ENVIRONMENTAL CONTAMINANTS ENCYCLOPEDIA

FUEL OIL NUMBER 5 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. 

Digital format users: No software was independently

developed for this project. Technical questions related

to software should be directed to the manufacturer of

whatever software is being used to read the files. Adobe

Acrobat PDF files are supplied to allow use of this

product with a wide variety of software and hardware

(DOS, Windows, MAC, and UNIX). 

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 Number 5 (No. 5 Fuel Oil, Bunker B Fuel Oil, Fuel Oil No.

5, Navy Special Fuel Oil, NSFO, Residual Oil No. 5)

Brief Introduction:

Br.Class: General Introduction and Classification

Information:

Fuel oils are comprised of mixtures of petroleum

distillate hydrocarbons [363,499]. Fuel oil no. 5

consists of straight-run and cracked distillates and

residuals, and contains aliphatics and aromatics [606].

ASTM specifications list two grades of No 5, one of which

is lighter and under some climatic conditions may be

handled and burned without preheating [498]. No. 5 fuel

oil has two general categories: light and heavy [641]:

Light no. 5: This residual oil of intermediate

viscosity is used in burners capable of handling

fuel more viscous than fuel oil no. 4 without

preheating. In some cases, preheating may be

necessary in some types of equipment and in colder

climates for handling.

Heavy no. 5: This residual fuel oil is more

viscous than grade no. 5 (light), but is intended

for similar use (see above). Preheating to 170-220

F is recommended before handling or use. 

The viscous residuum fuel oils, numbers 5 and 6,

sometimes referred to as bunker B and bunker C fuels,

respectively, usually must be preheated before being

burned [498].

Fuel oil numbers 4, 5, and 6 are commonly known as

"residual oils" since they are manufactured in whole or

in part from distillation residues from refinery

processing [747]. These three heavy fuel oils are also

known as gas oils and are composed of hydrocarbons

ranging from C19 to C25 [872]. Residual oils are complex

mixtures of relatively high molecular weight compounds

and are difficult to characterize in detail. Molecular

types include asphaltenes, polar aromatics, naphthalene

aromatics, aromatics, saturated hydrocarbons and

heteromolecules containing sulfur, oxygen, nitrogen, and

metals [747]. 

Br.Haz: General Hazard/Toxicity Summary:

Many of the hazards to fish and wildlife from Fuel oil 5

are a result of the presence of polycyclic aromatic

hydrocarbons (PAHs). Due to their relative persistence
and potential for various chronic effects (like

carcinogenicity), PAHs, (and particularly the alkyl PAHs)

can contribute to long term (chronic) hazards of fuel 5

in contaminated soils, sediments, groundwater, or

biological tissues (see PAHs entry). A NOAA protocol

[828] GC/MS/SIM expanded scan for PAHs in a sample of

fresh NSFO (Fuel Oil 5) revealed the presence of all 39

PAHs and alkyl PAHs analyzed, with the lowest

concentration being 0.6 ppm for Benzo(k)fluoranthene and

the highest concentration being 4865 ppm for C2-

Naphthalenes. A groundwater sample contaminated with

weathered versions of the same NSFO product from Colonial

National Historical Park also revealed the presence of

all 39 PAHs and alkyl PAHs analyzed, with the lowest

concentration being 39.7 ppt for Benzo(k)fluoranthene and

the highest concentration being 48336 ppt for C4-

Naphthalenes. In this Park Service groundwater

investigation at Colonial National Historical Park, 92.4%

of the total concentration values of the PAHs detected in

groundwater were alkyl PAHs; parent compound PAHs

analyzed in typical EPA scans accounted for only 7.6% of

the PAHs and were below typical EPA scan detection

limits, so EPA scans would have given false negatives.

(see Chem.Detail section below for more details). This

provides a good example of why the standard EPA scans are

inappropriate for hazard, damage, or risk assessment.

Total naphthalenes in these groundwater samples exceeded

107,000 ppt (Roy Irwin, National Park Service, Personal

Communication, 1996). 

Regarding potential effects on humans, chronic effects of

some of the constituents in fuel 5 (including PAHs such

as naphthalenes) include changes in the liver and kidney

[766]. Fuel oil #5 would be expected to be a skin, eye

and respiratory irritant and a CNS depressant from

inhalation of large amounts of the vapor or mist [606].

