ENVIRONMENTAL CONTAMINANTS ENCYCLOPEDIA … · ... General Introduction and Classification...

ENVIRONMENTAL CONTAMINANTS ENCYCLOPEDIA

ASPHALT ENTRY

July 1, 1997

COMPILERS/EDITORS:

ROY J. IRWIN, NATIONAL PARK SERVICE

WITH ASSISTANCE FROM COLORADO STATE UNIVERSITY

STUDENT ASSISTANT CONTAMINANTS SPECIALISTS:

MARK VAN MOUWERIK

LYNETTE STEVENS

MARION DUBLER SEESE

WENDY BASHAM

NATIONAL PARK SERVICE

WATER RESOURCES DIVISIONS, WATER OPERATIONS BRANCH

1201 Oakridge Drive, Suite 250

FORT COLLINS, COLORADO 80525

WARNING/DISCLAIMERS:

Where specific products, books, or laboratories arementioned, no official U.S. government endorsement isimplied.

Digital format users: No software was independentlydeveloped for this project. Technical questions relatedto software should be directed to the manufacturer ofwhatever software is being used to read the files. AdobeAcrobat PDF files are supplied to allow use of thisproduct with a wide variety of software and hardware(DOS, Windows, MAC, and UNIX).

This document was put together by human beings, mostly bycompiling or summarizing what other human beings havewritten. Therefore, it most likely contains somemistakes and/or potential misinterpretations and shouldbe used primarily as a way to search quickly for basicinformation and information sources. It should not beviewed as an exhaustive, "last-word" source for criticalapplications (such as those requiring legally defensibleinformation). For critical applications (such aslitigation applications), it is best to use this documentto find sources, and then to obtain the originaldocuments and/or talk to the authors before depending tooheavily on a particular piece of information.

Like a library or most large databases (such as EPA'snational STORET water quality database), this documentcontains information of variable quality from verydiverse sources. In compiling this document, mistakeswere found in peer reviewed journal articles, as well asin databases with relatively elaborate quality controlmechanisms [366,649,940]. A few of these were caughtand marked with a "[sic]" notation, but undoubtedlyothers slipped through. The [sic] notation was insertedby the editors to indicate information or spelling thatseemed wrong or misleading, but which was neverthelesscited verbatim rather than arbitrarily changing what theauthor said.

Most likely additional transcription errors and typoshave been added in some of our efforts. Furthermore,with such complex subject matter, it is not always easyto determine what is correct and what is incorrect,especially with the "experts" often disagreeing. It isnot uncommon in scientific research for two differentresearchers to come up with different results which leadthem to different conclusions. In compiling theEncyclopedia, the editors did not try to resolve suchconflicts, but rather simply reported it all.

It should be kept in mind that data comparability is amajor problem in environmental toxicology sincelaboratory and field methods are constantly changing andsince there are so many different "standard methods"published by EPA, other federal agencies, state agencies,and various private groups. What some laboratory andfield investigators actually do for standard operatingpractice is often a unique combination of variousstandard protocols and impromptu "improvements." Infact, the interagency task force on water methodsconcluded that [1014]:

It is the exception rather than the rule thatwater-quality monitoring data from differentprograms or time periods can be compared on ascientifically sound basis, and that...

No nationally accepted standard definitions existfor water quality parameters. The differentorganizations may collect data using identical orstandard methods, but identify them by differentnames, or use the same names for data collected bydifferent methods [1014].

Differences in field and laboratory methods are alsomajor issues related to (the lack of) data comparabilityfrom media other than water: soil, sediments, tissues,and air.

In spite of numerous problems and complexities, knowledgeis often power in decisions related to chemicalcontamination. It is therefore often helpful to be awareof a broad universe of conflicting results or conflictingexpert opinions rather than having a portion of thisinformation arbitrarily censored by someone else.Frequently one wants to know of the existence ofinformation, even if one later decides not to use it fora particular application. Many would like to see a highpercentage of the information available and decide forthemselves what to throw out, partly because they don'twant to seem uniformed or be caught by surprise bypotentially important information. They are in a betterposition if they can say: "I knew about that data,assessed it based on the following quality assurancecriteria, and decided not to use it for thisapplication." This is especially true for users near theend of long decision processes, such as hazardous sitecleanups, lengthy ecological risk assessments, or complexnatural resource damage assessments.

For some categories, the editors found no information andinserted the phrase "no information found." This doesnot necessarily mean that no information exists; it

simply means that during our efforts, the editors foundnone. For many topics, there is probably information"out there" that is not in the Encyclopedia. The moretime that passes without encyclopedia updates (none areplanned at the moment), the more true this statement willbecome. Still, the Encyclopedia is unique in that itcontains broad ecotoxicology information from moresources than many other reference documents. No updatesof this document are currently planned. However, it ishoped that most of the information in the encyclopediawill be useful for some time to come even with outupdates, just as one can still find information in the1972 EPA Blue Book [12] that does not seem wellsummarized anywhere else.

Although the editors of this document have done theirbest in the limited time available to insure accuracy ofquotes as being "what the original author said," theproposed interagency funding of a bigger project withmore elaborate peer review and quality control stepsnever materialized.

The bottom line: The editors hope users find thisdocument useful, but don't expect or depend onperfection herein. Neither the U.S. Government northe National Park Service make any claims that thisdocument is free of mistakes.

The following is one chemical topic entry (one file among118). Before utilizing this entry, the reader isstrongly encouraged to read the README file (in thissubdirectory) for an introduction, an explanation of howto search for power key section headings and how to usethis document in general, an explanation of theorganization of each entry, an information qualitydiscussion, a discussion of copyright issues, and alisting of other entries (other topics) covered.

See the separate file entitled REFERENC for the identityof numbered references in brackets.

HOW TO CITE THIS DOCUMENT: As mentioned above, forcritical applications it is better to obtain and cite theoriginal publication after first verifying various dataquality assurance concerns. For more routineapplications, this document may be cited as:

Irwin, R.J., M. VanMouwerik, L. Stevens, M.D.Seese , and W. Basham. 1997. EnvironmentalContaminants Encyclopedia. National Park Service,Water Resources Division, Fort Collins, Colorado.Distributed within the Federal Government as anElectronic Document (Projected public availability

on the internet or NTIS: 1998).

Asphalt (Asphaltic bitumen, bitumen, petroleum asphalt, asphaltcements, CAS number 8052-42-4)

Br ief Introduction:

Br.Class : General Introduction and ClassificationInformation:

Asphalt is a complex mixture of many chemical compounds,the exact composition of which depends upon theindividual source. According the US Coast GuardEmergency Response Notification System (ERNS), asphalt isone of the most commonly spilled petroleum products theU.S [635].

Asphalts are bituminous materials which occur naturallyor are derived from nondestructive separation ofpetroleum fractions [749]. Typically, this is achievedthrough fractional distillation or solvent de-asphalting[749]. Asphalt should not be confused with tar, which isobtained through destructive processing of coal, wood, orpetroleum [749]. Asphalt contains aliphatic hydrocarbons[749] in addition to the mononuclear aromatics andpolycyclic aromatic hydrocarbon (PAH) mixtures found inboth asphalt and tars [749].

Structurally, asphalt is considered to be either acolloid consisting of asphalt micelles suspended in oilsor an intermicellar resin phase; or a solution ofasphaltenes dissolved in the oil-resin phase [749].Asphalt materials are categorized as asphalt cements orliquid asphalts (see Forms section below) [749].

Asphalt paving materials typically are composed ofaggregate and/or sand (90-95% by weight) and asphalt (5-10% by weight). The aggregate and/or sand is responsiblefor the primary load-bearing properties, while asphaltserves as the binder and as a protective coating. Theasphalt binder functions best when the aggregate/sandparticles are "wetted" with asphalt. To ensure goodadhesion between the asphalt and the aggregate or sandparticles, moisture and clays are to be avoided [749].

Hazardous Substances Lists including Asphalt or AsphaltParameters:

The following state lists were provided by VeraHudson of the National Library of Medicine in Aprilof 1993. The format calls for the CAS number (withhyphens deleted) followed by the name of thesubstance, with no space between the CAS number andthe start of the substance name. To convert the

CAS number to the more standard style, move onedigit to the left of the (right) end of the numberand place a hyphen between the last two numbers,then move two more spaces over to the left andinsert another hyphen. Using this conversion, theCAS number listed below for lactic acid, 000050215,becomes 50-21-5. Substances with no CAS number arelisted last.

Massachusetts Toxic Substances List:

008052424Asphalt (CAS number 52-42-4)

008052424Asphalt (cutback) 008052424Asphalt (liquid rapid-curing)

Illinois Toxic Substances List:

008052424Asphalt (petroleum) vapor

Hazardous Substances, New Jersey Right-to-Know List

008052424Asphalt fumes

Br.Haz : General Hazard/Toxicity Summary:

Hazards to fish, wildlife, and aquatic life:

The main hazard associated with asphalt is from thePAHs and alkyl PAHs in asphalt that can move intothe ecosystem from the breakdown of asphalt (seeBr.Fate section below). Since asphalt contains somany toxic and carcinogenic compounds and sinceleaching of harmful PAH compounds has beendocumented even in water pipe use, asphalt shouldbe kept out of rivers, streams, and other naturalwaters to the extent possible (see Water DataInterpretation section below).

