ENVIRONMENTAL CONTAMINANTS ENCYCLOPEDIA

FUEL OIL NUMBER 6 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 80525WARNING/ 

### 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. T echnical 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
comp iling or summarizing what other human beings have writt en. Therefore, it most likely contains some mistakes and/or potential misinterpretations and should be used primarily as a way to search quickly for basic inform ation and information sources. It should not be viewed as an exhaustive, "last -word" source for critical applications (such as those re quiring 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 jo urnal 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 arb itrarily changing what the author said.

Most likely additional transcription errors and typos have b een 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 di fferent results which lead them to different conclusions. In compiling the Ency clopedia, 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 pract ice 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].

Differ ences in field and laboratory methods are also major issues related to (the l ack 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 informat ion. 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; itsimply 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 refere nce 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.

Alth ough the editors of this document have done their best in the limited time avail able 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 bo ttom 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 introduct ion, an explanation of how to use this document in general, an explanation of how to search for power key section h eadings, 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 6 (No 6 Fuel Oil, Fuel Oil No. 6, Bunker C, CAS number 68553-00-4)

Br ief 

### Introduction:

Br.Class : General Introduction and 

### Classification Information:

Fuel oils are comprised of mixtures of petroleum distillate hydrocarbons [363,499]. Fuel oil #6 is a petroleum distillate fraction with a boiling point >400 degrees F [369]. Fuel oil No. 6 is the highest boiling fraction of the heavy distilla tes from petroleum. No. 6 oils represent approximately 5 to 8% of the original crude petroleum, but the exact yield depends on the source, refinery design and operations, and product requirements [557].

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. Residual oils are complex and variable mixtures of relatively high molecular weight compounds and are difficult to characterize in detail. Molecular composition includes asphaltenes, polar aromatics, naphthalene aromatics, aromati cs, saturated hydrocarbons and heteromolecules containing sulfur, oxygen, nitrogen and metals (see Chem.Detail for detailed analysis) [747]. Dimethyl and trimethyl naphthalenes are important components of Fuel No. 6. The viscous residuum fuel oils, numbers 5 and 6, sometimes referred to as bunker fuels, usually must be preheated before being burned [498].

Fuel oil No. 6 contains about 15% paraffins, 45% naphthenes, 25% aromatics, and 15% non-hydrocarbon compounds; the hydrocarbons contain 30 and greater carbon
atoms [557]. It consists of straight-run and cracked distillates and residuals and contains aliphatics and aromatics [369].

Appreciable concentrations of polycyclic aromatic hydrocarbons (PAHs) are present in residual fuels because of the common practice of using both uncracked and

crac ked residues in their manufacture. Most blending stocks are likely to contain 5% or more of four- to sixring condensed aromatic hydrocarbons (see the Chem.Detail
sect ion below for details). The exact identities and concentrations of PAHs in a pa rticular sample depends on the nature and amounts of blending stocks as well as the 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].

According the US Coast Guard Emergency Response Notification System (ERNS), fuel oil no. 6 is one of the most commonly spilled petroleum products the U.S [635].

Br.Haz : General 

### Hazard/ToxicitySummary:

Hazards to Aquatic Biota, Wildlife, and Various Living Things Other than Humans:

In the aquatic environment, the main concern is the
aromat ics in Fuel oil 6. Benzene, Toluene, Ethyl Benzene, and Toluene (BTEX) compounds, although they do not make up a large percentage of this product, are present and could represent an acute toxicity risk. Due to their relative persistence and potential for various chronic effects (like carcinogenicity), the heavier aromatic PAHs, (and particularly the alkyl PAHs) in Fuel oil 6 can pose long term (chronic) hazards in contaminated soils, sediments, and groundwater.

Heavy oils (Including Heavy Cr ude Oils, No. 6 fuel, and Bunker C) are prone to severe impacts to waterfowl and fur-bearing mammals (coating and ingestion) [741,777]. They may weather slowly, and potentially sink (depending on product density and water density) to impact benthic organisms. However, in general, residual fuels are less acutely toxic relative to other oil types [777].

Many of the PAHs found in this product (see Chem.Detail section below) are more toxic in sunlight or other UV source than elsewhere (see PAHs as a group entry).

One of the hazardous groups of compounds in fuel oil is PAHs. PAHs may be trans located in plants and may accumulate in plants grown in contaminated soil [40]. Presumably this also oc curs 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 metabolicpathways have not been clearly defined. This is an important factor since when PAHs do degrade through meta bolism, 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 wil dlife, 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 grow th-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].

For additional information on the effects of spilled Bunker C on plants, see Tis.Misc. section below.

Hazards to Humans:

Fuel oil #6 would be expected to be a skin, eye and respiratory irritant and a CNS depressant from inhala tion of large amounts of the vapor or mist. Prolon ged or repeated contact with the skin may produce a defatting dermatitis with dryness and cracking. This product may contain substances which have caused kidney damage in laboratory animals [369].

Chronic effects of some of the constituents in fuel6 (such as naphthalenes) include changes in the liver and kidney [766].

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].

Br.Car : Brief Summary of Carcinogenicity/ 

### CancerInformation:

No studies were found for fuel oil #6 [369]. The PAHs in this product include both carcinogenic and noncarcinogenic compounds. 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.