Prolonged or repeated contact with the skin may produce

a defatting dermatitis with dryness and cracking [606].

One of the hazardous groups of compounds in fuel oils is

PAHs (see PAHs entry). PAHs may be translocated in

plants and may accumulate in plants grown in contaminated

soil [40]. Presumably this also occurs in sediments and

aquatic plants and therefore might impact herbivorous

species of fish and wildlife. Although some research

seems to indicate that interior portions of above-ground

vegetables do not accumulate high concentrations of PAHs,

plants do translocate PAHs from roots to other plant

parts, such as developing shoots [40]. Some plants can

evidently catabolize benzo(a)pyrene, but metabolic

pathways have not been clearly defined. This is an

important factor since when PAHs do degrade through

metabolism, they often break down into even more toxic,

carcinogenic, and mutagenic compounds [40]. Metabolic
transformations of PAHs into even more hazardous

chemicals could also happen through microbial degradation

of PAHs in soils or sediments. This provides an

additional example of a situation where human health

based standards are not protective of fish and wildlife,

since it casts doubt on the environmental safety margin

provided by EPA's human health-based soil guideline of

=<100 ppm carcinogenic PAHs.

However, in a series of soil and hydrocultures of

the higher plants, tobacco, rye, and radish, as

well as algae cultures of lower plants (Chlorella

vulgaris, Scenedesmus obligurus, and

Ankistrodesmus) /results indicate/ that certain

polycyclic aromatic hydrocarbons (PAHs) have

growth-promoting effects on plants. Further, the

degree of the promoting effect corresponded to the

oncogenic activity of the hydrocarbon. The six

polycyclic aromatic hydrocarbons found in plants

were tested one at a time or in combination.

Considerable growth-promotion was noted (near to

100% in some cases) with the effectiveness of

hydrocarbons ranked as follows: (1) Benzo(a)pyrene

(2) Benzo(a)anthracene (3) Indeno (1,2,3-cd)pyrene,

Benzo(b)fluoranthene (4) Fluoranthene (5)

Benzo(ghi)perylene. [Graf W, Nowak W; Arch Hyg Bakt

150: 513-28 (1968) as cited in Health & Welfare

Canada; Polycyclic Aromatic Hydrocarbons p.67

(1979) Report No. 80-EHD-50] [366].

See also: PAHs as a Group entry.

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

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].

No studies were found for fuel oil #5 [606]. However,

residual fuel oils contain appreciable concentrations of

polynuclear aromatic hydrocarbons (PAHs) [747]. Fuel Oil

Number 5 is typically about 75-80% Fuel Oil no. 6 [641],

and the content of PAHs in Fuel Oil No. 6 is better

documented (see: Fuel Oil No. 6). Dimethyl and trimethyl

naphthalenes are important components of Fuel No. 6 (and

also no. 5). Most blending stocks of residual fuel oils

are likely to contain 5% or more of four- to six-ring

condensed aromatic hydrocarbons [747]. This is important

since some of the heavier PAHs are carcinogenic. When

certain PAHs degrade through metabolism, they often break

down into even more toxic, carcinogenic, and mutagenic
compounds [40]. Since more information is available on

Fuel Oil 6, see also Fuel Oil Number 6 entry.

The debates on which PAHs, alkyl PAHs, and other

aromatics found in 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).

See also: PAHs as a Group entry.

Br.Dev: Brief Summary of Developmental, Reproductive,

Endocrine, and Genotoxicity Information:

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

or endocrine disruptors [561]. 

The results are mixed, but some reproductive and

fetotoxic effects have been associated with a few of the

compounds found in fuel no. 5 [766] (see entries on

individual compounds for more details). 

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.Fate: Brief Summary of Key Bioconcentration, Fate,

Transport, Persistence, Pathway, and Chemical/Physical

Information:

Fuel Oil Number 5 is typically about 75-80% Fuel Oil no.