According to the Coast Guard CHRIS manual, theeffects of low concentrations of asphalt to aquaticlife or waterfowl is unknown [367].

Hazards to Humans:

Hazards include inhalation of compounds in heatedor fresh asphalt as well as ingestion of PAHsentering the food chain as the result of breakdownof asphalt (see Br.Fate Section below). Finishedwaters from various treatment sites are transportedto consumers through a variety of pipelines. PAH's(polynuclear aromatic hydrocarbons) leach from the

tar or asphalt linings of these pipes, resulting inincreased concentrations of these compounds inwater reaching the consumers [366]. Cement-linedpipes produce lower PAH concentrations [366].

NIOSH urges caution related to human exposure toasphalt. Current NIOSH research indicates thatasphalt products are carcinogenic to laboratoryanimals and, therefore may be more toxic to humansthan previously believed [366].

Air concentrations of PAHs have been shown toincrease to potentially dangerous levels inNational Parks in response to forrest fires andasphalt roads burned by lava flows; although thehuman health risks from low levels of PAHs is notprecisely known, the National Institute ofOccupational Safety and Health position is that anyexposure to certain carcinogenic PAHs is too muchand therefore the exposure should be limited asmuch as possible (Dr. Dawn Tharr, NIOSH,Cincinnati, personal communication).

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

Asphalt is considered a potential carcinogen due to thefact it typically may contain many carcinogeniccompounds, including many PAHs. See also: PAHs as agroup entry. Current NIOSH research indicates thatasphalt products are carcinogenic to laboratory animalsand, therefore may be more toxic to humans thanpreviously believed [366].

Found to contain carcinogens. Positive [609].

The debates on which PAHs and alkyl PAHs found in thisproduct to classify as carcinogens, and the details ofexactly how to perform both ecological and human riskassessments on the complex mixtures of PAHs typicallyfound at contaminated sites, are likely to continue.There are some clearly wrong ways to go about it, butdefining clearly right ways is more difficult. PAHsusually occur in complex mixtures rather than alone.Perhaps the most unambiguous thing that can be said aboutcomplex PAH mixtures is that such mixtures are oftencarcinogenic and possibly phototoxic. One way to approachsite specific risk assessments would be to collect thecomplex mixture of PAHs and other lipophilic contaminantsin a semipermeable membrane device (SPMD, also known asa fat bag) [894,895,896], retrieve the contaminantmixture from the SPMD, then test the mixture forcarcinogenicity, toxicity, and phototoxicity (JamesHuckins, National Biological Service, and Roy Irwin,

National Park Service, personal communication, 1996).

Toxic Hazard Rating [609]:

There is inadequate evidence that bitumens aloneare carcinogenic to humans. /Bitumens/ [IARC.Monographs on the Evaluation of the CarcinogenicRisk of Chemicals to Man. Geneva: World HealthOrganization, International Agency for Research onCancer,1972-PRESENT. (Multivolume work).,p. V35 71(1985)].

There is sufficient evidence for thecarcinogenicity of extracts of steam-refinedbitumens, air-refined bitumens and pooled mixturesof steam- and air-refined bitumens in experimentalanimals. /Bitumens/ [IARC. Monographs on theEvaluation of the Carcinogenic Risk of Chemicals toMan. Geneva: World Health Organization,International Agency for Research on Cancer,1972-PRESENT. (Multivolume work).,p. V35 71 (1985)].

There is limited evidence for the carcinogenicityof undiluted steam-refined bitumens and forcracking-residue bitumens in experimental animals./Bitumens/ [IARC. Monographs on the Evaluation ofthe Carcinogenic Risk of Chemicals to Man. Geneva:World Health Organization, International Agency forResearch on Cancer,1972-PRESENT. (Multivolumework).,p. V35 71 (1985)].

There is inadequate evidence for thecarcinogenicity of undiluted air-refined bitumensin experimental animals. /Bitumens/ [IARC.Monographs on the Evaluation of the CarcinogenicRisk of Chemicals to Man. Geneva: World HealthOrganization, International Agency for Research onCancer,1972-PRESENT. (Multivolume work).,p. V35 71(1985)].

Br.Dev : Brief Summary of Developmental, Reproductive,Endocrine, and Genotoxicity Information:

There is some evidence of mutagenic effects and DNAdamage in animals due to asphalt exposure [609]. Asphaltmay cause irreversible yet not life threatening toxicreproductive effects to humans [369].

See also: PAHs as a group entry.

Br.Fate : Brief Summary of Key Bioconcentration, Fate,Transport, Persistence, Pathway, and Chemical/PhysicalInformation:

Asphalt is often a residue from petroleum refining, andconsists primarily of PNA (polynuclear aromatichydrocarbons) and alkylated PNA, as well as highly polarcompounds [497]. PNA is usually a synonym of PAH (seePAHs as a group entry). Asphalt contains paraffinic andaromatic hydrocarbons and heterocyclic compoundscontaining carbon, sulfur, nitrogen, and oxygen [363].

A comprehensive review of the physicochemical propertiesof several oils and oil products found their persistencein the aquatic environment to rank as follows (from mostpersistent to least persistent): Residual asphaltenes >Heavy crude oil > Medium crude oil > Fuel oil #6 > Lightcrude oil > Lube oils > Fuel oil #2 > Jet fuel > Gasoline[791].

Asphalt used on roads and in water pipes is supposedlyused in a manner which binds most of the harmfulcompounds together as part of a tough, cement-like solid.In layman's terms, the good news is that the many harmfulcompounds typically found in asphalt are presumably boundin place fairly tightly in many roadway and othercontrolled uses. The bad news is that some of theseharmful compounds may not always be as firmly and asuniversally "locked in place" as some have assumed (RoyIrwin, National Park Service, personal communication,1996).

Asphalt and other solidification and stabilizationproducts are designed to lower contaminant leaching rates[478]. However, the amount the leaching is lowereddepends on the physical and chemical characteristics ofthe particular environment.

Chemical and physical insults as diverse as cattle urineand molten lava have been known to breakdown asphaltroadways. Greases can soften asphalt, while xylene andtoluene can diffuse through it [478]. In spite of suchpotential complications, various formulations of asphaltand binders have been used to cover or encapsulatehazardous waste. Under certain conditions, solvents androad salts can accelerate breakdown of asphalt. However,at present (1989), there are no established standards andprotocols for testing and predicting the performance ofsolidification and stabilization (S/S) products such asasphalt for treating non-radioactive hazardous wastes[478].

Road dust and other erosion fractions originating fromslowly wearing-away asphalt roadways are considered onepotential source of PAHs in the sediments of urban riversand bays, although the amount of PAHs coming from thissource versus other sources would be difficult to assess.Asphalt wear products were suggested to be responsible

for some of the petroleum in urban runoff as well as forsome of the PAHs found in the sediments of some urbanlakes [750]. The fraction of hydrocarbons contributedfrom asphalt should decline as the pavement ages. Asphaltcan also contribute to hydrocarbon loads by physicalabrasion [750].

Asphalt generally contains some of the heaviest and leastvolatile fractions of petroleum distillates. In theaquatic environment, asphalt will sink to bottom as adark tarry substance [368].

The CHRIS manual states that the food chain concentrationpotential of asphalt is unknown [367]. However, it isknown that a few of the PAHs known to be found in asphalthave a moderate to low bioaccumulation potential (seePAHs entry).

Petroleum distillates in order of decreasing volatilityinclude [366]:

1. Petroleum ether or benzine 2. Gasoline 3. Naphtha 4. Mineral spirits 5. Kerosene 6. Fuel oil 7. Lubricating oils 8. Paraffin wax 9. Asphalt or tar.

Since asphalt coating in water pipes have been documentedto slowly leach PAH compounds into water [366], asphaltin rivers and other natural waters may also slowly leachharmful compounds into the water.

A controversial topic is "asphalt incorporation" ofpetroleum contaminated soils. Asphalt incorporation atpetroleum contaminated sites involves mixing thecontaminated soils with asphalt as a whole or partialsubstitute for the customary aggregate. Subsequently theasphalt is either used in road construction or is brokenup and landfilled, or crushed and used for road base.Low molecular weight hydrocarbons are volatilized andpyrolyzed; higher molecular weight hydrocarbons areincorporated into the asphalt [661].