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
contam inated sites, are likely to continue. There are some clearly wrong ways to go about it, but defining clearly right ways is more difficult. Perhaps the most unambiguous thing that can be said about complex mixtures of PAHs and other aromatics 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 S PMD, then test the mixture for carcinogenicity, toxicity, and phototoxicity (James Huckins, National Biological Service, and Roy Irwin, National Park Service, personal communication, 1996).

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].

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 experts disagree about the extent to which the two are synonomous (see PAHs as a group entry).One investigator found increased lethality in rats exposed to fuel oil,but no increase in malformations were found [559].

Studies showed that contamination of quail eggs with Bunker C via maternal routes resulted in reduced egg production and reduced egg viability [558].

No reproductive studies were found for fuel oil #6 [369]. The results are mixed, but some reproductive and fetotoxic effects have been as sociated with a few of the compounds found in fuel no. 6 [766] (see sections on individual compounds for more details).

Exposure of avian eggs to hydrocarbons may be direct or maternal. Small amounts of exposure (50-100 uL) by direct transfer of oil on plumage to the eggs in the nest has been shown to be toxic to embryos. Studies showed that c ontamination of quail eggs with Bunker C via maternal routes resulted in reduced egg production and reduced egg viability (Grau et al., 1977) [558].

Br. 

### Fate : Brief Summary of Key Bioconcentration, Fate, Transport, Persistence, Pathway and Chemical/Physical Information:

Fuel oil number 6 is a heavy oil with little or no evaporation or dissolution potential [741,777]. As such, fuel oil 6 may be highly persistent, with the potential for long-term sediment contamination. Other fate characteristics of heavy oils (Including Heavy Crude Oils, No. 6 fuel, and Bunker C) include the following [741]:

-Water-soluble fraction likely to be <10 ppm -Heavy contamination of intertidal areas likely -Long-term contamination of sediments possible -Weathers very slowly -Dispersion seldom effective -Shoreline cleanup difficult under all conditions

Among the fuel oils, number 6 is the heaviest, with a specific gravity of about one. One of the three types of (unusual) scenarios in which one might tend to worry most about sinking fractions of oil includes spills of very heavy oils in freshwater, such as spills of heavy No. 6 fuel (Jackie Michel, Research Planning Inc., S. Carolina, Personal Communication,1995). For example, in the Mobil oil spill in the Columbia River near Portland, Oregon (03/19/84), spilled oil was distributed on the surface of the river, throughout the water column, and on the river bottom. Oil in the river bottom formed a pool in the eddy created by the hull of the Mobil oil [555].In general, even though density of oil increases through weathering, the density will rarely increase to that of freshwater (approximately 1000 kg/m3) or marine water (about 1024 kg/m3). However, heavy fuels such as no. 6
may weather to densities heavier that water since the unweathered density already ex ceeds 900 kg/m3 (a typical No. 6 fuel oil is API 12.3 which corresponds to a density of 971 kg/m3 at 22 +or- 2 degrees Celsius) [554].

During a spill, the high visco sity of No. 6 fuel oil can often lead to the formation of "pancake" like tar globs when the temperature of the wa ter is lower than the pour point of the oil [555]. These semi-solid, tar-like oils have low substrate penetrating ability, and are difficult to remove from contaminated surfaces. Emulsions formed by No. 6 fuel oils are very stable [555]. Examples of No. 6 fuel oil spills with pan cake formation include the Presidente Rivera in the Delaware River (06/24/89), and the Argo Merchant near Nantucket Island, Massachusetts (12/15/76) [555]. For a more complete discussion of sinking oil, and oil spills in general, see the Oil Spill entry.

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.



### Syn onyms/ Substance Identification:

BUNKER C [499,557,558,560] GRADE 6 [499] FUEL OIL NO. 6 [365,369] FUEL OIL #6 [369] HEATING OIL NO. 6 [369] HEATING OIL #6 [369] NO. 6 FUEL OIL [369,365,637] NO. 6 HEATING OIL [369] #6 FUEL OIL [369] #6 HEATING OIL [369]

The United States Navy refers to bunker C as "Navy heavy" [637].



### As sociatedChemicals or Topics (Includes Transformation Products):

See also individual entries:

Fuel Oil, General LAPIO (A very heavy #6 fuel oil) [775].Oil Spills Petroleum, General

See also entries on various PAHs and Alkyl PAHs. All 39 PAHs in the NOAA expanded scan [628] have been found in this product; these include, but are not limited to:

Phenanthrene 1-Methylphenanthrene Fluoranthene Pyrene Benz(a)anthracene Chrysene Benzo(a)pyrene Benzo(e)pyrene

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



### Wa ter DataInterpretation, 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.Hi gh (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.Typ ical (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 individualcomponents of this mixture.