6 [641]. For concentrations of PAHs in the Fuel Oil 6,

see Fuel Oil Number 6 entry. Dimethyl and trimethyl

naphthalenes are important components of Fuel Oils

Numbers 5 and 6.
Appreciable concentrations of polynuclear aromatic

hydrocarbons (PAHs) are present in residual fuels because

of the common practice of using both uncracked and

cracked residues in their manufacture [747]. Most

blending stocks of residual fuel oils are likely to

contain 5% or more of four- to six-ring condensed

aromatic hydrocarbons. The exact identities and

concentrations of various PAHs depend on the nature and

amount of the low viscosity blending stocks and the

proportions of virgin and cracked residues [747]. 

Oil-soluble compounds of calcium, cerium, iron, or

manganese may be added to residual fuel oils to improve

combustion [747]. Concentrations vary with fuel oil, but

typically range between 50 to 300 ppm weight of the

active material ingredient [747]. 

Fuel oil number 5 is a heavy oil with little or no

evaporation or dissolution potential (however, light fuel

no. 5 would be more likely to experience some

evaporation) [777]. As such, fuel oil 5 may be highly

persistent, with the potential for long-term sediment

contamination. In general, residual fuels are less

acutely toxic relative to other oil types. They may

weather slowly, and potentially sink depending on product

density and water density (for a more complete discussion

of sinking oil, see the Oil Spills entry). Impacts to

waterfowl and fur-bearing animals can be severe during a

spill of residual oil due to coating and ingestion [777].

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.

Synonyms/Substance Identification:

Residual Fuel Oil [560]

Navy Special [560]

Bunker B Fuel Oil [560]

Light Fuel Oil No. 5 [560]

Heavy Fuel Oil No. 5 [560]

FUEL OIL NO. 5 [606]

FUEL OIL #5 [606]

HEATING OIL NO. 5 [606]
HEATING OIL #5 [606]

NO. 5 FUEL OIL [606]

NO. 5 HEATING OIL [606]

#5 FUEL OIL [606]

#5 HEATING OIL [606]

Fuel Oil UNSP [962]

Navy Special Fuel Oil (NSFO), Heavy Fuel Oil [ARCO MSDS Sheet]

Commercial 535, ASTM No. 5 [ARCO MSDS Sheet]

Associated Chemicals or Topics (Includes Transformation

Products):

See also individual entries: 

Fuel Oil, General

Fuel Oil Number 6

Oil Spills

Petroleum, General

PAHs as a group

Naphthalene

C1-Naphthalene

C2-Naphthalene

C3-Naphthalene

C4-Naphthalene

Biphenyl 

Acenaphthylene

Acenaphthene

Fluorene

C1-Fluorene

C2-Fluorene

C3-Fluorene

Anthracene 

Phenanthrene

C1-Phenanthrene/anthracene

C2-Phenanthrene/anthracene

C3-Phenanthrene/anthracene

C4-Phenanthrene/anthracene

Dibenzothiophene

C1-Dibenzothiophene 

C2-Dibenzothiophene

C3-Dibenzothiophene

Fluoranthene

Pyrene

C1-Fluoranthene/pyrene

Benzo(a)anthracene

Chrysene

C1-Chrysene

C2-Chrysene

C3-Chrysene

C4-Chrysene

Benzo(b)fluoranthene

Benzo(k)fluoranthene
Benzo(e)pyrene

Benzo(a)pyrene

Perylene

Indeno(1,2,3-c,d)pyrene 

Dibenz(a,h)anthracene 

Benzo(g,h,i)perylene 

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):

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.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):

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.

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):

Seven large and medium size west coast ports were

surveyed during August 1990 to determine their

involvement with hydrocarbon contaminated soils and

activities associated with the characterization and

remediation of these soils [735]. All ports surveyed

indicated that they have hydrocarbon contaminated soil

problems [735]. At one site, a soil investigation

revealed one or more of four underground petroleum

pipelines, all idle or abandoned, near the center of the

redevelopment area may have leaked. The presence of

petroleum contamination in the soil was confirmed. The

petroleum could not be identified, but appeared to be of

a heavy petroleum type (diesel, bunker oil (bunker B is

fuel oil no. 5, bunker C is fuel oil no. 6), or possibly

very weathered crude) rather than gasoline [735]:
CONTAMINANT CONCENTRATION (ppm)

Total Petroleum Hydrocarbon (TPH) 

 EPA Method 418.1 69,300

Total Petroleum Hydrocarbon (TPH) 

 EPA Method 8015 modified for diesel 43,000

Benzene 40.7

Toluene 102

Xylene 67

Ethylbenzene 171

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):

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. See also:

Br.Haz section above.

