright issues, and a

listing of other entries (other topics) covered. 

See the separate file entitled REFERENC for the identity

of numbered references in brackets. 

HOW TO CITE THIS DOCUMENT: As mentioned above, for

critical applications it is better to obtain and cite the

original publication after first verifying various data

quality assurance concerns. For more routine

applications, this document may be cited as:

Irwin, R.J., M. VanMouwerik, L. Stevens, M.D.

Seese, and W. Basham. 1997. Environmental

Contaminants Encyclopedia. National Park Service,

Water Resources Division, Fort Collins, Colorado.

Distributed within the Federal Government as an

Electronic Document (Projected public availability

on the internet or NTIS: 1998).
Fuel Oil, General

Brief Introduction:

Br.Class: General Introduction and Classification

Information:

The purpose of this entry is to provide an overview on

fuel oils in general. For specific information on a

particular type of fuel oil, see the following entries:

Kerosene (Fuel Oil Number 1), Fuel Oil Number 2, Fuel Oil

Number 4, Fuel Oil Number 5, and Fuel Oil Number 6.

Fuel oils are comprised of mixtures of petroleum

distillate hydrocarbons [363,499]. The various kinds of

fuel oils are obtained by distilling crude oil, and

removing the different fractions.

Fuel oil is any liquid petroleum product that is burned

in a furnace for the generation of heat or used in an

engine for the generation of power, except oils having a

flash point of approximately 100 degrees F and oils

burned in cotton or wool-wick burners. The oil may be a

distillated fraction of a crude petroleum, a residuum

from refinery operations, or a blend of these [498]. 

Fuel oil numbers 1 and 2 are referred to as distillate

fuels oil, while fuel oil numbers 4, 5, and 6 are

labelled residual [747] (see the

Forms/Preparations/Formulations section below). Two

major categories of fuel oil are burned by combustion

sources: distillate oils and residual oils [663]. These

oils are further distinguished by grade numbers, with

Nos. 1 and 2 being distillate oils; Nos. 5 and 6 being

residual oils; and No. 4 either distillate oil or a

mixture of distillate and residual oils [663]. No. 6

fuel oil is sometimes referred to as Bunker C [663]. 

According to the USCG Emergency Response Notification

System (1993), fuel oils are some of the top most spilled

petroleum hydrocarbon products in U.S. waters, both by

volume and the number of notifications [635]. 

Diesel oils are among the products considered "fuel oils"

in a broad sense [962] (see Diesel Oil entries).

Br.Haz: General Hazard/Toxicity Summary:

The most toxic components of fuel oils are the aromatics,

such as benzene, toluene, xylene, naphthalene and others.

These aromatics are relatively highly soluble in water.

After the aromatic fraction, toxicity decreases from
olefins through naphthenes to paraffins. Within each of

these groups, the lower molecular weight hydrocarbon

tends to be more acutely toxic [641]. 

Fuel oils have a moderately broad range of volatility and

solubility [777]. For example, fuel 1 and 2 are

moderately soluble and volatile, while fuel 4, 5, and 6

are not very soluble [777]. Short-term toxicity decreases

as the type of fuel oil becomes less volatile (that is,

no. 1 and 2 are moderately toxic, while toxicity

decreases through no.4, no.5, and no.6) [641]. Fuel 1

and 2 possesses moderate to high acute toxicity to biota

with product-specific toxicity related to the type and

concentration of aromatic compounds, while fuels 5 and 6

are considered to be less acutely toxic relative to other

oil types [777]. Fuel 4 has variable acute toxicity,

depending on the amount of light fraction [777].

Short-term hazards of some of the lighter, more volatile

and water soluble compounds (such as toluene,

ethylbenzene, and xylenes) in fuel oils include potential

acute toxicity to aquatic life in the water column

(especially in relatively confined areas) as well as

potential inhalation hazards. Fuel oil spills could

result in potential acute toxicity to some forms of

aquatic life. Oil coating of birds, sea otters, or other

aquatic life which come in direct contact with the

spilled oil is another potential short-term hazard. In

the short term, spilled oil will tend to float on the

surface; water uses threatened by spills include:

recreation; fisheries; industrial, potable supply; and

irrigation [608]. 

Long-term potential hazards of some of the lighter, more

volatile and water soluble compounds (such as toluene and

xylenes) in fuel oils include contamination of

groundwater. Long-term water uses threatened by spills

include potable (ground) water supply. Chronic effects

associated with middle distillates are mainly due to

exposure to aromatic compounds [661]. 

Long-term effects are also associated with polycyclic

aromatic hydrocarbons (PAHs), alkyl PAHs, and alkyl

benzene (such as xylene) constituents of fuel oil.

Although PAHs, particularly heavy PAHs, do not make up a

large percentage of distillate fuel oils by weight, there

are some PAHs in these fuel oils, including naphthalene,

alkyl naphthalenes, phenanthrene, and alkyl phenanthrenes

[177,747]. Residual fuel oils may contain considerable

amounts of PAHs [177,747]. Due to their relative

persistence and potential for various chronic effects,

PAHs (particularly the alkyl PAHs) can contribute to

long-term (chronic) hazards of fuel oils in contaminated

soils, sediments, and groundwater. Chronic effects of
some of the constituents in fuel oils (toluene, xylene,

naphthalenes, alkyl benzenes, and various alkyl PAHs)

include changes in the liver and harmful effects on the

kidneys, heart, lungs, and nervous system. Increased

rates of cancer, immunological, reproductive, fetotoxic,

genotoxic effects have also been associated with some of

the compounds found in fuel oils (see entries on

individual compounds for more details). 

Further detail on potential risks for PAHs in

this product: Acute toxicity is rarely

reported in humans, fish, or wildlife, as a

result of exposure to low levels of a single

PAH compound. PAHs in general are more

frequently associated with chronic risks.

These risks include cancer and often are the

result of exposures to complex mixtures of

chronic-risk aromatics (such as PAHs, alkyl

PAHs, benzenes, and alkyl benzenes), rather

than exposures to low levels of a single

compound. This product is an example of such

a complex mixture (Roy Irwin, National Park

Service, Personal Communication, 1996, based

on an overview of literature on hand). 

See also: PAHs as a group entry. 

Exposure to petroleum in soil is predominantly of concern

through a number of possible exposure pathways, including

dermal contact with soil, ingestion of soil, inhalation

of soil particulates, and ingestion of contaminated

groundwater [824].

Many of the PAHs found in this product (see Chem.Detail

section below) are phototoxic, that is they display

greatly enhanced toxicity in sunlight or other UV source

than elsewhere (see PAHs as a group entry).

Summaries of the hazards to humans and animals of many of

the aromatic and alkane constituents and additives in

fuel oils were summarized by the Air Force Installation

Restoration Program in 1990; hexane may be the most

highly toxic of the alkanes [875]. Many of the alkanes

are CNS depressants and general irritants [875]. 

See also: ATSDR toxicological profile on fuel oils 1

(kerosene), 1-D, 2, 2-D, and 4 [962].

Br.Car: Brief Summary of Carcinogenicity/Cancer Information:

Distillate fuel oils (no. 1 and 2) are not classifiable

as to their carcinogenicity to humans [747]. However,

certain carcinogenic effects have been associated with
some of the other compounds found in distillate fuel oils

(see entries on individual compounds for more details).

There is sufficient evidence for the carcinogenicity in

experimental animals of residual (heavy) fuel oils and

cracked residues derived from the oil refining of crude

oil [747]. Residual (heavy) fuel oils are possibly

carcinogenic to humans [747].

The debates on which PAHs, alkyl PAHs, and other

aromatics in complex mixtures such as this product to

classify as carcinogens, and the details of exactly how

to perform both ecological and human risk assessments on

the complex mixtures of PAHs typically found at

contaminated sites, are likely to continue. There are

some clearly wrong ways to go about it, but defining

clearly right ways is more difficult. PAHs usually occur

in complex mixtures rather than alone. Perhaps the most

unambiguous thing that can be said about complex PAH

mixtures is that such mixtures are often carcinogenic and

possibly phototoxic. One way to approach site specific

risk assessments would be to collect the complex mixture

of PAHs and other lipophilic contaminants in a

semipermeable membrane device (SPMD, also known as a fat

bag) [894,895,896], retrieve the contaminant mixture from

the SPMD, then test the mixture for carcinogenicity,

toxicity, and phototoxicity (James Huckins, National

Biological Service, and Roy Irwin, National Park Service,

personal communication, 1996).

Painting Fuel Oil 2 on mice was positive for

carcinogenesis [875].

See also: the ATSDR toxicological profile on fuel oils 1

(kerosene), 1-D, 2, 2-D, and 4 [962].

See Chem.Detail section for compounds in this product,

then see individual compound entries for summaries of

information on individual components of this mixture.

See also: PAHs as a group entry.

Br.Dev: Brief Summary of Developmental, Reproductive,

Endocrine, and Genotoxicity Information:

The results are mixed, but some immunological,

reproductive, fetotoxic, and genotoxic effects have been

associated with a few of the compounds found in fuel oils

[764,765,766,767] (see entries on individual compounds

for more details). 

Some of the PAHs found in fuel oil are either AHH active

or endocrine disruptors [561].
See also: ATSDR toxicological profile on fuel oils 1

(kerosene), 1-D, 2, 2-D, and 4 [962].

Br.Fate: Brief Summary of Key Bioconcentration, Fate,

Transport, Persistence, Pathway, and Chemical/Physical

Information:

Distillate oils are more volatile and less viscous than

residual oils. They have negligible nitrogen and ash

contents and usually contain less than 0.3 percent sulfur

(by weight) [663]. 

Because residual oils are produced from the residue

remaining after the lighter fractions (gasoline,

kerosene, and distillate oils) have been removed from the

crude oil, they contain significant quantities of ash,

nitrogen, and sulfur [663]. 

Fuel oils have a broad range of volatility and mobility

[661]. Most fuel oils contain a combination of lighter,

less persistent and more mobile compounds as well as

heavier, more persistent and less mobile compounds. The

general amount of these two groups of components varies

by fuel type (for example, fuel 1 contains more lighter

components, while fuel 6 contains more heavier

components). These two different groups are associated

with two distinctly different patterns of fate/pathway

concerns: 

The relatively lighter, more volatile, mobile, and

water soluble compounds in fuel oils will tend to

evaporate fairly quickly into the atmosphere or

migrate to groundwater. When exposed to oxygen and

sunlight, most of these compounds will tend to

break down relatively quickly. However, in

groundwater, many of these compounds tend to be

more persistent than in surface water, and readily

partition on an equilibria basis back and forth

between water and solids (soil and sediment) media.

Cleaning up groundwater without cleaning up soil

contamination will usually result in a rebound of

higher concentrations of these compounds

partitioning from contaminated soils into

groundwater (Roy Irwin, Personal Communication,

1995).

The compounds in fuel oils which will tend to be

somewhat more persistent and more bound to solid

particles will include the PAHs, alkyl PAHs, and

alkyl benzenes. Higher concentrations of heavier

PAHs will tend to be in adjacent contaminated soils

than in groundwater, but cleaning up groundwater

without cleaning up soil contamination will
nevertheless usually result in at least some

rebound of higher concentrations of these compounds

partitioning from contaminated soils into

groundwater (Roy Irwin, personal communication).