W.Con cern 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 Benchm arks Related to Protection of Aquatic Biota in General; Includes Water Concentrations Versus Mixed or General Aquatic Biota):

Information from OHM/TADS [499]:

Aquatic toxicity:

Freshwater toxicity text (Conc.* in ppm):
Conc.|Expos|Specie |Effect|Test Environment | | (Hr)| | | |

------------------------ ------------------------------- 2400| 48|JUVENILE |TLM | | | |AMERICAN SHAD | | | > 127| 96|BLUEGILL |LC50 | |

Saltwater toxicity text (conc.* in ppm):
Conc.|Expos|Specie |Effect|Test Environment | | (Hr)| | | |

------------------------ ------------------------------- 2,417| 48|JUVENILE |TLM | | | |AMERICAN SHAD | | | 10| 96|MENHADEN |LC50 | | 1,952| 96|JUVENILE |TLM | | | |AMERICANSHAD | | | 26| 96|GRASS SHRIMP |LC50 | | 1,302| 96|JUVENILE |NO | | | |AMERICAN SHAD |KILL | |

Aquatic toxicity data from Environment Canada [560]:

Toxicity (mg/L): Juvenile American shad-- 48h TLm*

1. Freshwater 2400 #1 2. Saltwater 2417 #2

*Note from Roy Irwin: I don't know of any lab method which measures the concentration of this product as a whole after it has been spilled in open waters, so these may reflect lab concentrations estimated by dilution ratios. Since this information can't be replicated in the field, it has questionablevalue related to spills and the information which one instead needs to obtain to compare to benchmarks and standards includes the concentrations of individual PAHs and alkyl PAHs [828].

W.Pl ants (Water Concentrations vs. Plants):

Information from OHM/TADS [499]:

Toxicity to plants: Aquatic plants (ppm): 75*

*Note from Roy Irwin: I don't know of any lab method which measures the concentration of this product as a whole after it has been spilled in open waters, so these may reflect lab concentrations estimated by dilution ratios (Roy Irwin, National Park Service, Personal Communication, 1996). Since this information can't be replicated in the field, it has questionable value related to spills and the information which one instead needs to obtain to compare to benchmarks and standards includes the concentrations of individual PAHs and alkyl PAHs [828].

Abstract Contributed by Carol Schuler, Fish and Wildlife Service, Portland Oregon):

AUTHOR: Giddings JM; Washington JN PUBLICATION YEAR: 1981 TITLE: Coal-Liquefaction Products, Shale Oil, and Petroleum. Acute Toxicity to Freshwater Algae JOURNAL: Environmental Science and Technology SOURCE: Vol 15, No 1, p 106-108, January, 1981. 2 Tab, 31 Ref. KEYWORDS: Fuels; Toxicity; Synthetic fuels; Oil spills; Aquatic life; Aquatic algae; Aquatic plants; Coal liquefaction industry; Shale oil industry; Cyanophyta KEYWORDS(*): *Oil pollution; *Water pollution effects; *Algae MAJOR TOPIC: Water Quality Management, Protection - Effects of Pollution ABSTRACT: Freshwater algae, Selenastrum capricornutum (a green alga) and Microcystis aeruginosa (a blue-greenalga), showed acute toxic effects from exposure to water soluble frac tions (WSF) of oils in the following order: coal liquefaction products>shale oil products>petroleum products. WSF's were tested in concentrations of 0.1, 1, 10, and 100%. Most of the 11 coal liquefaction products were toxic at 1% and greater; 4 at 0.1%. Three unrefined shale oils inhibited photosynthesis at 10% and greater and were variably toxic at 1% and less. Two refined shale oils and the 5 petroleum products (DFM, No 2 diesel oil, and three No 6 fuel oils) showed little toxicity at all concentrations with the except ion of some at 100% WSF. All samples were tested for absorbance at 254 nm, the absorption maximum for benzene and an approximation of aromatic content. The products with higher absorbances tended to be the most toxic to algae. (Cassar-FRC) INST. AUTHOR: Oak Ridge National Lab. AUTHOR ADDRESS: TN. Environmental Sciences Div.

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.Fi sh (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.Wild life (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 Ot her 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.



### Sed iment DataInterpretation, 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.Hi gh (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.Typ ical (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.Con cern Levels, Sediment Quality Criteria, LC50 Values, Sediment Quality Standards, Screening Levels, Dose/Response Data and Other Sediment Benchmarks:

Sed.Gen eral (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.Pl ants (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.Inv ertebrates (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.Fi sh (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.Wild life (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 DataInterpretation, 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.Hi gh (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

reme diation of these soils [735]. All ports surveyedindicated 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 abandon ed, 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 identif ied, 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 w eathered crude) rather than gasoline [735]. The concentrations found [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.Typ ical (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.Con cern Levels, Soil Qual ity Criteria, LC50 Values, Soil Quality Standards, Screening Levels, Dose/Response Data and Other Soil Benchmarks:

Soil.Gen eral (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):

In 1988, New Jersey started us ing a total petroleum hydrocarbon concentration of 100 ppm as a soil cleanup guideline thought to ensure that concentrations in ground water do not exceed drinking water standards; 100 ppm is thought to be relatively conservative and designed to identify potential problems [347]. More recently, the New Jersey standard was broken down by fuel type: if number 6 or 4 fuel oils, the guideline is 100 ppm; if number 2 fuel oil or diesel the guideline is 1,000 ppm (Steve Tatar, New Jersey Leaking Underground Storage Tank project, personal communication). The latest New Jersey values are part of a proposed cleanup standard (March 31, 1992, NJ Administrative Code) for all soil values(not j ust leaking underground tanks). Most New Jersey officials seem to believe the TPH guidelines in NJ are in dry weight, since soil values for other parameters are, but they hadn't yet been able to find the written confirmation as of this writing.

