530R88113
Agency
&EPA Research and
Development
Investigation of the Fate of Oily Wastes
in Streams as a Tool for Hazardous
Waste Screening: A Preliminary
Identification of Research Approach
and Model Development
Prepared for
Office of Solid Waste
Office of Solid Waste and Emergency Response
U.S. Environmental Protection Agency
Prepared by
Environmental Research
Laboratory
Athens GA 30613
March 1988
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INVESTIGATION OF THE FATE OF OILY WASTE IN STREAMS AS A TOOL FOR
HAZARDOUS WASTE SCREENING: A PRELIMINARY IDENTIFICATION
OF RESEARCH APPROACH AND MODEL DEVELOPMENT
by
Steve C. McCutcheon* Ph.D., P.E.
with the assistance of
William Vocke**
(on the sections defining oily waste
and investigation of existing criteria)
Assessment Branch
Environmental Research Laboratory
U.S. Environmental Protection Agency
Athens, GA 30613
(404) 546-3301
** Analysis/Models Section
Office of Solid Waste and Emergency Response
U.S. Environmental Protection Agency
Washington, D.C.
U.S. Environmental Protection Agency
Library. Room S-
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CONTENTS .... . -
Page
ABSTRACT 2
ACKNOWLEDGMENTS 3
PROBLEMS PRESENTED BY OILY WASTES INTRODUCED INTO STREAMS 1
Re-concentration of Oily Wastes 1
Definition of Oily Wastes .- 3
DEVELOPMENT OF PROCEDURES TO ANALYZE THE POTENTIAL IMPACT OF
OILY WASTE
DISPOSAL ON STREAMS 5
Determination of When Oily Wastes Become Hazardous 5
Investigation of Low Intensity Nonpoint Sources 7
Sources of Oily Wastes 8
Pathways to Streams 8
Screening Level Model 12
CRITERIA GOVERNING OILY WASTES 16
Drinking Water Criteria 18
Discharge Criteria .' 19
Protection of Wildlife 21
EFFECTS OF OILY WASTES IN STREAMS -.' 23
Human Effects 24
Aesthetics 24
Tainting of Fish Flesh 28
Taste and Odor 31
Toxicity to Plants and Animals 31
Toxicity of the Oily Phase 33
Toxicity of Contaminated Sediments 37
Toxicity of Emulsions 39
Toxicity of the Dissolved Phase 41
Other Effects of Oily Wastes 45
BEHAVIOR OF OILY WASTES IN STREAMS .' 46
Advection and Spreading 46
Formation of Films, Globs, Pools, Mixed Droplets, and Emulsions . . 51
Volatilization 57
Dissolution 57
Photochemical Oxidation, Hydrolysis, and Toxic Daughter
Products 58
Biodegradation 58
Sedimentation 59
Coating Surfaces 59
iii
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CONTENTS - continued
Page
INVESTIGATION OF REASONABLE ENDPOINTS 60
Concentration vs. Thickness Criteria 60
Backcalculation of Allowable Amounts to Avoid Oily Tastes
in Fish and Invertebrates 64
Exposure to Emulsions 65
Exposure to Soluble Fraction and Other Dissolved Components 65
Calculation of Oily Material Flux to Avoid Formation of
Visible Oil Films, Films that Effect Surface Breathers,
Pools on the Bottom, and Coatings 66
Calculation of Detectable Oil Coatings on Shores, Banks,
Vegetation and Debris 68
Effect of Oily Films on Gills and Benthic Biotic Surfaces 69
DEVELOPMENT OF A SCREENING LEVEL MODEL " 69
PROJECTION OF FUTURE MODEL DEVELOPMENT NEEDS 69
APPENDIX I - REVIEWS OF THE PROPOSED ANALYSIS METHOD CONDUCTED
FEBRUARY 26, 1988 76
APPENDIX II - 1986 "GOLD BOOK" CRITERIA FOR OIL AND GREASE 77
APPENDIX III - PARAMETERS IN THE DATA BASE FOR HAZARDOUS
CHEMICALS DEVELOPED FOR THE OFFICE OF SOLID WASTES 78
iv
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Figures
Number Page
1 Potential sources and pathways of oily waste to streams:
A. Ordinary "Title D" Landfills 8
B. Other Landfill Facilities '
C, Lagoons
D. Land Application
2 Lighter than water, oily waste entering a stream as
overland flow 9
3 Heavier than water, oily waste entering a stream as
overland flow ." 9
4 Pathways through groundwater system 9
5 Thin stratified oil waste plume intersecting a stream 10
6 Interception of a plume of heavier than water oily waste
by a stream that fully penetrates the surficial aquifer 10'
7 Deep plume emulsion intercepted by a stream that does not
fully penetrate the surf icial aquif ier . . . -. 11
8 Thick groundwater plume not fully intercepted by a stream
that only partially penetrates the suficial aquifre 11
9 Ideal relationship between screening and design models 12
10 Goals for incremental improvement of the screening model
over the range generally encountered or in the vicinity
of criteria , 15
11 The set of know pathways and potential effects of oily
waste in streams 15
12 Process affecting heavier and lighter than water oily
wastes. Adopted in part from Nelson-Smith (1972) who
originally credits FAO (1970) and Parker, Freegarde,
and Hatchard (1971) 46
13 Processes that effect concentrations of oily waste in
streams 46
14 Verticle distribution of oily immisible waste in streams
with a density different from the density of water .
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Figures - continued
Number Page
15 Velocity differences in streams that have a surface film or
pool of oil with a thickness of 10 percent of the depth of
water flow 47
16 General behavior of heavy and light oily wastes in pool and
riffle streams 50
17 Longitudinal distribution of heavy and light oil waste
downstream of a discontinuous source 50
18 Typical micelle 52
19 Crude parameterization of oil film stability based on the
theoretical and observational study of Wilkinson (1972, 1973)
with extrapolation to other conditions 54
20 Interfacial stability as a function of Ku or Ro 55
21 Influence of interfacial stability on the formation of
emulsion 56
22 Forces at the interface : 56
23 Potential occurances of pools and globs on irregular stream
beds 56
24 Effect of dissolution and emulsification on the thickness
of globs on a flat stream bottom 57
25 Mass balance for dispersed oily wastes or for components
where dose-response relationships are based on average
amounts of oily waste present 61
26 Mass balance for oil film on streams 61
vi
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Tables
Number
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
Page
Criteria governing the visible detection of oil films
on water surfaces 26
Concentrations of oily materials or components of oily
wastes that taint edible fish and invertebrates 29
Concentrations of the oily phase that are toxic to
aquatic wildlife 35
Concentrations or amounts of oily wastes in sediments
that are toxic to aquatic wildlife 38
Concentrations of -the emulsions that are toxic to
aquatic wildlife 41
Concentrations of the dissolved components of oily
wastes that are toxic
43
Relationship between point velocities and vertically
- averaged mean velocities 49
Table 8.
68
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ABSTRACT
An approach is established for the development of procedures for
analyzing the impact on streams of oily waste disposal practices. The
appraach includes a review of the present state of scientific knowledge
concerning the processes that affect the transport and transformation
of oily materials in water. An initial screening level model for evalu-
ating potential harmful exposures is proposed for use on a nation-wide
basis. The data and procedures developed will be available should more
site specific models be needed in the regulatory process.
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ACKNOWLEDGMENTS
Dr. Steve C. McCutcheon wrote the majority of this document and is
therefore, responsible for its content. Mr. William Vocke of the office of
Solid Waste and Emergency Response researched and wrote the definition of oily
wastes. Both Dr. McCutcheon and Mr. Vocke are responsible for the definition
of what constitutes an oily waste. Much of the background information on water
quality criteria was compiled by Mr. Vocke and Dr. McCutcheon incorporated this
research into the manuscript. —
Dr. Zubair Saleem, Office of Solid Waste; Mr. William Vocke, Office of
Solid Waste; Mr. Thomas Barnwell, Jr., Mr. Robert Ambrose, Mr. Lee Mulkey, and
Dr. James Martin of the Environmental Research Laboratory in Athens, Georgia
have provided significant technical discussions during the course of the study.
These discussion have significantly contributed to this project. Dr. Edwin
Herricks, University of Illinois; Dr. Dan Reible, Louisiana State University;
and Dr. Peter Shanahan, consultant, provided a preliminary review of the study
and those critisia and comments aided in the writing of this document. In the
course of the requiste administrative review, Mr. Barnwell, Mr. Mulkey, and Dr.
Robert Swank offered useful technical critisms that improved the document.
These tactful efforts to assist in improving clarity and readibility that seem
to be beyond the minimun requirements are appreciated.
We have used information from Mr. Ben Smith of the Waste Characterization
Branch of the Office of Solid Waste in noting the characteristics of oily
wastes. Dr. Gate Jenkins of the office of Solid Waste reviewed a preliminary
version of the text and commented to Mr. Vocke on technical priorities and
approach.
Mr. Bob Ryans of the Environmental Research Laboratory in Athens, Georgia
edited the manuscript and with his consumate skill, has significantly improved
the clarity and readability of the text. Other members of the Environmental
Research Laboratory in Athens, Georgia have also provided valuable assistance.
Ms. Lisa Sealock, a technical writer, assisted with editing, rewriting, and
drafting of select sections from notes. Mr. William Chung is responsible for
the drafting and artwork. His skill and dedication are very much appreciated.
Mr. Michael Bell assisted, with the editing and preparation of the manuscript.
His assistance has meant the difference in meeting more than one deadline. Ms.
Chris Podeszwa, Ms. Tawnya Robinson, and Ms. Jessica Edwards provided
additional clerical assistance.
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INVESTIGATION OF THE FATE OF OILY WASTE IN STREAMS AS A TOOL FOR
HAZARDOUS WASTE SCREENING: A PRELIMINARY IDENTIFICATION
OF RESEARCH APPROACH AND MODEL DEVELOPMENT
PROBLEMS PRESENTED BY OILY WASTES INTRODUCED INTO STREAMS
Re-concentration of Oily Wastes
Aquatic contaminants generally disperse in the environment and become less
harmful because many wastes easily dissolve in water. When wastes easily
dissolve and disperse, it is a simple matter to determine the critical effect
of the waste at or near the source before dispersive processes take full effect
n reducing the concentration. Oily, immiscible wastes are an exception to this
general rule because of their ability to reconcentrate after some initial
dispersion in the environment. As a result of this reconcentrating ability,
"hot spots" of acute or chronic toxicity may develop downstream of a source
when flow conditions change from highly turbulent to quiescent. Equally
detrimental is the formation of visible manifestations of the oily materials as
films and sheens on the water and as coatings on bed materials and plants.
These visible manifestations are important because they are not in accordance
with past and of present criteria [EPA 1973, 1976, and 1986 and Federal Water
Pollution Control Administration (FWPCA)1968) and lead to the perception that a
stream is more polluted and seriously impaired than may actually be the case.
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The ability to reconcentrate arises because oily wastes may have an
interfacial tension with significantly different from that of water. Thus the
wastes may rise to the surface to form a film, sink to the bottom to coat
sensitive benthic surfaces and to form pools and globs of oily materials, or
form suspended globs.
The ability of oily wastes to reconcentrate may cause both direct and
indirect effects. Oily wastes can be directly toxic to wildlife and plants in
streams. Oil films, pools, globs, emulsions,"and dissolved oily materials kill
and impair the growth of plants, fish and other wildlife. The indirect effect
of greatest concern occurs when the oily waste concentrates otherwise immobile
hydrophobic organic contaminants. The hydrophobic contaminants of concern
may already be present from other sources of pollution (FWPCA 1968 discusses
pesticide mobilization) or in the stream maybe mobilized from a landfill,
lagoon, or in the bed of the stream and associated surficial aquifer connecting
the landfill or lagoon of interest to the nearest stream.
Definition of Oily Wastes
There is no single accepted definition for oily waste. Within the U.S.
EPA, each program office uses a definition appropriate for their particular
regulatory activity. Because the procedure being developed in this effort is
intended to support many different program areas, it is difficult to provide a
precise definition of oily wastes. Therefore, a general definition suitable
for the many uses of the procedure is being proposed. To further aide in
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defining oily wastes, Important examples and typical chracteristics are
summarized.
An oily waste contains sufficient oils of animal, vegetable or mineral
origin to form a separate non-aqueous phase in water. These waste will have a
significant interfacial tension with water that allows the formation of
separate phases. Waste that do not have an interfacial tension with water and
thus readily dissolve, except where mixing may be precluded by density
differences, are typically not considered to be oily wastes. Wastes that form
a separate aqueous phase due to density differences resulting solely from
temperature differences or the concentration of dissolved chemicals (e.g.
brines) are not considered oily wastes. Generally the density of the waste
will be different form water but not necessarily in every case. Complex waste
mixtures such as those derived from wood preserving may contain oils heavier
and lighter than water that have a combine density of water. Peter Shanahan
notes in his review in Appendix I that cresote is typically mixed with a
carrier that is lighter-than-waster fuel oil. Therefore, interfacial tension
with water seems to be the only fully distinguishing characteristic but density
differences with water are very typical.
t
Important examples of oily waste include wood preserving wastes (K001 -
waste designation by Industry and the U.S. EPA - see 40 CFR, Chap. 1, Subpart
D, Section 261), by-products from petroleum production and refining (K048
through K052), distillate bottoms or residues (F024), and by-products from
processes that employ petroleum-based materials (written communication, Ben
Smith, Waste Characterization Branch, Office of Solid Waste, U.S. EPA, December
1986). .--.'• . • - .
—t
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Waste properties, at the least, cover the spectrum of oil properties.
In addition, oily wastes may contain appreciable levels of water and
solids. When water is present, emulsions often are formed and may be
either water in oil or oil in water. Significant volumes of wastes come
from: 1) pond sludges, 2) product and crude oil storage tank bottoms, 3)
API (American Petroleum Institute) separator sludge, 4) contaminated
near surface soils, and 5) used motor oils (written communication, Ben
Smith, Waste Characterization Branch, Office of Solid Waste, US EPA,
December 1986).
Typical volumes for oily wastes include 500 to 200,000 gallons per
disposal event. One to two million metric tons of oily wastes are
generated by approximately 180 refineries each year. Surface impound-
ments typically cover 405 to 405,000 square meters (0.01 to 100 acres) at
refineries and other facilities (written communication, Ben Smith, Waste
Characterization Branch, Office of Solid Waste, US EPA, December 1986).
There seems to be four important categories of constituents in oily
wastes. Metals, such as Arsenic (As), Lead (Pb), Nickel (Ni), Chromium
(Cr), Selenium (Se), Cadmium (Cd), and Mercury (Hg) comprise the first
category. The second category includes benzene, toluene, and xylene.
The third category contains polynuclear aromatic hydrocarbons, especially
benz(a)pyrene, benz(a)anthracene, and dibenz(a,h)anthracene. Halogenated
dioxins and furans make up the fourth category of constituent types (written
communication, Ben Smith, Waste Characterization Branch, Office of Solid
Waste, US EPA, December 1986).
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The Office of Solid Waste has determined that, as of early 1987, oil and
gas wastes were disposed of in 125,074 surface impoundments and on 726 separate
land application areas. The number of landfills accepting these wastes has not
yet been determined.
Wastes that are derived from vegetable and animal oils are not expected to
present a significant problem (McKee and Wolf, 1963). Unlike petroleum-based
oils, animal and vegetable oils of recent origin, are unlikely to be toxic or
contain materials that are toxic. In addition, mineral oils may produce less
detectable tastes and odors. Therefore, it "is anticipated that mineral oils
will not present a significant problem.