Petroleum distillates in order of decreasing volatility

include [363]:

 1. Petroleum ether or benzene

 2. Gasoline

 3. Naphtha

 4. Mineral spirits

 5. Kerosene 

 6. Fuel oils

 7. Lubricating oils

 8. Paraffin wax

 9. Asphalt or tar.

LAPIO, a particularly heavy kind of Fuel Oil 6, can float,

sink, become neutrally buoyant, or fractionate and possess all

three characteristics, it poses significantly different risks

to natural resources, compared to floating oil spills [775].

For details see Fate.Detail section below.

See also: ATSDR toxicological profile on fuel oils 1

(kerosene), 1-D, 2, 2-D, and 4 [962].

Synonyms/Substance Identification:

No information found; see Chem.Detail section for compounds in

this product, then see individual compound entries for

summaries of information on individual components of this

mixture.

Associated Chemicals or Topics (Includes Transformation

Products):

See also individual entries: 

Kerosene (Fuel Oil Number 1)

Fuel Oil Number 2

Fuel Oil Number 4

Fuel Oil Number 5

Fuel Oil Number 6

LAPIO (A very heavy #6 fuel oil) [775].

Petroleum, General

Oil Spills

PAHs as a group

Site Assessment-Related Information Provided by Shineldecker

(Potential Site-Specific Contaminants that May be Associated

with a Property Based on Current or Historical Use of the

Property) [490]:
Raw Materials, Intermediate Products, Final Products, and

Waste Products Generated During Manufacture and Use:

& Benzene

& Creosote

& Ethyl benzene

& Polynuclear aromatic hydrocarbons

& Toluene

& Xylenes

Water Data Interpretation, Concentrations and Toxicity (All Water

Data Subsections Start with "W."):

W.Low (Water Concentrations Considered Low):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

W.High (Water Concentrations Considered High):

Water Information on Fuel Oils from ATSDR [962] (see

ATSDR for identification of embedded references): 

Analysis of drinking water from Cincinnati, Ohio,

in February of 1980, showed the presence of

numerous hydrocarbons associated with petroleum

products at concentrations ranging from 5 ng/L for

naphthalene to 843 ng/L for benzene (Coleman et

al. 1984). Kerosene was detected at monitoring

wells (concentrations were not reported) located

at the perimeter of a spent nuclear fuel processing

plant in western New York State in 1983. The

kerosene had been used as an extractant during

plant operations from 1966 to 1972 (DOE 1989c).

Groundwater samples taken from monitoring wells at

gasoline stations undergoing remediation in

Florida contained both kerosene and fuel oil at

unspecified concentrations (Thomas and Delfino

1991a). Fuel oil no. 2 was detected along with

gasoline in groundwater wells in Tiverton, Rhode

Island. Over a 19-month period, total hydrocarbon

concentrations in the water from one well decreased

from 2,350 to 1,580 ug/L during which time the

proportion of hydrocarbons associated with fuel

oil increased from 42% (987 ug/L) to 78% (1,232

ug/L), probably as a result of the more rapid

degradation of the gasoline (Zheng and Quinn

1988). Kerosene was detected in a whole water

sample from monitoring wells for municipal intakes

in California in the ug/L range (STORET 1992).

Background concentrations of total hydrocarbons in
Narragansett Bay, Rhode Island, ranged from 0.7 to

4.0 ug/L (Gearing and Gearing 1982a). 5.4.3 Soil

No data were located on levels of fuel oils

detected in soils. 

No other information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

W.Typical (Water Concentrations Considered Typical):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

W.Concern Levels, Water Quality Criteria, LC50 Values, Water

Quality Standards, Screening Levels, Dose/Response Data, and

Other Water Benchmarks:

W.General (General Water Quality Standards, Criteria, and

Benchmarks Related to Protection of Aquatic Biota in

General; Includes Water Concentrations Versus Mixed or

General Aquatic Biota):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

W.Plants (Water Concentrations vs. Plants):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

W.Invertebrates (Water Concentrations vs. Invertebrates):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

W.Fish (Water Concentrations vs. Fish):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

W.Wildlife (Water Concentrations vs. Wildlife or Domestic

Animals):
No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

W.Human (Drinking Water and Other Human Concern Levels):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

W.Misc. (Other Non-concentration Water Information):

Petroleum is a complex mixture of thousands of different

hydrocarbons and related substances, all with different

physical and chemical properties [770]. As such,

determination of the fate and toxicity of a particular

oil is a difficult task. Solubility-fate relationships

must be considered. Generally, the relative toxicity of

an oil will be the result of the fractional toxicities of

the different hydrocarbons present in the aqueous phase

[770]. In an often referenced study, the quantitative

hydrocarbon composition and behavior in seawater of

water-soluble fractions (WSF) and oil-in-water

dispersions (OWD) of 4 oils was investigated (namely

South Louisiana crude, Kuwait crude, and two refined oils

- No. 2 fuel oil and bunker C residual oil) [770]. In

the study, differences in the solubilities and

composition of the test oils were described, as well as

variations in sensitivity to oil of several marine

species. One of the findings of this study is that, at

least with the 4 oils tested in this study, the toxicity

of an oil is largely a function of its di- and triaromatic hydrocarbon content [770]. This and other

findings in this study demonstrate that a prediction of

environmental impact must take into consideration the

specific characteristics of the particular oil spilled as

well as the particular spill environment (that is,

whether the spill occurs in the open sea, or a confined

water body). See the W.Misc section of the Petroleum,

General entry for the complete summary of this study

[770].

Sediment Data Interpretation, Concentrations and Toxicity (All

Sediment Data Subsections Start with "Sed."):

Sed.Low (Sediment Concentrations Considered Low):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.
Sed.High (Sediment Concentrations Considered High):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

Sed.Typical (Sediment Concentrations Considered Typical):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

Sed.Concern Levels, Sediment Quality Criteria, LC50 Values,

Sediment Quality Standards, Screening Levels, Dose/Response

Data and Other Sediment Benchmarks:

Sed.General (General Sediment Quality Standards,

Criteria, and Benchmarks Related to Protection of Aquatic

Biota in General; Includes Sediment Concentrations Versus

Mixed or General Aquatic Biota):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Sed.Plants (Sediment Concentrations vs. Plants):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Sed.Invertebrates (Sediment Concentrations vs.

Invertebrates):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Sed.Fish (Sediment Concentrations vs. Fish):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Sed.Wildlife (Sediment Concentrations vs. Wildlife or

Domestic Animals):

No information found; see Chem.Detail section for
compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Sed.Human (Sediment Concentrations vs. Human):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Sed.Misc. (Other Non-concentration Sediment Information):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

Soil Data Interpretation, Concentrations and Toxicity (All Soil

Data Subsections Start with "Soil."):

Soil.Low (Soil Concentrations Considered Low):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

Soil.High (Soil Concentrations Considered High):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

Soil.Typical (Soil Concentrations Considered Typical):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

Soil.Concern Levels, Soil Quality Criteria, LC50 Values, Soil

Quality Standards, Screening Levels, Dose/Response Data and

Other Soil Benchmarks:

Soil.General (General Soil Quality Standards, Criteria,

and Benchmarks Related to Protection of Soil-dwelling

Biota in General; Includes Soil Concentrations Versus

Mixed or General Soil-dwelling Biota):

No information found; see Chem.Detail section for

compounds in this product, then see individual
compound entries for summaries of information on

individual components of this mixture.

Soil.Plants (Soil Concentrations vs. Plants):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Soil.Invertebrates (Soil Concentrations vs.

Invertebrates):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Soil.Wildlife (Soil Concentrations vs. Wildlife or

Domestic Animals):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Soil.Human (Soil Concentrations vs. Human):

No information found on this complex and variable

mixture. See Chem.Detail section for chemicals

found in this product, then look up information on

each hazardous compound. Some individual compounds

found in petroleum products have low-concentration

human health benchmarks for soil (see individual

entries).

Soil.Misc. (Other Non-concentration Soil Information):

As of 1996, several States were considering allowing

natural attenuation (the "do nothing and let nature clean

up the mess through bioremediation" option) to proceed

near leaking storage tanks in situations where drinking

water was not being impacted and where human rather than

environmental resources were the main resources in the

immediate area (Roy Irwin, National Park Service,

personal communication, 1996). 

The trend of thinking towards natural attenuation was

given a boost by a Lawrence Livermore National Laboratory

(LLNL) report entitled "Recommendations to Improve the

Cleanup Process for California's Leaking Underground Fuel

Tanks;" which stressed the use of passive bioremediation

for petroleum product contaminated soils, whenever

possible, based on the relatively low number of cases
where drinking water was impacted [969]. EPA has pointed

out some limitations of the LLNL report, including the

lack of adequate consideration of PAHs and additives such

as MTBE, as well limited consideration of (non-human)

exposure pathways and various geologic conditions [969].

Others would point out that fuel oil spills into soils

are not necessarily a trivial environmental threat

related to ecotoxicology (emphasis on living things other

than humans), due to the many hazardous compounds in fuel

oils (see Chem.Detail section below).

Exposure to petroleum in soil is predominantly of concern

through a number of possible exposure pathways, including

dermal contact with soil, ingestion of soil, inhalation

of soil particulates, and ingestion of contaminated

groundwater [824].

No other information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

Tissue and Food Concentrations (All Tissue Data Interpretation

Subsections Start with "Tis."):

Tis.Plants:

A) As Food: Concentrations or Doses of Concern to Living

Things Which Eat Plants:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

B) Body Burden Residues in Plants: Typical, Elevated, or

of Concern Related to the Well-being of the Organism

Itself:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Tis.Invertebrates:

A) As Food: Concentrations or Doses of Concern to Living

Things Which Eat Invertebrates:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on
individual components of this mixture.

B) Concentrations or Doses of Concern in Food Items

Eaten by Invertebrates:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

C) Body Burden Residues in Invertebrates: Typical,

Elevated, or of Concern Related to the Well-being of the

Organism Itself:

Information on Fuel Oils from ATSDR [962] (see

ATSDR for identification of embedded references): 

Shellfish taken from unpolluted waters have

been found to contain between 1 and 12 ug/g

wet weight of total hydrocarbons while fish

have been found to contain between 4 and 14

ug/g total hydrocarbons (steam distillables)

(Connell and Miller 1980). Following a spill

of fuel oil no. 2 in the Cape Cod Canal in

Massachusetts, edible mussels ( Mytilus

edulis ) contained average concentrations of

various hydrocarbons up to 4.69 ug/g dry

weight on day 1 of the spill; background

hydrocarbon levels in the controls did not

exceed 0.29 ug/g (Farrington et al. 1982a).

Limpets in close proximity to onshore

accumulations of hydrocarbon contaminants

caused by diesel fuel spillage and leakage

related to ship and boating activities in

Arthur Harbor on the Antarctic Peninsula have

incorporated PAHs into their tissues

(Kennicutt et al. 1992b). However, 2 years

after the release of 150,000 gallons of

diesel fuel in the harbor, little spillrelated contamination could be detected in

intertidal limpets (Kennicutt and Sweet 1992).