Soil.Pl ants (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.Inv ertebrates (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.Wild life (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).

Others would point out that fuel oil spills into soils are not necessarily a trivial environmental threat related to ecotoxicology (emphasis on living things otherthan 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.

Tis sue and Food Concentrations (All 

### Tissue DataInterpretation Subsections Start with "Tis."):

Tis.Pl ants:

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.Inv ertebrates:

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 Lev els 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.Wild life: 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 W ell into Other Categories, Includes Oral Doses Administered in Laboratory Experiments):

Information from RTECS [365]:LD50/LC50 - LETHAL DOSE/CONC 50% KILL

RAT: LD50; ROUTE: Oral; DOSE: 5300 mg/kg;
REFERE NCE: Acute Toxicity Data. Journal of the American College of Toxicology, Part B 1:139, 1990.

LDLO/LCLO - LOWEST PUBLISHED LETHAL DOSE/CONC

RABBIT: LDLo; ROUTE: Skin; DOSE: 5200 mg/kg;
REFERE NCE: Acute Toxicity Data. Journal of the American College of Toxicology, Part B 1:139, 1990. 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):

NOTE: Below are three case studies on the effects of spilled Bunker C on plants (Selected highlights copied from NOAA Restoration Guidance Document by permission of Eli Reinharz of NOAA DART Team) [622]:

Case Study 1:In October 1978 the ship Howard Star released ~40, 000 gallons of Bunker C and lubricating oils into Tampa Bay, Florida. At least 20 km of fringe mangrove shoreline was affected [622].

The oiled sites in Tampa Bay were visited 2 months, 9 months, 14 months and 16 months after the discharge. Each discharge site and adjacent reference sites were examined by aerial surveys to locate defoliated areas. Areas with obvious defoliation and reference areas were selected for subsequent ground surveys. The heaviest defoliation of mangroves, seed ling mortalities, and mortalities of canopy-dwelling animals were observed where the heaviest oiling had occurred. The degree of oiling was controlled largely by geomorphic features of the forest [622].

On the basis of geomorphic features, two types of oil impacts were observed in Tampa Bay: outer fringe and an inner basin impacts. Impact to the outer fringe occurred at two sites where defoliation was concentrated in the outer mangroves. In these areas, mangrove mortality appeared to be related to (1) degree of exposure to

waves and currents and (2) degree of oil penetration into the forest substrate. The latter was enhanced by the presence or absence of burrowing crabs. In Tampa Bay, exposed areas contained few burrows, and oil was removed by wave action within a few weeks. Impact to the inner basin was observed in two oiled areas of Tampa Bay where high tides moved oil up over coastal berms and into shallow basins behind them, spreading the oil over a wide area with a less well defined effects [622].

Case Study 2:

In December 1978 the barge Peck Slip released 440,000-460,000 gallons of Bunker C fuel oil into Bahia Medio Mundo, Puerto Rico, oiling at least 10 km of mangrove-dominated shoreline. In 1981 the oiled sites in Midia Mundo were visited immediately after the discharge, and 3-4 months and 10 months after the discharge. As in the Howard Star discharge, each discharge site and adjacent reference sites were examined by aerial surveys to locate defoliated areas. Areas with significant defoliation and reference areas were selected for subsequent ground surveys. The heaviest defoliation of mangroves, seed ling mortalities, and mortalities of canopy-dwelling animals were observed where the heaviest oiling had occurred.The degree of oiling was controlled largely by geomorphic features of the forest [622].

On the basis of geomorphic features, two areas of oil impact were observed at Media Mundo, an inner fringe impact and an inner basin impact. In the inner fringe impact, oil was concentrated on the inner mangroves, which are located on the inner berm of the forest. The affected inner berm site became heavily defoliated within 2 months of oiling, and remained so 18 months later, with the substrate and prop roots remai ning oiled even after
Hurr icane David in 1979. An inner basin impact, simi lar to that described in Tampa Bay, was also observed at Media Mundo [622].

Case Study 3:

In December 1968, the tanker Witwater ran aground off the Caribbean coast of Panama, releasing 20,000 barr els of diesel oil and bunker C fuel oil. Injury to mangrove habitats was assessed qualitatively approximately 2 months after the discharge. The pneumatophores of black mangroves were thickly covered with a mi xture of mud and oil. Prop roots of red Mangroves were coated with a thick layer of oil. Red mangrove seedlings were covered with oil and suffered massive mortality. Populations of crabs, Uca sp., were reduced relative to non-oiled areas [622].

Bio.Detail : Detailed Information on 

### Bioconcentration, Biomagnification, or Bioavailability:

The alkyl PAHs tend to bioaccumulate more than their parent compounds (see PAHs entry).

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.



### Int eractions:

May act as synergist to pesticides [499].

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.



### Us es/Sources:The vi scous 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 oper ations, and industrial power plants, and usually must be preheated before being bu rned [498]. Bunker C is used primarily for firing steam boilers in the generation of e lectricity, large-scale heating, and powering marine vessels [557]. Bunker C fuel oil (fuel oil no. 6) is a heavy fuel oil used by ships, by industry, and for large-scale heating installations [637].