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):

Acute Toxicity Highlights from RTECS [365]: 

LDLO/LCLO - LOWEST PUBLISHED LETHAL DOSE/CONC

RABBIT: LDLo; ROUTE: Skin; DOSE: 5200 mg/kg;

REFERENCE: Acute Toxicity Data. Journal of

the American College of Toxicology, Part B

1:139, 1990. 
 IRRITATION SKIN - STANDARD DRAIZE TEST,

RABBIT, ROUTE: Skin; DOSE: 500 mg; REACTION:

mild; REFERENCE: Acute Toxicity Data. Journal

of the American College of Toxicology, Part B

1:139, 1990. 

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). 

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 this

product (see Chem.Detail section below).

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:

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.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):

 LD50/LC50 - LETHAL DOSE/CONC 50% KILL, RAT, LD50;

ROUTE: Oral; DOSE: 5300 mg/kg; REFERENCE: Acute

Toxicity Data. Journal of the American College of

Toxicology, Part B 1:139, 1990 [365]. 

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:

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

referred to as bunker fuels, are used in furnaces and boilers of

utility power plants, ships, locomotives, metallurgical operations,

and industrial power plants, and usually must be preheated before

being burned [498].

Forms/Preparations/Formulations:

Fuel oil no. 5 can be prepared by combining 20 to 25 percent

no. 2 fuel oil with 75 to 80 percent no. 6 fuel oil [641].

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 No. 5 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

No. 5 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.

The heavy fuel oils (fuels oils number 4,5, and 6) contain 15-

40% aromatics, dominated by alkyl phenanthrenes and naphthalenes

[872].

Fuel Oil Number 5 is typically about 75-80% Fuel Oil no. 6

[641]. For concentrations of PAHs in Fuel Oil no. 6, see Fuel Oil

No. 6 entry. Dimethyl and trimethyl naphthalenes are important

components of Fuel No. 6 (and also No. 5). 

Physicochemical information from ORNL [875]:

Log KOW [875]: 3.3 to 7.06

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

Solubility in Water [875]: ~5 mg/L.

Odor [875]: like kerosene.

Vapor Pressure: 2.12 to 26.4 mm Hg at 21 degrees C [875].

SOLUBILITY [498]: 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]. 

API GRAVITY (60/60 degrees F) [560]:

NOTE: Created by the American Petroleum Institute (API),

API gravity is an arbitrary scale expressing the gravity
or density of liquid petroleum products [637]. This

scale was created in order to compare the densities of

various oils. 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.

 min. 11.5

METAL CONTENT [560]:

 

 Other Metals (ppm):

 Vanadium 152

 Nickel 29.0

 Chromium 1.076

 Cobalt 0.198

 Iron 24.0

 Molybdenum 0.117

 Manganese 0.248

 Zinc 1.73

 Copper 0.321

SPECIFIC GRAVITY [498]: 

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

DENSITY: 

Density (g/mL) [560]:

For temperatures of oil (T) between 0 and 30 C:

Density = 0.97871 - 0.000710 T 

NOTE: The densities of crude oils and oil products

are dependent on the temperature and degree of

weathering (i.e., as temperature goes down and/or

the fraction of weathered oil increases, density

increases). The following density values are at

"0% Weathering Volume" - in other words, fresh No.

5 fuel oil. 

 Temp( C) Density (at 0% Weathering Volume)

 0 0.932 to 0.957

 15 0.923 to 0.948

 16 0.935

 20 0.920 to 0.945

 30 0.913 to 0.938

The Density is Less than 1 g/cm(3) for Fuel oils Nos 1, 2, 4,

and 5 [498].