Synonyms/Substance Identification:

Road Oil [560]Slow Curing Asphalt [560]Petroleum Asphalt [367, 560, 609]Liquid Asphalt [560]

Asphaltic bitumen [367, 609]Bitumen [367, 609]Asphalt cements [367]Asphaltum [609] Judean pitch [609] Mineral pitch [609]Petroleum bitumen [609] Petroleum pitch [609]Petroleum refining residues, asphalts [609]Trinidad pitch [609]Caswell No. 062 [609]Caswell No. 106 [609]EPA Pesticide Chemical Code 022001 [609] EPA Pesticide Chemical Code 022002 [609]Bituminous materials, asphalt [609]Mineral rubber (VAN) [609]

Associated Chemicals or Topics (Includes Transformation Products):

See also individual entries:

Oil SpillsPetroleum, GeneralPAHs as a groupIndividual PAH entries

Site Assessment-Related Information Provided by Shineldecker(Potential Site-Specific Contaminants that May be Associatedwith a Property Based on Current or Historical Use of theProperty) [490]:

General Types of Associated Materials:

& Petroleum hydrocarbons& Solvents& Tar

Raw Materials, Intermediate Products, Final Products, andWaste Products Generated During Manufacture and Use:

& Copper& Creosote& Dichloroethane& Ethylenediamine& Phenols& Polynuclear aromatic hydrocarbons

Water Data Interpretation, Concentrations and Toxicity (All WaterData 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 compoundentries for summaries of information on individualcomponents of this mixture.

W.Hi gh (Water Concentrations Considered High):

No information found; see Chem.Detail section forcompounds in this product, then see individual compoundentries for summaries of information on individualcomponents of this mixture.

W.Typ ical (Water Concentrations Considered Typical):

Experiments were conducted to find out whether the use ofpetroleum-asphalt seal coating in ductile-iron pipe wouldcontribute significant concn of polynuclear aromatichydrocarbons (PAH) in drinking water distribution systems[609]. The results of the analyses were compared withthe WHO recommendation for maximum allowable concn of PAHin drinking water of 200 ng/l. The highest concn found in3 experiments was 5 ng/l [609]. [Miller HC et al; AMWater Works Assoc J 74 (3): 151-6 (1982)].

W.Concern Levels, Water Quality Criteria, LC50 Values, WaterQuality Standards, Screening Levels, Dose/Response Data, andOther Water Benchmarks:

W.General (General Water Quality Standards, Criteria, andBenchmarks Related to Protection of Aquatic Biota inGeneral; Includes Water Concentrations Versus Mixed orGeneral Aquatic Biota):

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

No information found; see Chem.Detail section forcompounds in this product, then see individualcompound entries for summaries of information onindividual components of this mixture.

W.Inv ertebrates (Water Concentrations vs. Invertebrates):


W.Fi sh (Water Concentrations vs. Fish):


W.Wild life (Water Concentrations vs. Wildlife or DomesticAnimals):


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


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

Finished waters from various treatment sites aretransported to consumers through a variety of pipelines.PAHs (polynuclear aromatic hydrocarbons) leach from thetar or asphalt linings of these pipes, resulting inincreased concentrations of these compounds in waterreaching the consumers. Cement-lined pipes produce lowerPAH concentrations, possibly because PAHs are adsorbedfrom water [366]. Water uses threatened: potable supply,fisheries, industrial, irrigation [368].

Sediment Data Interpretation, Concentrations and Toxicity (AllSediment Data Subsections Start with "Sed."):

Sed.Lo w (Sediment Concentrations Considered Low):


Sed.Hi gh (Sediment Concentrations Considered High):


Sed.Typ ical (Sediment Concentrations Considered Typical):


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 AquaticBiota in General; Includes Sediment Concentrations VersusMixed or General Aquatic Biota):


Sed.Pl ants (Sediment Concentrations vs. Plants):


Sed.Inv ertebrates (Sediment Concentrations vs.Invertebrates):


Sed.Fi sh (Sediment Concentrations vs. Fish):


Sed.Wild life (Sediment Concentrations vs. Wildlife orDomestic Animals):


Sed.Human (Sediment Concentrations vs. Human):


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

Polycyclic aromatic hydrocarbons (PAH) in sediment coresfrom Lake Lucerne, Lake Zurich and Greifensee,

Switzerland, and Lake Washington, northwest USA, wereisolated, identified and quantified by glass capillarygas chromatography and gas chromatography/massspectrometry [609]. A comparison of PAH distributions inthe same sediments and in possible source materials showsthat urban runoff of street dust may be the mostimportant PAH input to these lacustrine sediments [609].A significant contribution to the PAH content of streetdust comes from material associated with asphalt [609].[Wakeham SG et al; Geochim Cosmochim Acta 44 (3): 403-14(1980)].

Soil Data Interpretation, Concentrations and Toxicity (All SoilData Subsections Start with "Soil."):

Soil.Lo w (Soil Concentrations Considered Low):


Soil.Hi gh (Soil Concentrations Considered High):


Soil.Typ ical (Soil Concentrations Considered Typical)


Soil.Con cern Levels, Soil Quality Criteria, LC50 Values, SoilQuality Standards, Screening Levels, Dose/Response Data andOther Soil Benchmarks:

Soil.Gen eral (General Soil Quality Standards, Criteria,and Benchmarks Related to Protection of Soil-dwellingBiota in General; Includes Soil Concentrations VersusMixed or General Soil-dwelling Biota):


Soil.Pl ants (Soil Concentrations vs. Plants):


compounds in this product, then see individualcompound entries for summaries of information onindividual components of this mixture.

Soil.Inv ertebrates (Soil Concentrations vs.Invertebrates):


Soil.Wild life (Soil Concentrations vs. Wildlife orDomestic Animals):


Soil.Hum an (Soil Concentrations vs. Human):

No information found on this complex and variablemixture. See Chem.Detail section for chemicalsfound in this product, then look up information oneach hazardous compound. Some individual compoundsfound in petroleum products have low-concentrationhuman health benchmarks for soil (see individualentries in individual compound).

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

A controversial topic is "asphalt incorporation" ofpetroleum contaminated soils. Asphalt incorporation atpetroleum contaminated sites involves mixing thecontaminated soils with asphalt as a whole or partialsubstitute for the customary aggregate. Subsequently theasphalt is either used in road construction or is brokenup and landfilled, or crushed and used for road base.Low molecular weight hydrocarbons are volatilized andpyrolyzed; higher molecular weight hydrocarbons areincorporated into the asphalt [661]. Studies thatdiscuss the advantages and disadvantages of asphaltincorporation are listed below:

1) Support for asphalt incorporationmethodologies:

Research sponsored by the EPA, the ElectricalResearch Institute, and several state agencieshas suggested that asphalt incorporation maybe useful for treating petroleum contaminatedsoils and other wastes. However, the most

often cited reservation about this technologyis the potential for PAH releases andhydrocarbon air emissions. In most cases,these studies were based on the use of hotbatching technologies (see also Forms section)[749].

While cold mix technologies produces a lowergrade pavement, these pavements may besuitable for light duty use. The asphaltgrade employed in this technology ischaracterized by a low PAH content and, in thecase of slow curing blends, are relativelynonvolatile. Hydrocarbon emissions are alsoreduced because the mixing occurs at ambienttemperatures avoiding the potential emissionsfrom fuel combustion and volatilization of thelighter asphalt fractions. For this reason,cold mix asphalt incorporation is not subjectto permitting by the South Coast Air QualityManagement District in California [749].

As part of a California feasibility studyconducted in the spring of 1989 to determinewhether sandy soils contaminated with residualfuel oil could be stabilized with an asphaltbinder and used as a paving mixture, biossaytesting determined that [749]:

The asphalt pavement produced from fueloil contaminated sands represented nogreater environmental risk that pavementproduced from clean sands.

Neither the control or experimentalasphalt pavement would be classified as ahazardous waste pursuant to existingCalifornia regulation.

The control sample yielded 78.2 mg ofextractable hydrocarbon per gram of sample.Four organics (2,6-Dimethylnaphthalene; 2,3,5-Trimethylnaphthalene; Phenanthrene; andBenzo(a)anthracene) were just over their limitof detection (0.5 ug/kg). The experimentalsample yielded 80.6 mg of extractablehydrocarbon per gram of sample. The same fourorganics detected in the control were found inthe experimental sample. In each case, theconcentration of the four organics was less inthe experimental than in the control. Thissuggest that the source of PAHs is from theasphalt and less from the fuel oil. All othervolatile and semivolatile organic compounds

were below their respective detection limits[749].

The study results indicate that sandy soilscontaminated with residual fuel oil can besuccessfully stabilized with liquid asphalt,and the resultant pavement does not pose asignificant environmental risk. Study resultsindicate that both experimental and controlasphalt pavements would not be classified ashazardous under current California hazardouswaste testing protocol.

NOTES: The authors of this studyacknowledge that the PAH content observedin this study may reflect thecharacteristics of the slow curing liquidasphalt and may not be characteristic ofother asphalt grades (see the Formssection above). This technology cannotbe universally applied to all petroleumcontaminated soils, and is not yetapplicable to contaminated clay soils.Stabilizing soils contaminated withresidual fuel oil with an asphalt binderhas limited application for treatingpetroleum contaminated soils with highclay fractions and a high capacity forwater retention. The applicability ofthis technology to other petroleumcontaminates such as gasoline was notdetermined by this study [749].