DEVELOPMENT OF PROCEDURES TO ANALYZE THE POTENTIAL IMPACT
OF OILY WASTE DISPOSAL ON STREAMS
Determination of When Oily Wastes Become Hazardous
The objective of this study is to determine when oily materials should be
treated as hazardous wastes. Once this determination is made, the wastes would
be disposed of in a subtitle C hazardous waste disposal facility.
The analysis procedure to be initially pursued will consistent of a
simple, well-coneieved out, screening level model. The model will be designed
for application to all potential sites in the continental United States. We
hope to balance scientific rigor, conceptual simplicity, and environmental
conservatism in such a screening-level model. The model will be combined with
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Monte Carlo analysis of the variation in site characteristics that can occur
across the nation to provide estimates of uncertainty. The analysis will be
further improved by compensating for uncertainty in environmental process and
data for streams and oily waste disposal. The proposed Monte Carlo procedure
will allow officials to chose a level of protection based on defined regulatory
risk managemnet polices.
We seek to incorporate the necessary scientific understanding of the
principle processes that influence the assimilation of oily wastes into the
stream environment. Initially we will focus only on processes that are involved
in the potential transport of the material to critical exposure zones in
streams. To judge what is necessary, we will review, in greater depth than is
needed for the initial screening level model, the present understanding of
processes that influence the transport and transformation of oily material in
streams. The objective of this review will be to separate processes that affect
the transport and concentration of oily materials from those that transform the
waste into lower concentrations.
If we incorporate only the processes that transport or oncentrate the oily
wastes in the initial screening model, we expect to be able to determine if
current or projected waste disposal practices are environmentally sound. If the
screening analysis indicates that disposal practices are not sound, then we
expect that the development of more rigorous models will be necessary to
demonstrate the extent of the problem. Additional model development and data
collection will focus on the processes that reduce the exposure of stream biota
and humans. Therefore, later phases will develop more precise models if the
need to do so is demonstrated.
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As a part of the development of a procedure to analyze oily waste disposal
on a nationwide basis, we will also determine the processes that effect
concentrations of the material. As a result, this work will also lay the
groundwork for more site-specific models that may be useful in a wavier process
if that is later deemed necessary.
Investigation of Low Intensity Nonpoint Sources
In this investigation, we have concentrated on the effect of low
intensity, approximately constant nonpoint sources of oily materials. In doing
this, we have excluded full consideration of spills and the more dynamic
introduction of oily materials into streams until a later date. As a result, we
do not expect to be able to address problems associated with spills where large
quantities overwhelm the stream ecosystem for a short time until some later
date.
We are currently advising others on the application of the WASP model
(Water Quality Analysis and Simulation Package, early 1988 Ambrose et al. 1988)
in a post-audit study of the Ohio River oil spill. From the emergency response
to that event we have found that there is a clear need to develop an
operational model and we expect that this review of the processes that affect
the fate of oily materials will better position us for such an investigation in
the future. At this time, however we will do no more than take note where this
effort may later be useful for other problems.
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Sources of Oily Wastes
In this analysis, we will consider oily liquids and sludges placed in
landfills, in lagoons, and on land application units as potential sources of
stream contamination (see Figure 1A through ID). We expect that liquid oily
wastes in leaking drums and other containers, sludges, and tank bottoms will be
placed in landfills. Liquid effluents and sludges will be placed in lagoons and
sludge drying beds. Migration out of lagoons such as those in a wastewater
treatment plant may be a significant source. Oily wastes, especially those from
wood preserving operations, have frequently been disposed of by application to
land. These practices are presently under review, however.
Pathways to Streams
We have considered two pathways from the sources of oily materials to the
stream -- overland flow and groundwater flow. We have assumed that
volatilization from the source and subsequent deposition in the stream is not a
significant pathway for this type of material.
At this time, we have not fully considered the dynamic nature of the pulse
loading to streams by overland flow. Initially, we will treat overland flow by
averaging over periods of time that may be inconsistent with the period of time
during which some events may actually occur. In the meantime, we have
commissioned a consulting firm to determine the importance of this pathway for
oily wastes and other materials. In the interim, the modeling approach that we
will take will assume that the waste will enter the stream as a combination of
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a separate phase, partially dispersed droplets, emulsions, or a dissolved
component of the overland flow.
The density of the waste will control whether the waste will tend to form
a film on the surface or pool along the bottom of the stream. As illustrated in
Figure 2, lighter than water oily wastes will tend to form a surface film.
Heavier-that-water oily wastes will tend to sink to the bottom (see Figure 3).
Emulsions of oil in water and dissolved components will begin to mix in the
stream. Partially dispersed droplets also will tend to mix and disperse if
the turbulence in the stream is sufficient. 'Otherwise, droplets will tend to
coalesce into films, pools or globs.
We expect the groundwater path to be the predominant route to the stream.
As a result, screening level procedures will focus initially on approximately
continuous, steady-state introduction of oily materials to streams. Depending
on the density of the waste relative to water, and the processes that attenuate
concentrations, we expect that the waste may arrive at the stream in a number
of forms. This is illustrated in Figure 4.
Oily wastes migrating through groundwaters are expected to be in the
following forms:
1. A separate oil phase moving along the surface of the aquifer or the
bottom (perhaps moving towards the bottom) of the aquifer (interface
with the aquiclude),
2. A mixture of partially dispersed oil droplets,
3. An emulsion of oil in water, and
4. A solution of oil and water.
13
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POSITIVELY BUOYANT CASE
OVERLAND
FLOW
EMULSION
FIGURE 2. Lighter Than Water, Oily Waste
Entering a Stream as Overland
Flow
14
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NEGATIVELY BUOYANT CASE
OVERLAND
FLOW
FIGURE 3. Heavier Than Water, Oily Waste Entering a Stream
As Overland Flow
15
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In addition, emulsions of water in oil may occur in groundwater systems. At
this time, however, we do not fully understand whether such an occurrence will
significantly change the properties of the separate oily phase enough to
influence the mixing and dispersion of the waste in a stream.
The density of the waste will control, to some extent, what combination of
forms the waste will be in as it enters the stream. Lighter-than-water oily
wastes will tend to move along the top of the groundwater table and almost all
of this material will eventually reach a stream or other water body (see Figure
5). Heavier-than-water oily wastes will tend to migrate to the bottom of the
surficial aquifer. If the slope of the aquiclude (impermeable layer underlying
an aquifer) is towards a stream and the stream fully cuts through the surficial
aquifer as shown in Figure 6, then all of this form of the waste also will
eventually arrive at the stream.
If the aquiclude slopes away from streams into depressions or into
connections with deeper aquifers, it is unlikely that any of the heavier-than-
water non-aqueous
liquid phase will be introduced into the stream unless it pools in the
depressions and spills out. If the stream does not fully cut through the
aquifer, then some heavier-than-water wastes may move under the stream. In eithi
than water oily wastes may not arrive at a stream or other surface water body.
These cases are serious groundwater contamination problems because the
reservoirs for these wastes in groundwater are finite. In determining
the impact on streams, however, these transport processes represent a reduction
of the mass of material that reaches the stream.
17
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THIN-
RATIFIED-
PLUME
SURFACE
:• WATER •-•
PLUME'
UNCONTAMINATED
AQUIFER
FIGURE 5. Thin Stratified Oil Waste Plume Intersecting a Stream
18
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NEGATIVELY BUOYANT PLUME
Contaminate
Plume
Width
Clean
Aquifer
Heavy Oily Phaser &
Bedrock or Aquiclude
FIGURE 6. Interception of a Plume of Heavier than Water Oily Waste
by a Stream that Fully Penetrates the Surficial Aquifer
19
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We have not fully investigated the formation of partially dispersed
droplets or emulsions in groundwaters but we do believe that they occur based
on our limited understanding of the groundwater pathway. In addition, a recent
review of this work (Danny Reible, Department of Chemical Engineering,
Louisiana State University, personal communication, February 26, 1988)
indicates that this is a reasonable assumption. Dispersed droplets and
emulsions are important if the leachate plume is thicker than the depth of the
stream penetration into the surficial aquifer. In such a case, not all of the
material will be intercepted by the stream as illustrated in Figures 7 and 8.
Some of the partially dispersed droplets arid emulsified plume will continue
downgradient past the stream.
In earlier studies (Ambrose et al. 1987), we have investigated the
behavior of dissolved materials such as those that will dissolve from oily
wastes at the source and in transit to the stream. From our previous work, we
anticipate that the dissolved phase will migrate in a fashion similar to that
shown in Figures 4 through 8. If the dissolved plume is shallower than the
penetration of the stream into the surficial aquifer, then we expect all of the
plume to be intercepted. If this is not the case, we anticipate that some of
the dissolved material in the lower part of the plume will not be intercepted
and will continue downgradient past the stream. Ambrose et al. (1987) describe
the analytical procedures to handle mixing of dissolved materials into streams.
In our initial analysis, we will conservatively assume that all of the
oily material will reach the stream. This is equivalent to assuming that the
source is at the edge of the stream. We will design the initial model to accept
oily waste in the form of a non-aqueous phase liquid, partially dispersed
20
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FILM FORMED FROM EMULSION
//// tilVIUUOIWlN // .
•i~- _.;_£> • _ ™-_- . --;.^-; " - - 5^!*- - -T'
'//, EMULSION y
POOL FORMED FROM EMULSION
Figure 7. Deep Plume Emulsion Intercepted by a Stream that Does Not
Fully Penetrate the Surficial Aquifer
21
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DEEP PLUME:
POSITIVELY BUOYANT CASE
Groundwater
Plume
Intersecting
Stream
. . . .
• Plume- ..'.'•
FIGURE 8. Thick Groundwater Plume not Fully Intercepted by a Stream
that only Partially Penetrates the Surficial Aquifer
22
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droplets, emulsions, and a dissolved component. We do this so that this effort
will mesh with other work that the Office of Solid Waste is doing on the
attenuation of oily materials in the groundwater pathway. Specifically, the
Office of Solid Waste is currently designing a compatible analysis procedure to
simulate the groundwater transport of oily waste leachate. Eventually, we
anticipate that the allied effort will be able to simulate the amount of the
leachate that is intercepted by streams. We also expect that the groundwater
modeling will be designed to predict how much of the intercepted plume is
partitioned between the non-aqueous liquid phase, partially dispersed droplets,
emulsion, and dissolved components. We also anticipate that the allied project
will quantify any attenuation of the leachate caused by volatilization and
biodegradation if these prove to be important.
Screening Level Model
The initial screening model will ignore the processes that tend to
attenuate or dissipate the waste until a need to consider these effects is
demonstrated. As a result, the initial screening level model will be
conservative in most cases. There may be a few cases where, the analysis may
not be fully conservative because of a lack of full knowledge about
geomorphology and ecology of streams and the fate of oily wastes in streams.
Ideally, a screening level model should also always conservatively predict
effects as shown in Figure 9. In Figure 9, we illustrate the relationship
between an environmentally conservative screening model and perfect knowledge
of the system under investigation. Unfortunately, we do not know where the line
23
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DESIGN MODEL
MULTIPIED BY A
SAFETY FACTOR
ENGINEERING DESIGN
MODEL AND UNCERTAINTY
ENVELOPE OF ± n STD. DEV.
OR n th PERCENT1LES
Predicted Concentration
POSSIBLE
DESIGN
OBJECTIVES
INITIAL
REGULATORY
OBJECTIVE
SCREENING LEVEL
MODEL + n STD. DEV.
OR n th PERCENTILE
FIGURE 9. Ideal Relationship Between Screening and Design Models
24
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of perfect agreement lies unless we are able to precisely measure impacts.
Under practical conditions, we can not be absolutely sure that the screening
level model is, in fact, conservative for all conditions. We can usually be
reasonably sure that the model is conservative over a limited range of
conditions where we have collected validation measurements, however.
Figure 9 also illustrates the relationship one would expect between
screening models and precise design models. Ideally, we would hope that design
models are only slightly conservative and that the discrepancies between the
line of perfect agreement and the predictive ability of the design model are
small. In practice, however, design models may be slightly nonconservative or,
at the very least, the uncertainty envelope about the predictive curve of the
design model (defined by + n times the standard deviation, or + the n
percentile) may be nonconservative. Traditionally, the possibility of non-
conservative design is taken into account by strictly limiting the conditions
over which the method is applied and by multiplying results by a conservative
safety factor (see Figure 9). Safety factors of 2 or 2.5 are typically used for
bridge and building design. Factors as high as an order of magnitude may be
used when the risks are perceived to be high and the predictive method is based
on limited knowledge.
Better risk management is possible if the uncertainty is quantified using
the standard deviation or similar statistic. In this case, we will use a Monte
Carlo analysis to quantify uncertainty and use a designated percentile to
provide a quantifiable margin of safety for the analysis. Figure 9 contrasts
the approach of using a traditional safety factor versus a margin of safety
based on the uncertainty of the design method. The percentile chosen as the
25
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margin of saftey will be designated by the regulatory decision makers as part
of the risk management process.
The n percentile may or may not be less conservative than a
traditional safety factor. However, the n percentile can be quantified
whereas the traditional safety factor does not seem readily applicable to risk
analysis because of its empirical and subjective nature. In either case,
information about the response of the ecological system under study must be
collected to determine the appropriate factors. Traditional engineering
approaches have relied on an accumulation of observational evidence. Current
risk assessment procedures are based upon these same observational data but
provides a more rational organization of the information available. This
approach helps to determine if the observations available are adequate to
validate the designated margin of safety and to provide more precise
extrapolation.
The use of a margin of safety for a screening level analysis when a
conservative approach is used is necessary when the effect of assumptions are
not known to be fully conservative. Initially, there will be only very limited
data (if any is available) to validate the conservative nature of the screening
model. As a result, we propose to develop a conservative screening model with a
margin of safety based on the n percentile (as shown in Figure 9) as the
initial objective to support the this regulatory process.
Such a screening model will allow us to conservatively determine when the
disposal of oily wastes will not present an environmental problem. The
screening analysis will not allow us to definitively determine if a problem
26
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will occur but it will tell us when refinement of the modeling approach is
necessary. In refining the model, we expect the curve representing the
screening model in Figure 9 to migrate towards the position of the design model
and we would expect that generally the uncertainty envelop would shrink. If
necessary, the final model would be an engineering design model for the
evaluation of waivers (if permissible under present or future regulations).
Incremental improvement of the screening model should be focussed on
limited ranges of known applicability or in the vicinity of criteria as shown
in Figure 10. This is consistent with limited validation over the range of
expected stream conditions and for the potential range of properties of oily
wastes that can be generated.
We presently conceive of the initial model as a screening tool because our
introductory investigation indicates that only a simple, conservative model is
achievable in the initial phases of this work. One preliminary assessment of
the nature of the model to be proposed indicates that we may underpredict the
amounts of oily materials reaching streams by an order of magnitude (Danny
Reible, written communication, 1988 - see Appendix I). If this is true, we
expect to develop the necessary modeling refinements in increments until we
have developed an adequately incorporated the important processes.
To design an environmentally conservative approach, we have focussed on
critical exposure zones in streams and the important pathways between the
sources of interest and these zones (see Figure 11). This involves
consideration of the following potential effects of oily wastes in streams:
27
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c
(0
•*•»
0)
o
c
o
o
•o
<5
O
o
13
3
RANGE GENERALL
ENCOUNTERED
DESIGN
MODEL
SCREENING
LEVEL
MODEL
Predicted Concentration
FIGURE 10. Goals for Incremental Improvement of the Screening Model
Over the Range Generally Encountered or in the Vicinity
of Criteria
28
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LANDFILL
0
33
o
D
s
m
x
SET OF
KNOWN POTENTIAL
EFFECTS
^
w////////////.