PAHs in NSFO (Fuel Oil 5):
A NOAA protocol [828] GC/MS/SIM expanded scan for PAHs in a

sample of fresh NSFO (Fuel Oil 5) revealed the presence of all

39 PAHs and alkyl PAHs analyzed, with the lowest concentration

being 0.6 ppm for Benzo(k)fluoranthene and the highest

concentration being 4865 ppm for C2-Naphthalenes. A

groundwater sample contaminated with weathered versions of the

same NSFO product from Colonial National Historical Park also

revealed the presence of all 39 PAHs and alkyl PAHs analyzed,

with the lowest concentration being 39.7 ppt for

Benzo(k)fluoranthene and the highest concentration being 48336

ppt for C4-Naphthalenes (Chuck Rafkind, National Park Service,

Personal Communication, 1996). Total naphthalenes in these

groundwater samples exceeded 107000 ppt, far above the 2.8 ppt

cancer risk (10-6 level) benchmark given for human health (see

naphthalene section).

Details of PAH content (ng/mg or ppm) in one fresh sample of

NSFO (Fuel Oil 5, Chuck Rafkind, National Park Service,

Personal Communication, 1996):

Naphthalene: 34.3

C1-Naphthalene: 4086.9

C2-Naphthalene: 4865.4

C3-Naphthalene: 4793.7

C4-Naphthalene: 2688.5

Biphenyl: 3.5 

Acenaphthylene: 4.1

Acenaphthene: 111.2

Fluorene: 216.0

C1-Fluorene: 658.8

C2-Fluorene: 1277.0

C3-Fluorene: 1243.8

Anthracene: 96.4

Phenanthrene: 778.2

C1-Phenanthrene/anthracene: 2116.3 (includes both)

C2-Phenanthrene/anthracene: 2716.7 "

C3-Phenanthrene/anthracene: 1923.3 "

C4-Phenanthrene/anthracene: 820.5 "

Dibenzothiophene: 25.7

C1-Dibenzothiophene: 1396.1 

C2-Dibenzothiophene: 2155.9

C3-Dibenzothiophene: 1975.5

Fluoranthene: 31.6

Pyrene: 177.9

C1-Fluoranthene/pyrene: 566.1

Benzo(a)anthracene: 41.1

Chrysene: 74.3

C1-Chrysene: 312.1

C2-Chrysene: 370.8

C3-Chrysene: 29.9

C4-Chrysene: 19.7

Benzo(b)fluoranthene 11.0

Benzo(k)fluoranthene: 0.6

Benzo(e)pyrene: 29.8
Benzo(a)pyrene: 19.3

Perylene 10.6

Indeno(1,2,3-c,d)pyrene: 2.3

Dibenz(a,h)anthracene: 4.0

Benzo(g,h,i)perylene: 11.4

Note: The above PAHs and alkyl PAHs were analyzed

by a GC/MS/SIM NOAA protocol [828] modified with

methylene chloride extraction for use with water

samples (Guy Denoux, Geochemical and Environmental

Research Group, Texas A&M University, personal

communication, 1996).

Details of PAH content (ng/L or ppt, compare to the above

listed ppm concentrations by dividing the below-listed ppt

concentrations below by 1,000,000) in one sample of

groundwater subjected to long term contamination of NSFO (Fuel

Oil 5), possibly mixed with some JP-4, motorgas, and JP-8,

Colonial National Historical Park Groundwater Site MW-10

(Chuck Rafkind, National Park Service, Personal Communication,

1996):

Naphthalene: 530.8

C1-Naphthalene: 2463.7

C2-Naphthalene: 12044.7

C3-Naphthalene: 45345.1

C4-Naphthalene: 48336.8

Biphenyl: 129.7

Acenaphthylene: 81.2

Acenaphthene: 1517.6

Fluorene: 1229.3

C1-Fluorene: 11424.5

C2-Fluorene: 28680.7

C3-Fluorene: 32509.9

Anthracene: 1972.5

Phenanthrene: 7136.3

C1-Phenanthrene/anthracene: 31377.0 (includes both)

C2-Phenanthrene/anthracene: 49447.3 "

C3-Phenanthrene/anthracene: 41754.1 "

C4-Phenanthrene/anthracene: 22250.2 "

Dibenzothiophene: 8377.8

C1-Dibenzothiophene: 24742.0 

C2-Dibenzothiophene: 44033.0

C3-Dibenzothiophene: 43900.3

Fluoranthene: 818.8

Pyrene: 5900.6

C1-Fluoranthenes/pyrenes: 16248.3 (includes both)