### Fo rms/ Preparations/Formulations:

Conventional #6 fuel oil is a mixture of the heavy residual oil left after the lighter components of crude oil are removed through a refining process, which is then blended with lighter oils to meet specifications for viscosity, pour point, and API gravity [775]. No. 2 fuel oil is a common ble nding agent, used to reduce the viscosity of conventional #6 fuel oils. Because #2 fuel oil (which is a good solvent for many blended residual fuel oils) is used as the cutter stock, #6 fuel oils are usually well-blended mixtures that are stable during long-term storage and do not tend to separate when spilled [775]. Like fuel oil #6, LAPIO (Low-API gravity oils) is a blend of heavy and light oil, but it ge nerally 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:

Since PAHs are important hazardous components of this product, risk a ssessments should include analyses of PAHs and alkyl PAHs utilizing the NOAA protocol expanded scan [828] or other rigorousGC/MS/SIM methods. PAHs and alkyl PAHs in this product can be analyzed to risk assessment-appropriate (low; 1-10 ppb or lower) detect ion limits using the GC/MS/SIM NOAA protocol expanded scan [828].

Caution: Every individual petroleum product has a unique "fingerprint," or distinct combination of concentrations of various PAHs and other petroleum constituents. Due to the varying properties of the same general category of a petroleum product (for example, each source and stage of a No. 6 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. For example, the API gravity of No. 6 fuel oils ranges from 7 to 14. Therefore, the below comments on No. 6 fuel oils are to be considered as representative, but not absolute values typical of every batch of the product with the same name.

Fuel oil No. 6 contains about 15% paraffins, 45% naphthenes, 25% aromatics, and 15% non-hydrocarbon compounds; the hydrocarbons contain 30 and greater carbon atoms [557]. Another source lists 21.1% saturates, 34.2% aromati cs, 30.3% polar aromatics, and 14.4% asphaltenes [747]. Fuel oil No. 6 consists of straight-run and cracked distillates and residuals and contains aliphatics and aromatics [369]. Appr eciable concentrations of PAHs are present in residual fuels because of the common practice of using both uncracked and cracked residues in their manufacture. Most blending stocks are likely to contain 5% or more of four- to six-ring condensed aromatic hydrocarbons. The following table lists the concentrations of three- to fi ve-ring aromatics determined in one sample of No. 6 fuel oil (NOTE: The exact identities and concentrations of PAHs in a particular sample depends on the nature and amou nts of blending stocks as well as the virgin and cracked residues) [747]:

Hydrocarbon Concentration (ppm)

Phenanthrene 482 2-Methylphenanthrene 828 1-Methylphenanthrene 43 Fluoranthene 240 Pyrene 23 Benz(a)anthracene 90 Chrysene 196 Triphenylene 31 Benzo(a)pyrene 44 Benzo(e)pyrene 10 Perylene 22

Octanol Water Log: 3.3 to 7.06 [875].Henry's Law Const. 5.9E-05 to 7.4 [875].

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]:

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

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].

14.1 10 7.3 15.5 12.3

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 weat hering. The following density values are at "0% Weathering Volume" - in other words, fresh No. 6 fuel oil.

Temp( C) Density (at 0% Weathering Volume) 0 0.969 to 0.980 0.986 0.980 0.9941 5 0.976 0.9904 10 0.973 0.963 0.9867 15 0.974 0.969 0.9830 15.6 0.959 to 0.972 0.9710 0.963 20 0.956 to 0.970 0.966 0.97880.9483 (estimated) 25 0.964 0.9749 30 0.950 to 0.964 0.9718

HYDROCARBON GROUP [560]:

NOTE: The main constituents of oil are generally grouped into the below categories. As phaltene content increases with increasing weathering, as does wax content.

Hydrocarbon Group Analysis (Weight %):

Saturates 21.1 21.1 20.98 15 24.4 21.1 Aromatics 34.2 34.2 33.83 25 54.6 34.2 Polars 30.3 30.3 7.39 15 14.9 30.3 Asphaltenes 14.4 14.4 6.17 9.28 14.4 6.73 6.5 Naphthenes 45

Wax Content (Weight %): 11.7 55.4

METAL CONTENT [560]:

Other Metals (ppm):

Nickel 62 89 35 8.6 34.3Vanadium 25 73 272 42 270 Molybdenum < 0.6 272 ppb Potassium < 1.5 Zinc 1.61 1.22 Lead < 3 Iron 35 13.2 Chromium < 1.5 440 ppb Magnesium 23.9 Copper 1.2 0.60 Titanium < 0.6 Barium < 0.3 Cobalt 197 ppb Manganese 149 ppb

SOLUBILITY:

Aqueous Solubility (mg/L) [560]: The solubility of oil in water can be determined by bringing to equilibrium a volume of oil and water, and then analyzing the water phase. Oil's aqueous solubility is expressed as the cumulative concentration of the individually dissolved components. Solubility is significantly reduced by weathering.

(Temp not given) 20 C 22 C Seawater 2.29 6.3 Distilled Water 1.7 0.4 Fresh Water 4.45

Solubility [554]:

1.95 mg/L (salt H2O3, at 22 +or- 2 degrees Celsius) 4.23 mg/L (d.d H2O, at 22 +or- 2 degrees Celsius)

Solubility: about 5 mg/L [875].