No data were located that discussed

concentrations of fuel oils in other

environmental media such as food or

terrestrial plants and animals [962].

No other information found; see Chem.Detail section

for compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Tis.Fish:

A) As Food: Concentrations or Doses of Concern to Living
Things Which Eat Fish (Includes FDA Action Levels for

Fish and Similar Benchmark Levels From Other Countries):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

B) Concentrations or Doses of Concern in Food Items

Eaten by Fish:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

C) Body Burden Residues in Fish: Typical, Elevated, or of

Concern Related to the Well-being of the Organism Itself:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Tis.Wildlife: Terrestrial and Aquatic Wildlife, Domestic

Animals and all Birds Whether Aquatic or not:

A) As Food: Concentrations or Doses of Concern to Living

Things Which Eat Wildlife, Domestic Animals, or Birds:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

B) Concentrations or Doses of Concern in Food Items

Eaten by Wildlife, Birds, or Domestic Animals (Includes

LD50 Values Which do not Fit Well into Other Categories,

Includes Oral Doses Administered in Laboratory

Experiments):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

C) Body Burden Residues in Wildlife, Birds, or Domestic

Animals: Typical, Elevated, or of Concern Related to the

Well-being of the Organism Itself:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.
Tis.Human:

A) Typical Concentrations in Human Food Survey Items:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

B) Concentrations or Doses of Concern in Food Items

Eaten by Humans (Includes Allowable Tolerances in Human

Food, FDA, State and Standards of Other Countries):

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

C) Body Burden Residues in Humans: Typical, Elevated, or

of Concern Related to the Well-being of Humans:

No information found; see Chem.Detail section for

compounds in this product, then see individual

compound entries for summaries of information on

individual components of this mixture.

Tis.Misc. (Other Tissue Information):

No information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual

components of this mixture.

Bio.Detail: Detailed Information on Bioconcentration,

Biomagnification, or Bioavailability:

No information found; see Chem.Detail section for compounds in

this product, then see individual compound entries for

summaries of information on individual components of this

mixture.

Interactions:

No information found; see Chem.Detail section for compounds in

this product, then see individual compound entries for

summaries of information on individual components of this

mixture.

Uses/Sources:

Distillate oils are used mainly in domestic and small

commercial applications [663]. Being more viscous and less

volatile than distillate oils, the heavier residual oils (Nos. 5
and 6) must be heated for ease of handling and to facilitate proper

atomization. Residual oils are used mainly in utility, industrial,

and large commercial applications [663]. See the

Forms/Preparations/Formulations section below. 

Forms/Preparations/Formulations:

Because fuel oils are used with burners of various types and

capacities, different grades are required. ASTM has developed

specifications for six grades of fuel oil, namely numbers 1, 2, 4,

5, and 6 [498]: 

Fuel oil No 1 (essentially the same composition as kerosene)

is a straight-run distillate used almost exclusively for

domestic heating. 

Fuel oil No 2 (diesel oil and heating oil) is a straight-run

or cracked distillate used as a general purpose domestic or

commercial fuel in atomizing-type burners.

Fuel oil No 4 is made up of heavier straight-run or cracked

distillates and is used in commercial or industrial burner

installations not equipped with preheating facilities. 

The viscous residuum fuel oils, Nos 5 and 6, sometimes

referred to as bunker fuels B and C, respectively, usually

must be preheated before being burned. These fuels are used in

furnaces and boilers of utility power plants, ships,

locomotives, metallurgical operations, and industrial power

plants. 

Like fuel oil #6, LAPIO (Low-API gravity oils) is a blend of

heavy and light oil, but it generally contains more of the heavier

components. Therefore, LAPIO could be considered as a very heavy

#6 fuel oil [775]. Additional Details about LAPIO:

A low-API gravity fuel oil, or LAPIO, is defined as an oil

having an API gravity less than 10 degrees at 60 degrees F

(see note below). This means that its specific gravity is

less than or equal to 1.00 mg/L (which is the same as

freshwater). Therefore, LAPIOs can float, be neutrally

buoyant, or sink in water depending on the specific properties

of the spilled oil and the salinity of the receiving waters

[775]. LAPIO is an industry term [776].

NOTE:

API gravity = (141.5/specific gravity [60/60

degrees F]) - 131.5

where specific gravity [60/60 degrees F] is the oil

density at 60 degrees F divided by the density of

water at 60 degrees F [560].
Chem.Detail: Detailed Information on Chemical/Physical

Properties:

Caution: Every individual petroleum product has a unique

"fingerprint," or distinct set of constituents most commonly

identified by a gas chromatograph analysis. Due to the

varying properties of the same general category of a petroleum

product (each source and weathering stage of a fuel oil has a

unique gas chromatograph "fingerprint"), careful assessment of

the toxicity, specific gravity, and other physical

characteristics of each individual oil must be taken into

consideration to determine the exact effects of the product on

the environment. Therefore, the below comments on fuel oils

are to be considered as representative, but not absolute

values typical of every batch of the product with the same

name.

Since PAHs are important hazardous components of this product,

risk assessments should include analyses of PAHs and alkyl PAHs

utilizing the NOAA protocol expanded scan [828] or other rigorous

GC/MS/SIM methods.

Octanol Water Log: 3.3 to 7.06 [875].

Henry's Law Const. 5.9E-05 to 7.4 [875].

Physicochemical Information from Hazard Management Data Base [498]:

SPECIFIC GRAVITY

Less than 1 (Fuel oils Nos 1, 2, 4, 5)

1 (+/-) (Fuel oil No 6)

DENSITY

Less than 1 g/cm(3) (Fuel oils Nos 1, 2, 4, 5)

1 (+/-) g/cm(3) (Fuel oil No 6)

SOLUBILITY

Fuel oil is insoluble (sic, actually "relatively insoluble")

in water.

NOTE on Solubility: No exact numbers can be given for

solubilities of fuel oil in water because the composition

of an oil varies from refinery to refinery. Generally,

hydrocarbons of a lower molecular weight are more soluble

than those of a higher molecular weight. Branching of

hydrocarbon isomers, as well as ring formation, also

tends to increase solubility. For two rings with the

same carbon number, an unsaturated ring is more soluble

in water than a saturated ring. The solubility of

hydrocarbons in sea water is less than in fresh water.

Also, an increase in temperature will greatly increase

the amount of hydrocarbons which dissolve in water.

Turbulence will also increase the rate of solubility
[641]. 

FLASH POINT

Fuel oil No 1: 100 to 162 degrees F

Fuel oil No 2: 126 to 204 degrees F

Fuel oil No 4: 142 to 240 degrees F

Fuel oil No 5 (light): 156 to 336 degrees F

Fuel oil No 5 (heavy): 160 to 250 degrees F

Fuel oil No 6: 150 to 270 degrees F

COLOR: Fuel oils are straw yellow to dark colored liquids.

REACTIVITY: When heated to decomposition, fuel oils emit

acrid smoke and irritating fumes. Fuel oils can react

vigorously with oxidizing materials.

The following table summarizes chemical component classes by

percent weight for several representative petroleum products [773]:

CHEMICAL REFINED OILS

COMPONENT (wt %) Gasoline Kerosene* #2 Fuel #6 Fuel

 Oil Oil

Saturates 39.6 85.0 61.8 24.4

Aromatics 46.2 15.0 38.2 54.6 

Polars -- -- 0.0 14.9

Asphaltenes N/A N/A 0.0 6.2

Sulfur (%) 0.07 0.5 0.32 2.0

The following table summarizes the physical properties of several

representative petroleum products [773]:

PHYSICAL REFINED OILS

PROPERTIES Gasoline Kerosene* #2 Fuel #6 Fuel

 Oil Oil

API Gravity** 60.0 37.0 31.6 10.0

Density (at 20C) 0.734 0.83 0.84 0.966

Pour point (C) <-40.0 -18.0 -20.0 6.0

Flash point (C) -40.0 38.0 55.0 80.0

NOTES:

* Kerosene is essentially the same composition as Fuel

Oil #1.

** API gravity = (141.5/specific gravity at 60 F or 15.6

C) - 131.5.

Physical Characteristics and Chemical Properties of Two Refined

Products [558]:

 No. 2 No.6

Characteristic Fuel Bunker C

or Component Oil* Fuel oil
API gravity (20 C) (API)** 31.6 7.3

Sulfur (wt %) 0.32 1.46

Nitrogen (wt %) 0.024 0.94

Nickel (ppm) 0.5 89

Vanadium (ppm) 1.5 73

Saturates (wt %) 61.8 21.1 

 n-paraffins 8.07 1.73

 C10 + C11 1.26 0

 C12 0.84 0

 C13 0.96 0.07

 C14 1.03 0.11

 C15 1.13 0.12

 C16 1.05 0.14

 C17 0.65 0.15

 C18 0.55 0.12

 C19 0.33 0.14

 C20 0.18 0.12

 C21 0.09 0.11

 C22 0 0.10

 C23 0 0.09

 C24 0 0.08

 C25 0 0.07

 C26 0 0.05

 C27 0 0.04

 C28 0 0.05

 C29 0 0.04

 C30 0 0.04

 C31 0 0.04

 C32 Plus 0 0.05

 Isoparaffins 22.3 5.0

 1-ring cycloparaffins 17.5 3.9

 2-ring cycloparaffins 9.4 3.4

 3-ring cycloparaffins 4.5 2.9

 4-ring cycloparaffins 0 2.7

 5-ring cycloparaffins 0 1.9

 6-ring cycloparaffins 0 0.4

Aromatics (wt %) 38.2 34.2

 Benzenes 10.3 1.9

 Indans and tetralins 7.3 2.1

 Dinaphthenobenzenes 4.6 2.0

 Naphthalenes 0.2 b

 Methylnaphthalenes 2.l b 2.6

 Dimethylnaphthalenes 3.2 b

 Other naphthalenes 0.4

 Acenaphthenes 3.8 3.1

 Acenaphthalenes 5.4 7.0

 Phenanthrenes 0 11.6

 Pyrenes 0 1.7

 Chrysenes 0 0

 Benzothiophenes 0.9 1.5

 Dibenzothiophenes 0 0.7

Polar materials c (wt %) 0 30.3

Insolubles (pentane)c (wt %) 0 14.4
* This is a high aromatic material; a typical No. 2 fuel oil would

have an aromatic content closer to 20-25%. From Vaughan (26).

** API gravity = (141.5/specific gravity at 60 F or 16 C) - 131.5.

NOTE: The above analyses represent typical values for two

different refined products; variations in composition can be

expected for similar materials from different crude oil stocks

and different refineries. 

Trimethyl benzenes may occur in this product [875].