Benzo(a)anthracene: 1053.5

Chrysene: 1817.1

C1-Chrysene: 7398.8

C2-Chrysene: 9910.6

C3-Chrysene: 1048.5

C4-Chrysene: 625.9

Benzo(b)fluoranthene 399.2
Benzo(k)fluoranthene: 39.7

Benzo(e)pyrene: 1062.3

Benzo(a)pyrene: 602.7

Perylene 428.6

Indeno(1,2,3-c,d)pyrene: 106.8

Dibenz(a,h)anthracene: 117.1

Benzo(g,h,i)perylene: 421.4

Note: The above PAHs and alkyl PAHs were analyzed

by a GC/MS/SIM NOAA protocol [828] modified with

methylene chloride extraction for use with water

samples (Guy Denoux, Geochemical and Environmental

Research Group, Texas A&M University, personal

communication, 1996).

Additional Detailed Physicochemical information from Environment

Canada [560]: 

NOTE: In this section, for properties with more than one

value, each value came from its own source; in other words, if

API Gravity at 60 F was measured several times and several

different answers were obtained, all of the answers are

provided [560]:

 VISCOSITY

NOTE: Viscosity is a measure of the internal friction or the

resistivity to flow of a liquid [637]. The viscosities of

crude oils and oil products are dependent on the temperature

and degree of weathering (i.e., as temperature goes down

and/or the fraction of weathered oil increases, viscosity

increases). The following viscosity values are at "0%

Weathering Volume" - in other words, fresh No. 5 fuel oil. 

Kinematic Viscosity (mm2/sec or cSt):

Temp( C) Light Heavy 

 10 200 to 473 > 473

 15 152 to 313 > 313

 20 123 to 233 > 233

 25 100 to 165 165 to 327

 30 74 to 125 125 to 200

 38 26.4 to 65 65 to 194

 40 40 to 75 75 to 100

NOTE: Data obtained from a graph (Curl 77)

Pour Point (degrees C): 

Pour point is the lowest temperature at which an oil sample is

observed to flow when cooled under prescribed conditions. It

is affected by weathering (i.e., the larger the fraction of

oil weathered, the higher the pour point).
 max -9.4

 -17.8

 FIRE AND REACTIVITY

NOTE: Flash point is the lowest temperature at which vapors

arising from the oil will ignite momentarily (i.e., flash) on

application of a flame under specific conditions [637].

Flash Point (degrees C):

 > 54

 min 60

 min 55

 > 54.4

Flammability Limits (Volume %):

 in air: 1 to 5

 DISTILLATION

NOTE: Distillation data provides an indication of an oil's

volatility and relative component distribution. Distillation

data is reported as volume % recovered. 

 Boiling Range (degrees C): 

 

 218 to > 570

 SENSATION

 

 Color 

 Brown 

 OTHER

Reid method Vapor Pressure (kPa):

Temp( C) Pressure 

 37.8 0.689 (estimated)

 Information from OHM/TADS [499]:

FIRE/EXPLOSION/CORROSION HAZARDS

Fire hazard:

Flammability: MODERATE. COMBUSTION WITH HEATING MODERATE

HAZARD

Standard codes: NFPA - -,2,0

Toxic combustion products: NO GREAT HAZARD

Flash point (degrees C): 66

Autoignition temperature (degrees C): 408
Fate.Detail: Detailed Information on Fate, Transport,

Persistence, and/or Pathways:

See Br.Fate section above for additional information.

 Persistency [499]: Loss of fuel oil after 40 hour in bubbler

apparatus - 2.% Evaporated, .005% Dissolved.

Laboratory and/or Field Analyses:

As documented in sections of above, Fuel oil 5 contains a wide

variety of PAHs. In fact, both fresh fuel oil 5 and a groundwater

sample contaminated with weathered versions of the same Fuel Oil 5

revealed the presence of all 39 PAHs and alkyl PAHs analyzed by a

GC/MS/SIM NOAA protocol [838] modified for use with water samples

(see Chem.Detail section above). 

Appreciable concentrations of PAHs are present in residual

fuels because on the common practice of using both uncracked and

cracked residues in their manufacture [747]. 