2) Cautions and limitations on asphaltincorporation methodologies:

Very few contaminated soils are actuallysuited to the manufacture of asphalt forroadway use. Lighter molecular weighthydrocarbons are incompatible with asphalt;they act as solvents and soften and degradethe asphalt. Soils should be incorporated ata rate of less than 5% of the final asphaltproduct. Clays and sands do not incorporatewell. Gravels and conglomerate are suitable[661].

Soils heavily contaminated with volatilehydrocarbons, such as gasoline, are notsuitable for this method. Soil parameterswhich complicate asphalt incorporation includehigh moisture content and the presence ofother contaminants. Other problems that willpreclude or limit the use of asphalt

incorporation include the following [661]:

A high metal content;

High organic content, which reducesefficiency;

Soil contaminated with waste or used oil;

Large particle size, which limits thesurface area and reduces volatilizationnecessary for combustion;

Large debris such as boulders, concreteor asphalt blocks, roots, branches, etc.,which will damage equipment;

Plastic, which will foul the mixingchamber.

Asphalt incorporation is currently (1990) classed asdevelopmental. The basic engineering research to fix theparameters for asphalt incorporation has not been done,at least to the extent of carefully defining the type andmix of contaminants and soils that can be successfullyincorporated. Therefore, this method remains largelyempirical and dependent on the experience of the facilityoperator. Even when the experience is there, the methodmay not meet approval of regulatory agencies [661].

No other information found; see Chem.Detail section forcompounds in this product, then see individual compoundentries for summaries of information on individualcomponents of this mixture.

Tis sue and Food Concentrations (All Tissue Data InterpretationSubsections Start with "Tis."):

Tis.Pl ants:

A) As Food: Concentrations or Doses of Concern to LivingThings Which Eat Plants:


B) Body Burden Residues in Plants: Typical, Elevated, orof Concern Related to the Well-being of the OrganismItself:


compounds in this product, then see individualcompound entries for summaries of information onindividual components of this mixture.

Tis.Inv ertebrates:

A) As Food: Concentrations or Doses of Concern to LivingThings Which Eat Invertebrates:


B) Concentrations or Doses of Concern in Food ItemsEaten by Invertebrates:


C) Body Burden Residues in Invertebrates: Typical,Elevated, or of Concern Related to the Well-being of theOrganism Itself:


Tis.Fish :

A) As Food: Concentrations or Doses of Concern to LivingThings Which Eat Fish (Includes FDA Action Levels forFish and Similar Benchmark Levels From Other Countries):


B) Concentrations or Doses of Concern in Food ItemsEaten by Fish:


C) Body Burden Residues in Fish: Typical, Elevated, or ofConcern Related to the Well-being of the Organism Itself:


Tis.Wild life: Terrestrial and Aquatic Wildlife, DomesticAnimals and all Birds Whether Aquatic or not:

A) As Food: Concentrations or Doses of Concern to LivingThings Which Eat Wildlife, Domestic Animals, or Birds:

No information found as yet. However, there isinformation available on some of the compoundsfound in this product (see individual PAH entriesin individual compound).

B) Concentrations or Doses of Concern in Food ItemsEaten by Wildlife, Birds, or Domestic Animals (IncludesLD50 Values Which do not Fit Well into Other Categories,Includes Oral Doses Administered in LaboratoryExperiments):

From OHM-TADS [368]:Toxicity to animals:Livestock toxicity (ppm): 30

C) Body Burden Residues in Wildlife, Birds, or DomesticAnimals: Typical, Elevated, or of Concern Related to theWell-being of the Organism Itself:


Tis.Hum an:

A) Typical Concentrations in Human Food Survey Items:


B) Concentrations or Doses of Concern in Food ItemsEaten by Humans (Includes Allowable Tolerances in HumanFood, FDA, State and Standards of Other Countries):


C) Body Burden Residues in Humans: Typical, Elevated, orof Concern Related to the Well-being of Humans:


Tis.Misc. (Other Tissue Information):


Bio.Detail : Detailed Information on Bioconcentration,Biomagnification, or Bioavailability:

Some of the PAHs in asphalt can accumulate in certain biotasuch as shellfish, but biomagnification potential is low.

Information from OHM-TADS [368]:

Food chain Potential for accumulation: NEGATIVEFood chain concentration: NEGATIVE

Int eractions:

Asphalt may act as a synergist to pesticides [368].The PAHs in asphalt interact with sunlight and other things(see PAHs as a group entry in individual compound).

Uses/Sources:

Major Uses [609]:

Making roads, roofs; making tanks watertight [the merck index.10th ed. Rahway, new jersey: merck co., Inc., 1983. 122].

Paints; adhesive in electrical laminates & hot-meltcompositions; diluent in low-grade rubber products; fluid losscontrol in hydraulic fracturing of oil wells; medium forradioactive waste disposal; pipeline & underground cablecoating; rust-preventive hot-dip coatings; base for syntheticturf; water-retaining barrier for sandy soils; supporter ofrapid bacterial growth in converting petroleum components toprotein [Sax, N.I. and R.J. Lewis, Sr. (eds.). Hawley'sCondensed Chemical Dictionary. 11th ed. New York: Van NostrandReinhold Co., 1987. 102].

Paving material for airfields, road construction-eg, asasphalt mix; construction material for dams, reservoirs & seadefenses, roofs & flooring, for corrosion protection of

metals; wrapping & jointing compounds for electricalinsulation; sound insulation material-eg, car bodies & machinemounts; coatings for oil & water pipelines; binder for coalbriquettes & for recovery of steel wastes; coating for paper;component of electrical batteries, paints; rubber-processingagent.

Asphalt blocks [ITII. Toxic and Hazarous Industrial ChemicalsSafety Manual. Tokyo, Japan: The International TechnicalInformation Institute, 1982. 55].

Natural Sources [609]:

Occurs in west indies (chiefly trinidad), venezuela, dead sea,switzerland, etc. [The Merck Index. 10th ed. Rahway, NewJersey: Merck Co., Inc., 1983. 122].

Occurrence: California ... Cuba, Canada (Athabasca tar sands).[Sax, N.I. and R.J. Lewis, Sr. (eds.). Hawley's CondensedChemical Dictionary. 11th ed. New York: Van Nostrand ReinholdCo., 1987. 102].

Artificial Sources [609]:

Waste gases from an asphalt plant contained hydrocarbons,tars, hydrogen sulfide, & mercaptans. Anthracene was onlypolycyclic aromatic cmpd detected in the gases. [Mutko B etal; Ochr Powietrza 8 (5): 134-8 (1974)].

Vapors from asphaltic bitumen can be neglected as factorinjurious to plants because of small amt generally released byhot mix asphalt plants. Vegetation damage observed was due tosulfur dioxide, dust and soot. [KRONBERGER W, HALBWACHS G; EURJ FOR PATHOL 5 (5): 267-74 (1975)].

Particle resuspension caused by moving vehicles weredetermined by solid zinc sulfide tracer particles placed on aroad. The fraction of particles resuspended from the road bysurface stresses was determined by a tracer mass balance. Thedownwind airborne tracer exposure & tracer ground depositionwere measured at vehicle speeds of 5-50 mile/hr. The fractionresuspended/vehicle pass was from 1x10-5 to 1x10-2 with thegreater resuspension corresponding to increased vehicle speeds& driving directly through the deposited tracer. For constantvehicular conditions and no intervening traffic, the fractionof particles initially present were resuspended & markedlywith an incr in days after the tracer was placed on the road.[SEHMEL GA; ERDA SYMP SER 38 (ATMOS- SURF EXCH PART GASEOUSPOLLUT): 859-82 (1974 & 1976)].

This program was undertaken to develop a quantitative estimateof the emission of volatile organic cmpd (VOC's) from drum-mixasphalt plants. This study was carried out by field samplingof 5 drum-mix plants under a variety of operating conditions.

The sampling method used was EPA Proposed Method 25, modifiedto filter out particulate emissions which would interfere withthe lab determination of VOC concn in the collected samples.The VOC emission factors for drum-mix plants are on the orderof 0.1-0.4 lb of VOC (as Carbon) per ton of asphalt concreteproduced. The nationwide emission of VOC's from all drum-mixasphalt plants is estimated to be about 20,600 tons/yr.[BeggsTW; Report: 78 pages (1981) EPA-600-2-81-026; Order No PB81-157943].

... Etching grounds /from intaglio printmaking/ containasphalt in an oil or solvent (asphaltum). [Hart C; Journal ofEnvironmental Health 49 (5): 282-86 (1987)].