Information on LAPIO, a particularly heavy kind of Fuel Oil 6:

Like conventional fuel oil #6 (Bunker C), LAPIOs are

mixtures of the heavy residual oil and lighter oils, but

LAPIOs generally contain more of the heavier components

[775]. The residual oils are derived primarily from

three sources: 1) atmospheric reduced crude, 2) vacuum

bottoms, and 3) heavy slurry oils. LAPIOs are heavy

residual products blended with some other product to meet

client specifications for viscosity, pour point, and

sulfur content, but LAPIOs do not have to meet a minimum

API gravity requirement. The amount and source of the

cutter stock and/or lighter residual oil blended with the

heavier residual oil to meet client specifications varies

widely, so the chemical composition of LAPIO will vary

case by case [775]. For example, fuel oil #2 is a

commonly used blending agent to reduce viscosity in fuel

oil #6, whereas LAPIO may be a blend of just residuals

without any light cutter stock. Sometimes these

residuals are incompatible, leading to asphaltene

precipitation during transportation and storage. This

can lead to changes in the physical properties of the oil

and problems during combustion. Incompatible or nonhomogenous blends can also physically separate into

components that float, sink, and/or become neutrally

buoyant when spilled on the water. When incompatible

blends are simply poured into a beaker full of water,

samples of visually homogenous oil will separate. The

potential for physical separation appears to be unique to

LAPIO [775]. For additional information on sinking oil,

see the Oil Spills entry.

The pour point of a LAPIO is not always high (most < 45

degrees F) due to low paraffin content [776]. Although

LAPIO has been compared to asphalt, this is a poor

analogy. Asphalt rapidly cools to form solid masses,

whereas most LAPIO will remain liquid at ambient

temperatures, will act like fluid when spreading, and is

less likely to be sticky [775].

See also: ATSDR toxicological profile on fuel oils 1

(kerosene), 1-D, 2, 2-D, and 4 [962].
Fate.Detail: Detailed Information on Fate, Transport,

Persistence, and/or Pathways:

The following information is from an assessment of potential

risks associated with the shipment and transfer of LAPIO, a

very heavy type of #6 fuel oil, in the St. John's River,

Florida [775]:

Because LAPIO can float, sink, become neutrally

buoyant, or fractionate and possess all three

characteristics, it poses significantly different

risks to natural resources, compared to floating

oil spills, for the following reasons [775]:

1. Neutrally buoyant or sinking LAPIO

weathers very slowly by evaporation, a

process that tends to remove the more

toxic fractions from floating oil slicks

and greatly reduces the acute toxicity of

the spilled oil. As a result, the toxic

components of a LAPIO spill are

introduced directly into the water column

at concentrations greater than

traditional spills. Animals in the water

column, such as fish, shellfish, and

marine mammals, can be exposed to these

higher concentrations [775].

2. LAPIO that is denser than the receiving

waters is not expected to sink

immediately to the bottom and remain

there. More likely, it will be suspended

in the water column by tidal and riverine

currents, eventually exiting the river

system with the net outflow of water.

Accumulation of oil on the bottom is

expected only in zones of low flow, such

as dredged channels, dead-end waterways,

and abandoned channels. Natural removal

rates by physical flushing would be very

slow for spills in the lacustrine section

of the St. Johns River system [775].

3. Benthic organisms are seldom at risk from

floating oil spills. However, with

heavier-than-water spills, additional

impacts to benthic resources are likely

to occur from smothering as well as

increased exposure to residual oil that

was not recovered. As a corollary,

impacts to shoreline habitats and animals

that use both the shoreline and water

surface should be less for sinking oil
spills [775].

4. Containment and removal efforts for

sinking oil will largely be ineffective.

As recently experienced during the Morris

J. Berman [Puerto Rico, 1994] oil spill,

removing submerged oil is very slow, and

usually generates large volumes of

contaminated water and sediment. In fact,

removal of the submerged oil in Puerto

Rico was conducted only where the oil was

contained by natural or existing

features. Oil sank in other areas, but

tidal currents dispersed the oil over

large areas, making it impractical to

recover [775].

5. Containment and removal efforts for

neutrally buoyant oil will likely be

ineffective. There are no proven

techniques for containing oil in the

water column, or for removing oil from

such large volumes of water [775].

6. Even standard techniques for location,

containment, and recovery will fail

unless conducted by contractors

experienced in the proper deployment and

maintenance of the equipment and the

special requirements of oil-spill

response [775].

The potential for spilled LAPIO on the water

surface, in the water column, and on the river

bottom will tend to affect a broad range of

resources (fish, shellfish, manatees, and

birds) in the St. Johns River. Manatees (a

protected species) are unlikely to be found in

the lower river segments in any great numbers,

only as single individuals traveling to and

from preferred habitats upstream [775].

Woodstorks (endangered) are also unlikely to

be affected as they prefer to roost in trees

and wade in upland freshwater marshes-areas

unlikely to be oiled. Additional injuries to

fishery and shellfish resources are more

likely to occur. Present response technology

is ill-equipped to deal with the potential

water-column and benthic habitat impacts from

a spill of LAPIO [775].

See ATSDR toxicological profile on fuel oils 1 (kerosene), 1-

D, 2, 2-D, and 4 [962].
No other information found; see Chem.Detail section for

compounds in this product, then see individual compound

entries for summaries of information on individual components

of this mixture. See also: entries starting with the phrase

fuel oil.

Laboratory and/or Field Analyses:

The recommended lab analyses method depends on the fuel oil

type in question. For example, recommended lab methods for the

detection of distillate fuel oils (1 and 2) differ slightly from

recommended methods for residual fuel oils (4, 5, and 6). See the

individual fuel oil entries for details.

See: ATSDR toxicological profile on fuel oils 1 (kerosene), 1-

D, 2, 2-D, and 4 [962]. See also: lab sections of fuel oil

products and lab sections on various components of fuel oils.

For additional details on protocols, including field

collection protocols, see the Oil Spills entry and the PAHs entry.

PAHs are one of the big issues with fuel oil spills (See also:

PAHs as a group entry). The following information relates to PAHs:

Recommended detection limits:

Most of the PAH methods which have been commonly used

historically for routine monitoring, including PAH parent

compound standard methods:

EPA 8270 (8270 includes several PAH parent

compounds along with a long list of other organics)

for solid waste/RCRA applications [1013], and 

EPA NPDES method 610 as specified in 40 CFR Part

136 (method 610 includes 16 PAH parent compounds)

[1010], 

EPA method 625 for Base/Neutral Extractables

(method 625 includes several PAH parent compounds

along with a long list of other organics) as

specified in 40 CFR Part 136 [1010],

are all inadequate for generating scientifically

defensible information for Natural Resource Damage

Assessments [468]. These standard EPA scans do not cover

important alkyl PAHs and do not utilize low-enough

detection limits. When biological effects, ecological

risk assessment, damage assessment, or bio-remediation

are being considered, detection limit should be no higher

than 1-10 ng/L (ppt) for water and 1 ug/kg ppb dry weight

for solids such as tissues, sediments, and soil. 

Note: Utilizing up to date techniques, many of the

better labs can use detection limits of 0.3 to 1

ppb for tissues, sediments, and soils. When no
biological resources are at risk, detection limits

for solids should nevertheless generally not be

above 10 ppb. One reason that low detection limits

are needed for PAHs is that so many of the

criteria, standards, and screening benchmarks are

in the lower ppb range (see various entries on

individual PAHs).

In the past, many methods have been used to analyze for PAHs

[861,1010,1013]. However, recent (1991) studies have indicated

that EPA approved methods used for oil spill assessments (including

total petroleum hydrocarbons method 418.1, semivolatile priority

pollutant organics methods 625 and 8270, and volatile organic

priority pollutant methods 602, 1624, and 8240) are all inadequate

for generating scientifically defensible information for Natural

Resource Damage Assessments [468]. These general organic chemical

methods are deficient in chemical selectivity (types of

constituents analyzed) and sensitivity (detection limits); the

deficiencies in these two areas lead to an inability to interpret

the environmental significance of the data in a scientifically

defensible manner [468].

For risk, damage assessment, drinking water, or to determine

if biodegradation has occurred, the NOAA expanded scan for PAHs and

alkyl PAHs [828], or equivalent rigorous and comprehensive scans.

(such as SW-846 method 8270 modified for Selective Ion Mode

detection limits and an equivalent list of parent compound and

alkyl PAH analytes), are recommended.

If a Park Service groundwater investigation at Colonial

National Historical Park performed in response to contamination by

Fuel Oil 5 had utilized EPA semi-volatile scan 8270 or any of the

other typical EPA scans (625, etc.) all of which only include

parent compounds and typically utilize detection limits in the 170-

600 ppb range, the false conclusion reached would have been that no

PAHs were present in significant (detection limit) amounts. This

false negative conclusion would have been made because the parent

compound PAHs present constituted only 7.6% of the PAHs detected in

groundwater by the expanded scan [828], and the highest

concentration found for any parent compound was 8.4 ppb, far below

the detection limits used on the older standard EPA scans.

Utilizing the NOAA protocol expanded scan [828], it was determined

that 92.4% of the total concentration values of the PAHs detected

in groundwater were alkyl PAHs, and that all 39 PAHs and alkyl PAHs

were present. Of course, all 39 PAHs were also present in the

fresh product, in much higher concentrations, and also having alkyl

compounds with the highest percentage of higher values compared to

parent compounds (see Chem.Detail section above for more details).

In a similar vein, if the Park Service sediment investigation

at Petersburg National Historical Battlefield (see Chem.Detail

section above, this study was performed in response to

contamination by Diesel) had utilized EPA semi-volatile scan 8270

or any of the other typical EPA scans (625, etc.), all of which

only include parent compounds and often utilize detection limits no

lower than the 170-600 ppb range, the false conclusion reached

would have been that only one PAH was present in significant
(detection limit) amounts. This false negative conclusion would

have been made because the parent compound PAHs present constituted

only 2.4% of the PAHs detected in sediments, and the highest

concentration found for any parent compound except pyrene was 85.5

ppb, far below the detection limits used on the older standard EPA

scans. Pyrene was 185 ppb, which would have been non-detected on

many of the EPA scans, but not all. However, utilizing the NOAA

protocol expanded scan [828], it was determined that 97.6% of total

quantity of PAHs detected in sediments were alkyl PAHs, and that

all 39 PAHs and alkyl PAHs were present in these sediments.

When taking sediment samples for toxic organics such as PCBs,

PAHs, and organochlorines, one should also routinely ask for total

organic carbon analyses so that sediment values may be normalized

for carbon. This will allow comparison with the newer EPA interim

criteria [86,127]. TOC in sediments influences the dose at which

many compounds are toxic (Dr. Denny Buckler, FWS Columbia, personal

communication).

Analyses of sediments: 

The past use of EPA method 8270 [861] for analyses of PAHs in

sediments was often deficient because the detection limits used

were too high. For example, the detection limit on phenanthrene in

sediments analyzed from a Park Service site at Fort Darling was

listed as 1600 ppb, whereas many now recommend using a detection

limit no higher than 10 ppb (1 ppb is best). In this case, harmful

levels of phenanthrene and other PAHs could have been present but

the test would not have detected them, because the detection limit

used was too high (Roy Irwin, National Park Service, personal

commuication, 1997]. It is usually better to perform an expanded

scan for PAHs and alkylated homologues [828], with detection limits

no lower than 1 ppb dry weight in solids. In some cases where the

expanded scans are too expensive, an alternative recommendation is

that one screen sediments with a size-exclusion high-performance

liquid chromatography (HPLC)/fluorescence method, utilizing sonic

extraction. 