Many lab methods have been used to determine PAHs, BTEX

compounds, and other common components of this fuel [861], but when

potential biological effects are to being considered, many of the

methods historically used have been determined to be inferior to

the NOAA protocol expanded scan [828] being recommended by many

risk assessment experts in 1996. Many historically used methods,

including EPA standard semi-volatile scan number 8270, do not cover

important alkyl PAHs and do not utilize low-enough detection limits

to use in ecological risk assessments. See also: PAHs as a Group

entry.

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]. 

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).

Due to the presence of light aromatics and PAHs in fuel oils,

we recommend the following decision tree: 

Decision Tree (dichotomous key) for selection of lab methods

for measuring contamination from midrange to heavy crude oils,

number 4 and heavier fuel oils, bunker C and all other oils

considered to be heavy):

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. Note: although heavy

products have a lower percentage of BTEX and other relatively

soluble compounds which typically threaten drinking water,

ground water, or water column organisms, some heavy oils

including crudes do contain some of these water soluble

compounds, so they cannot be ignored........................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 8240. The standard EPA GC/MS

method 8240 protocol will be 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 8240 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 8240), 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 8240 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 8240 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 8240 or modified EPA method 8240 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

8240 or modified EPA method 8240 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 expanded scan protocols for polycyclic aromatic

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

[828].

End of Decision Tree Key.

It is important to understand that contaminants data from

different labs, different states, and different agencies, collected

by different people, are often not very comparable (see also,

discussion in the disclaimer section at the top of this entry).

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]. 

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. 

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 inappropriate

methods. The use of inappropriate methods is particularly common

related to oil products.

Additional details:

The relative proportions of hazardous compound constituents

present in petroleum-based oil contamination is typically quite

variable. The farther one progresses from lighter towards heavier

oils (the general progression from light towards heavy is the

following: Diesel, No. 2 Fuel Oil, Light Crudes, Medium Crude Oils,

Heavy Crudes, No. 6 Fuel Oil, etc.) the greater the percentage of

PAHs and other semi-volatiles (many of which are not so immediately
toxic as the volatiles but which can result in long term/chronic

impacts). Heavier oils such as fuel oil 5 thus need to be analyzed

for the semi volatile compounds which typically pose the greatest

long term risk, PAHs and alkylated PAHs. 

Screening scans: Certain screening scans may be used to

monitor the position and magnitude of contamination. Below are a

few notes related to screening scans versus distillate fuels:

GC/FID: 

While a screening analysis such as GC/FID should be

adequate for mid-range products such as diesels, fuel oil

no. 2, and possibly jet fuels, lighter gasoline fractions

will be lost in a GC/FID analysis (which uses extraction

and burning) [657]. Distillate fuels in the C9 to C16

range normally have a boiling range well above the

boiling-point of benzene; accordingly, the benzene

content of this fraction is usually low [747]. 

Method 8015:

EPA Method 8015 (for Non-halogenated Volatile Organics)

is a gas chromatographic method sometimes recommended for

the analysis of volatile and semivolatile compounds. It

can be used to characterize light and midrange petroleum

distillates such as gasoline, diesel, fuel oil, and

kerosene. This method can be used to obtain some gross

fingerprint information for differentiation between

petroleum products, as well as detailed information that

can be used to differentiate between different batches of

the same product. The major limitation of Method 8015 is

its inability to detect nonvolatile compounds. The State

of California recommends a "modified method 8015"

(different from EPA's method 8015 and also different from

EPA method 418.1) for gasoline, kerosene, diesel oil, or

other fuels in soil and groundwater, as specified in the

Leaking Underground Fuel Tank (LUFT) Manual [465].

The California LUFT methods call for packed GC columns

which have poor resolving power and make it difficult to

obtain detailed information about the hydrocarbon type

[810]. Superior GC columns and superior methods (such as

ASTM 2887) are available [810]. For example, narrow-bore

capillary columns can analzye most of the gasoline,

entire diesel fractions, and a substantial portion of the

crude oil range [810].

Using the California LUFT manual methods, only an

experienced analyst will be able to differentiate diesel

fractions from aged gasoline [810]. The oversimplified

California methods and models are plagued with many

problems [808,810]. Choosing an appropriate solvent for

semivolatile analyses always presents a problem; some

solvents extract certain compounds better than others and
many present environmental or health risks [810].