Concentrations of PAHs in a re ference Bunker C residual oil versus Two Crude Oils Another Refined Oil [177]:

NOTE: The composition of chemicals making up petroleum hydrocarbon batches is quite variable, so in spill scenarios, it is often first necessary to determine the exact composition of the oil in the particular spill in question. The following concentrations in mg/kg (ppm)are from API reference oils:

South Kuwait No. 2 Bunker C Compound oil LA crude crude fuel oil residual

Naphthalene 400 400 4,000 1,000 1-Methylnaphthalene 800 500 8,200 2,800 2-Methylnaphthalene 900 700 18,900 4,700 Dimethylnaphthalenes 3,600 2,000 31,100 12,300 Trimethylnaphthalenes 2,400 1,900 18,400 8,800 Fluorenes 200 <100 3,600 2,400 Phenanthrene 70 26 429 482 1-Methylphenanthrene 111 - 173 43 2-Methylphenanthrene 144 89 7,677 828 Fluoranthene 5.0 2.9 37 240 Pyrene 3.5 4.5 41 23 Benz(a)anthracene 1.7 2.3 1.2 90 Chrysene 17.56 6.9 2.2 196 Triphenylene 10 2.8 1.4 31 Benzo(ghi)fluoranthene 1 <1 Benzo(b)fluoranthene <0.5 <1 Benzo(j)fluoranthene <0.9 <1 Benzo(k)fluoranthene <1.3 <1 Benzo(a)pyrene 0.75 2.8 0.6 44 Benzo(e)pyrene 2.5 0.5 0.1 10 Perylene 34.8 <O.l - 22 Benzo(ghi)perylene 1.6 <1

Phys ical 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 0.11C22 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 mate rial; 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 15.6 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.

PAHs in NSFO (Fuel Oil 5):

NOTE: The following information on fuel 5 is included for general information because fuel 5 is typically about 75- 80% of fuel 6 [641].

A NOAA protocol [828] GC/MS/SIM expanded scan for PAHs in asample 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: 19.3Perylene 10.6 Indeno[1,2,3-c,d]pyrene: 2.3 Dibenz(ah)anthracene: 4.0 Benzo(ghi)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

conc entrations 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: 39.7Benzo(e)pyrene: 1062.3 Benzo(a)pyrene: 602.7 Perylene 428.6 Indeno[1,2,3-c,d]pyrene: 106.8 Dibenz(ah)anthracene: 117.1 Benzo(ghi)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 Information on Physicochemical parameters [499]:

Physical parameters: Location/state of material: Dark, viscous, odiferous liquid. After 24 hour toc analysis revealed 11 ppm in solution; will float in slick on surface. Melting point (degrees C): -46 Boiling point (degrees C): 400 Reactivity: Synergistic materials: May act as synergist to pesticides.

Additional physicochemical parameters [554]:

Viscosity: 48000 cp (at 10 degrees Celsius)

Physicochemical Information on Specific Gravity:

Typical specific gravity of semi-solid tar like oils such as Fuel Oil 5, Fuel Oil 6, Fuel Oil 10, tall oil, asphalt, and heavy crude oil ( the oils that tend to form tar ba lls) is 0.94 - 0.97 (at 15 degrees Celsius), translating to API gravity < 15 [556].

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]. API gravity is < 15 for bunker C (usually in the range of 7 to 14) [558].

SPECIFIC GRAVITY is 1 (+/-) (for Fuel oil No 6) (NFPA, 1991)

NOTE: The specific gravity for the other fuel oils are: A. Less than 1 (Fuel oils Nos 1, 2, 4, 5) (NFPA, 1991), and B. 0.85 (Fuel oil No 2) (OHM/TADS, 1992).Additional Physicochemical Information [498]:

DENSITY

1 (+/-) g/cm(3) (Fuel oil No 6) Note: the other fuel oils are: A. Less than 1 g/cm(3) (Fuel oils Nos 1, 2, 4, 5)

Note: a typical no. 6 fuel oil is API 12.3 which corresponds to a density of 971 kg/m3 at 22 +or- 2 degrees Celsius [554].

FLASH POINT (NFPA, 1991): Fuel oil No 6: 150 to 270 degrees F Note: the other fuel oils are: 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

EXPLOSIVE LIMITS: Not listed IGNITION TEMPERATURE (NFPA, 1991): Fuel oil No 6: 765 F Note: the other fuel oils are: 1. Fuel oil No 1: 410 degrees F 2. Fuel oil No 2: 494 degrees F 3. Fuel oil No 4: 505 degrees F 4. Fuel oil No 5 (light): Not listed 5. Fuel oil No 5 (heavy): Not listed

ODOR: Petroleum-like odor (AAR, 1987).

TASTE: No information on the taste of fuel oil was found in available references at the time of this review.

COLOR: Fuel oils are straw yellow to dark colored liquids (AAR, 1987).

PH: No information on the pH of fuel oil was found in available references at the time of this review.

REACTIVITY: When heated to decomposition, fuel oils emit acrid smoke and irritating fumes (Sax & Lewis, 1989).