Forms/Preparations/Formulations:

Asphalt materials are categorized as asphalt cements or liquidasphalts [749] (reprinted by permission of CRC Press):

Asphalt cement - is the heaviest fraction of asphalt.Consistency ranges from between solid to semiliquid atroom temperature. In general, the heavier fractions ofasphalt are characterized by high concentrations ofaromatics (both mononuclear and polynuclear rings),nitrogen, sulphur, oxygen, and trace amounts of metals ororgano-metallic compounds. Asphalt cements are typicallyused in hot mix technologies.

Liquid asphalts - are produced from the lighter fractionsof the residual asphalt, or by dissolving asphalt cementsin solvent or emulsifying asphalt cements in water.These materials are used in cold mix technologies. Typesof liquid asphalts include:

Rapid curing (RC) - are produced by dissolvingrelatively hard asphalt cements in a kerosene ornaphtha solvent. These materials may be expectedto contain PAH compounds originating from the heavyasphalt solute and are characterized by a highvolatile organic compound (VOC) content due to thesolvent carrier.

Medium curing (MC) - are produced by dissolvingsofter asphalt cements in a kerosene type solvent.These material may also contain PAH compounds, butin lower concentration than the RC liquid asphalts,because they are derived from the lighter fractionsof asphalt cement. These materials may alsocontain a high VOC content due to the solventcarrier.

Slow curing (SC; or road oil) - may be derived fromdistillation, being the lightest fraction of the

asphalt, or by fluxing the lightest fraction of theasphalt cements with lighter oils. These materialsare most similar to residual fuel oils, which alsoare derived from the lighter ends of the petroleumdistillate. SC liquid asphalts are expected to becomposed primarily of chain-type aliphatics ratherthan aromatic compounds. Trace concentrations ofPAHs may be present. The SC liquid asphalts aresemivolatile or nonvolatile, and therefore thepotential for VOC emissions is not a major concern.

Asphalt emulsions - are produced by usingsurfactants to emulsify asphalt cements in water.Anionic, cationic and nonpolar asphalt emulsionsare available. These material may contain PAHs,depending upon the grade of asphalt cement fromwhich they are derived. Emulsions are relativelynonvolatile [749].

Information from HSDB [609]:

Formulations/Preparations: Each of the following isavailable in several grades: asphalt cement, rapid-curingliquid asphalt, medium-curing liquid asphalt, slow-curingliquid asphalt (road oil), emulsified asphalt, inventedasphalic emulsion, oxidized (air-blown) asphalt. [U.S.Coast Guard, Department of Transportation. CHRIS -Hazardous Chemical Data. Volume II. Washington, D.C.:U.S. Government Printing Office, 1984-5.].

Grade: Solution of residue from distillation in carbontetrachloride, 99.5% [Sax, N.I. and R.J. Lewis, Sr.(eds.). Hawley's Condensed Chemical Dictionary. 11th ed.New York: Van Nostrand Reinhold Co., 1987. 102].

Chem.Detail: Detailed Information on Chemical/Physical Properties:

Caution: Every individual petroleum product has a unique"fingerprint," or distinct set of constituents most commonlyidentified by a gas chromatograph analysis. Due to thevarying properties of the same general category of a petroleumproduct (each source and weathering stage of asphalt has aunique gas chromatograph "fingerprint"), careful assessment ofthe toxicity, specific gravity, and other physicalcharacteristics of each individual oil must be taken intoconsideration to determine the exact effects of the product onthe environment. Therefore, the below comments on asphalt areto be considered as representative, but not absolute valuestypical of every batch of the product with the same name.

Since PAHs are important hazardous components of this product,risk assessments should include analyses of PAHs and alkyl PAHsutilizing the NOAA protocol expanded scan [828] or other rigorous

GC/MS/SIM methods.

Information from [560] and [609]:

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 productsare dependent on the temperature and degree ofweathering. The following density values are at"0% Weathering Volume" - in other words, fresh roadoil.

Temp(C) Density (at 0% Weathering Volume) 25 0.9970 to 1.1964

Density/Specific Gravity [609]:

1.00-1.18 [The Merck Index. 10th ed. Rahway, New Jersey: MerckCo., Inc., 1983. 122].

Solubilities [609]:

Insol (sic, actually "relatively insoluble") in water, alc,acids, alkalies; sol in oil turpentine, petroleum, carbondisulfide, chloroform, ether, acetone [The Merck Index. 10thed. Rahway, New Jersey: Merck Co., Inc., 1983. 122].

Among the hazardous polycyclic aromatic hydrocarbons found inasphalt and/or in emissions from asphaltic processing are [366]:

1) Acenapthene

A constituent in asphalt.

2) Anthracene

Associated with coke ovens and asphalt processing anduse. In an outlet water spray tower of asphalt hot roadmix process. In an outlet of asphalt air blowingprocess: 220,000 ng/cu m.

3) Benzo(a)anthracene (CAS number 56-55-3)

Emissions from asphalt hot-mixing plant: 5 to 24 ng/cu m;(in high volume particulate matter): avg 11 ng/cu m.

4) Benzo(a)pyrene

In asphalt up to 0.027 wt%.

5) Benzo(e)pyrene (CAS Number 192-97-2)

Concentration of 0.03-52 MG/KG in petroleum asphalts.

6) Benzo(k)fluoranthene

Benzo(k)fluoranthene may be picked up in distributionsystems lined with coal tar or asphalt.

7) Fluoranthene (C16-H10, CAS number 206-44-0)

Distribution systems lined with coal tar or asphalt cansometimes contribute measurable amounts of fluoranthene.

Found in leachate samples from petroleum asphalt coatingson ductile-iron pipe.

Leachates from a cement- & asphalt-lined cast-iron pipewere tested using a number of analytical techniques.Fluoranthene (4-6 ng/l) was identified in water that hadbeen in contact with asphalt lining.

Distribution systems with asphalt or coal tar linings cancontribute fluoranthene to the tap water. In one extremecase (Portland Oregon) the raw water had 4 ng/l and thedistributed water 640 ng/l fluoranthene. Fluoranthenehas been found in Nordic tap water <0.58-24 ng/l anddetected at >0.1 ug/l in finished water from 5 of 10utilities in Ohio River Basin.

8) Phenanthrene (CAS number 85-01-8)

An evaluation conducted by/ NIOSH of a coal tar pitchtear-off, and the application of hot asphalt operations;total of 16 personal breathing-zone total dust sampleswere collected on seven workers. Analyses of the bulktear-off dust revealed the presence of phenanthrene.

9) Pyrene (The following statements were included under thepyrene heading in the HSDB):

Finished waters from various treatment sites aretransported to consumers through a variety of pipelines.PAH's (polynuclear aromatic hydrocarbons) leach from thetar or asphalt linings of these pipes, resulting inincreased concentrations of these compounds in waterreaching the consumers [366].

NIOSH considers coal tar products carcinogenic andconditions should be made to keep exposures as low aspossible. Current NIOSH research indicates that asphaltproducts are carcinogenic to laboratory animals and,therefore may be more toxic to humans than previouslybelieved.

Additional Physicochemical information from Environment Canada on

liquid asphalt (road oil) [560]:

NOTE: In this section, for properties with more than onevalue, each value came from its own source; in otherwords, if Density was measured several times and severaldifferent answers were obtained, all of the answers areprovided [560]:

INTERFACIAL TENSIONS

NOTE: Interfacial tension is the force of attraction betweenmolecules at the interface of a liquid. These tensions areessential for calculating the spreading rates and the likelyextent to which the oil will form oil-in-water and water-in-oil emulsions. The interfacial tensions of crude oils and oilproducts are dependent on the temperature and degree ofweathering. The following tension values are at "0%Weathering Volume" - in other words, fresh road oil.

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

Temp( C) Air-Oil Tension (at 0% Weathering Volume) 20 25 (estimated)

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

Temp( C) Oil-Seawater Tension (at 0% Weathering Volume) 20 50 (estimated) FIRE AND REACTIVITY

Flash Point ( C): 148.9 to 287.8 SENSATION Colour Dark brown to black

OTHER

Reid method Vapor Pressure (kPa):

Temp( C) Pressure 37.8 0.689 (estimated)

Information from HSDB [609]:

Color/Form:

The "syriac" asphalt (from dead sea) forms deep black,shining, brittle masses of conchoidal fracture; pitch-likeluster [The Merck Index. 10th ed. Rahway, New Jersey: MerckCo., Inc., 1983. 122].

Dark-brown to black cementitious material, solid or semisolidin consistency [Sax, N.I. and R.J. Lewis, Sr. (eds.). Hawley'sCondensed Chemical Dictionary. 11th ed. New York: Van NostrandReinhold Co., 1987. 102].

Softens to viscous liquid above 90 deg C [ITII. Toxic andHazarous Industrial Chemicals Safety Manual. Tokyo, Japan: TheInternational Technical Information Institute, 1982. 55].

Odor:

Pitch-like odor [The Merck Index. 10th ed. Rahway, New Jersey:Merck Co., Inc., 1983. 122].