LAGOON
LAND APPLICATION
KNOWN PATHWAYS
FIGURE 11. The Set of Known Pathways and Potential Effects of Oil Wastes in Strea
29 . " I'1
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1) Toxicity to fish and shell fish,
2) Taste and odor of the water,
3) Tainting of fish flesh,
4) Toxicity to plants, and
5) Aesthetic impairment.
To be sure we have considered the important processes and pathways, we
will briefly review our current understanding in this report. We expect that an
expanded review in the future should compile a full understanding of the
processes to determine when and if additional model development will be
necessary.
To select the appropriate endpoints, we will list the important effects
and classify these in a manner that will simplify the development of a
screening, exposure model. We will use the current criteria reviewed in the
next section and other information to determine endpoints that are easily
modeled and useful in dose-response relationships.
CRITERIA GOVERNING OILY WASTES
The analysis of oily wastes is hampered to some extent by a lack of
numerical criteria governing acceptable levels of oily materials in the aquatic
environment. The most recent criteria (U.S. EPA, 1987, see Appendix II) is
based on a narrative statement for protection of water supplies and aquatic
life. In addition, the latest criteria also recommends that one percent of the
lowest continuous flow 96-hour LC^Q (lethal concentration for 50 percent of
30
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the test organisms) for Important freshwater and marine species be used as
protection against harm to aquatic wildlife. It is recommended in the criteria
document that any test species demonstrably high susceptibility to oils and
petrochemicals.
In part, precisely defined numerical criteria are not available because of
the diverse nature of oily wastes. The oil and grease in oily wastes are not
definitive chemical classes but are diverse materials that do not readily mix
with water. Thousands of organic compounds with very different physical,
chemical, and toxicological properties are' lumped into this category. The
compounds may be volatile or not volatile, soluble or insoluble, and persistent
or easily degraded (U.S. EPA 1987).
If there were precise criteria for oily wastes, then this work to develop
regulatory procedures and standards might be unnecessary. As it is, the current
criteria are not sufficient, as we will indicate in the following review. As a
result, we will need to refine the interpretation of existing criteria and
develop new exposure endpoints.
McKee and Wolf (1963) seem to be the first to extensively compile water
quality criteria. They reviewed the effects of animal and vegetable oils as
well as petroleum-based oils. The Federal Water Pollution Control
Administration (FWPCA 1968) later provide refined narrative criteria. The 1972
Water Quality Criteria (EPA 1973) offered further refinements and the Quality
Criteria for Water 1976 (EPA 1976) seem to offer an even more practical
approach. The Quality Criteria for Water 1986 (1987) does not seem to offer
31
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any significant advance over the 1976 criteria for oil and grease. A review of
the criteria indicates that little interpretive work has occurred since the
early 1970s. In part, this may be one reason why a significant amount of work
is needed to develop regulatory methods.
Drinking Water Criteria
The FWPCA (1968, p. 25) recommends the avoidance of oil and grease in
water supplies because of the occurrence of scum lines, taste, and odor. To
achieve these conditions, the FWPCA (1968, p. 6) recommends that discharges be
free of oily substances that:
1. Settle to form objectionable deposits,
2. Float to form oil films and scum, and
3. Produce objectionable color, odor and taste.
The more recent criteria (EPA 1987) modifies the recommendation to indicate
that drinking water supplies should be "virtually free" of oil and grease.
The 1968 drinking water criteria seem to be overly strict in that a ban
on oily waste disposal upstream of locations where drinking water supplies are
withdrawn is implied. Given the widespread use of surface waters for drinking
in the United States, the strict application of these criteria indicates a
potential ban on oily waste disposal over large areas of the country. Such a
wide-scale ban is presumed to occur if one traces the stream water at a
potential water withdrawal point upstream to all points in the basin and
assumes that there is some potential for any amount of oily contaminant to flow
through the basin. As an extreme example, if one assumes (as some experiments
32
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indicate - see McKee and Wolf 1963) that oily wastes are not fully degraded in
streams and rivers, the strict interpretation of the drinking water criteria
for the withdrawal at New Orleans would seem to preclude disposal of oily
wastes in almost all of the Mississippi River Basin.
The more recent refinements of the criteria (EPA 1976, 1987) which
indicate that water supplies should be "virtually free" of oily material,
especially those that cause foul tastes and odors, seem to offer the latitude
to determine threshold concentrations that are to be avoided. Therefore, we
intend to investigate what guidance is available (McKee and Wolf 1963, EPA
1973) on threshold concentrations causing oily taste and odor and determine
whether the available data are sufficient to support the adoption of a single
criterion for all oily wastes. Otherwise criteria for broad classes of oily
wastes will be investigated. To be most successful, we project that a chemical-
by-chemical determination of taste and odor thresholds should be avoided if at
all possible.
According to the 1968 criteria, waters also should be free of oils to
avoid scum lines in water treatment plants. McKee and Wolf (1963) reviewed
other operational difficulties in water treatment plants that indicated the
need to have water supplies free of oil and grease. Unfortunately, there seems
to be little work defining what amounts of oil cause scum and other operational
difficulties. As a result, we will rely on the Monte Carlo analysis to provide
some margin of safety in this area where our knowledge is limited.
33
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Discharge Criteria
Criteria (FWPCA 1968) governing point source discharges of oil and grease
are somewhat more specific but are also subjective narrative descriptions that
must be quantified if reasonable regulatory procedures are to be proposed. In
general, objectionable deposits, odors, tastes and colors have not been defined
by numerical criteria. However, such a definition seems possible for at least
most of the narrative objectives. In a few cases, it is anticipated that some
new guidance will need to be developed in later stages of this study.
Initially, we find that "objectionable deposits" are difficult to quantify.
Odors, tastes and colors should be reasonably quantifiable.
More recent criteria do not specifically refer to point sources. The 1976
and 1986 criteria do indicate, however, that surface waters shall be virtually
free from floating oils. This is much better adapted to the design of analysis
procedures if we assume that "virtually free" implies that limited amounts of
oily wastes are permissible as long as the film is not visible, does not kill
or impair the growth of aquatic life, and does not contribute any other effect.
The 1968 criteria that discharges be free of oily materials if oil films
will be formed also has the practical effect of banning disposal of lighter-
than-water oily wastes. By definition, immiscible wastes with a density less
than water will form a film on the surface. The only condition that may not
lead to the formation of a film involves conversion of the oily phase to an
emulsion in the groundwater. Otherwise, a film should be expected whenever the
leashate plume reaches the stream. Therefore, this criterion seems overly
restrictive in light of current practice. As a result, it is proposed to
34
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investigate specific criteria for protection of aesthetic qualities and
wildlife and to regulate the wastes on the basis that streams will be virtually
free of films if the film is not visible, does not contribute to taste and
odors, and does not present a hazard to wildlife.
In considering the restrictive nature of the 1968 discharge criteria, it
should be noted that the migration of oily wastes from landfills, lagoons and
fields result in nonpoint sources of pollution. This distinction should make no
difference, however, because the more recent criteria seem to refer to
receiving water quality without regard to the" nature of the source.
Protection of Wildlife
For the protection of wildlife in streams, the FWPCA criteria (1968, p.
34) recommend that oils and petrochemicals not be added to receiving waters in
quantities that cause:
1. A visible color film on the surface,
2. An oily odor to the water,
3. An oily or noxious taste to edible fish and invertebrates,
4. Coating of banks and bottoms of the stream,
5. Tainting of the benthic biota, and
6. Toxicity.
In addition, all of the criteria documents give specific examples of
concentrations of oily materials that cause acute and chronic toxicity. The
most recent documents (EPA 1976, 1986) organize the state of our knowledge up
35
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until about 1973 Into criteria for the effects of classes of oily materials on
sensitive or indicator species. The 19.86 criteria also establish that the
appropriate level of protection is that concentrations should not exceed one
percent of the median lethal concentrations (LC5Q) for sensitive freshwater and
marine indicator species. The recommendation that the appropriate criteria to
avoid chronic toxicity is one percent of the LC^Q may also be an additional
safety factor to consider.
Tables 6 and 7 in Appendix II compile the most recent readily available
information on LC^Q values for sensitive species exposed to classes of oily
materials. There is a need to review these classes of oily materials to
determine if these adequately cover the oily wastes that are currently of
interest to the Office of Solid Waste. In addition, there is a need to re-
examine what are important freshwater indicator species of fish. In this
regard, we anticipate that the Office of Solid Waste will take a lead role in
indicating what important species should be included. In any event, we will
examine the present guidance and make recommendations as needed. If important
classes of oily wastes and indicator species are neglected in the current
criteria document, we will also be prepared to indicate to our colleagues at
the Environmental Research Laboratory at Duluth wahat bioassays are needed to
support this work.
The exposure criteria given in Appendix II, Tables 6 and 7, represent an
excellent basis for this analysis. However, the data in these tables do not
extend past 1974. Therefore, we will list other studies uncovered in our review
that can be used to update Tables 6 and 7.
36
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It should also be noted that Tables 6 and 7 do not distinguish between the
effects of exposure to specific oily.waste components such as films or
emulsions. Therefore, additional review of past dose-response studies to
distinguish between the effects of films, droplets, emulsions, and dissolved
components as well as indirect effects such as deoxygenation is indicated.
The Office of Solid Waste has not been able to find criteria protecting
fish and wildlife from the U.S. Fish and Wildlife Service.
EFFECTS OF OILY WASTES IN STREAMS
There are at least six effects of oily wastes in streams. First,
aesthetics are impaired by visible films on the water surface, pools of heavy
oily wastes, and coatings of oily wastes on the surfaces of stones and
vegetative debris in streams. Second, oily materials, especially petroleum
products, cause edible fish and invertebrates (such as clams) to taste bad.
Third, oily materials cause foul tastes and odors in drinking water. Fourth,
and perhaps most serious, pools, contaminated sediments, films, emulsions, and
the dissolved component of oily wastes are toxic to wildlife and biota. Fifth,
oily waste may serve as a solvent that mobilizes or concentrates materials that
are more toxic than oily waste components. Finally, oily wastes may have an
indirect effect on water quality due to influence on photosynthesis, reaeration
and other components of the dissolved oxygen balance.
These effects fall into at least three general categories. Aesthetic
impairment, foul tastes and odor, and tainting of fish flesh are human effects.
37
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Toxic effects on wildlife represent a second category. Indirect effects
represent a useful third category. -. ,
Human Effects
Past investigations (McKee and Wolf 1963, EPA 1987, also see John Hopkins
University 1956 in the Selected Bibliographt originally cited in EPA 1987)
indicate human toxicity only occurs at concentrations much higher than the
criteria for taste and odor. Apparently the same is true for other effects of
oily materials. Odor detection thresholds seem to be lower than levels at which
oily coatings become detectable to swimmers.
Aesthetics
Very minute quantities of an oily phase are visibly detectable on the water
surface because of the change in surface tension. The effect of a film on the
order of one to ten molecules in depth covering part of the surface can be
observed despite the fact that the oil is not be visible. Very thin films that
partially cover the surface are detectable because of the suppression of
capillary waves. Capillary waves are very small irregularities visible on an
agitated water surface. The contrast between slick patches of oil and the
remaining agitated surface is one manifestation of oily wastes that may present
at least a minor concern. In the event that the surface is completely covered
with an oily film.too .thin to be visible and the flow is very quiescent, it may
38
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not be possible to visibly detect the affect of the oily film. It seems rare,
however, that stream flows will not be sufficiently turbulent to break up the
very thin films or patches that are not visible. As a result, it seems
reasonable to conclude that oily wastes cause an aesthetic problem only when
the wastes are present in great enough quantities to cause a visible film on
the surface. However, this may be one important distinction for oily wastes
entering a quiescent lake that should be taken into account in extending these
methods to analyze other water bodies.
Visible detection of an oil film remains a subjective exercise. However,
the American Petroleum Institute (API) has long-standing criteria regarding
what thickness of an oily film is visible on a water surface (Nelson-Smith
1972, API 1963). Evidently, these criteria are traceable to a 1930 report to
the U.S. Congress by Stroop (see Selected Bibliography). Therefore, these
criteria should be unbiased and useful.
Table 1 is a listing of the thickness of an oily film having different
visible characteristics. The thickness of a barely visible film (0.038 microns)
would seem to be the most appropriate criterion for this analysis. Depending on
the regulatory objective, however, some of the other criteria may be useful
under different circumstances. For example, in secluded areas where it may be
rare that anyone visits the stream, a less restrictive criterion such as
avoidance od a silver sheen (thickness of 0.076 microns) may be useful. If this
analysis is later extended to include site-specific analyses of larger streams
where navigational uses and industrial development exclude recreational
activity, then less severe standards may be appropriate. Multiple film
thickness criteria can be incorporated into the Monte Carlo analysis but this
39
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involves a much more extensive mapping of stream reaches and the appropriate
reach criteria for film thickness. :•, -
Table 1.
Criteria governing the visible detection of oil films on water surfaces.
[source Nelson-Smith 1972, and American Petroleum Institute, 1963,
originally adopted from Stroop, 1930].
Thickness Quantity of oil
o n
inches microns ' gal/mile liter/km
Barely visible
Silvery sheen
Trace of color
Bright bands of color
Colors dull
Colors dark
0.0000015 0.038 25
0.0000030 0.076 50
0.0000060 0.152 100
0.0000120 0.305 - 200
0.0000400 1.016 666
0.0000800 2.032 1332
44
88
176
352
1170
2340
We intend to determine if criteria governing visibility of oil under ice
exists in the literature. However, it is anticipated that criteria related to
oil films under ice would be less restrictive than criteria governing the
visibility of films on open waters.
Oily material deposited on the bottom by either coagulation of light oils
with suspended sediments or the sinking of heavy oils, may be a less detectable
aesthetic problem. At this time, it is not clear how well this potential
aesthetic problem can be explored without reliance on fully subjective criteria
40
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(that will be difficult to defend from a technical viewpoint). However, the
difficulty in defining criteria to govern, the regulation of oily coatings and
sinking oily waste may not be critical to the overall analysis procedure
because other criteria related to acute and chronic toxicity may be more
restrictive. At this time a more restrictive criteria based on benthic toxicity
is expected because of the intimate influence of the benthic interface on food
chains in streams. There are many rooted and attached plants subject to harm.
Many aquatic animal species either begin or spend a significant portion of
their life cycle on the stream bed. Nevertheless, coatings on rocks, winter
ice, plants, and debris at the edge of a stream may represent a significant and
critical aesthetic problem that must be considered in the analysis until
additional study indicates otherwise. In addition, toxicity criteria for
benthic exposure is expected to also be difficult to define. Therefore,
aesthetic concerns can not be completely deferred until criteria based on
toxicity are derived.
In this regard, we will investigate any criteria related to the amount of
oil coatings that are visible. We will look for studies that quantify how thick
oil coatings must be to be visible or what quantity of oil in streams leaves
detectable coating on rocks, debris and vegetation and scum lines in water
treatment plants.
To better define the aesthetics of oil on stream bottoms, we will consider
what recreational and commercial activities may be impacted. The preliminary
review (see Appendix I) has provided some suggestions in this matter that
should be investigated.