Fuel oils can react vigorously with oxidizing materials (Sax & Lewis, 1989).

Additional 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 theanswers are provided [560]:

VISCOSITY

NOTE: The viscosities of crude oils and oil products are dependent on the temperature and degree of weathering. The following viscosity values are at "0% Weathering Volume" - in other words, fresh No. 6 fuel oil.

Dynamic Viscosity (mPa.s or cP):

Temp( C) Dynamic Viscosity (at 0% Weathering Volume) 0 73500000 1400000 10 28700000 15 48000 20 5980000 25 3180 50 545

Kinematic Viscosity (mm2/sec or cSt):

Temp( C) Kinematic Viscosity (at 0% Weathering Volume) 10 > 1000 20 > 500 40 > 130 55 90 to 2000 60 65 to 1000 70 65 to 360 80 65 to 180 Note: Data obtained from a graph

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.

-4 to 13 2 < 16 -1 15 6 7

INTERFACIAL TENSIONS

NOTE: Interfacial tension is the force of attraction between molecules at the interface of a liquid. These tensions are essential for calculating the spreading rates and the likely extent to which the oil will form oil-in-water and water-in-oil emulsions. The interfacial tensions of crude oils and oil products are dependent onthe temperature and degree of weathering. The following tension values are at "0% Weathering Volume" - in other words, fresh No. 6 fuel oil.

Air-Oil (mN/M or dynes/cm):

Temp( C) Air-Oil Tension (at 0% Weathering Volume) 0 N/M 15 N/M Room Temp. 27 25 (est.)

Oil-Seawater (mN/M or dynes/cm):

Temp( C) Oil-Seawater Tension (at 0% Weathering Volume) N/M

Oil-Water (mN/M or dynes/cm):

Temp( C) Oil-Water (at 0% Weathering Volume) 0 N/M 15 N/M Room Temp 39.82 50 (est.)

EMULSION

NOTE: Water-in-oil emulsions are stable emulsions of small droplets of water incorporated in oil. Termed "chocolate mousse," these stable water-in-oil emulsions can have different characteris tics than the parent crude oil. Emulsion characteristics of crude oils and oil products are dependent on the temperature and degree of weathering. The following typical values are at "0% Weathe ring Volume" - in other words, fresh No. 6 fuel oil. In general, No. 6 fuel oil is not likely to form emulsions (although Bunker C f rom the Arrow incident did form stable emulsions).

Emulsion Formation Tendency (in the NOT LIKELY range):

Temp( C) Fraction of oil that forms an emulsion (f initial) 0 0.1 0 15 0 0

Emulsion Stability (in the UNSTABLE range):

Fraction of oil in the emulsion:

Temp( C) that remains after settling (f final) 0 0.20 15 0.1 0

Water Content of Emulsion (volume %):

Temp( C) Water Content (at 0% Weathering Volume) 0 N/A 15 N/A

DISPERSIBILITY

Chemical Dispersibility (% Dispersed):

Dispersant Dispersibility

C 9527: 0 Dasic: 0 EN 700: 0 CRX-8: 5

Natural Dispersibility (% Dispersed):

Temp( C) Naturally Dispersed 15 0

FIRE AND REACTIVITY Flash Point ( C): >110 66 60. MIN 174 80 > 66 99 98 > 65.5

Fire Point ( C): >257 164

Auto Ignition Temperature ( C): 408 407

Combustion Results: Relatively long ignition time (1.9 min); 26.4 vol% residue.

Flammability Limits (Volume %): in air: 1 to 5

DISTILLATIONNOTE: Distillation data provides an indication of an oil's volatility and relative component distribution. Distillation data is reported as volume % recovered.

Distillation ( C):

(Vol%) Liquid Temp Vapor Temp IBP 324 115 151 78 5 391 222 126 10 414 310 248 166 15 422 259 199 20 427 335 267 217 25 428 272 225 30 432 345 277 231 35 435 282 233 40 438 350 286 234 45 440 293 235 50 441 355 299 235 55 445 304 235 60 448 367 312 235 65 449 318 235 70 370 326 75 375 333 80 344 85 357 90 387 95 417 FBP 441

Initial Boiling Point - IBP ( C): 180 to 500Final Boiling Point - FBP ( C): 212 to >> 588 400

NON-METAL CONTENT

Carbon Residue - using the Ram sbottom method (Weight %): 12

Nitrogen (Weight %): 0.34 0.94 149 ppb

Sulphur (Weight %): 2.40 1.46 2.24 1.5

OTHER:

Ash (Weight %): 0.08

Reid method Vapor Pressure (kPa):

Temp( C) Pressure 37.8 0.689 (estimated)

Compositional Analysis

Saturates: n-Alkanes C13+ 1.73 Isoalkanes 5.0 1-Ring Cycloalkanes 3.9 2-Ring Cycloalkanes 3.4 3-Ring Cycloalkanes 2.9 4-Ring Cycloalkanes 2.7 5-Ring Cycloalkanes 1.9 6-Ring Cycloalkanes 0.4

Aromatics: Benzenes 1.9 Indans and Tetralins 2.1 Dinaphtheno Benzenes 2.0 Methylnaphthalenes 2.6 Acenaphthenes 3.1 Acenaphthalenes 7.0 Phenanthrenes 11.6 Pyrenes 1.7 Benzothiophenes 1.5 Dibenzothiophenes 0.7Information 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 buoy ant 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 i nformation 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 anal ogy. Asphalt rapidly cools to form solid masses, whereas most LAPIO will remain liquid at ambient temperatures, will act like fl uid when spreading, and is less likely to be sticky [775].