Tarry odor [U.S. Coast Guard, Department of Transportation.CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.:U.S. Government Printing Office, 1984-5].

Boiling Point:

Greater than 700 deg F [National Fire Protection Association.Fire Protection Guide on Hazardous Materials. 9th ed. Boston,MA: National Fire Protection Association, 1986.,p. 325M-16].

Viscosity:

Liquid: 93.250 cp @ 220 deg F, 85.889 cp @ 230 deg F, 79.299cp @ 240 deg C, 73.379 cp @ 250 deg C, 68.049 cp @ 260 deg C,63.240 cp @ 270 deg C, 58.880 cp @ 280 deg C, 54.930 cp @ 290deg C, 51.930 cp @ 300 deg C, 48.060 cp @ 310 deg C, 45.080 cp@ 320 deg C, 42.340 cp @ 330 deg C, 39.840 cp @ 340 deg C,37.540 cp @ 350 deg C, 35.420 cp @ 360 deg C, 33.420 cp @ 370deg C, 31.670 cp @ 380 deg C, 30.000 cp @ 390 deg C(estimated) [U.S. Coast Guard, Department of Transportation.CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.:U.S. Government Printing Office, 1984-5].

Other Chemical/Physical Properties:

Burns with bright flame /syriac asphalt (from dead sea)/ [TheMerck Index. 10th ed. Rahway, New Jersey: Merck Co., Inc.,1983. 122].

Solid softens to viscous liq @ about 200 deg f; penetrationvalue (paving) 40-300 (roofing) 10-40; good electricalresistivity [The Merck Index. 10th ed. Rahway, New Jersey:Merck Co., Inc., 1983. 92].

Black, friable solid obtained by blowing air @ high tempthrough petroleum derived asphalt, with subsequent cooling;penetration value 10-40; softening point 85-121 deg C/asphalt, blown/ [Sax, N.I. and R.J. Lewis, Sr. (eds.).Hawley's Condensed Chemical Dictionary. 11th ed. New York: VanNostrand Reinhold Co., 1987. 102].

Saturated vapor pressure: 0.018 lb/sq in @ 210 deg F, 0.026lb/sq in @ 220 deg F, 0.037 lb/sq in @ 230 deg F, 0.053 lb/sqin @ 240 deg C, 0.074 lb/sq in @ 250 deg F, 0.103 lb/sq in @260 deg F, 0.142 lb/sq in @ 270 deg F, 0.193 lb/sq in @ 280deg F, 0.262 lb/sq in @ 290 deg F, 0.352 lb/sq in @ 300 deg F,0.470 lb/sq in @ 310 deg F, 0.622 lb/sq in @ 320 deg F, 0.817lb/sq in @ 330 deg F, 1.067 lb/sq in @ 340 deg F, 1.384 lb/sqin @ 350 deg F, 1.783 lb/sq in @ 360 deg F, 2.284 lb/sq in @370 deg F, 2.909 lb/sq in @ 380 deg F (estimated) [U.S. CoastGuard, Department of Transportation. CHRIS - HazardousChemical Data. Volume II. Washington, D.C.: U.S. GovernmentPrinting Office, 1984-5].

Consists of saturated cmpd (naphthenic or cycloparaffinic),aromatic cmpd (single ring mainly structures with long sidechains & condensed ring systems avg 3 rings with shorter sidechains & dimers of these molecules connected by saturatedrings or chains), & asphaltenes (high mol wt, highly condensedring cmpd in range of 2000 & upward) [Gosselin, R.E., R.P.Smith, H.C. Hodge. Clinical Toxicology of Commercial Products.5th ed. Baltimore: Williams and Wilkins, 1984.,p. II-158].

Liquid water interfacial tension: 70 dynes/cm = 0.07 N/m @ 77deg C [U.S. Coast Guard, Department of Transportation. CHRIS -Hazardous Chemical Data. Volume II. Washington, D.C.: U.S.Government Printing Office, 1984-5].

Thermal asphalts (products of a cracking process which makethem differ from other asphalts) have high specific gravity,low viscosity, & high temperature susceptibility and theycontain cokelike bodies (carbenes) [Kirk-Othmer Encyclopediaof Chemical Technology. 3rd ed., Volumes 1-26. New York, NY:John Wiley and Sons, 1978-1984.,p. V3 304].

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

No detailed information found; see Chem.Detail section forcompounds in this product, then see individual compoundentries for summaries of information on individual componentsof this mixture.

Laboratory and/or Field Analyses:

The relative proportions of hazardous compound constituentspresent in petroleum-based oil contamination is typically quitevariable. The lab analyses most appropriate for measuringdifferent types of oil contamination depend upon the type of oilinvolved and the reason for measuring the contamination. Thefarther one progresses from lighter towards heavier oils (thegeneral progression from light towards heavy is the following:Diesel, No. 2 Fuel Oil, Light Crudes, Medium Crude Oils, HeavyCrudes, No. 6 Fuel Oil, etc.) the greater the percentage of PAHs

and other semi-volatiles (many of which are not so immediatelytoxic as the volatiles but which can result in long term/chronicimpacts). These heavier oils thus need to be analyzed for the semivolatile compounds which typically pose the greatest long termrisk, PAHs and alkylated PAHs.

Asphalt contains paraffinic and aromatic hydrocarbons andheterocyclic compounds containing carbon, sulfur, nitrogen, andoxygen [363]. Asphalt is often a residue from petroleum refining,and consists primarily of PNA (polynuclear aromatic hydrocarbons)and alkylated PNA, as well as highly polar compounds [497]. Forlab methods for PAHs, see also: PAHs as a group entry.

Recent (1991) studies have indicated that EPA approved methodsused for oil spill assessments (including total petroleumhydrocarbons method 418.1, semivolatile priority pollutant organicsmethods 625 and 8270, and volatile organic priority pollutantmethods 602, 1624, and 8240) are all inadequate for generatingscientifically defensible information for Natural Resource DamageAssessments [468]. These general organic chemical methods aredeficient in chemical selectivity (types of constituents analyzed)and sensitivity (detection limits); the deficiencies in these twoareas lead to an inability to interpret the environmentalsignificance of the data in a scientifically defensible manner[468]. A great deal of uncertainty remains in the use of dose-response relationships based on crude oil as a whole mixture [734].

The relative proportions of hazardous compound constituentspresent in petroleum-based oil contamination is typically quitevariable. The lab analyses most appropriate for measuringdifferent types of oil contamination depend upon the type of oilinvolved and the reason for measuring the contamination. Thefarther one progresses from lighter towards heavier oils (thegeneral progression from light towards heavy is the following:Diesel, No. 2 Fuel Oil, Light Crudes, Medium Crude Oils, HeavyCrudes, No. 6 Fuel Oil, etc.) the greater the percentage of PAHsand other semi-volatiles (many of which are not so immediatelytoxic as the volatiles but which can result in long term/chronicimpacts). These heavier oils thus need to be analyzed for the semivolatile compounds which typically pose the greatest long termrisk, PAHs and (especially) alkylated PAHs.

Crude oil consists of thousands of individual compounds. Themajor groups include the saturated alkanes, alkenes, benzene,alkylated and aryl benzenes, polynuclear aromatics, heterocyclicaromatics, and hetro-atom substituted alkanes, alkenes andaromatics [783]. Some of the more toxic compound classes are: lowmolecular weight aromatics (such as benzene, toluene, xylene, othermonocyclic aromatics), and polynuclear aromatic hydrocarbons (PAH)[713, 745]. Due to the presence of light aromatics and PAHs in fuelcrude oil, we recommend the following decision tree:

As mentioned in the introductory sections of this entry, thegood news is that the many harmful compounds such as PAHs typicallyfound in asphalt are presumably bound in place fairly tightly inmany roadway and other controlled uses. The bad news is that someof these harmful compounds may not always be as firmly and asuniversally "locked in place" as some have assumed (Roy Irwin,National Park Service, personal communication, 1996).