41
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Tainting of Fish Flesh
Ingested oily wastes may not only affect the growth of fish but may also
impair the taste of sport fish (i.e. bass) and other edible fish. In addition,
oily wastes may impart oily and noxious tastes to edible invertebrates (i.e.
shellfish). Given the arbitrary and subjective nature of how humans distinguish
tastes and given the fact that various types of edible fish and invertebrates
may either enhance or mask objectionable tastes, it is expected to be difficult
to define precise, general criteria for the purpose of avoiding taste problems.
At this time it seems that it may be necessary to accept whatever guidance is
presently available and to determine if more work in this regard is necessary.
HcKee and Wolf (1963), FWPCA (1968) and EPA (1973) provide the best guidance of
which we are aware.-
Table 2 summarizes the readily available information on amounts of oily
substances that taint edible fish and invertebrates. We expect to use these
data and other data being compiled from EPA (1973) and McKee and Wolf (1963) to
determine what guidance may be formulated to develop concentration criteria for
all oily wastes or classes of oily wastes. For example, we anticipate that the
most useful criteria will be those for wood preserving wastes (because of the
phenolic compounds expected in the waste)and the five categories of refining
wastes (K48 through k52).
42
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Table 2.
Concentrations of oily materials or components of oily wastes that
taint edible fish and invertebrates.
Oily Material
kerosene or
diesel
chlorophenol
Species
bass and
bluegill
fish
Concentrations Reference Comment
or Amount
20 gal. /acre FWPCA persists for 4
(1968) to 6 weeks
0.0001 mg/L Boetius (1954)
PURE COMPOUNDS from FWPCA (1968)
Phenol
Cresols
Xylenols
Pyrocatechol
[C6H4(OH)2]
Pyrogallol
[C6H3(OH)3]
P-Quinone
(CgH402)
Pyridine
Naphthalene
Alpha Naphthol
Quinoline
(C9H7N)
Chlorophenol
Coal cooking
waste
Coal tar waste
Phenols in
polluted river
Sewage contain-
ing phenols
Trout , carp ,
eel, minnow,
blue gill,
pike
Trench , carp ,
eel, trout
Roach, perch,
carp
Perch, carp,
roach
Roach, carp
Carp , trench ,
roach
Roach, carp
Roach
Roach , carp
Roach , carp
Roach , carp
MIXED PHENOLIC
Freshwater
fish
Freshwater
fish
Minnows
Freshwater
fish
15 to 25 mg/L FWPCA
(1968)
*
10.0 mg/L
1 to 5 mg/L
2 to 5 mg/L
20 to 30 mg/L
0.05 mg/L
5.0 mg/L
1.0 mg/L
0.5 mg/L
0.5 to 1.0 mg/L
0.01 mg/L
WASTES from FWPCA (1968)
0.02 to 0.1 mg/L
0.1 mg/L
0.02 to 0.15 mg/L
0.1 mg/L
43
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We expect that definition of sensitive or indicator species will be
necessary. In this case, appropriate indicator species may be game fish or
commercially important species. Alternatively, it may be necessary to define
classes of organisms for which criteria can be defined using existing
bioassays. We will determine if additional bioassay and bioconcentration work
would be useful.
Taste and Odor
Oily wastes may cause odor when introduced into a stream and, if in the
course of swimming, water is consumed, a bad taste may be detected. Similarly
and perhaps more importantly, the taste and odor of drinking water may be
impaired by excessive oily wastes in stream waters. Because taste and odor are
subjective responses, differing from one person to another, criteria useful for
avoiding taste and odor problems also will be subjective. Nevertheless,
McKee and Wolf (1963) seem to provide enough useful information to derive
initial guidance.
The associate author (Vocke) also investigated drinking water standards
and determined that there are none available. A health advisory on gasoline in
water is expected by the summer of 1988. Upon reflection, the absence of
drinking water standards is not unexpected since taste and odor thresholds seem
to be lower that concentration that cause human toxicity (EPA 1987, McKee and
Wolf 1963).
44
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Toxicity to Plants and Animals
In this investigation, we are primarily interested in the physical
mechanisms that cause death and impair growth. These include coating of gills
and sensitive surfaces (i.e. feathers), ingestion (recognizing the overlap with
chemical toxicological mechanisms), and prevention of surface breathing. There
are a number of documented chemical toxicological effects as well that we will
not emphasize here. Chemical mechanisms causing toxicity can be chiefly related
to dissolved components. But since the dissolved components of oily wastes must
derive from the non-aqueous liquid phase in'the form of films, pools, globs,
droplets, or emulsions, we can not completely defer the consideration of these
effects to the allied investigations such as those underway at the Duluth
Environmental Research Laboratory. Studies that concentrate on the effects of
dissolved components are not complete without consideration of the transport
mechanisms being incorporated in this analysis. If more elaborate models are
needed, we expect them to be based on mass balances of the separate components
of oily materials. The dissolution of oil will be a critically important
process to be included in these mass balance simulations for streams.
Furthermore, we can easily include the effects of critical dissolved
concentrations in the proposed analysis procedure.
In regard to the previous discussion, we will catalog the readily
available information on chemical toxicity, but will not adopt a chemical-
specific approach in this analysis. The U.S. EPA has extensive listings of
specific chemicals and limitations on their concentrations that should
adequately cover the toxicity of most, if not all, of the highly toxic
components of oily wastes when those components are present in extraordinary
45
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quantities. Instead, we are interested in the composite effects of mixtures of
thousands of organic chemicals present in widely varying percentages, most of
which are below the regulatory thresholds for specific chemicals. We are
particularly interested in the effects of larger amounts of oily materials that
overwhelm physical mechanisms of plants and animals contrasted with trace
quantities that usually disable chemical mechanisms.
We propose to investigate toxicity to dissolved components at the same
time that we review the information in Tables 6 and 7 (Appendix II) and
elsewhere to determine the separate effects 'of oily films, pools, globs, and
emulsions. In this regard, consideration of the dissolved component merely
completes the full picture on the effect of oily waste.
In the long term, it will be necessary to fully understand partitioning of
chemicals between oily materials, solids and the water to explore suspicions
that oily materials may serve as physical concentrators of trace toxicants in
the stream or carry otherwise immobile toxicants from the source (i.e.
landfills).
It is also important for consistency with proposed work at the Duluth
Laboratory to consider all mechanisms of toxicity and the critical transport
mechanisms. We expect that the Laboratory at Duluth will conduct much needed
bioassays of oily materials and we hope to be able to suggest which waste
classifications are the most important to focus upon. We suspect that new
bioassay work may be important because the current criteria, as summarized in
Tables 6 and 7, have not been updated in 15 years.
46
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Toxicity of the Oily Phase
Coating of the gills by oily materials is one known mechanism that kills
fish (FWPCA 1968, p. 45) and presumably the coating of other sensitive surfaces
can kill fish and other invertebrates. FWPCA (1968, p. 45, Mckee and Wolf 1963)
notes that oily coatings kill plankton. Partial coatings of gills impair
respiration and thus contribute to indirect and chronic toxicity. Ingestion of
the oily phase is also toxic in a number of cases, especially for refinery
wastes. The oil may be directly ingested or oily coatings on food may be
ingested. Coatings on food may occur when the food particles fall through a
surface film or intersect oily patches on the bottom. As a result, oily films
on the surface can take on some added importance. Oily wastes can, in addition,
threaten water fowl by destroying the natural buoyancy and insulation of
feathers. Invertebrates, especially those in a larvae stage, may be killed when
a surface film prevents breathing. This mechanism has long been used to control
mosquitoes, but surface films can affect more desirable species of
invertebrates such as water boatmen, back swimmers, adult and larvae aquatic
beetles, and Diptera (flies) (FWPCA 1968). We expect to investigate the film
thickness required to kill and otherwise affect mosquitoes and other
invertebrates.
Table 3 summarizes our limited compilation of studies from FWPCA (1968)
that document the effects of the oily phase on aquatic wildlife. If time
permits, we will review other work on toxicity to fish (p. 72*72 FWPCA 1968,
also see Cairns 1957, Academy of Natural Science 1960, Galtsoff 1936, Chipman
and Galtsoff 1949, Outsell 1921, Cairns and Scheier 1958). We also hope to
include studies by Hartung (p. 96 FWPCA 1968) concerning egg laying inhibition
47
-------
in ducks and other effects on waterfowl and terrestrial animals that use
streams. -. ,.
Table 3.
Concentrations of the oily phase that are toxic to aquatic wildlife.
Oily Material
Species
Concentrations Reference Comment
or Amount
Crude oil
bass and .
bream
Wiebe
(1935)
cited in
FWPCA
(1968)
Found mortality
caused by
coating
gills and
soluble
fraction also
Crude oil
oysters
Crude oil
Settleable oily
substances
Oil film
Oil
algae and plankton
benthic organisms,
spawning organisms
aquatic
insects:
water
boatmen,
back swimmers,
aquatic
beetles, and
aquatic flies.
Waterfowl
Galtsoff
et al
(1935)
cited by
FWPCA
(1968)
FWPCA
(1968)
FWPCA
(1968)
FWPCA
(1968)
FWPCA
(1968)
very
toxic. Chronic
toxicity caused
by lower
concentrations
partially coating
the gills.
anesthetic
effect from the
soluble fraction.
Coats and destroys
Coats and
destroys.
Film prevents
respiration.
Destroy natural
buoyancy and
insulation.
48
-------
Table 3.
Concentrations of the oily phase that are toxic to aquatic wildlife - Continued
Oily Material
Species
Concentrations Reference Comment
or Amount
Motor oil
crayfish
European
small perch
5
4
to 50 mg/L
to 16 mg/L
Seydell
(1913)
cited in
FWPCA
(1968)
30 to 35 g
organisms died
within 18 to 60
hours .
Lethal within 18
to 60 hours .
Russia crude oils:
methano-aromatic
type high in
asphalt, tar
compounds,
sulfur, and
benzene-ligroin
but low in
paraffin.
and white
fish (fam.
Corregonida)
crucian carp
(Carassius
carassius)
7 to 9 cm
in length
0.4 mL/L
((340 mg/L)
(average
survival: 17
days)
4 mL/L
(C3400 mg/L)
(average
survival:
3 days)
Gasoline
fish and
macro-
vertebrates:
midge-
Orthocladius
mayflies,
stone flies
not known
Veselov Crucian carp
(1948) considered to be
cited in a hardy fish.
FWPCA Soluble oil
(1968) extracted by
shaking 15 mL of
oil in 1 L for 15
minutes. Oil film
removed by
filtration. DO
controlled.
Involved 154 tests
of 242 fish.
Seydell (1913)
indicated that
toxicity is due
to naphthenic
acids, small
quantities of
phenol, and
volatile acids.
Bugbee gasoline spill
and probably ranging
Walter from undiluted-to
(1973) highly diluted
killed fish and
prevented
invertebrate
recolonization
for at least six
months.
49
-------
Table 3.
Concentrations of the oily phase that are toxic to aquatic wildlife - Concluded
Oily Material
Species
Concentrations Reference Comment
or Amount
Crude oil
fish
0.3 mg/L
Chipman
and
Galtsoff
(1949)
cited in
FWPCA (1968)
extremely toxic
Oil refinery
effluents
Oil
Diesel oil
fathead
minnows
-
marine
mollusks (Mya
arenaria)
sea urchins 0 . 1 percent
(Strongylo- emulsion
centrotus
purpuratus)
Dorris et
al.
(1960)
cited in
FWPCA
(1968)
Nelson
(1925)
cited in
FWPCA
(1968)
North et
al.
(1964)
cited in
FWPCA
(1968)
3.1 to 21.5
percent mortality
after 48 hours
exposure to
untreated
effluents .
Toxicity due to
chemical
reactivity rather
than depleted
oxygen.
Killed on tidal
flats .
dies in about
one hour.
Toxicity of Contaminated Sediments
Although the exact mechanisms causing organisms to die are not well
understood, contaminated sediments have also been shown to be toxic to fish and
other organisms, including organisms not in direct contact with the sediments
(McKee and Wolf 1963). Bioassays of four species involving crude oil absorbed
by carbonized sand (a product developed during World War II to soak up spills
of oil on water) were reported by FWPCA (1968) and are summarized in Table 4.
50
-------
In addition, a reviewer of this document (Dr. Robert Swank, Athens
Environmental Research Laboratory) points out studies by the Environmental
Research Laboratories at Corvallis, Duluth, and Naragansett on sediment
criteria that may be of interest. This will be followed up as time permits.
Table 4.
Concentrations or amounts of oily wastes in sediments
that are toxic to aquatic wildlife.
Oily Material
Crude oil in
carbonized sand
with no free
oil
Species
Toadfish
(Opsanus
tau)
Concentrations Reference Comment
or Amount
Chipman Very hardy
marine fish in
the yolk sac
stage.
Barnacle
(Balanus
balanoides)
Oyster
(Crassoctrea
virginica)
Hydrozoan
(Tubularia
crocea)
At this time it is not clear that the exact mechanisms causing toxicity
to fish in the water column can be clearly elucidated. Furthermore, the effects
on benthic organisms may need to be defined with additional bioassay studies.
51
-------
Toxicity of Emulsions
It is not clear in all bioassay studies of the toxicity of oily materials
that the effects of emulsions have been clearly identified. It is expected that
the important mechanisms will be ingestion and coalescence of emulsions on the
gills and skin. The formation of emulsions will also greatly increase surface
area of contact between water and oil. Enhanced toxicity of the dissolved phase
due to increased dissolution will be an indirect effect of the formation of
emulsions. This seems to have been observed in a few studies of the toxicity of
emulsions.
In terms of relative impacts, it is expected that emulsions will be less
effective that films and heavy pools of oily wastes in causing coatings on
gills and outer surfaces. However, emulsions can represent a greater danger to
organisms that will not ordinarily be in contact with the surface and bottom.
Therefore, it is not clear that it is conservative to assume that criteria for
films and pools will be fully adequate to protect wildlife from emulsions. It
is anticipated that criteria describing the effect of ingestion is equally
applicable to emulsions and separate oil phases.
It is expected that the indirect effect of enhanced dissolution of the
oily waste due to the formation of an emulsion will be difficult to quantify.
In a pure water-oil system, surface tension will dictate the formation of a
uniform size emulsion. Conceptually, it would seem to be a straightforward task
to formulate mass transfer descriptions for an emulsion of uniform droplets.
However, in natural systems, a variety of unpredictable combinations of natural
surfactants will be present. These surfactants are expected to change the
52
-------
surface tension and thus affect the droplet size. Being unable to readily
predict droplet size indicates that mass transfer will be difficult to predict.
Therefore, the importance of enhanced dissolution will need to be investigated.
The effect of surfactants on the emulsions is to form micelles. Micelles
are, as illustrated in Figure 12, droplets with surfactant molecules forming a
layer between the water and oil phases. Given the diverse number of different
surfactants in natural waters, and a paucity of knowledge about the interaction
of surfactants, it seems unlikely that surface tension effects on droplet size
and mass transfer can be readily determined.
As of yet, the effect of emulsions on fisheries has not been fully
investigated. The most useful criterion discovered so far is from the work of
Grushko (1968) indicating that a limit of 0.05 mg/L for dissolved and
emulsified oils may be adequate protection for fisheries. The U.S. Fish and
Wildlife Service does not seem to have similar criteria.
The results of further review of the literature (McKee and Wolf 1963) will
be reported in Table 5 if time permits.