The utility and practicality of the HPLC bile and sediment

screening analyses were demonstrated on board the NOAA R/V Mt.

Mitchell during the Arabian Gulf Project. Estimates of petroleum

contamination in sediment and fish were available rapidly, allowing

modification of the sampling strategy based on these results [522].

(see HPLC sections below for more detail).

Some labs (such as Coastal Environments Lab in Encinitas,

California) have recommend P450 Reporter Gene System (RGS)

screening for sediments to determine which are most severely

contaminated with PAHs before proceeding to GC/MS testing.

However, the system is also activated by certain PCBs, dioxins, and

other compounds (see biomarker section below for details).

Compounds in Expanded Scans:

An "expanded scan of PAHs" done by the Geochemical and

Environmental Research Group Laboratory includes parent compounds

and various alkyl homologs [828]: The expanded list includes most
of the PAHs recommended by the NOAA's National Status and Trends

program [680,828]:

Acenaphthene

Acenaphthylene 

Anthracene

Benzo(a)anthracene

Benzo(a)fluoranthene

Benzo(k)fluoranthene

Benzo(g,h,i)perylene 

Benzo(e)pyrene

Benzo(a)pyrene

Biphenyl

Chrysene

Chrysene, C1-

Chrysene, C2-

Chrysene, C3-

Chrysene, C4-

Dibenzo(a,h)anthracene

Dibenzothiophene

NOTE: Although opinions differ as to whether

dibenzothiophene is a PAH, it is listed as such in

several sources [795,468,495].

Dibenzothiophene, C1-

Dibenzothiophene, C2-

Dibenzothiophene, C3-

Fluoranthene

Fluoranthenes/Pyrenes, C1-

Fluorene

Fluorene, C1-

Fluorene, C2-

Fluorene, C3-

Ideno(1,2,3,c,d)pyrene

Naphthalene

Naphthalene, C1-

Naphthalene, C2-

Naphthalene, C3-

Naphthalene, C4-

Perylene

Phenanthrene

Phenanthrenes/Anthracenes, C1-

Phenanthrenes/Anthracenes, C2-

Phenanthrenes/Anthracenes, C3-

Phenanthrenes/Anthracenes, C4-

Additional Details on NOAA expanded scan: PAHs Lab Analyses,

NOAA Protocol Expanded Scan for PAHs and Alkyl Homologues of PAHs

Using Gas Chromatography-Mass Spectrometry with Selective Ion Mode

Enhanced Detection Limits (GC/MS/SIM) [828]:

Recommended by: National Park Service Staff, Fish and

Wildlife Service Contaminants Program, NOAA Status and

Trends Program, EPA EMAP Program, Many Consultants

working on Exxon Valdez Spill, Many Laboratories.
Pros: A more complete list of analytes including alkyl

homologues, suitably low detection limits, good utility

for both risk/hazard assessment and for obtaining basic

clues about possible sources (provides a crude

fingerprint). 

Cons: A bit more expensive than EPA standard method 8270

and substantially more expensive than rough screening

scans. Not all labs are set up to do it.

Detection limits: 

Recommended water sample detection limits are 1-10

ng/L (ppt) while recommended tissue, soil, and

sediment sample detection limits for the expanded

scan for PAHs are 1 ug/kg (ppb) dry wt.

Typical Costs per Sample (based on a survey of several

laboratories in 1995):

Lab 1 (BSEQ): $425 per sample including extraction.

Lab 2 (GERG): $250 to $400 per sample depending on

details. For low numbers of samples with no

previous extractions, $400 for water, $425 for

sediment, and $450 for tissues. As low as $250 if

extraction not included (less than standard 8270

scan).

Lab 3 (BNW): $425 including extraction, or as low

as $225 each for 40 samples if extraction already

done.

Lab 4 (CAS): $300 for one class of chemicals

(PAHs), up to $600 for all 8270 method analytes and

lower detection limits (Method 8270/SIM, detection

limits 1 ppb water, 20 pb tissues, and 10 ppb

sediments).

Lab 5 (ADL): $425 to $600 including extraction. If

a lot of extra chemical classes or advance

fingerprinting is specified: up to $1000 per

sample.

Summary: An alternative which works for many purposes

(hazard assessment, source determination, surveys of

hazardous compounds in weathered as well as fresh oils.

Examples of standard method protocols for PAHs published by

various parts of EPA as well as some other agencies are outlined

below:

Holding Times: 
Water Samples: 

Both NPDES effluent discharge permit applications

[1010] and RCRA (SW-846) solid and hazardous waste

applications [1013] call for the following maximum

holding times: 7 days until extraction and 40 days

after extraction. 

Solids Samples: 

EPA RCRA methods for semi-volatiles in solids in

SW-846 call for holding times of 14 days until

extraction and 40 days after extraction [1013]. 

The need to get rid of headspace to prevent loss of

certain PAHs (such as naphthalenes) tends to

discourage the freezing of soil and other samples.

However, the Fish and Wildlife Service and some

other groups nevertheless freeze some soil samples.

If this can be accomplished without compromising

the sample (for example, breaking a glass

container), the freezing tends to stop

biodegradation. Once frozen, holding times for

samples of semi-volatiles such as PAHs in solids is

on the order of decades (John Moore, Fish and

Wildlife Service, Personal Communication, 1997).

Containers: 

Both EPA and APHA (Standards Methods Book) recommend

glass containers for the collection of organic compounds

[141,1010,1013]. EPA also recommends teflon lined caps

for solids samples of semi-volatiles [1010,1013]. 

Guidance from other federal agencies (USGS, FWS, NOAA)

also recommends glass containers for organics, and

discourages the use of plastic containers for a variety

of reasons (Roy Irwin, National Park Service, Personal

Communication, 1997, based on a glance through recent

internal guidance of several agencies). 

Some federal agency quality control procedures call for

voiding or red-flagging the results of organic analyses

if the lab receives the sample in plastic containers (Roy

Irwin, National Park Service, Personal Communication,

1997). The APHA pointed out some the potential hazards

of the use of certain plastic containers for storing

organic samples [141]: 

A) Potential contamination of the sample via

leaching of compounds from the plastic, and/or

B) The plastic container walls can sometimes be

attacked by certain organics and fail, and/or
C) The possibility that some of organic compound

will dissolve into the walls of the plastic

container, reducing the concentration of the

compound in the container [141]. For the relatively volatile PAHs such as naphthalenes,

not even vials are not the best choice for avoiding false

negatives in soil samples through volatilization losses,

since the use of brass liners for collection resulted in

19 fold higher VOCs than when 40 mL vials were used [798]

The third update of EPA's SW-846 RCRA guidance authorizes

the storage of soil samples of volatiles in EnCore TM (or

equivalent, no government endorsement implied) samplers

as long the sample is analyzed within 48 hours after

collection [1013]. Several states also authorize the use

of EnCore TM or equivalent containers for temporary (48

hour) storage containers (Donalea Dinsmore, State of

Wisconsin DNR, personal communication, 1997).

Certain plastic polymers present less of a problem

related to potential losses of volatiles than others.

Some plastic is found in the latest approved EnCore TM

samplers. Some states also give the reader the option of

using plastic in collecting devices. For example,

related to methods for gasoline range petroleum

hydrocarbons, Wisconsin states that organics can be

collected using a 30 ml plastic syringe with the end

sliced off, a brass tube, an EnCore TM sampler or other

appropriate devices (Donalea Dinsmore, State of Wisconsin

DNR, personal communication, 1997). A plastic syringe is

also mentioned as an option in the third update of RCRA

methods in SW-846 [1013]. The thinking appears to be

that plastic is less of a threat in a collecting device,

with momentary contact, than in a storage container where

contact times are longer. 

Typical "standard method" protocols recommend proper

cleaning of glass containers before use. Some collectors

simply use pre-cleaned jars from I-Chem, Eagle Pitcher,

or other private suppliers (no government endorsement

implied). EPA [1010], USGS, and most other federal

agencies recommend cleaning procedures for the glass

containers, usually involving detergent rinsing, baking,

and sometimes HCL rinses (Roy Irwin, National Park

Service, Personal Communication, 1997).

Field Protocols:

Standard field collection method protocols are published

or internally distributed by the Fish and Wildlife

Service, the USGS, DOE, NOAA, and EPA. These

recommendations change over time, with the newest

recommendations sometimes being quite different than the

old, thereby producing different results. The USGS NAWQA
protocols call of sieving of sediment samples composites,

a practice that might result in the loss of relatively

volatile PAHs such as the naphthalenes. 

The Fish and Wildlife Service methods are similar in many

ways to NOAA field protocols [676]. Many recommended EPA

field methods for organics are not very detailed,

although the 3rd update of SW-846 for RCRA solid waste

methods is becoming more detailed [1013]. 

The various EPA methods for organics are different from

each other, with the selection of the appropriate method

depending upon the specific application (RCRA vs. CERCLA

vs. NPDES permits, vs. Drinking Water, etc.)

[861,1010,1013]. The EPA-recommended field methods are

scattered through various EPA and ASTM publications. 

EPA methods typically include recommendations that grab

samples rather than composites be utilized for organics,

and require the proper cleaning of collection bottles and

collecting gear for both volatile and semi-volatile

organics [1010,1013]. In other publications, EPA

recommends caution in the use of composite soil samples

whether organic or inorganic, citing statistical

complications and stating that the compositing of samples

cannot, in general, be justified unless for a stated

specific purpose and unless a justification is provided

[1017]. 

For PAHs (lab method 610) and other semi-volatiles, EPA

recommended in 1994: that "conventional sampling

practices" be followed as specified by ASTM D-3370 (3370-

95a is a recent number), "Standard Practices for Sampling

Water from Closed Conduits" [1010,1012]. No field

methods are specified when not sampling from pipes

[1010,1012].

Regardless of what lab methods are used, the investigator

should take special precautions to prevent the escape of

relatively light PAHs during sample shipment, storage,

extraction, and cleanup [798]. This is especially true

for soil and sediment sampling. The results of analyses

of the lighter semi-volatiles (such as naphthalenes) can

be dramatically effected by small details such as how the

samples are collected, stored, held, and analyzed in the

lab, since volatile compounds can readily volatilize from

samples in both field and lab procedures. If the

investigator knows that the sample will contain

significant quantities of the lighter semi-volatiles such

as naphthalenes, field and lab precautions should be

taken just as if the investigator were handling volatiles

(see Benzene entry for details). For example, for the

lighter semi-volatiles, it may be prudent to use EPA

method 5021 in SW 846, a generic "headspace" method for
the collection of volatiles in soils and sediments

[1013]. 

Standard field methods for sampling contaminated soils

for various types of contaminants were summarized by EPA

in 1991 [1020]. These methods seem generally consistent

with SCS recommendations, but are not necessarily 100%

consistent with other protocols suggested by other parts

of EPA [1013], and are not consistent with methods

suggested by other agencies, such as the Fish and

Wildlife Service.