Asphalt is heavier and more solidified than "heavy oils."Nevertheless, in deciding which lab methods to use for asphalt, itis still instructive to consider the following characteristics ofheavy oil products [741]:

Heavy Oils (Heavy Crude Oils, No. 6 fuel, Bunker C) [741]:

-Heavy oils with little or no evaporation or dissolution(also true of asphalt)-Water-soluble fraction likely to be <10 ppm (also trueof asphalt)-Heavy contamination of intertidal areas likely (not astrue of asphalt)-Severe impacts to waterfowl and fur-bearing mammals(coating and ingestion) (not as true of asphalt)-Long-term contamination of sediments possible (true ofasphalt mostly just as solid chunks)-Weathers very slowly (even more true of asphalt)-Dispersion seldom effective (true)-Shoreline cleanup difficult under all conditions (not astrue of asphalt)

The following decision tree (dichotomous key) for selection of labmethods for measuring contamination from midrange to heavy crudeoils, number 6 and heavier fuel oils, bunker C and all other oilsconsidered to be heavy) has some bearing on asphalt decisions sinceasphalt is a heavy product (in using this key, understand thatasphalt is heavier and more immobile than the heavy crudes andother heavy oils discussed herein):

1a. Your main concern is biological effects of petroleumproducts....................................................2

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

2a. The resource at risk is primarily humans via a drinking waterpathway, either the contamination of groundwater used fordrinking water, or the fresh* or continuing contamination ofsurface waters used as drinking water, or the risk isprimarily to aquatic species in confined** surface waters froma fresh* spill, or the risk is to surface waters re-emergingfrom contaminated groundwater resources whether the spill isfresh* or not; the medium and/or pathway of concern is waterrather than sediments, soil, or tissues. Note: although heavyproducts have a lower percentage of BTEX and other relativelysoluble compounds which typically threaten drinking water,ground water, or water column organisms, some heavy oilsincluding crudes do contain some of these water solublecompounds, so they cannot be ignored........................4

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

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

composition: If required to do so by a regulatory authority,perform whichever Total Petroleum Hydrocarbon (TPH) analysisspecified by the regulator. However, keep in mind that due toits numerous limitations, the use of the common EPA method418.1 for Total Petroleum Hydrocarbons is not recommended asa stand-alone method unless the results can first beconsistently correlated (over time, as the oil ages) with thebetter NOAA protocol expanded scan*** for polycyclic aromatichydrocarbons (PAHs) and alkyl PAHs. If not required toperform an EPA method 418.1-based analysis for TPH, insteadperform a Gas Chromatography/Flame Ionization Detection(GC/FID) analysis for TPH using the spilled substance as acalibration standard. GC/FID methods can be sufficient forscreening 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) usingCalifornia LUFT manual methods (typically a modified EPAmethod 8015) [465] or a locally available GC/FID method ofequal utility for the product spilled. However, no matterwhich TPH method is used, whether based on various GC/FID orEPA method 418.1 protocols, the investigator should keep inmind that the effectiveness of the method typically changes asoil ages, that false positives or false negatives arepossible, and that the better Gas Chromatography-MassSpectrometry-Selected Ion Mode (GC/MS/SIM) scans (such as theNOAA expanded scan***) should probably be performed at the endof remediation to be sure that the contamination has trulybeen cleaned up. Another option for fresh oil: in cases wherean inexpensive screening scan is desired, consider using anHPLC/Fluorescence scan method for sediment or bile metabolitesamples. Such scans are available from laboratories at TexasA. and M., Arthur D. Little, and the NOAA lab in Seattle.This scan is not much more expensive, and less prone to falsenegatives and various other problems than some of the morecommon screening methods (TPH-EPA 418.1 and Oil and Grease).Screening measures the total fluorescence of oil componentswhile GC/MS measures individual aromatic compounds [521].Thus, HPLC/fluorescence screening allowed detecting lowerconcentrations of petroleum-related aromatic compounds insamples contaminated by Prudhoe Bay Crude Oil than didanalysis by GC/MS [521].

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 ofvolatiles using EPA GC/MS method 8240. The standard EPA GC/MSmethod 8240 protocol will be sufficient for some applications,but the standard EPA method 8240 (and especially the lessrigorous EPA BTEX methods such as method 8020 for soil andmethod 602 for water) are all inadequate for generatingscientifically defensible information for Natural Resource

Damage Assessments [468]. The standard EPA methods are alsoinadequate for risk assessment purposes. Thus, whencollecting information for possible use in a Natural ResourceDamage Assessment or risk assessment, it is best to ask thelab to analyze for BTEX compounds and other volatile oilcompounds using a modified EPA GC/MS method 8240 method usingthe lowest possible Selected Ion Mode detection limits andincreasing the analyte list to include as many alkyl BTEXcompounds as possible. Also analyze surface or (ifapplicable) ground water samples for polycyclic aromatichydrocarbons (PAHs) and alkyl PAHs using the NOAA protocolexpanded scan*** modified for water samples using methylenechloride extraction. If the contaminated water isgroundwater, before the groundwater is determined to beremediated, also analyze some contaminated sub-surface soilsin contact with the groundwater for BTEX compounds (EPA GC/MSmethod 8240), and PAHs (NOAA protocol expanded scan***). Themagnitude of any residual soil contamination will provideinsight about the likelihood of recontamination of groundwaterresources through equilibria partitioning mechanisms movingcontamination 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 polycyclicaromatic hydrocarbons (PAHs) and alkyl PAHs. If there is anyreason to suspect fresh* or continuing contamination of soilsor sediments with lighter volatile compounds, also perform EPAGC/MS method 8240 using the lowest possible Selected Ion Mode(SIM) detection limits and increasing the analyte list toinclude as many alkyl Benzene, Toluene, Ethyl Benzene, andXylene (BTEX) compounds as possible.

7a. The problem is direct coating (oiling) of wildlife or plantswith spilled oil product.....................................8

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

8. Perform NOAA protocol expanded scan*** for polycyclic aromatichydrocarbons (PAHs) and alkyl PAHs and/or GC/FIDfingerprinting of the coating oil only if necessary toidentify the source or exact oil. If the source is known andno confirmation lab studies are necessary: dispense withadditional chemical laboratory analyses and instead documentdirect effects of coating: lethality, blinding, decreasedreproduction from eggshell coating, etc., and begin cleaningactivities if deemed potentially productive after consolationswith the Fish and Wildlife Agencies.

9a. The concern is for impacts on water column organisms such asfish or plankton)...........................................10

9b. The concern is for something else (including benthicorganisms)..................................................11

10. If exposure to fish is suspected, an HPLC/Fluorescence scanfor polycyclic aromatic hydrocarbon (PAH) metabolites in bilemay be performed to confirm exposure [844]. TheHPLC/fluorescence scan looks for the presence of metabolitesof PAHs: naphthalene, phenanthrene, and benzo[a]pyrene. Thetechnique does not identify or quantify actual PAH compounds,but subsequent gas chromatography analyses can be done toconfirm the initial findings. Even the semi-quantitativeTotal Scanning Fluorescence (TSF) done inexpensively by labssuch as GERG are a better measure of PAH contamination thanGC/FID, which measures less persistent and less hazardousaliphatics. For bottom-dwelling fish such as flounders orcatfish, also analyze the bottom sediments (see Step 6 above).Fish which spend most of their time free-swimming above thebottom in the water column can often avoid toxicity from toxicpetroleum compounds in the water column, but if fish areexpiring in a confined** habitat (small pond, etc.), EPA GC/MSmethod 8240 and the NOAA protocol expanded scan*** for PAHscould be performed to see if Benzene, Toluene, Ethyl Benzene,and Xylene (BTEX), naphthalene, and other potentially toxiccompounds are above known acute toxicity benchmarkconcentrations. Zooplankton populations impacted by oilusually recover fairly quickly unless they are impacted invery confined** or shallow environments [835] and the aboveBTEX and PAH water methods are often recommended rather thandirect analyses of zooplankton tissues.

11a. The concern is for benthic invertebrates: analyze invertebratewhole-body tissue samples and surrounding sediment samples forpolycyclic aromatic hydrocarbons (PAHs) and alkyl PAHs usingthe NOAA protocol expanded scan***. If the spill is fresh* orthe source continuous, risk assessment needs may also requirethat the sediments which form the habitat for benthicinvertebrates be analyzed for Benzene, Toluene, Ethyl Benzene,and Xylene (BTEX) and other volatile compounds using EPA GC/MSmethod 8240 or modified EPA method 8240 in the Selected IonMode (SIM). Bivalve invertebrates such as clams and musselsdo not break down PAHs as well or as quickly as do fish ormany wildlife species. They are also less mobile. Thus,bivalve tissues are more often directly analyzed for PAHresidues than are the tissues of fish or wildlife.

11b. The concern is for plants or for vertebrate wildlife includingbirds, mammals, reptiles, and amphibians: polycyclic aromatichydrocarbons (PAHs) and other petroleum hydrocarbons breakdown fairly rapidly in many wildlife groups and tissues arenot usually analyzed directly. Instead direct effects areinvestigated and water, soil, sediment, and food itemsencountered by wildlife are usually analyzed for PAHs andalkyl PAHs using the NOAA protocol expanded scan***. If thespill is fresh* or the source continuous, risk assessment

needs may also require that these habitat media also beanalyzed for Benzene, Toluene, Ethyl Benzene, and Xylene(BTEX) and other volatile compounds using EPA GC/MS method8240 or modified EPA method 8240 in the Selected Ion Mode(SIM). Less is known about plant effects. However, the samemethods recommended above for the analyses of water (Step 4above) and for sediments or soils (Step 6 above) are usuallyalso recommended for these same media in plant or wildlifehabitats. If wildlife or plants are covered with oil, seealso Step 8 (above) regarding oiling issues.