53
-------
WATER
HYDROPHILIC
END
OILY MATERIAL
Figure ^.Typical Micelle
-------
Table 5.
Concentrations of emulsions that are toxic to aquatic wildlife.
Oily Material Species Concentrations Reference Comment
or Amount
Oily wastes
Diesel oil
Fish
Sea urchins
0.05 mg/L
0.1 %
Grushko (1968)
North et al.
Toxicity of the Dissolved Phase
A significant fraction of oily materials, especially crude oils and their
derivatives, dissolve in water. For some oily materials, these fractions may be
the most toxic component. Examples of toxic soluble fractions include phenols.
There is some guidance on the weathering of petroleum products that should
allow us to compute the dissolution from oil films, pools and emulsions. These
methods, however, will be difficult to implement. It will be necessary to
investigate mass transfer rates. These rates are governed by the geometry of
the nonaqueous phase liquid in the stream. Films, droplets and pools will have
different geometries.
It is also recognized that oily wastes act as solvents for other more
toxic materials that can be dissolved into the water or remain concentrated in
the oily carrier. It is suspected that films, and especially oily wastes pools
on streeam beds, may concentrate pesticides in streams (FWPCA. 1968). These are
potential effects that we do not expect to be able to address initially because
the need to do so is not presently clear.
Limited data describing the effects of dissolved oily waste components are
given in Table 6. We do not intend to imply that a chemical-specific approach
will be pursued from this listing of specific components.
55
-------
Table 6.
Concentrations of the dissolved components of oily wastes that are toxic.
Component
Species
Concentrations Reference Comment
or Amount
Petrochemicals:
benzene,
chlorobenzene,
.**
.**
0-cresol
0-chlorophenol'
chloropropene,
cyclohexane
«
ethyl benzene,
isoprene ,
methyl
methacrylate ,
phenol,
0-phthalic
anhydride,
styrene,
toluene,
vinyl acetate, and
xylene
fathead
minnows,
bluegills,
guppies, and
goldfish.
12 to 368 mg/L Pickering Standard bioassays
(96-hour TLffl)
and
Henderson
(1966b)
cited in
FWPCA
(1968)
in hard and soft
water. Chemical
blended into 500
mL water before
dilution in test.
Pure oxygen was
added to keep
dissolved oxygen
high.
*i
least toxic
**
most toxic
56
-------
Table 6.
Concentrations of the dissolved components of
oily wastes that are toxic - Concluded.
Component
Species
Concentrations Reference Comment
or Amount
Naphthenic acid
(cyclohexane
carbolic acid)
bluegill
sunfish
(Lepomis
macrochirus)
96-hour
Soft Hard Water
5.6 7.1 mg/L McKee
(18 to 20 °C) and
5.6 7.0 mg/L Wolf
(30°C) (1963)
pulmonate 6.6- 11.8 mg/L
snail 7.5
(Physa (20°C)
heterostropha) 18-19 11.7 mg/L
(20°C)
Petroleum extract
used in the
manufacture of
insecticides,
paper and rubber.
diatoms
(Navicula
seminulum)
41.8 79.8 mg/L
(22°C)
41.8 56.0 mg/L
(28°C)
43.4 28.2 mg/L
(30°C)
European
perch
4 to 16 mg/L
Crayfish
minnows
snail .and
fish
5 to 50 mg/L
5.0 mg/L
2.0 mg/L (20°C)
18 to 60 hours
72 hours
when dissolved
oxygen is low.
57
-------
Other Effects of Oily Wastes
Oil films on the surface may reduce gas transfer and affect
photosynthesis. In addition, there has been some suspicion that oily materials
add appreciable oxygen demand (McKee and Wolf 1963).
Surface films are expected to have an indirect effect on the dissolved
oxygen balance of a stream by reducing reaeration and photosynthesis. We
intend, if time permits, to review the work of Tsivoglou and Wallace (1972) and
Thibodeaux (1979 also see Reible's comment in Appendix I) to determine if the
effect can be readily quantified. However, we expect only a marginal influence
at the present time. Nevertheless, we recognize that many disposal areas may be
near urban areas where dissolved oxygen levels are chronically depressed.
The effect of reduced sunlight penetration on photosynthesis is a concern
that arises from the water quality criteria of 1968 (FWPCA 1968) and McKee and
Wolf (1963). We also intend to consider this further when time is available. If
we fully investigate the photooxidation of oil at a later stage, it may be
appropriate to determine the adsorptive capacity that oil has for sunlight.
Several older studies - indicate that oily wastes may also add appreciable
oxygen demand (McKee and Wolf 1963). Evidently, there has been some debate over
the exact effect of refinery wastes. Some have held that fish kills resulted
from lack of oxygen during oil spills rather than from the toxic effect of the
dissolved phase. Some discharges seemed to have involved large amounts of
oxygen demand as well. Therefore, when we have estimated typical amounts of
oily wastes that may be permitted in streams based on other factors, it should
t
be possible to estimate the influence on the oxygen balance as well.
58
-------
BEHAVIOR OF OILY WASTES IN STREAMS -. ,.•
The transport of oily wastes in streams is important because of the
mechanisms that concentrate waste constituents. Processes that transform wastes
may attenuate concentrations of some components, but if wastes are transformed
into components that are more toxic, then transformation processes may take on
added importance in defining critical processes.
The processes that may affect the weathering of oily wastes are summarized
in Figure 13. The most important expected in streams (see Figure 14) are
advection, spreading, formation of films and pools, partial dispersion of
droplets, emulsification, volatilization, dissolution, photochemical reaction
and hydrolysis, biodegradation, sedimentation, and attachment to surfaces
(coating, wetting, and sorption). These important processes are shown in Figure
14 and are briefly discussed below.
Advection and Spreading
The transport of oily wastes is complicated by the tendency to concentrate
and move at different velocities than the average stream velocity. The
different average velocity of the oil causes spreading not found in other water
bodies or dilution by association with larger than expected volumes of stream
water.
59
-------
DOWNSTRE/
ADVECTION
ATMOSPHERIC
OXIDATION
RAIN AND
FALL-OUT
EVAPORATION
WIND
SPRAY ff
I /BURSTING
/[BUBBLES
SPREADING
WATER
SURFACE
WATER-IN-OIL
EMULSIONS
DROPLETS
OIL-IN-WAT
EMULSIONS
CHEMICAL
REACTION
BUBBLE
TRANSPORT
DISTRIBUTION CONVECTION
BY PLANKTON AND UPWELLINQ
DISSOLUTION
BIODEGRADATION
CONSUMPTION
BY PLANKTON
SINKING ON
PARTICLES
TARRY
LUMPS
DISSOLUTION
WATER
COLUMN
DROPLETS
OIL-IN-WATER
EMULSIONS
CHEMICAL
REACTION
ADVECTION
BIODEGRADATION
WATER-IN-OIL
EMULSIONS
BENTHOS
STREAM
BED
FIGURE 13. Processes Affecting Heavier and Lighter Than Water Oily
Wastes. Adopted in part from Nelson-Smith (1972) who •*:•;.
-•_-• i-i.. —.,»,*•! «-o TTAfi n<37fn anH ParlfPT- TT^aono-r^o anH Hafrhard (1971
-------
LANDFILL
/ A-v LECH ATE PLUME
EMULS1FICATION
SEDIMENTATION
STREAM
PHOTOCHEMICAL
OXIDATION
SPREADING & MIXING
ADVECTION
EVAPORATION
AREA OF SIGNIFICANT
RECREATIONAL USE
Figure ^.Processes that effect concentrations of oily
wastes in streams.
61
-------
In general , oil films spread over the surface until buoyancy forces are
balanced by interfacial tension between the oil and water. There are a number
of spreading regimes of films in open water. However, until there is time to
investigate more thoroughly, it seems probable that lateral spreading (usually
on the order of 10 to 100 kilometers) is limited by the banks. Spreading along
the stream channel occurs because the oil film at the surface moves faster than
the average stream velocity,
The longitudinal spreading process is illustrated in Figures 15 and 16.
When a film or pool exists or when partially dispersed droplets are unevenly
spread over the depth of flow, the oil moves faster or slower that the average
stream velocity. Lighter -than-water oily wastes tend to move faster than the
average water velocity. Heavier- than-water wastes move slower. When the waste
is completely dissolved or dispersed evenly over the depth, the velocity of the
waste is equal to the water velocity. Wastes introduced by a continuous source
do not spread longitudinally after the leachate plume is well mixed over the
depth and across the width of the stream.
Figure 16 illustrates the difference in velocity of a film and the water
and the difference in velocity in a pool and of the water. In this case, the
thickness is greatly exaggerated. In most streams, the ratio of oil film
velocity, u , to the average water velocity, U, is
where Ujjjgjj is the maximum water velocity at the surface. For a significant
number of streams throughout the continental United States, "max/U " 1.15
62
-------
o
m
S
o
a:
u.
tu
o
<
v>
VERTICAL PROFILES
V
OIL FILM
POSITIVELY
BUOYANT
OIL POOL
NEGATIVELY
BUOYANT
CLEAR
WATER
2ND PHASE
CONCENTRATION
RIFFLES AND TURBULENT FLOWS
o
o
CO
o
o:
u.
lu
o
POSITIVELY
BUOYANT
EMULSION
WELL MIXED
FOR EXTREME
TURBULENCE
NEGATIVELY
BUOYANT EMULSION
CLEAR
WATER
FIGURE 1
f.
2ND PHASE
CONCENTRATION
Vertical Distributions of Oily Immisible Wastes in Streams
with a Density Different from the T^-.sity of Water
-------
TYPICAL VELOCITY PROFILE IN STREAMS
0.9D
5
o
I-
o
03
o
cc
u.
IU
u
z
<
w
o
0.4D - -
0.1D --
D = DEPTH
u x s SHEAR VELOCITY
S = SLOPE OF CHANNEL
jj = AVERAGE VELOCITY OF
WATER AND NEUTRALLY
BUOYANT CONTAMINATE!
U p = VELOCITY OF O.1D
POSITIVELY BUOYANT
OILY FILM
U n= VELOCITY OF O.ID
NEGATIVE BUOYANT
POOL OF OIL
n
MAX
VELOCITY, U
FIGURE 1^. Velocity Differences in Streams that Have a Surface Film or
Pool of Oil with a Thickness of 10 percent of the Depth of
Water Flow. Z is the depth above the stream bottom, k is
von Karraan's coefficient (O.Al), and U _.. is the maximum
max
stream velocity that usually occurs at or near the surface.
64
-------
(McCutcheon 1989, Rantz et al. 1982, Corbett et al. 1962). This ratio has been
derived from at least two different assumptions about the mathematical form
used to represent the water velocity profile -- namely that the velocity
profile can be described by a lograthmic or power law function. More
importantly, the ratio of 1.15 is consistent with a number of observations at
U.S. Geological Survey stream gaging sites and other locations on streams
(Rantz 1982, Hulsing et al. 1966) summarized in Table 7. The effects of
secondary circulation accounted for in the USGS observations are, therefore,
minor. Secondary circulation in a stream is the cross current circulation that
arises because of the irregularity of stream channels. It causes the maximum
vertical velocity that would otherwise occur at the surface to be depressed to
a depth on the order of 1 to 10 percent of the total depth.
Table 7
Relationship between point velocities and vertically-averaged mean velocities
[McCutcheon 1989, originally from Rantz et al., 1982]
Relative depth
(from surface)
0.05
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.95
Ratio of point velocity to vertically-averaged velocity
1.16
1.16
1.15
1.13
1.11
1.07
1.02
0.95
0.87
0.75 .
0.65
65
-------
The near-vertical shape of the velocity profile near the water surface
indicates that the ratio u/U is very insensitive to the film thickness. Just
the opposite is expected for oil pools on the stream bottom where the velocity
changes very rapidly with depth. In this area, u /U will be very sensitive to
oil thickness and channel irregularities will be a significant influence.
Secondary circulation, however, will not be important.
In general, a nonhomogeneous distribution of oily wastes is expected
downstream of a continuous source because the intensity of mixing will vary.
Mixing intensity and the transition from surface films and globs on the bottom
to dispersions of droplets and emulsions will be especially pronounced in pool-
and-riffle streams (see Figure 17). Of greatest interest is the reformation of
bottom globs and surface films downstream where the water is pooled or where
debris dams and obstructions operate to skim or pool wastes (see Figures 17 and
18). These areas of reconcentration seem almost certain to occur in any stream.
These potential hot spots of concentrated exposure to oily wastes also will
generally coincide with the most important ecological area of typical streams.
In this regard, the information available about the distribution of pools
and riffles is sparse. It is believed that riffles are separated along the
stream by an average distance of seven times the depth (Edwin Herricks,
Department of Civil Engineering, University of Illinois, personal
communication, February 26, 1988 -- also see Appendix I). We will investigate
typical stream geomorphology further, but at this time we are unable to
adequately predict the occurrence of quiescent areas where oily waste may
accumulate. As a result, we are initially forced to assume (our observations
generally support this) that quiescent areas will always be present and we will
base the analysis on this assumption.
66
-------
EXPECTED LONGITUDINAL BEHAVIOR OF OILY WASTES
- CONTINUOUS SOURCE
RELATIVE
VELOCITY
OILY POOLS,
FILMS & EMULSION
EMULSION
OILY POOLS,
FILMS & EMULSION
EMULSION
CROSS-SECTION
i
MAXIMUM CONCENTRATION
PURE 2ND
k ^ PHASE
PHA^i/' : i ' 1
COH \\ /-""""\ 1 I
/ / ^.JL .^XT}"""X\ »
/ / / 1 "I \ *
/ ; /| ': v ^ NEUTRALLY
, : / , '\ \ \ BUOYANT
1 : / ' 1 :. \ \ FRONT
' ;' / l / '• X \
/ / ./ ^ . -. \ POSITIVELY
• / S ^ ' \ BUdYANT
' / ^' ': \ FR^NT
1 '"^ \ >. SLOW MOVlhfl \
'••• FRONT \ \
. _ - .. N xh».
DISTANCE DOWNSTREAM
NEUTRALLY BUOYANT
POSITIVELY BUOYANT
NEGATIVELY BUOYANT
67
FIGURE li. General Behavior of Heavy and Light Oily Wastes in Pool and - -
Riffle Streams. Note the potential to form hot spots of exposure
. In critical ecological zones. Stations (1) and (2) refer to _.";...^
^illustrations of vertical profiles in F<«»..T-» i/. •••*
-------
EXPECTED LONGITUDINAL BEHAVIOR OF OILY WASTES
- CONTINUOUS SOURCE
RELATIVE
VELOCITY
OILY POOLS,
FILMS & EMULSION
EMULSION
OJLY POOLS,
FILMS & EMULSION
EMULSION
<
cc
K
Ul
o
O
O
til
o
-------
We anticipate some differences in distribution of oily wastes downstream
of discontinuous sources. We will investigate this matter further.
Formation of Films, Globs, Pools, Mixed Droplets, and Emulsions
Oily wastes have been observed in a number of forms in streams. Lighter-
than-water oils form floating films in many streams. We can think of only rare
instances where there would be no potential for a film to form. All natural
streams have quiescent areas at either bank 'and many streams are connected to
backwaters or wetlands. Natural streams usually have debris and natural dams
that acts as skimmers. A number of streams are a series of pools and riffles
during periods of low flow. As a result, it is rare that films would not form
and casual observations of streams in urban areas where oily materials are
usually present, bear this out. In addition, many water quality sampling plans
assume that films are present when designing stream sampling procedures
(McCutcheon et al. 1985).