### Fate.Detail : Detailed Information on Fate, Transport, Persistence, and/or Pathways:

Fuel oil 6 is less volatile than:

Petroleum ether or benzine Gasoline Naphtha Mineral spirits Kerosene, and Lighter Fuel oils [363].

It is more volatile than:Lubricating oils Paraffin wax Asphalt or tar [363].

Persistency [499]: Loss of fuel oil after 40 hour in bubbler apparatus - 2.% Evaporated, .005% Dissolved.

Expe riments designed to study the effects of weathering on density of four common heavy fuel oils studied the five
proc esses believed to contribute to an increase in oil density: evaporation, dissolution, photolysis, attachment of foreign matter, and water uptake. The study concluded that the primary causes of increased density are evaporation of the more volatile and less dense components of the oil (although the study results show that No. 6 fuel oil is unlikely to sinkby evaporation alone), and the incorporation of denser-thanwater mineral matter into the oil [554]. As a result of these two processes and the beginning high density of No. 6 fuel oil, these type of oil spills are at a higher risk of sinking.
For exa mple, a spill of Bunker C occurred in San Francisco Bay (1975). The spilled oil first increased in density by evaporative losses of its lighter fractions, and then was mixed through the water column by strong tidal currents and wind. Some of the oil globules carried to the bottom by the turbulence then mixed with sandy and gravelly sediments, thus causing the oil to remain near the bottom. The oil eventually moved to eastern San Pablo Bay after being transported landward by the near-bottom water currents [558].

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 lacustr ine 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 thespecial 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].

Lab oratory and/or Field 

### Analyses:

As mentioned in the Chem.Detail section above, fuel oil No. 6 contains about 15% paraffins, 45% naphthenes, 25% aromatics, and 15% no n-hydrocarbon compounds; the hydrocarbons contain 30 and greater carbon atoms [557]. Appreciable concentrations of PAHs are present in residual fuels because of 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 o rganics 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 selectiv ity (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]. Decision Tree (dichotomous key) for selection of lab methodsfor measuring contamination from midrange to heavy crude oils including Fuel Oil 6 (bunker C):

1a. Your main concern is biological effects of petroleum products...................... ..............................2

1b. Your main concern is cleanup or remediation but no ecological or human res ources are at risk............3

2a. The resource at risk is primar ily 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 includ ing crudes do contain some of these water soluble compounds, so they cannot be i gnored........................4

2b. The resource at risk is someth ing 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 hydroc arbons (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 calibr ation 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 me thod 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 endof 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 pos sible 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
compou nds as possible. Also analyze surface or (if applicable) ground water samples for polycyclic aromatic hydr ocarbons (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 p rotocol expanded scan***). The magnit ude 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 co ntinuing 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 incl ude 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................................98. Perform NOAA protocol expanded scan*** for polycyclic aromatic hydrocarbons (PAHs) and alkyl PAHs and/or GC/FID fing erprinting of the coating oil only if necessary to identify the source or exact o il. 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 hydroc arbon (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
popu lations 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 as sessment 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 b reak 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 breakdown fairly rapidly in many wildlife groups and tissues are
not usually analyzed directly. Instead direct effects are inves tigated 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 pl ant 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 r ecommended 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 comp ounds (such as the Benzene, Toluene, Ethyl Benzene, and Xylene compounds) would be expected to di sappear 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 scenari os. 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 br eakdown (cold, no-wind, cloudy, oil-microbe-poor conditions, etc.) the more likely it would be that in the professional judgement experts the oil w ould 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 fres her 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 evaporatinginto the atmosphere. However, in some cases, certain water soluble frac tions of oil including Benzene, Toluene, Ethyl Benzene, and Xylene (BTEX) compounds move down into groundwater. BTEX compounds are included in the more volat ile 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
compou nds, 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 bot tom, 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 "confin ed" waters. This is because much of the oil tends to stay with a surface slick or becomes tied up in subsur face 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 imposs ible to attribute significant impacts to fish or other pelagic or strong swimming mobile species in open waters. Lethal ity 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, co llectedby 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
cont rol 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 bioconcen tratable 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 st rongly 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
pres ent 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 imme diately 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. Screen ing 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 beadequate 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 analy sis (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 s emivolatile compounds. It can be used to characterize li ght 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 Ca lifornia 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 analyze 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 HPL C/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 screen ing methods (TPH-EPA 418.1and Oil and Grease). HPLC/Fluorescence is less expensive than s ome 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 G C/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 effectivetool 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 v ersus 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 Scie nce 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 agen cies, 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 cons tituents in oil. Low values tend to give the mistaken impression that asite is clean when it really isn't (prone to false
nega tives). 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
sugges ted 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), indic ated that very littlebioremediation of hazardous alkyl PAHs and multiring P AHs was actually taking place [727]. Thus, utiliz ing 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
expos ure. See also: PAHs as a group and Fuel Oil, general entries.