 Variation in concentrations of organic contaminants may

sometimes be due to the typically great differences in how

individual investigators treat samples in the field and in the lab

rather than true differences in environmental concentrations. This

is particularly true for volatiles and for the relatively lighter

semi-volatiles such as the naphthalene PAHs, which are so easily

lost at various steps along the way. Contaminants data from

different labs, different states, and different agencies, collected

by different people, are often not very comparable. In fact, as

mentioned in the disclaimers section, the interagency task force on

water methods concluded that [1014]:

It is the exception rather than the rule that water-quality

monitoring data from different programs or time periods can be

compared on a scientifically sound basis, and that...

No nationally accepted standard definitions exist for water

quality parameters. The different organizations may collect

data using identical or standard methods, but identify them by

different names, or use the same names for data collected by

different methods [1014].

 

As of 1997, the problem of lack of data comparability (not

only for water methods but also for soil, sediment, and tissue

methods) between different "standard methods" recommended by

different agencies seemed to be getting worse, if anything, rather

than better. The trend in quality assurance seemed to be for

various agencies, including the EPA and others, to insist on

quality assurance plans for each project. In addition to quality

control steps (blanks, duplicates, spikes, etc.), these quality

assurance plans call for a step of insuring data comparability

[1015,1017]. However, the data comparability step is often not

given sufficient consideration. The tendency of agency guidance

(such as EPA SW-846 methods and some other new EPA methods for bioconcentratable substances) to allow more and more flexibility to

select options at various points along the way, makes it harder in

insure data comparability or method validity. Even volunteer

monitoring programs are now strongly encouraged to develop and use

quality assurance project plans [1015,1017]. The basics of these

quality assurance plans for chemical analyses should include the

following quality control steps:
At minimum, before using contaminants data from diverse

sources, one should determine that field collection methods,

detection limits, and lab quality control techniques were

acceptable and comparable. The goal is that the analysis in

the concentration range of the comparison benchmark

concentration should be very precise and accurate. Typical

lab quality control techniques should have included the

following considerations (Roy Irwin, National Park Service,

Personal Communication, 1997, summary based on various EPA and

FWS documents):

Procedural Blanks should be analyzed to assure that no

contaminants are added during the field and lab processing of

the samples. The standards for adequacy depend on the method

and the media being measured.

Different federal agencies publish different acceptable

limits. For one program, NOAA stated that at least 8% of

samples should be blanks, reference or control materials

[676].

The basic idea is that neither samples nor blanks should

be contaminated. Because the only way to measure the

performance of the modified procedures is through the

collection and analysis of uncontaminated blank samples

in accordance with this guidance and the referenced

methods, it is highly recommended that any modifications

be thoroughly evaluated and demonstrated to be effective

before field samples are collected [1003].

Duplicate samples are analyzed to provide a measure of

precision of the methods. The standards for adequacy depend

on the method and the media being measured. 

Different federal agencies publish different acceptable

limits. There appears to be an inverse relationship

between precision and sensitivity [676].

 

Some EPA methods state that a field duplicate must be

collected at each sampling site, or one field duplicate

per every ten samples, whichever is more frequent [1003].

Some protocols call for the preparation of one Ongoing

precision and recovery (OPR) standard for every ten or

fewer field samples. Great care should be taken in

preparing ongoing precision and recovery standards

[1003].

Spiked samples are analyzed to provide a measure of the

accuracy of the analysis methods. The standards for adequacy

depend on the method and the media being measured.

Different federal agencies publish different acceptable

limits. 
It should be kept in mind that quality control field and lab

blanks and duplicates will not help in the data quality assurance

goal as well as intended if one is using a method prone to false

negatives. Methods may be prone to false negatives due to the use

of detection limits that are too high, the loss of contaminants

through inappropriate handling, or the use of an inappropriate

methods such as many of the EPA standard scans. This is one reason

for using the NOAA expanded scan for PAHs [828]; or method 8270

[1013] modified for SIM detection limits (10 ppt for water, 0.3 to

1 ppb for solids) and additional alkyl PAH analytes; or alternative

rigorous scans. These types of rigorous scans are less prone to

false negatives than many of the standard EPA parent compound PAH

scans (Roy Irwin, National Park Service, Personal Communication,

1997).

PAHs are often analyzed when fuel oil products are spilled.

This is as it should be, since PAHs are among the more hazardous of

the constituents in fuel oils (see Chem.Detail sections of Fuel oil

entries). However, it is not always easy to determine which

combinations of lab methods to use for oil products. The following

is a proposed decision Tree (dichotomous key) for selection of lab

methods for measuring contamination from mid-range petroleum

products (Roy Irwin, National Park Service, Personal Communication,

1997):

In choosing a lab method, it should be kept in mind that many

mid range products (such as Diesel, No. 2 Fuel Oils, and Light

Crudes) can be expected to exhibit the following

characteristics [741]:

-Moderately volatile; will leave residue (up to 1/3

of spilled amount)

-Moderate concentrations of toxic (soluble)

compounds

-Will "oil" intertidal resources with long-term

contamination potential

-Has potential for subtidal impacts (dissolution,

mixing, sorption onto suspended sediments)

-No dispersion necessary

-Cleanup can be very effective

Decision Tree (dichotomous key) for selection of lab methods for

measuring contamination from light crude oils and middle distillate

petroleum products (all diesels, jet fuels, kerosene, Fuel oil 2,

Heating Oil 2):

1a. Your main concern is biological effects of petroleum

products....................................................2

1b. Your main concern is cleanup or remediation 

but no ecological or human resources are at risk............3

2a. The resource at risk is primarily humans via a drinking water

pathway, either the contamination of groundwater used for
drinking water, or the fresh* or continuing contamination of

surface waters used as drinking water, or the risk is

primarily to aquatic species in confined** surface waters from

a fresh* spill, or the risk is to surface waters re-emerging

from contaminated groundwater resources whether the spill is

fresh* or not; the medium and/or pathway of concern is water

rather than sediments, soil, or tissues ....................4

2b. The resource at risk is something else......................5

3a. The spilled substance is a fresh* oil product of known

composition: If required to do so by a regulatory authority,

perform whichever Total Petroleum Hydrocarbon (TPH) analysis

specified by the regulator. However, keep in mind that due to

its numerous limitations, the use of the common EPA method

418.1 for Total Petroleum Hydrocarbons is not recommended as

a stand-alone method unless the results can first be

consistently correlated (over time, as the oil ages) with the

better NOAA protocol expanded scan*** for polycyclic aromatic

hydrocarbons (PAHs) and alkyl PAHs. If not required to

perform an EPA method 418.1-based analysis for TPH, instead

perform a Gas Chromatography/Flame Ionization Detection

(GC/FID) analysis for TPH using the spilled substance as a

calibration standard. GC/FID methods can be sufficient for

screening purposes when the oil contamination is fresh*,

unweathered oil and when one is fairly sure of the source

[657]. If diesel 1D was spilled, perform TPH-D (1D) using

California LUFT manual methods (typically a modified EPA

method 8015) [465] or a locally available GC/FID method of

equal utility for the product spilled. However, no matter

which TPH method is used, whether based on various GC/FID or

EPA method 418.1 protocols, the investigator should keep in

mind that the effectiveness of the method typically changes as

oil ages, that false positives or false negatives are

possible, and that the better Gas Chromatography-Mass

Spectrometry-Selected Ion Mode (GC/MS/SIM) scans (such as the

NOAA expanded scan***) should probably be performed at the end

of remediation to be sure that the contamination has truly

been cleaned up. 

3b. The spilled product is not fresh* or the contamination 

is of unknown or mixed composition........................6

4. Analyze for Benzene, Toluene, Ethyl Benzene, and Toluene

(BTEX) compounds in water as part of a broader scan of

volatiles using EPA GC/MS method 8260. The older standard EPA

GC/MS method 8240 protocol was sufficient for some

applications, but the standard EPA method 8240 (and especially

the less rigorous EPA BTEX methods such as method 8020 for

soil and method 602 for water) are all inadequate for

generating scientifically defensible information for Natural

Resource Damage Assessments [468]. The standard EPA methods

are also inadequate for risk assessment purposes. Thus, when

collecting information for possible use in a Natural Resource
Damage Assessment or risk assessment, it is best to ask the

lab to analyze for BTEX compounds and other volatile oil

compounds using a modified EPA GC/MS method 8260 method using

the lowest possible Selected Ion Mode detection limits and

increasing the analyte list to include as many alkyl BTEX

compounds as possible. Also analyze surface or (if

applicable) ground water samples for polycyclic aromatic

hydrocarbons (PAHs) and alkyl PAHs using the NOAA protocol

expanded scan*** modified for water samples using methylene

chloride extraction. If the contaminated water is

groundwater, before the groundwater is determined to be

remediated, also analyze some contaminated sub-surface soils

in contact with the groundwater for BTEX compounds (EPA GC/MS

method 8260) [1013], and PAHs (NOAA protocol expanded

scan***). The magnitude of any residual soil contamination

will provide insight about the likelihood of recontamination

of groundwater resources through equilibria partitioning

mechanisms moving contamination from soil to water.

5a. The medium of concern is sediments or soils..................6

5b. The medium of concern is biological tissues..................7

6. Perform the NOAA protocol expanded scan*** for polycyclic

aromatic hydrocarbons (PAHs) and alkyl PAHs. If there is any

reason to suspect fresh* or continuing contamination of soils

or sediments with lighter volatile compounds, also perform EPA

GC/MS method 8260 [1013] using the lowest possible Selected

Ion Mode (SIM) detection limits and increasing the analyte

list to include as many alkyl Benzene, Toluene, Ethyl Benzene,

and Xylene (BTEX) compounds as possible.

7a. The problem is direct coating (oiling) of wildlife or plants

with spilled oil product.....................................8

7b. The problem is something else................................9

8. Perform NOAA protocol expanded scan*** for polycyclic aromatic

hydrocarbons (PAHs) and alkyl PAHs and/or GC/FID

fingerprinting of the coating oil only if necessary to

identify the source or exact oil. If the source is known and

no confirmation lab studies are necessary: dispense with

additional chemical laboratory analyses and instead document

direct effects of coating: lethality, blinding, decreased

reproduction from eggshell coating, etc., and begin cleaning

activities if deemed potentially productive after consolations

with the Fish and Wildlife Agencies.

9a. The concern is for impacts on water column organisms such as

fish or plankton)...........................................10

9b. The concern is for something else (including benthic

organisms)..................................................11
10. If exposure to fish is suspected, an HPLC/Fluorescence scan

for polycyclic aromatic hydrocarbon (PAH) metabolites in bile

may be performed to confirm exposure [844]. For bottomdwelling fish such as flounders or catfish, also analyze the

bottom sediments (see Step 6 above). Fish which spend most of

their time free-swimming above the bottom in the water column

can often avoid toxicity from toxic petroleum compounds in the

water column, but if fish are expiring in a confined** habitat

(small pond, etc.), EPA GC/MS method 8260 and the NOAA

protocol expanded scan*** for PAHs could be performed to see

if Benzene, Toluene, Ethyl Benzene, and Xylene (BTEX),

naphthalene, and other potentially toxic compounds are above

known acute toxicity benchmark concentrations. Zooplankton

populations impacted by oil usually recover fairly quickly

unless they are impacted in very confined** or shallow

environments [835] and the above BTEX and PAH water methods

are often recommended rather than direct analyses of

zooplankton tissues.