It is less readily observed, but heavier oil can pool on stream bottoms or
sit on the bottom in discrete volumes frequently referred to as globs. Globs or
slugs of heavy or light oils may also be broken off from a floating film or
pool and move through the water column in a suspended fashion (Perziosi 1987).
Hore frequently observed are smaller droplets that break away from the separate
oil phase and become partially dispersed. When intensive mixing is present,
extremely fine droplets can be formed that are fully dispersed in the water.
These are oil-in-water emulsions that remain approximately well mixed when a
minimum level of turbulence is maintained after complete mixing has occurred.
69
-------
The fine droplets in an emulsion that are covered with surfactants are
Micelles. . . .
A typical micelle is shown in Figure 12. The droplet is covered with
surfactants that originate from waste sources or from natural materials.
Natural surfactants are assumed to be widely available in all natural waters
but it is not clear how much is known about the properties of natural
surfactants as they relate to the formation of micelles. Ideally it would be
useful to know how the type of surfactant is related to the diameter of
emulsion droplets to be able to estimate dissolution from droplets. It would
also be useful to know what effect surfactants have on the formation of
droplets. Since surfactants influence interfacial tension, it is assumed that
the presence of surfactants must affect droplet formation and size.
At present we do not understand the relationship of suspended globs,
droplets, emulsions, and micelles and intend to investigate further. We will
investigate maximum drop sizes (Hu and Kintner 1955) and interfacial stability.
We are most interested in the potential for globs, droplets, and emulsions
to reform separate oil films and pools after stream turbulence decreases. At
this point, we suspect that an important distinction between micelles and other
discrete oil particles (droplets too big to be covered by surfactants and
globs) are that micelles do not coalesce into films, pools, globs or other
larger droplets whereas other oil bodies do when the flow becomes quiescent.
We have investigated simple parameters to describe interfacial stability
to determine if it is possible use gross stream properties such as depth and
70
-------
velocity and readily available chemical properties of wastes to determine if
films and pools will break down into globs, droplets, or emulsions. At this
time, we have been unable to derive the appropriate simple criteria that
matches the few data available -- flow, depth, velocity and major chemical
characteristics of oily wastes. For this reason the initial screening model
must be less elaborate than we had originally hoped. Because we are unable to
conveniently determine how much of an oily waste will be dispersed, we must
conservatively assume that there are reasonable opportunities within a stream
for the waste to exist solely as a surface film or pool on the bottom and that
at other locations alond the stream the wastes could be fully dispersed as
droplets. It is very likely that every stream of interest will have quiescent
areas where films will form. It is not as likely that all streams of interest
will completely convert a source of oily waste into dispersed droplets. This
represents a distinct divergent from calculating a mass balance of oily
materials. However, for an initial screening, it is not unrealistic.
We have initially investigated the use of the densimetric Froude number to
determine when films or pools of oily waste on the bottom and emulsions can be
expected to be present in a stream. The densimetric Froude number is defined as
U
Fr -- (2)
vo
where U was defined earlier as the average stream velocity, g is the
acceleration of gravity, vo is the difference in density between water and the
oily waste, and o is the density of water. The densimetric Froude number is
also the inverse of the gross Richardson number, which has been used
extensively to crudely characterize mixing in density- stratified waters. As
71 -
-------
such, the Froude number does not fully take into account important physical
characteristics of streams and chemical . characteristics of the oily waste.
Specifically, the effects of interfacial tension, fluid viscosity, and fluid
turbulence and shear are not explicitly taken into account when the Froude
number is used to define interfacial stability between oil and water.
We expect that the Froude number may be of limited usefulness based on the
work of Wilkinson. Wilkinson (1972, 1973) found that oil slicks behind barriers
began to mix with the water underneath if the densimetric Froude number based
on depth of flow exceeded 0.5. Between 0.5 and 1.0 both an emulsion and film
will coexist if we assume that any film will break up as the flow becomes
supercritical (see Figure 19). Interfacial instability at Froude numbers less
than one is consistent with the observations of thermal discharges in streams
(Polk et al. 1968) where interfacial tension between warm and cold water does
not exist. Polk found that miscible density interfaces of the general geometric
type that Wilkinson studied were stable if the densimetric Froude number was
less than 0.75.
The difficulty in applying the densimetric Froude number as a measure for
interfacial stability in this investigation is that there are significant
geometric differences in the flows. Wilkinson (1973) studied an oil slick
trapped behind a dam that extended part way into the flow from the water
surface. Shear stresses arose from the flow of water underneath the stationary
slick and dam. With a film on the surface, the film and surface of the water
move at almost the same velocity. Therefore, the more significant source of
turbulent mixing would seem to be local eddies near the interface that were
generated by shear on the bottom of the stream channel rather than shear at the
72
-------
LO
O
U
LLC
X
LU
LU
A
0)
H
x
UJ
2
O
3
HI
<
LU
CC
z
LU
o
iu
H
co
o
LJL
O
LU
Q.
CO
CC
O
U.
LU
O
LU
m
DC
H
O
O
O
LU
O
LU
CC
O
T3
C
O O
•H 4-1
4J
0) C
M O
O -rl
0) U
JS (8
Hf3
Q) Q.
O W
u
-H
•H O\
I-f *->
•H
ja •<
to CM
•H C
fH O
(0
•H C
•H -rl
O ^4
•iH
M-l -H
O 3
O O
•H
U >>
OJ T3
N 3
•H AJ
M 01
(U
0)
C
o
0) CO 4J
6 C 1*
tfl O T3
H «H C
« j-j o
em « o
0) M Vi
•o
-------
interface. As a result, it is necessary to further investigate interfacial
stability criteria. .-, .
From the study of the mixing of miscible fluids (i.e. water stratified by
heat, salt, or sugar - McCutcheon 1977, French 1975, McCutcheon and French
1977, French 1979, McCutcheon 1980), we know that there is a more elaborate
dependence of interfacial stability on the Reynolds number and channel
friction. We will revisit the derivation of the Keulegan parameter, which is a
combination of the Reynolds number, Re, and densimetric Froude number, Fr. The
Keulegan parameter is written as
K - U3/(v0 g vo/o) or K = l/(Re Fr2) (3)
where VQ is the kinematic viscosity of oil. The critical value of this
parameter was 180 for entrainment to begin. French (1979) determined that other
parameters were also important, including a flow Richardson number
Ro = g(vo/o)(D)/u*2 (4)
(where u* is the shear velocity) and a friction factor U/u* relatable to the
Manning n (a channel roughness coefficient). Figure 20 is the appropriate form
ofthe stability diagram for miscible fluids.
In addition, we will enlarge the necessary dimensional analysis to include
effects of interfacial tension. Here we expect that the Weber number must be
introducted to account for the effect of surface tension on the formation of
emulsions and drops. The Weber number is written as
74
-------
O
.c:
:o
.fc-
1 »-•• •
jO
'S£
•I*** \
-Ito.
.'*t
fe
1*3
1H
o
Ui
til
fc-
A5CRATORY DATA
w
q
*t£ P
P£3 M iJ Q.|[.
• '••*••••••.' ; ••• • . ji •
o
•414*
&
o
-------
oU2D ...
W - (5)
where s is interfacial tension.
Important variables that should be considered in any dimensional analysis
include: water velocity, U in L/T
density of water, o in M/L
3
density difference, vo in M/L
o
interfacial tension, s in M/T -usually in dynes per cm or
ergs per cm2 [(force along a length 1, F=ls (CRC 1987)]
depth of flow, D in L
stream slope (shear determinate) , S in L/L
depth of the oil pool , d in L
o
water viscosity, n in L/T
oil viscosity, nQ in L2/T
where L desinates units of length, M designates units of mass, and T designates
units of time.
From the work in miscible fluid interfacial stability, we expect that an
approximate analog of the Froude number may be possible. However, significant
laboratory and field investigations may be necessary to establish critical
parameter values.
Interfacial stability controls the formation of drops and emulsions as
shown in Figure 21. A qualitative outline of the forces involved is presented
in Figure 22.
" '
We expect pools of oily wastes to form in the irregularities of the
76
-------
EXISTANCE OF FILMS, POOLS AND EMULSIONS
- INTERFACIAL STABILITY PROBLEM
2 PHASE FLOW
OIL
INTERFACE
OIL
WATER
WATER-IN-O1L
EMULSION
°y \o
« >—' o
° o<, o - •
OIL-IN-WATER „ , M ^^^
EMULSION ^ O WATER
WAVES
FORM
WAVES
BREAK-FORMS
EMULSION
o
37
m
>
CO
o
CO
m
m
O
o
H
<
O
00
C
O
m
*r» ^
O
FIGURE 21. Influence of Interfacial Stability on the Formation of Emulsions.
-------
FORCES AT THE INTERFACE
SHEAR DUE TO VELOCITY DIFFERENCE
VISCOUS FORCES
INTERFACIAL TENSION FORCES
FORCES DUE TO DENSITY DIFFERENCES
IMPORTANT PARAMETERS
STREAM VELOCITY OR VELOCITY DIFFERENCE
DEPTH OR DISTANCE OVERWHICH AV ACTS
BUOYANCY-DENSITY DIFFERENCE g
VISCOSITY
TURBLENCE-SHEAR VELOCITY U* * J gDS K
INTERFACIAL TENSION - (EFFECT OF SURFACTANTS)
FIGURE 22. Forces at the Interface
7ft
-------
DUNES
POTHOLES AND DEPRESSIONS
FLOW
GLOBS
SURFACE TILT INCREASES
WITH INCREASED VELOCITY
•*- FLOW
GLOBS
-------
channel bed as shown Figure 23. The existence and depth of pools will depend on
the shear of flowing water shear pulling oil out of the depression, turbulence
entraining droplets, and dissolution. At low stream velocity, we expect pools
to be deep. At high velocity we expect the pools to shallow because of
increased dissolution, entrainment, and shear.
Volatilization
From oil spills on the oceans, we know 'that significant amounts of crude
oil and fuels evaporate (Nelson-Smith 1972). Usually 20 to 30 percent of the
light fractions of crude oil volatilize within a few days. However, the heavy
ends (or fractions) may not volatilize. McKee and Wolf (1963) report that water
in long term tests evaporates before some types of oils can be significantly
volatilized. Therefore, evaporation can"be important and should be
investigated further. In this regard, it should be possible to develop the
appropriate mass transfer theory and use the extensive work in stream
reaeration and lake evaporation to adequately quantify volatilization.
Dissolution
Nelson-Smith (1972) also indicates the importance of dissolution in
reducing the mass of the oil phase. Dissolution is enhanced by the increase in
surface area that occurs when droplets form. The influence of surfactants is
not presently understood.
Dissolution will not only control how fast oily wastes are dispersed in
80
-------
STREAM FLOW
DISSOLVED WAKE
— .
FLUX
TG
FLUX IN
FLAT SURFACE
STREAM FLOW
DISSOLVED AND
EMULSIFK-.D WAKE
FLUX EMUL
FLUX pig o
tmmm,
FLAT SURFACE
FLUX IN
81
-------
streams but it also will control the amounts of oily wastes accumulate at
various places in streams. At equilibrium between the flux out of the stream
bed at the point where globs and pools form and the flux into the water column
due to dissolution, the rate of dissolution and eraulsification controls the
size (thickness and extent) of oil globs (see Figure 24).
The rate of dissolution can be quantified for simple geometry (see
Thibodeaux 1977, for example) but it appears that the mass transfer
calculations for complex natural conditions have not been fully explored.
As a conservative approach, we intend to investigate specification of the
soluble fraction of oily materials from measurements and determine if we can
conservatively assume that the dissolution of oily waste components occurs
simultaneously from surface films later when we attempt a better mass balance
analysis. We will also investigate the same procedure for computing the
toxicity of the dissolved phase when a non-aqueous phase is originaaly present
in the stream. This may require that some solubility measurements be
considered. In this regard, we intend to investigate the WASTBASE data set
being put together for Office of Solid Waste by Development 'Planning Research
Associates, Inc. to determine if the parameter SOLUB will be adequate for this
purpose. Appendix III describes WASTBASE and the parameter SOLUB. The mass
transfer rates must still be considered in other cases (i.e., computing the
thickness of globs on the bottom), however.
82
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Photochemical Oxidation, Hydrolysis, and Toxic Daughter Products
The effect of chemical reactions has not been fully explored as a need to
do does not seem to be indicated. The primary interest in this process is the
possible formation of more toxic daughter products (Edwin Herricks, Department
of Civil Engineering, University of Illinios, personal communication, February
26, 1988, preliminary review) rather that a significant reduction of the mass
of oil.
Biodegradation
We have not investigated the effect of biological assimilation. We suspect
that it is more important for long term weathering of oils in open waters and
the eventual assimilation of spills. Lags in-acclimation of native bacteria
lead to a reduction in immediate importance for discontinuous releases of oily
material into streams. However, a continuous source should allow acclimation of
native flora if the waste is biodegradable and especially if a lengthly aerobic
groundwater pathway is involved. At this time, it is not clear how many oily
wastes are readily biodegradable. Nor is it known how important biodegradation
may be in the assimilation of wastes.
Sedimentation
In oil spills, a significant amount of the oil can be removed from the
water column by attachment to particles that settle. In general, the
83
-------
partitioning between the nonaqueous phase, dissolved phase, and solid surfaces
is not well understood. At this time, however, we believe that sorption
mechanisms are are important to the overall fate of oily wastes in streams.
Coating Surfaces
The coating and wetting of surfaces and adsorption solids are important
not only in the removal of oil from the water column but also relative to
aesthetic and toxicological impacts. The formation of scum lines in water
treatment plants is to be avoided (FWPCA 1968). The coating of banks, debris,
and vegetation is a serious but presently unquantifiable problem. There is some
guidance on the amounts of oil that attach to shorelines during oil spills that
may be useful (Shen et al. 1987). Beynond this, we have discovered no other
guidance of significance.
INVESTIGATION OF REASONABLE ENDPOINTS
Concentration vs. Thickness Criteria
We have earlier identified at least ten criteria that may be appropriate
as exposure endpoints. These include:
1. Drinking water standards,
2. Taste and odor criteria,
3. Threshold concentrations causing tainting of fish and shellfish,
4. Concentration of emulsions that are toxic,
84
-------
5. Concentration of dissolved components that are toxic,
6. Visibly-detectable surface film thickness,
7. Thickness of surface films killing or impairing surface breathers,
8. Thickness of detectable bottom deposits of heavy oil,
9. Detectable coatings on banks, debris, and plants, and
10. Quantities of oil phase that are toxic.
These endpoints are, with one ambiguous exception, of two types. The first five
endpoints (1 through 5) can be expressed as a concentration criteria. The next
four (6 through 9) can be expressed as a limiting thickness of oil on the
surface of the stream or elsewhere. The tenth endpoint is ambiguous at this
time because it is not clear if it would be best to specify the concentration
of oil averaged over the volume of stream reaches as a criteria or to specify a
limiting thickness of oil on gills, skin or other surface (i.e., the water
surface). Suitable classification requires further investigation.