* Discussion of the significance of the word "fresh": The word"fresh" cannot be universally defined because oil breaks downfaster in some environments than in others. In a hot, windy,sunny, oil-microbe-rich, environment in the tropics, some of thelighter and more volatile compounds (such as the Benzene, Toluene,Ethyl Benzene, and Xylene compounds) would be expected to disappearfaster by evaporation into the environment and by biodegradationthan in a cold, no-wind, cloudy, oil-microbe-poor environment inthe arctic. In certain habitats, BTEX and other relatively watersoluble compounds will tend to move to groundwater and/orsubsurface soils (where degradation rates are typically slower thanin a sunny well aerated surface environment). Thus, the judgementabout whether or not oil contamination would be considered "fresh"is a professional judgement based on a continuum of possiblescenarios. The closer in time to the original spill of non-degraded petroleum product, the greater degree the source iscontinuous rather than the result of a one-time event, and the morefactors are present which would retard oil evaporation or breakdown(cold, no-wind, cloudy, oil-microbe-poor conditions, etc.) the morelikely it would be that in the professional judgement experts theoil would be considered "fresh." In other words, the degree offreshness is a continuum which depends on the specific productspilled and the specific habitat impacted. Except for groundwaterresources (where the breakdown can be much slower), the fresher themiddle distillate oil contamination is, the more one has to beconcerned about potential impacts of BTEX compounds, and otherlighter and more volatile petroleum compounds.

To assist the reader in making decisions based on the continuum ofpossible degrees of freshness, the following generalizations areprovided: Some of the lightest middle distillates (such as JetFuels, Diesel, No. 2 Fuel Oil) are moderately volatile and solubleand up to two-thirds of the spill amount could disappear fromsurface waters after a few days [771,835]. Even heavier petroleumsubstances, such as medium oils and most crude oils will evaporateabout 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 solublefractions of oil including Benzene, Toluene, Ethyl Benzene, andXylene (BTEX) compounds move down into groundwater. BTEX compoundsare included in the more volatile and water soluble fractions, andBTEX compounds as well as the lighter alkanes are broken down morequickly by microbes than heavier semi-volatiles such as alkyl PAHs

and some of the heavier and more complex aliphatic compounds. Thusafter a week, or in some cases, after a few days, there is lessreason to analyze surface waters for BTEX or other volatilecompounds, and such analyses should be reserved more forpotentially contaminated groundwaters. In the same manner, as theproduct ages, there is typically less reason to analyze for alkanesusing GC/FID techniques or TPH using EPA 418.1 methods, and morereason to analyze for the more persistent alkyl PAHs using the NOAAprotocol expanded scan***.

** Discussion of the significance of the word "confined": Like theword "fresh" the word "confined" is difficult to define preciselyas there is a continuum of various degrees to which a habitat wouldbe considered "confined" versus "open." However, if one isconcerned about the well-being of ecological resources such as fishwhich spend most of their time swimming freely above the bottom, itmakes more sense to spend a smaller proportion of analyticalfunding for water column and surface water analyses of Benzene,Toluene, Ethyl Benzene, and Xylene (BTEX) and other volatile oracutely toxic compounds if the spill is in open and/or deep watersrather than shallow or "confined" waters. This is because much ofthe oil tends to stay with a surface slick or becomes tied up insubsurface tar balls. The petroleum compounds which do passthrough the water column often tend to do so in smallconcentrations and/or for short periods of time, and fish and otherpelagic or generally mobile species can often swim away to avoidimpacts from spilled oil in "open waters." Thus in many large oilspills in open or deep waters, it has often been difficult orimpossible to attribute significant impacts to fish or otherpelagic or strong swimming mobile species in open waters.Lethality has most often been associated with heavy exposure ofjuvenile fish to large amounts of oil products moving rapidly intoshallow or confined waters [835]. Different fish species vary intheir sensitivity to oil [835]. However, the bottom line is thatin past ecological assessments of spills, often too much money hasbeen spent on water column analyses in open water settings, whenthe majority of significant impacts tended to be concentrated inother habitats, such as benthic, shoreline, and surface microlayerhabitats.

*** The expanded scan protocols for polycyclic aromatichydrocarbons (PAHs) and alkyl PAHs have been published by NOAA[828].

End of key.

It is important to understand that contaminants data fromdifferent labs, different states, and different agencies, collectedby 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 (notonly for water methods but also for soil, sediment, and tissuemethods) between different "standard methods" recommended bydifferent agencies seemed to be getting worse, if anything, rather

than better. The trend in quality assurance seemed to be forvarious agencies, including the EPA and others, to insist onquality assurance plans for each project. In addition to qualitycontrol steps (blanks, duplicates, spikes, etc.), these qualityassurance plans call for a step of insuring data comparability[1015,1017]. However, the data comparability step is often notgiven sufficient consideration. The tendency of agency guidance(such as EPA SW-846 methods and some other new EPA methods for bio-concentratable substances) to allow more and more flexibility toselect options at various points along the way, makes it harder ininsure data comparability or method validity. Even volunteermonitoring programs are now strongly encouraged to develop and usequality assurance project plans [1015,1017].

At minimum, before using contaminants data from diversesources, one should determine that field collection methods,detection limits, and lab quality control techniques wereacceptable and comparable. The goal is that the analysis in theconcentration range of the comparison benchmark concentrationshould be very precise and accurate.

It should be kept in mind that quality control field and labblanks and duplicates will not help in the data quality assurancegoal as well as intended if one is using a method prone to falsenegatives. Methods may be prone to false negatives due to the useof detection limits that are too high, the loss of contaminantsthrough inappropriate handling, or the use of inappropriatemethods. The use of inappropriate methods is particularly commonrelated to mixed oil products containing PAHs, such as asphalt.

Although EPA method 418.1: Petroleum Hydrocarbons expressed asTotal Petroleum Hydrocarbons (TPH), is recommended by many Stateagencies, some consulting firms, and some laboratories for certainregulatory and screening applications (often leaking undergroundstorage tanks), this method is not well suited to crude oilcontamination or to the more persistent hazardous constituents inoil. Low values tend to give the mistaken impression that a siteis clean when it really isn't (a false negative). For example, afield test of bioremediation of soils contaminated with Bunker C (aheavy fuel) at a refinery in Beaumont, Texas, utilized oil andgrease data, which (although the data was quite variable) seemed toindicate bioremediation was taking place [728]. A comparison of theoil and grease data at this site with TPH data at this sitesuggested the same thing, that the data was quite variable but ifanything, the oil was being slowly being cleaned up bybioremediation (Bruce Herbert, Texas A. and M., Department ofGeology, personal communication, 1995). However, a later study ofthe same site utilizing the expanded scan for PAHs [828] (amodified EPA 8270 including alkyl homologues and lower detectionlimits), indicated that very little bioremediation of hazardousalkyl PAHs and multi-ring PAHs was actually taking place [727].Thus, utilizing either oil and grease or TPH analyses would tend tolead one to the faulty conclusion that the harmful compounds werebeing naturally cleaned up at an acceptable rate. This is partlybecause the TPH and oil and grease methods tend to favor thelighter and less alkylated PAHs, whereas many of the carcinogenicand longer lasting PAHs are the heavier multi-ringed and alkylated

compounds.

A few notes related to screening scans versus asphalt:

1) Although EPA method 418.1: Petroleum Hydrocarbonsexpressed as Total Petroleum Hydrocarbons (TPH), isrecommended by many State agencies, some consultingfirms, and some laboratories for certain regulatory andscreening applications (often leaking underground storagetanks), this method is not well suited to asphaltcontamination or to the more persistent hazardousconstituents in oil. Low values tend to give themistaken impression that a site is clean when it reallyisn't (prone to false negatives). This method is said toreadily detects the heavy petroleum products such asmotor oil, tar, and asphalt [497] (but misses manyhazardous heavy PAHs.

2) EPA Method 8015 (for Non-halogenated VolatileOrganics): not appropriate for asphalt

Method 8015 is a gas chromatographic method that isexcellent for the analysis of volatile andsemivolatile compounds. It can be used tocharacterize light and midrange petroleumdistillates such as gasoline, diesel, fuel oil, andkerosene. This method can be used to obtain somegross fingerprint information for differentiationbetween petroleum products, as well as detailedinformation that can be used to differentiatebetween different batches of the same product. The major limitation of Method 8015 is itsinability to detect nonvolatile compounds.Residual petroleum products such as asphalt and tarwill not be seen using EPA Method 8015 [497].

Asphalt Summary from Calabrese [497]:

The Thin-Layer Chromatography (TLC) pattern, using hexane asthe eluting solvent, will resemble an elongated teardropstretching from Rf 0.0 to Rf 0.5 and will be visible underboth short and long wave UV light. At high concentrations,this teardrop will extend from Rf 0.0 to 0.8 and at lowconcentrations from 0.0 to 0.2. This band is visible withiodine staining. A band at Rf 0.9 will sometimes be seenwhich consists of saturated hydrocarbons that are left in theproduct.

See also: PAHs as a group entry.

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