11a. The concern is for benthic invertebrates: analyze invertebrate

whole-body tissue samples and surrounding sediment samples for

polycyclic aromatic hydrocarbons (PAHs) and alkyl PAHs using

the NOAA protocol expanded scan***. If the spill is fresh* or

the source continuous, risk assessment needs may also require

that the sediments which form the habitat for benthic

invertebrates be analyzed for Benzene, Toluene, Ethyl Benzene,

and Xylene (BTEX) and other volatile compounds using EPA GC/MS

method 8260 or modified EPA method 8260 in the Selected Ion

Mode (SIM). Bivalve invertebrates such as clams and mussels

do not break down PAHs as well or as quickly as do fish or

many wildlife species. They are also less mobile. Thus,

bivalve tissues are more often directly analyzed for PAH

residues than are the tissues of fish or wildlife.

11b. The concern is for plants or for vertebrate wildlife including

birds, mammals, reptiles, and amphibians: polycyclic aromatic

hydrocarbons (PAHs) and other petroleum hydrocarbons break

down fairly rapidly in many wildlife groups and tissues are

not usually analyzed directly. Instead direct effects are

investigated and water, soil, sediment, and food items

encountered by wildlife are usually analyzed for PAHs and

alkyl PAHs using the NOAA protocol expanded scan***. If the

spill is fresh* or the source continuous, risk assessment

needs may also require that these habitat media also be

analyzed for Benzene, Toluene, Ethyl Benzene, and Xylene

(BTEX) and other volatile compounds using EPA GC/MS method

8260 or modified EPA method 8260 in the Selected Ion Mode

(SIM). Less is known about plant effects. However, the same

methods recommended above for the analyses of water (Step 4

above) and for sediments or soils (Step 6 above) are usually

also recommended for these same media in plant or wildlife

habitats. If wildlife or plants are covered with oil, see

also Step 8 (above) regarding oiling issues. 
* Discussion of the significance of the word "fresh": The word

"fresh" cannot be universally defined because oil breaks down

faster in some environments than in others. In a hot, windy,

sunny, oil-microbe-rich, environment in the tropics, some of the

lighter and more volatile compounds (such as the Benzene, Toluene,

Ethyl Benzene, and Xylene compounds) would be expected to disappear

faster by evaporation into the environment and by biodegradation

than in a cold, no-wind, cloudy, oil-microbe-poor environment in

the arctic. In certain habitats, BTEX and other relatively water

soluble compounds will tend to move to groundwater and/or

subsurface soils (where degradation rates are typically slower than

in a sunny well aerated surface environment). Thus, the judgement

about whether or not oil contamination would be considered "fresh"

is a professional judgement based on a continuum of possible

scenarios. The closer in time to the original spill of nondegraded petroleum product, the greater degree the source is

continuous rather than the result of a one-time event, and the more

factors are present which would retard oil evaporation or breakdown

(cold, no-wind, cloudy, oil-microbe-poor conditions, etc.) the more

likely it would be that in the professional judgement experts the

oil would be considered "fresh." In other words, the degree of

freshness is a continuum which depends on the specific product

spilled and the specific habitat impacted. Except for groundwater

resources (where the breakdown can be much slower), the fresher the

middle distillate oil contamination is, the more one has to be

concerned about potential impacts of BTEX compounds, and other

lighter and more volatile petroleum compounds. 

To assist the reader in making decisions based on the continuum of

possible degrees of freshness, the following generalizations are

provided: Some of the lightest middle distillates (such as Jet

Fuels, Diesel, No. 2 Fuel Oil) are moderately volatile and soluble

and up to two-thirds of the spill amount could disappear from

surface waters after a few days [771,835]. Even heavier petroleum

substances, such as medium oils and most crude oils will evaporate

about one third of the product spilled within 24 hours [771].

Typically the volatile fractions disappear mostly by evaporating

into the atmosphere. However, in some cases, certain water soluble

fractions of oil including Benzene, Toluene, Ethyl Benzene, and

Xylene (BTEX) compounds move down into groundwater. BTEX compounds

are included in the more volatile and water soluble fractions, and

BTEX compounds as well as the lighter alkanes are broken down more

quickly by microbes than heavier semi-volatiles such as alkyl PAHs

and some of the heavier and more complex aliphatic compounds. Thus

after a week, or in some cases, after a few days, there is less

reason to analyze surface waters for BTEX or other volatile

compounds, and such analyses should be reserved more for

potentially contaminated groundwaters. In the same manner, as the

product ages, there is typically less reason to analyze for alkanes

using GC/FID techniques or TPH using EPA 418.1 methods, and more

reason to analyze for the more persistent alkyl PAHs using the NOAA

protocol expanded scan***. 

** Discussion of the significance of the word "confined": Like the
word "fresh" the word "confined" is difficult to define precisely

as there is a continuum of various degrees to which a habitat would

be considered "confined" versus "open." However, if one is

concerned about the well-being of ecological resources such as fish

which spend most of their time swimming freely above the bottom, it

makes more sense to spend a smaller proportion of analytical

funding for water column and surface water analyses of Benzene,

Toluene, Ethyl Benzene, and Xylene (BTEX) and other volatile or

acutely toxic compounds if the spill is in open and/or deep waters

rather than shallow or "confined" waters. This is because much of

the oil tends to stay with a surface slick or becomes tied up in

subsurface tar balls. The petroleum compounds which do pass

through the water column often tend to do so in small

concentrations and/or for short periods of time, and fish and other

pelagic or generally mobile species can often swim away to avoid

impacts from spilled oil in "open waters." Thus in many large oil

spills in open or deep waters, it has often been difficult or

impossible to attribute significant impacts to fish or other

pelagic or strong swimming mobile species in open waters.

Lethality has most often been associated with heavy exposure of

juvenile fish to large amounts of oil products moving rapidly into

shallow or confined waters [835]. Different fish species vary in

their sensitivity to oil [835]. However, the bottom line is that

in past ecological assessments of spills, often too much money has

been spent on water column analyses in open water settings, when

the majority of significant impacts tended to be concentrated in

other habitats, such as benthic, shoreline, and surface microlayer

habitats.

*** The lab protocols for the expanded scan of polycyclic aromatic

hydrocarbons (PAHs) and alkyl PAHs have been published by NOAA

[828].

End of decision tree key.

In response to oil spills, it is important to analyze samples

for petroleum PAHs, important alkyl PAHs, and the standard PAHs

using the expanded scan of PAHs [828]. This degree of specificity

is necessary because oil spill effects are related not so much to

the gross amount of oil present as to the levels of key toxic

components [468]. Expanded scans typically search for a long list

of PAHs and alkylated PAHs at very low detection limits [828].

PAHs in such scans are typically identified by Gas Chromatography

with Mass Spectrometry (GC/MS) in the selective ion mode (SIM). In

the SIM mode, the GC/MS records intensify for ions that are

diagnostic for specific PAHS. Modifications of older lab practices

are necessary to get appropriately low detection limits.

Other information on analytical methods that are available

for detecting and/or measuring and monitoring fuel oils in

environmental media and in biological samples, information from the

ATSDR Toxicological Profile (See ATSDR Profile for embedded

reference identification) [962]. 

BIOLOGICAL MATERIALS [962]: Fuel oils are mixtures of
aliphatic and aromatic hydrocarbons (Air Force 1989).

Most analytical methods for detecting fuel oils in

biological media focus on the detection of kerosene

components, as this is a commonly used fuel for

residential heaters. Analytical methods for detecting

other fuel oils in biological media were not located.

.....For more analytical methods information, see the

previous profiles on some of the individual components

of fuel oils (e.g., benzene, toluene, total xylenes, and

PAHs) (AT SDR 1989, 1990a, 1991a, 1991b). The primary

method for detecting kerosene in biological materials

such as blood is gas chromatography (GC). GC may be

combined with mass spectroscopy (MS) for peak

identification with the gas chromatograph in the electron

impact mode (Kimura et al. 1988, 1991). Quantification

methods include the use of mass fragmentography (Kimura

et al. 1988). Hydrocarbon components of kerosene are

determined based on analysis of headspace gas above the

sample (Kimura et al. 1991). This method is useful for

distinguishing between kerosene intoxication and

gasoline intoxication as kerosene gives a high toluene

peak and has a pseudocumene-to-toluene ratio only half

that of gasoline. Capillary columns are used, with

either Porapak, Chromosorb or Chemipak, giving acceptable

results (Kimura et al. 1988). The percent recoveries of

these methods were not provided. Wide-bore capillary

columns have also been used (Hara et al. 1988) for GC/MS

analysis combined with flame ionization detectors (FID).

This method determined levels of m- and o-xylene

(components of kerosene) in the blood, urine, and

stomach contents. The sensitivity and precision of this

method was generally good (93-100% recovery) [962]. 

ENVIRONMENTAL SAMPLES [962]: Because fuel oils are

composed of a mixture of hydrocarbons, there are few

methods for the environmental analysis of fuel oils as a

whole, but methods are reported for the analysis of

their component hydrocarbons. The methods most commonly

used to detect the major hydrocarbon components of fuel

oils in environmental samples are GC/FID and

GC/MS......Several of the components of fuel oils have

been discussed in detail in their individual

toxicological profiles (e.g., benzene, toluene, total

xylenes, and PAHs), which should be consulted for more

information on analytical methods (ATSDR 1989, 1990a,

1991a, 1991b). GC is the most commonly used method to

selectively detect, identify, and quantify the volatile

hydrocarbon components of fuel oils in air (Andrasko

1983; Baldwin 1977; NIOSH 1994). Air samples may be

collected on adsorbent tubes such as charcoal, Florisil

, Tenax , Porapak , or Chromosorb. Active carbons wires

have also been used (Andrasko 1983). The hydrocarbons

are extracted from the tubes by thermal desorption or

with a liquid solvent such as carbon disulfide and
analyzed on the gas chromatograph. Precision is good

(relative standard deviation=0.052) using the charcoal

tubes (NIOSH 1994); recovery data were not reported for

the other types of adsorption tubes, although desorption

from the active carbon wires ranged between 90% and 99%

recovery, with a detection limit in the ppb range. A

Tenax-TA sorbent trap has been used with subsequent

thermal desorption (Andrasko 1983). Combining sample

concentration with the headspace method allows for

sampling of smaller air volumes and for other

environmental samples, such as kerosene combustion

debris, that have undergone significant evaporation; the

headspace method requires concentrating the sample prior

to analysis (Andrasko 1983; Baldwin 1977). An

exploratory study indicates that, with additional

research, the microanalytical evolved gas analysis

technique (EGA) can be further developed to measure

kerosene soot in indoor aerosols (Daisey and Gundel

1991) [962].