85
-------
The categorization of endpoints into two groups simplifies model
calculations. Both types of computations are based, however, on a selective
mass balance of oil and water. All endpoints specified as a concentration can
be related to the amount of oily wastes to be disposed of over a specified
period of time, 1oii> as shown in Figure 25. A mass balance of the stream
segment shown in Figure 25 is written as
1oil>CCRIT
If we assume that the concentration of oily wastes disposed of in a landfill or
other facility is 100 percent oily waste or nearly so (such that C = 1.00),
that the background concentration of oily material is approximately zero
upstream of the intersection of the stream with the leachate plume (CQ = 0) ,
and that the volume of oily waste is small compared to the volume of water that
flows in the stream, then Equation (6) reduces to
If the waste is diluted with water either before disposal or during transit
between the source and the stream and the diluting flow is included in the
measurement of stream flow, Q, then these occurrences are easily taken into
account. It is also a simple matter to account for upstream oily waste disposal
by assuming that CQ is not equal to zero. Therefore, more than onr disposal
facility per watershed can be included in the analysis.
The mass balance to relate allowable disposal rates of oily material to
critical film or pool thickness is similar as shown in Figure 26.
86
-------
qoil - UoilTW - TWKQ/WD - TKQ/D ; . . (8)
Note that it is not necessary to know the width of the stream for this
calculation. This follows from the definition of relationships between average
water velocity and discharge (Uj^o ~ Q/DW) , the average velocity of the oil
film and the disposal rate (UQ.Q - qQ£-^/TW) and the relationship between the
average velocity of the oil film and the stream as noted earlier (UQ^^ —
UH2o^) • *fc is assumed that an oil film does not exist upstream, but any effect
of this type can be easily incorporated. It 'is further assumed that Q is much
larger than qoji , which is expected for low intensity leaching of this type.
To conceptually simplify the basis of the screening approach, the analysis
method is focussed on the volumetric flux of oily material being deposited in
landfills, in lagoons, and on field application units. For consistency with the
preferred regulatory approach (stressing intensive parameters such as leachate
concentration of oily wastes) , it is conceptually straightforward to relate
to leachate concentration, C, as
where QL is the leachate flow rate into a stream. QL can be estimated using
leachate and groundwater models or may be measured for specific site
investigations.
87
-------
Q,C0
* 100% OILY WASTE
I OIL
'CRIT
Q
FOR Cn = 0
AND Q » q
OIL
(Q + qol, ), C
FIGURE 25. Mass balance for dispersed oily wastes or for components
where dose-response relationships are based on average
amounts of oily waste.present.
-------
U
H2O
U
O,L
'OIL
Q
WD
= KUH,0
• U01UTW
Q
'OIL
TKQ
mm^
D
FIGURE 26. Mass balance for oil film on streams.
Note that the Thickness, T, can be used to characterize average
film thickness, pool depth, glob;thickness or even conceptual,
average coating thickness on banks, debris or vegetation.
89a
-------
At this point, we have developed the two important computational forms for
concentration and thickness criteria to ,be applied in the initial screening
level model.
Calculation of the Amount of Oily Waste that
May Cause Detectable Oily Tastes and Odors
For the initial analysis procedure, it will be assumed that significant
recreational uses and drinking water withdrawals will occur as soon as the oily
wastes are well mixed across the stream. In 'general, stream segments in which
recreational use is prevalent and drinking water withdrawals may be located at
some distance downstream of the point at which the oily leachate enters the
stream. Over the distance from the point where the leachate enters the stream
to the recreational areas and water withdrawals, the oily waste can volatilize,
settle attached to particles, biodegrade, and photooxidize as illustrated in
Figure 13. Of the processes that may affect oily waste concentrations,
volatilization and dissolution may be the most important based on current
knowledge.
In the initial analysis, however, all processes attenuating exposure
concentrations will be ignored until it becomes clear that these processes are
important for a significant number of potential sites. In effect, it will be
assumed that recreation use and drinking water withdrawals will occur at the
location where the leachate enters the stream. It is proposed that the
importance of processes that reduce oily concentrations be systemically
investigated if it is found that the initial assessments will significantly
affect current or future disposal practices.
89
-------
The minimum concentration from odor thresholds and taste thresholds will
be applied to avoid oily tastes and odors in recreational areas based on the
expectation that some recreational uses (e.g., swimming) will involve the same
close contact with the water experienced in consumption. Boating, wading, and
fishing will involve similar close contact where any odors will be detectable.
In fact, the odor at the stream may be more detectable than any odor criteria
may account for. For instance, if the ratio of the volume of contaminated water
in the stream to the limited volume of air just above the stream is larger than
than on which the criteria are based, then the volatilized components of the
oily waste may be present in higher concentrations in the vicinity of the
stream and cause a more intense odor for the same concentration of oily wastes
in the water. Therefore, the basis for odor criteria will need to be
investigated in light of this proposed application.
As an initial calculation, the amount of oily wastes that can be disposed
of on a continuous basis in a disposal facility can be expressed as
. Codor> ^
Q
where min(Cjjy, Ctaste, Codor) is a mathematical abbreviation indicating that
the smaller of the criteria for oily waste concentrations governing taste,
Ctaste' and odor> Codor snoul^ be larger than or equal to the ratio of the rate
of disposal of oily materials, q0«i , to the flow rate of water in the stream,
Q. qo^ and Q may be specified in units of volume or mass per time as long as
the units are the same or the appropriate conversions are applied. Convenient
units might be gallons per day, or pounds per month for the oily waste and
cubic feet per second for the stream flow.
90
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Backcalculation of Allowable Amounts to Avoid
Oily Tastes in Fish and Invertebrates .• . .
Limiting concentrations will be computed as
Ctaint *
qoil
-
Q
If the readily available criteria are in terms of concentrations in the fish
flesh, Cflesh' and a bio-concentration factor relating concentration in the
water to the concentration in the edible flesh, BF, is known, then the limiting
concentration in the water can be computed as
Ctaint
Exposure to Emulsions
Exposure criteria will be expressed simply as
Cemul ^
where the allowable concentration of the emulsion for a class of oily waste
exposed to an important species or group of species must be specified from past
or future bioassay work. This value should be the lowest 96-hour LCrQ or an
equivalent. The safety factor X is specified as 0.01 in the current criteria
91
-------
(EPA 1987). The bioassays should be designed to maintain an emulsion during the
96-hour test. •. .
Exposure to Soluble Fraction and Other Dissolved Components
Exposure criteria will be expressed simply as
(qoil)SOLUB
Cdis
where the dissolved concentration for a class of oily waste exposed to an
important species or group of species should be specified from past or future
bioassay work that partitions the waste into a dissolved fraction if SOLUB is
taken as unity. This value should be the lowest 96-hour LC5Q or an equivalent.
The current criteria (EPA 1987) specifies that X should be 0.01. If the
bioassay does not partition the waste into a dissolved component, SOLUB must be
measured or estimated by theoretical mass transfer calculations.
Calculation of Oily Material Flux to Avoid Formation of Visible Oil Films,
Films that Affect Surface Breathers, Pools on the Bottom, and Coatings
The allowable oily waste disposal rate (or leachate concentration if
leachate flow rate into the stream is known) can be computed from a mass
balance as
qoil - T K Q/D (15)
92
-------
where T is the thickness of the oil film permissible to avoid a visible oil
film outside the mixing zone, K is a coefficient relating average stream
velocity to surface velocity and has a value of approximately 1.09 to 1,15, Q
is the stream velocity, and D is the depth of flow. We expect that a value of
0.038 microns will be an appropriate specification of T. If the film thickness
affecting surface breathers, T_^, is less than T, this value should be used in
place of T.
For oily waste pools, the permissible thickness based on aesthetic
considerations should be used to specify T in Equation (15). The coefficient,
K, (in effect a dilution factor) will assume a much smaller value of at least
less than 0.65. The exact factor can be derived later. In addition, the
dilution factor should also incorporate a correction for the difference in
width of pools or globs (on average) compared to the width of the stream. This
can also be developed at a later date.
The thickness of oily waste pools or globs on the bottom should be
compared to the capillary
thickness determined from the interfacial tension and density difference
(Thibodeaux 1977). Thibodeaux expresses that thickness as
2s
gvo
Tg - (— ) (16)
where s is the interfacial tension between the oily waste and water and vo is
the difference in density between the waste and water.
93
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The smaller of the arbitrarily selected value for the oily pool depth or
the capillary height defined in Equation ,(.16) should be specified for T in
Equation (8) or (14). As a first approximation, we intended to compute the
capillary height from Equation (16) assuming that the bottom is a flat plate.
the thickness on a flat surface.
It remains to be determined what quantity of oily material on the bottom
constitutes an aesthetic nuisance. This criterion must be in terms of areal
extent and thickness. We expect that wetting characteristics of the oil onto
sediments and the porous nature of the bed'must be considered. Until we can
more precisely determine potential aesthetic impacts, these criteria will be
under continued investigation.
The correction of the dilution factor, K, for width difference may also
need to be considered to account for the filling of holes and depressions in
the bed that may not extend across the channel. We will continue to consider
the use of the Manning n and any geomorphological observations to determine
what estimate may be appropriate. In addition, the geological and
morphological trends given in Table 8 will be considered.
94
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Table 8..
Geomorophological trends of bed forms and sediment type
Bed form
Bed material flat
clay-silt X
sand X
gravel -boulders
ripples
X
X
dunes anti- dunes irregular
X X
X X
Calculation of Detectable Oil Coatings
on Shores, Banks, Vegetation and Debris
This calculation has not been formulated because of a lack of data
quantifying the amount or thickness of coatings that are detectable. If
average thicknesses criteria can be located in the literature, these will be
used to specify T. If volumes of oil released are reported with length of
shoreline coated, we will attempt to estimate benthic surface area to estimate
T or, perhaps better, we may be able to express the allowable quantity of oil
as an average concentration.
95
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Effect of Oily Films on Gills
and Benthic Biotic Surfaces
These calculations also have not been formulated. We expect to use our
experience in estimating gill surface areas for selected species of fish plus
any reports of oil thicknesses that cause mortality or impairment and apply the
one percent safety factor suggested by the criteria document (EPA 1987) unless
there is more information on this subject in the literature than we suspect.
DEVELOPMENT OF A SCREENING LEVEL MODEL
The initial screening level model will be based on calculation of the
minimum thickness criteria and minimum concentration criteria for sensitive
species and important classes of oily wastes. The next phase of development
will define data needs and the exact structure of the model. This will be
subject of the next progress report.
96
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PROJECTION OF FUTURE MODEL DEVELOPMENT NEEDS
We have not yet had time to compile our detailed expectations for future
model development needs outlined in earlier sections. This will be done later
if necessary, but we already see a need to reduce the conservative nature of
the screening model in several areas. Chiefly we need to employ a mass balance.
To refine the endpoints, we need to incorporate the work on Habitat Suitability
Indices by the U.S. Fish and Wildlife Service to better define the following
important classifications:
Classification by vertical location':
- Benthic fish, larvae, and invertebrates
- Water column fish
- Surface insects
Classification by stream velocity:
- Quiescent zone fish, larvae, and plants
- High velocity zone fish
97
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Classification by vertical location:
- Benthic fish, larvae, and invertebrates
- Water column fish
- Surface insects
Classification by stream velocity:
- Quiescent zone fish, larvae, and plants
- High velocity zone fish
98
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REFERENCES
Ambrose, Robert B., et al, WASP4, A Hydrodynamic and Water Quality
Model--Model Theory, User's Manual, and Programmer's Guide.
EPA-600/3-87/039, US Environmental Protection Agency, Athens,
Georgia, 1988. 297.
Ambrose, Robert B., and Scarlett B. Vandergrift. SARAH, A Surface
Water Assessment Model for Back Calculating Reductions in Abiotic
Hazardous Wastes. EPA-600/3-86/058, US Environmental Protection
Agency, Athens, Georgia. 1986. 95. (SARAH II documentation to be
published in 1988.)
American Petroleum Institute. Manual on Disposal of Refinery Wastes
Volume 1, Seventh Edition, 1963. pp. 104.
Cairns, John. Environment and Time in Fish Toxicity. Industrial
Wastes, Vol. 2, No, 1. Scranton Gillette Publication. January -
February 1957. pp. 1-5.
Corbett, D. M., et al. Stream Gaging Procedure: A Manual Describing
Methods and Practices of the Geological Survey. USGS Water Supply
Pap. 888. Washington. D.C. 1962. pp. 37-38.
Federal Water Pollution Control Administration. Report of the
Committee on Water Quality Criteria, Second Edition. United States
Department of the Interior, Washington, D.C. 1968. pp. 234.
Galtsoff, P. S., H. F. Prytherch, R. 0. Smith, and V. Koehring.
Effects of Crude Oil Pollution on Oysters in Louisiana Waters. Bull.
Bur. Fish. 1935. 46: 489-508.
Grushko, 1968. 40.
Hu, Shengen, and R. C. Kintner. The Fall of Single Liquid Drops
Through Water. AIChE, Vol. 1, No. 1. March, 1955. pp. 42-48.
Hushling, H., Smith, W. and Cobb, E.D. Velocity-Head Coefficients in
Open Channels, USGS Water-Supply Pap. 1869-C, Washington, D.C. 1966.
V / »
McCutcheon, Steve C. Discussion of Interfacial Stability in Channel
Flow, by Richard French. Journal of the Hydraulics Division, ASCE,
Vol. 106, No. HY12, December, 1980. pp. 2067-2068.
McCutcheon, Steve C. The Stability of a Two Layer Flow Without Shear
in the Presence of Boundary Generated Turbulence: Field Verification.
Thesis in Engineering, Vanderbilt University.
McCutcheon, Steve C., et al. Water Quality and Streamflow Data for the
West Fork Trinity River in Fort Worth, Texas. USGS Water Resources
Investigation Report, NSTL, Mississippi. 1985. 101.
McCutcheon, Steve C. Water Quality Modeling: Applications to Rivers.
CRC Press, Boca Raton, Florida. 1989, (in preparation).
McCutcheon, Steve, and French, R. H. The Stability of a Two Layer Flow
Flow Without a Shear in the Presence of Boundary Generated Turbulence:
Field Verification. Proceeding of the 25th. Annual Hydraulics Specialty
Conference, ASCE. 1977. pp. 212-219.
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McKee, Jack Edward, and Harold W. Wolf. Water Quality Criteria.
State Water Quality Control Board. Sacramento, California. 1963.
pp. 34, 72-73, 548. .-. -
Nelson-Smith, A. Oil Pollution and Marine Ecology. Paul Elek
(Scientific Books) Ltd., London, England. 1972. 260 pp.
Preziosi, Luigi, Kangping Chen, and Daniel D. Joseph. Lubricating
Pipelining: Stability of Core-Annular Flow. National Science Founda-
tion Project. August, 1987. 48.
Quality Criteria for Water. EPA-440/9-76-023, U.S. Environmental
Protection Agency, Washington, D.C. 1976.
Quality Criteria for Water. EPA-440/5-86-001, U.S. Environmental
Protection Agency, Washington, D.C. 1987
Rantz, S. E., et al. Measurement and Computation of Streamflow:
Volume 1. Measurement of Stage and Discharge, and Volume 2. Computa-
tion of Discharge. USGS Water-Supply Pap. 2175. Washington, D.C.
1982. pp. 81-90, 97-123, 132-140, 179-183, 294-326, 439-470,
485-543.
Reible, Danny D., and Tissa H. Illangasekare. Modeling Transport
of Multiphase Subsurface Contaminants. Presented at the First Annual
Symposium on Hazardous Waste Research, LSU Hazardous Waste Research
Center. October, 1987. 19.
Reible, Danny D. Subsurface Contamination by Multiphase Processes.
Research and Policy Implications for EPA. 1987. 104.
Shen, Hung Tao, Poojitha D. Yapa, and Mark E. Petroski. A Simulation
Model for Oil Slick Transport in Lakes. Water Resources Research,
Vol. 23, No. 10. October, 1987. pp. 1949-1957.