HPLC screening scans:

In cases where a less expensive screening scan is

desired, consider using an HPLC/Fluorescence scan method

for sediment or bile metabolite samples. Such scans are

available from laboratories at Texas A. and M., Arthur D.

Little, and the NOAA lab in Seattle. This scan is less

prone to false negatives and various other problems than

some of the more common screening methods (TPH-EPA 418.1

and Oil and Grease). HPLC/Fluorescence is less expensive

than some of the more rigorous scans. The

HPLC/fluorescence scan can be used for analyses of fish

bile: the scan looks at bile directly for the presence of

metabolites of PAHs: naphthalene, phenanthrene, and

benzo(a)pyrene. The technique does not identify or

quantify actual PAH compounds, but subsequent gas

chromatography analyses can be done to confirm the

initial findings. Even the semi-quantitative Total

Scanning Fluorescence (TSF) done inexpensively by labs

such as GERG are a better measure of PAH contamination

than GC/FID, which measures less persistent and less

hazardous aliphatics. Additional Pros: HPLC Fluorescence screening

methods have been performed extensively by NOAA to

locate hotspots for crude oil contamination.

NOAA's experience with the Exxon Valdez spill

indicated that concentrations of aromatic

hydrocarbons measured by HPLC/Fluorescence

screening were highly correlated with the sums of

Aromatic hydrocarbons determined by GC/MS, thus

validating the screening method as an effective

tool for estimating concentrations of petroleumrelated aromatic hydrocarbons in sediments.

Moreover, differences in HPLC chromatographic

patterns among sediments suggested different

sources of contamination, e.g., crude oil or diesel

fuel. Allows crude determinations related to

sources: HPLC/Fluorescence analyses allowed at

least rough differentiation between aromatic

hydrocarbons which may have originated from diesel

fuel versus those from boat traffic [521] and The

procedure was successfully applied to

fingerprinting' gasolines, kerosines, diesel oils,

heavy fuel oils, lubricating oils, and ship bilge

oils [AUTHOR: Saner WA; Fitzgerald GE, II

PUBLICATION YEAR: 1976 TITLE: Thin-Layer

Chromatographic Technique for Identification of

Waterborne Petroleum Oils JOURNAL: Environmental

Science and Technology SOURCE: Vol. 10, No. 9, p

893-897, September 1976. 6 fig, 4 tab, 7 ref.]. 
EPA 418.1 for TPH:

Although EPA method 418.1: Petroleum Hydrocarbons

expressed as Total Petroleum Hydrocarbons (TPH), is

recommended by many State agencies, some consulting

firms, and some laboratories for certain regulatory

and screening applications (often leaking

underground storage tanks), this method is not well

suited to fuel oil no. 6 contamination or to the

more persistent hazardous constituents in oil. Low

values tend to give the mistaken impression that a

site is clean when it really isn't (prone to false

negatives). For example, a field test of

bioremediation of soils contaminated with Bunker C

at a refinery in Beaumont, Texas, utilized oil and

grease data, which (although the data was quite

variable) seemed to indicate bioremediation was

taking place [728]. A comparison of the oil and

grease data at this site with TPH data at this site

suggested the same thing, that the data was quite

variable but if anything, the oil was slowly being

cleaned up by bioremediation (Bruce Herbert, Texas

A. and M., Department of Geology, personal

communication, 1995). However, a later study of

the same site utilizing the expanded scan for PAHs

(a modified EPA 8270 including alkyl homologues and

lower detection limits), indicated that very little

bioremediation of hazardous alkyl PAHs and multiring PAHs was actually taking place [727]. Thus,

utilizing either oil and grease or TPH analyses

would tend to lead one to the faulty conclusion

that the harmful compounds were being naturally

cleaned up at an acceptable rate. This is partly

because the TPH and oil and grease methods tend to

favor the lighter and less alkylated PAHs, whereas

many of the carcinogenic and longer lasting PAHs

are the heavier multi-ringed and alkylated

compounds. For more information, see Petroleum

Hydrocarbons entry. 

See also: Laboratory and/or Field Analyses section in Oil

Spills entry for information on biological indicators of oil

exposure. See also: PAHs as a Group entry.