Abbreviations: Al2O3=aluminum oxide; CCl 4 = carbon

tetrachloride; CH 2 CS 2 = dichloromethane (methylene

chloride); CS 2 = carbon disulfide; FID = flame

ionization detector; GC = gas chromatography; GLC = gas

liquid chromatography; KOH = potassium hydroxide; MS =

mass spectrometry; Na 2 SO 4 = sodium sulfate; NaOH

= sodium hydroxide; NR = not reported; PID =

photoionization detector; TLC = thin-layer

chromatography [962]. 

GC/FID and GC/MS have been used to measure the watersoluble components of fuel oils, particularly kerosene,

in industrial effluents and estuarine water (Bianchi et

al. 1991), sea water (Boyland and Tripp 1971), drinking

water (Coleman et al. 1984; Dell' Acqua and Bush 1973),

and groundwater (Thomas and Delfino 1991a). Purge-andtrap sample preparation methods have been used to

determine purgeable (volatile) aromatic components of

fuel oils. This method requires a trap with a Tenax /

Chromosorb absorbent and the use of a gas chromatograph

with a photoionization detector (PID) (EPA 1991c), an

ion trap detector (ITD), or FID (Thomas and Delfino

1991a). A modification of the purge-and-trap method uses

ambient temperatures, has the advantage of being

applicable to a variety of waters, requires virtually no

sample preparation (no solvents are required), and has an

analysis time of approximately 30 minutes (Bianchi et

al. 1991). While this method may be used for determining

the presence of petroleum contaminants in water, it

cannot distinguish between various sources of this

contamination, e.g., between gasoline, kerosene, and

diesel oil. Distinctions between water-soluble fractions

of mixed hydrocarbons may be made by using solvent

extraction of the water-soluble base/neutral and acid
fractions with methylene chloride (EPA 1991c; Thomas and

Delfino 1991a). This separation of base/neutral and acid

fractions will permit the GC resolution of the type of

water soluble hydrocarbons present in the aqueous phase.

Hexane has also been used as a solvent (Dell' Acqua and

Bush 1973), as has pentane (Coleman et al. 1984). A

dynamic thermal stripper has also been used to detect low

levels (ppb range) of fuel oil no. 2 and kerosene

present in water samples (Belkin and Esposito 1986).

This method traps the fuels on an adsorption tube using

helium gas for purging. The fuel is then thermally

desorbed and backflushed to a gas chromatograph with

FID. This method also does not require any solvent and

needs only a 15 mL sample. Recovery for this method is

good (91-114%) with precision ranging from 6.4 to 14.3%

relative standard deviation. A modified Grob closedloop-stripping method, which uses a wall-coated open

tubular glass capillary column combined with GC/MS, has

been used to extract and quantify low levels (ppt) of

hydrocarbons in water samples. The method continually

recirculates an ambient air stream through the 3.8-liter

water sample for approximately 2 hours and collects the

vapor on an activated carbon filter, followed by

extraction with carbon disulfide and analysis (Coleman et

al. 1981). An optical fiber fluorescence spectroscopy

system has been used for real- time in situ measurements

of low levels (at ppb of diesel fuel marine equivalent)

of petroleum hydrocarbons in sea water, showing temporal

and spatial variability (Lieberman et al 1993). A

qualitative method for determining diesel oil in water

has been proposed that is based on changes in the

internal reflection of an optical fiber coated with an

organophilic compound caused by the presence of

hydrocarbons. The method does not require any sample

preparation but is limited to relatively high

concentrations of contaminants, e.g., 17 mg/L for diesel

oil (Kawahara et al. 1983). An alternative method uses

a Fourier transform infrared spectrometer (FTIR). This

method has the advantage of no sample preparation, a

short analysis time (20-30 seconds), and good accuracy (+

or -20%). A detection limit of 0.5 ppb has been

determined for a 1-liter sample of sea water; 10 mL is

sufficient if a detection limit of 0.05 ppm is

acceptable. The FTIR may be coupled with a GC or liquid

chromatography for the analysis of complex mixtures

(Mille et al. 1985). GC/FID (Galin et al. 1990a), gas

liquid chromatography (GLC) with FID (Midkiff and

Washington 1972), and elevated temperature purge and trap

with GC (Chang et al. 1990) have been used to measure

fuel oils in soils. An enzyme immunoassay has been

developed using a monoclonal antibody reagent that

detects gasoline and diesel fuel in soil;

commercialization of this assay will offer significant

advantages over current testing methods of gasoline and
fuel contamination levels in soil (Allen et al. 1992b).

GLC has also been used to determine fuel oils in marine

sediments (Gearing et al. 1980) and other environmental

samples such as paper, cloth, and wood (Midkiff and

Washington 1972). Extraction is used to concentrate the

sample because fuel oils do not provide sufficient

vapors to allow the use of a headspace sampling method.

Carbon tetrachloride is the recommended solvent as it

causes less interference with the chromatographic peaks

of the fuel oils (Galin et al. 1990a; Midkiff and

Washington 1972). Quantification of fuel oil hydrocarbons

from sediments is a more elaborate process. Following

extraction, the saturated and olefinic hydrocarbon

fraction is separated from the aromatic hydrocarbon

fraction using thin-layer chromatography or column

chromatography. Fractions are subsequently analyzed by

GLC (Gearing et al. 1980). Recovery, sensitivity, and

levels of detection data were not reported.

Quantification of oils and grease, by gross weight only,

in soils and sludges may be accomplished by extraction

with a Soxhlet apparatus using either

trichlorotrifluoroethane (APHA 1985) or methylene

chloride (Martin et al. 1991) as the solvent, although

this method may not be used to identify the specific

type of oil or grease present in the soil sample.

Synchronous scanning fluorescence spectroscopy can be

used to identify kerosene, fuel oil number 2, fuel oil

number 5, and other aromatic- containing products in

groundwater and soil samples. This analytical method is

more efficient than chromatographic methods, and its

spectra are easier to interpret for identification

purposes (Pharr et al. 1992). Fluorescence spectroscopy

has been used for in situ detection of petroleum

hydrocarbon plumes in soil; this technique allows for

measurements in soils before monitoring wells are

drilled and is thus independent of the fractionation and

transport problems inherent when sampling well fluids

(Apitz et al. 1992). The age of diesel oil in the

subsurface soil environment can be determined by

utilizing the fact that the composition of the diesel oil

(the ratio between n-alkanes and isoprenoids) changes due

to biodegradation. In one study, the ratio of C 17 to

pristane was highly correlated with the residence time

of diesel fuel at 12 test locations (Christensen et al

1993). A set of neural networks has been trained to

identify seven classes of petroleum hydrocarbon based

fuels from their fluorescence emission spectra; this

technique correctly identified at least 90% of the test

spectra (Andrews and Lieberman 1994). High-performance

liquid chromatography (HPLC), followed by GC/MS, has

been used to fractionate and then quantitate the

aliphatic and aromatic hydrocarbons present in liquid

fuel precursors in order to determine the fuel potential

of the compounds. Kerosene had the advantage of not
requiring any sample preparation. Other light fuel oils

may require the use of methylene chloride as a solvent

prior to HPLC analysis (Lamey et al. 1991). The

sensitivity, precision, and recovery of this method were

not reported. An alternative method for fractionating

and purifying petroleum hydrocarbons prior to GC or HPLC

separation has been developed (Theobald 1988). The method

uses small, prepacked, silica or C 18 columns that

offer the advantage of rapid separation (approximately

15 minutes for a run); good recovery of hydrocarbons

(85% for the C 18 column and 92% for the silica column);

reusability of the columns; and for the silica column in

particular, good separation of hydrocarbon from nonhydrocarbon matrices as may occur with environmental

samples. Infrared analysis and ultraviolet spectroscopy

were used to analyze the aromatic content in diesel

fuels; these methods are relatively inexpensive and

faster than other available methods, such as mass

spectrometry, supercritical fluid chromotography, and

nuclear magnetic resonance (Bailey and Kohl 1991). Due

to the tendency of hydrocarbons in the soil to undergo

subsurface oxidation, measuring CO 2 levels in the soil

gas could be used as a cost-effective field screening

tool. In one soil-gas survey, CO 2 levels in soil gas

correlated well with petroleum hydrocarbons in the soil

(Diem et al. 1988). A two-dimensional supercritical

fluid chromotography (SFC) system has been developed for

the determination of saturates, alkenes, and mono-, di-,

and tri- aromatics in diesel fuel. This technique results

in a short analysis time (less than 8 minutes) and good

relative standard deviations at low alkene content

(Andersson et al. 1992). The principal method for

detecting kerosene or its components in biota is GC

(Blumer et al. 1970; Farrington et al. 1982a; Newton et

al. 1991). Aliphatic and aromatic hydrocarbon components

of fuel oils taken up by shellfish (whole mussels

without shells) were isolated by column chromatography

following extraction. Both the alkane/cycloalkane and

alkene/aromatic fractions were analyzed by GC with

recoveries in the range of 67-100% for alkanes and 71-

78% for some aromatics; these aromatics were also

analyzed using GC/MS with recoveries between 49% and 74%

(Farrington et al. 1982a). Determination of hydrocarbons

may also be accomplished by fractionating the hydrocarbon

components. Extraction of hydrocarbons from contaminated

shellfish may be accomplished using Soxhlet extraction

with methanol followed by reextraction with pentane. The

extracts are then dried and concentrated prior to

injection into the GC (Blumer et al. 1970). Other data

on detection limits and precision were not provided

[962]. 

Identification of Data Needs [962]: Methods for

Determining Biomarkers of Exposure and Effect. No
biomarkers of exposure were identified for fuel oils

because, while standard procedures exist for identifying

or quantifying exposure to fuel oils based on

hydrocarbon components in blood, urine, and stomach

contents (Hara et al. 1988; Kimura et al. 1988, 1991),

none of these are applicable solely to fuel oils. These

methods are sensitive enough to measure the levels at

which health effects occur and may be adequate for

determining background levels in the population;

however, they cannot distinguish between exposure to

different fuel oils or other types of hydrocarbon

mixtures. Analytical methods are needed for measuring

the hydrocarbon components of fuel oils in lungs.

Biomonitoring studies are needed to adequately assess

exposure to fuel oils. No biomarkers of effects were

identified for fuel oils because the effects associated

with exposure to fuel oils are not unique for them, i.e.,

the effects may be caused by other chemicals or

hydrocarbon mixtures. Analytical methods do exist for

determining angiotensin-converting enzyme activity in the

lungs. This enzyme may be used to determine the lung

damage caused by a fuel oil. Analytical methods are

needed to determine whether the tissue damage is

specific to fuel oils and the target organs. Methods for

Determining Parent Compounds and Degradation Products in

Environmental Media. Methods exist to detect major

hydrocarbon components of fuel oils in air (Andrasko

1983; Baldwin 1977; NIOSH 1994), water (Bianchi et al.

1991; Boyland and Tripp 1971; Dell'Acqua and Bush 1973;

EPA 1991c), sediment (Gearing et al. 1980), and soil

(Galin et al. 1990a; Midkiff and Washington 1972). The

most commonly used methods are GC/FID and GC/MS. These

methods are relatively sensitive, selective, and

reliable, and can be used to detect the levels of the

various components of fuel oils found in the environment

and levels at which health effects occur. 6.3.2 On-going

Studies No on-going analytical methods studies were

located [962].