Thibodeaux, L. J. Mechanism and Idealized Dissolution Modes for
High Density (rho > 1), Immiscible Chemicals Spilled in Flowing Aqueous
Environments. AIChE, Vol. 23, No. 4. July, 1977. pp. 544-553.
Thibodeaux, L. J. Chemodynamics. Wiley, New York. 1979.
Tsivoglou and Wallace. 1972.
Water Quality Criteria 1972, A Report of the Committee on Water Quality
Criteria. EPA-R3-73-033, U.S. Environmental Protection Agency,
Washington, D.C. March, 1973.
Wiebe, A. H. The Effect of Crude Oil on Fresh Water Fish. Amer.
Fish. Soc., Trans. 1935. 65: 324-350.
Wilkinson, David L. Dynamics of Contained Oil Slicks. Journal of the
Hydraulics Division, ASCE, Vol. 98, No. HY6. June, 1972. pp. 1014-
SELECTED BIBLIOGRAPHY
Academy of Natural Science. 1960.
Cairns, , and Scheier. 1958. 34.
100
-------
Chipman, W. A., and P. S. Galtsoff. Effects of Oil Mixed with
Carbonized Sand on Aquatic Animals. US Fish and Wildlife Service,
Sepc. Rep. Fish. No. 1. 1949, 52 pp. .-
Dorris, T. C., W. Gould, and C. R. Jenkins. Toxicity Bioassay of
of Oil Refinery Effluents in Oklahoma. 1960. pp. 2/6-285.
In: Biological Problems in Water Pollution. 1959. Seminar, Trans.
PHS Tech. Report W60-3. (Robert A. Taft Sanitary Engineering Center,
Cincinnati, Ohio.)
Gustell, 1921.
Johns Hopkins University. Final Report to the Water Quality Sub-
committee of the American Petroleum Institute, Project PG 49.41.
1957. (Cited in the Quality Criteria for Water 1986.)
Pickering, Q. H., and C. Henderson. Acute Toxicity of Some
Important Petrochemicals to Fish. J. Water Poll. Control Fed. 1966b
38(9): 1419-1429.
Seydell, E. Ueber die Wirking von Minerololen auf Fischwasser.
Mitteilungen d'Fisherei-Vereins fur die Provinz Brandenburg 1913.
5(3): 26-28.
Veselov, E. A. The Effect of Crude Oil Pollution on Fishes.
Rybone Khoziastvo 1948. 12: 21-22. (In Russian.)
101
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APPENDIX I
Reviews of the Proposed Analysis Method Conducted February 26, 1988
2. Review Comments of:
1. Review Comments of: Dr. Danny Reible
Associate Professor
Department of Chemical Engineering
Louisiana State University
Baton Rouge, Louisiana
Dr. Peter Shanahan
Consultant
HydroAnalysis Inc.
Acton, Massachusetts
3. Preliminary Suggestions of: Dr. Edwin E. Herricks
Associate Professor of
Environmental Biology
Department of Civil Engineering
University of Illinois
Urbana-Champaign, Illinois
102
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Dq'iii tim'itt of Oif'iiiVnl
LOUISIANA STATE UNSVERSITY AND AGRICULTURAL AND MtciiAMCAL COLLEGE
.'ATOM UOUC-E • LOUISIANA- 70803-7.W3 5041388-1426
.March 14, 1988
Brian Bicknell
Aqua Terra Consultants
2672 Bayshore Parkway, Suite 1001
Mountain View, CA 94043-1011
Dear Brian: •
I have attached brief comments on the methodology proposed at our recent
meeting with Steve McCutcheon in Atlanta to assess the stream impact of oily
discharges from landfills. As I indicated over the phone, the cjommj2jiit3__gjre.
dj r:e_cted_ toward the...p rel i mi nary mode 1 i n j_J_trajegy and are general in nature.
Since any decision to pursue a more sophisticated mr del ing approach 1s de-
pendent on the results of the preliminary model, I r'elt that it would be
PJiejpature__l.a_iacus, too much attention on the specif i ^processes that must be
included in such a model. In keeping with the focus of the meeting, I have
y?.!L-?dAress.§d_t.ne transport jmd attenuation processes between the disposal
site and the stream although these processes would likely have a very strong
effect on the ultimate stream impact.
I have a1 so ?:'»t tid;irp-->sed t.!x.> specific wording of the draft document
that w^s mailc-j '.••_• mo jjrinr to tiir meeting. ~It seemed_ to_me_that much pjf
t'he document is fomset! '.;:i the nt'-.-o ^ophi sticated Second level model and
therefore need not be addressed at this time.
I look forward to the results of the preliminary model. If a more so-
phisticated moci"i:-.'i .if-prnach is warranted by the results, I will be happy
to provide any c?^ i i,uifn:i: possibly including ljtera_ture j-efecences that I
have found on oil pha>^ bohavior in :;oils and streams. Please feel free to
contact me if you liave iiiy questions.
Sincerely,
•J ''
Danny Reible
Associate Professor
DDR
ATTACHMENT
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Comments en
"Proposed Method to Analyze Oily Wastes Expected to Enter Streams"
by Steve C. McCutcheon
The proposed method is divided into at least two stages:
1. Preliminary assessment assuming no loss or attenuation of the oily
wastes.
2. More sophisticated estimtte(s) as suggested by preliminary assessment.
This is clearly the logical and appropriate approach to assessing the po-.
tential need for regulations limiting the disposal of oily wastes in land-
fills. My prunaTy_cpncern_ is that the initiraj _ assessment_may not provide
a significant amount of information and that it will be necessary^ to 1m-
plement some level_o_f_jstage_2 analysi_s_. It seems likely that sufficiently
conservative assumptions can be made to ensure trat a potential problem
with the disposal of oily wastes exists. The stag_e__l analysis_,is_j.tJUl,
however, the necessary starting point to begin to identify the magnitude
of the problem and procedures for its quantitative assessment. Since the
meeting with Or. McCutcheon of February 25 was focused on the preliminary
assessment let ni<- rocuf> my comment;, mi that stage of the, analysis.
The kay require_me.n_t of the preliminary assessment is conferva tism^.
Dr. McCutcheon1s plan to neglect loss and attenuation between the landfill
and the stream discharge and to treat the entire discharge as contained in
-------
the phase causing the most significant impact is appropriate. In addi-
tion, the consideration of both health and aesthetic impacts ensures that
both criteria will be satisfied. The procedures outlined for surface film
and in-stream impacts are reasonable and appropriate. It is important to
recognize, however, that the term oily discharges encompasses a large
range of materials. It will provs difficult to adequately characterize
the physical and environmental properties of the oily wastes. Wherever
possible sptci •'!••. iiiipur'-cmt compounds or classes of compounds should be
examined in the analysis.
Some questions were raised during the meeting with Dr. HcCutcheon re-
garding the pn»:"Jurcj to handle submerged pools of oily wastes. I indi-
cated at the lime .-.nd still fsal that a reasonable and conservative
estimate, can I"- in.tdc by assuming that the pool spreads over the entire
stream bottom to i.h-; limiting thickness imposed by the surface tension
with water. From Thibodeaux (Chemodynamics, Wiley, 1979), this thickness
is
h = v/(2o/AP)
Since the density difference between water and typical oily phases is <
0.5 g/cc and the intsrfacial tension is of the order of 50 dyne/cm (0.05
g/cm), this height is about 5 mm. An estimated water profile over an un-
contaminated sediment can be usixi to estimate the velocity of the oil
layer by assuming continuity of shear stresses at the interface. The spe-
cific form of the approximation for the oil layer velocity would depend on
the thickness, density and viscosity of the oil. Since the above proce-
dures provide an oil phase volume and velocity, the treatment of the bot-
tom-residing pool is essentially identic?.! to the proposed procedure for
the surface film.
-------
The assumption of ste.idy state stream flow and oily discharge condi-
tions is appropriate as a preliminary analysis but it should be recognized
that these conditions may not represent conservative assumptions. The
worst case condition may be the accumulation of oily discharges over time
in a lake or pond adjacent to a disposal site. In addition, the contam-
ination nay only affect some fraction of the stream or stream bed. It is
therefore suggested that some preliminary assessment calculations be made
to identify- the impact of stream or discharge heterogeneity might have on
the results.
Examples pf potential problems include the tendency of small oily dis-
charges to form a patchy oil film rather than a continuous film. Thus
aesthetic problems could result from a much smaller discharge of oil than
predicted by the outlined procedure. In addition, an oil film will tend
to form In quiescent regions of a stream rather than in the main channel
or in riffles, again suggesting that the proposed preliminary assessment
procedure may underestimate the actuc-1 aesthetic impacts. Since oily con-
taminants are likely to concentrate in quiescent regions, the greatest im-
pact on aquatic life will also be noted in these regions rather than in
the entire stream.
My expectation is that these problems will lead to a preliminary Im-
pact assessment that miuht be as much as en order of magnitude too low
(that is, a cotiS"r-'/,itiv- srtimate uf the allowable oily discharges might
be an order of magnitude lower than the preliminary assessment might sug-
gest). I suggest, therefore, that the stream oily discharge impacts be
increased by a factor of ten, or alternatively the allowable disposal
level decroased by a factor of ten, over tha estimates of the planned pre-
liminary procedure. This correction can be viewed as neglecting stream
-------
contamination that affects less than 10% of th? total stream area. Since
the purpose of the preliminary assessment is identification of potential
problems requiring further analysis, I do not feel that this factor is un-
duly conservative.
Let me ~1ose by ir.-k.ing a few statements about the more sophisticated
analysis that will br nocessar" tu more quantitatively assess the impact
of landfill disposal of oily wastes on stream quality. The basic trans-
port processes AS outlined by Dr. McCutcheon should be included in the
analysis. In addition, however, the original listing of contaminant and
stream processes neglected the importance of adsorption and subsequent re-
distribution oT Contaminants through sediment movement. The oil spill
literature would indicate that this is a significant fate and transport
mechanism.
The partitioning of the oily wastes between films, drops, pools and
emulsions is heavily dependent upon the stream velocity. This suggests
that the more sophisticated modeling approach planned for the second stage
must explicitly consider the pool-riffle nature of most streams. Stream
morphology will likely control thi.> fate and transport of the oily wastes.
If the oreliminary assessment suggests that this more detailed analysis is
necessary, I would be happy to provide additional information such as cur-
rent reference:- in this area, and provide any other assistance that I can.
-------
sis Inc
/329T,
Acfcn.
PO Box 6
uset's C172
\\J I
March 11, 1988
Ref: JOB-REV
Mr. Brian Bicknell
Aqua Terra Consultants
2672 Bayshore Parkway, Suite 1001
Mountain View, CA 94043-1011
Subject: Review of USEPA Draft Oily
Wastes Procedure
Dear Brian:
The f01 lc--.-= tjq --re my rT.'-*i''v: consents on the draft
procedure to <~ '.::>. ly.tr oily wir :pis in streams prepared by
Steve McCutcheon or che USETA Athens Environmental Research
Laboratory. My review includes two main sections: one
focusing on technical comments and the other on the draft
document. Ky comments in these two sections have rather
different £ocu;;o3. The first section is primarily technical
in naturr. Thn second section derives, at least in part,
from r.iy cxperA'M-.fie 'n working :;or the American Petroleum
Institute (API). My experience with API includes critical
review and drafting letters of commt'nt on past proposed EPA
regulations an-1 guidance. I have tried to anticipate the
kind cf comments thr.t michc be received from API and the
wood-treating industry. J hope this perspective will be
helpful in preparing the final document.
*£.' \, f~>^-
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Te c h n ic a1 Commc n t s "•'
In general, I believe thr* proposed procedure is
technically sound ac a yreli'Binary screening procedure. I
think that eventually it would be useful to investigate a
more complete phenomenologicnl model of oil behavior in
streams. Such an investigation would initially be a
research effort; >.>ut could lead to a useful assessment and
regulatory tool.
There are prvorn.l specific technical items that I
believe need further review. Some of these are a
reiteration of comments I made in the review meeting on
February 26, but: 1 Bought it would be useful to record them
in writing.
One technical concern (that also has regulatory
implications) is the definition of oily wastes. The oily
wastes of the wood-treating industry may behave very
differently in the environment than petroleum fuel oils.
The major oily waster; from the wood-treating industry
include the following:
o Creosote oils and coal-tar derived oils - Coal-tar
derived oils are substantially.heavier than water
and behave in the environment accordingly.
o Creosote/oil mixtures - Creosote is often mixed
with .a carrier oil for use as a wood preservative.
Typically, a lightc-r-than-water fuel oil is used
as the carrier.
o Pentachlorophenol - Pentachlcrophenol is also
often mixed with a carrier oil. The type of oil
depends upon the application. Fuel oils are used
for most woods, but mineral oil may be used for
some fine woods (for example, treated wood doors
and windows).
The density of creosote oil nnrl coal tar is a significant
factor in their environmental transport. I am sending to
Steve McCutcheon two papers by Villaume c-t al. (1S83 and
1985) on a coal-tar contamination site end his analysis of
the density effects on subsurface transport. The particular
site he worked on is an inactive co=l-g£S plant that was
first discovered to be a problem when coal tsr seeped into
an adjace>nt stream. I am also sending another paper by
Lafornara et al. (1582) on the same site and a chapter from
the rough draft of a wood-treating site handbook prepared by
-------
ERT. The handbook was never completed, so I am sending a
draft as the best copy available. Nonetheless, I think it
supplies useful general background on oils from the wood-
treating industry.
The discussion in thr. draft oily wastes document of
regulations for solvents is somewhat misplaced. As far as I
know, there are no regulations for solvents per se. Rather,
certain solvents (including many chlorinated organic
solvents) are regulated because they are toxic. On the
other hand, a great many solvents are not particularly toxic
and thus' are not regulated. The latter include alcohols,
ethers and many petroleum-based solvents.
The formula presented in the document to calculate the
limit on oily material flux to avoid formation of visible
oils may not be conservative. The formula is:
qon = T K Q/D
This formula assumes a uniform distribution of oil over the
entire water surface. This neglects the ability of floating
oily material to collect and reconccntrate in a small
fraction of the water-body surface. Perhaps a quiescent
area coefficient that accounts for the turbulence of the
stream could be jrr-luded in .he formula. In a highly
turbulent stream v.hp guies<"°rit area would be a small
fraction of 1. In a very ^Isw-moving stream or backwater it
would be nearly 1.
The turbulence environmsnt of ri£fle-and-pool streams
was discussed sevi-ral tirr.os in th2 February 26 meeting. I
am sending to Ste-« a paper by Bsncsla and Walters (1983) on
solute transport in a riffle-and-pool stream that might be
useful in develop: rig an oil transport model.
The is5'.T* cf tcxicity is somewhat confused in the draft
document. J v ?. cc: •.snendec? in the meeting that this procedure
should deal w.i.th t;he physical and toxicological properties
that: pertain to oily wastes generically. For example, toxic
effects that; this procedure can validly address include
interference with gill mechanisms by oil emulsion droplets,
toxicity to benthic organisms by blanketing with oil,
effects on insects through interference with emergence, etc.
The method should not include tcxicity due to trace
compounds found in some oils. This type of toxicity is
adequately treated by chemical-specific criteria and
approaches. Moreover, the trace chemical makeup of various
-------
oils may differ widely (for example, wood-treating oils vs
petroleum hydrocarbon fuels). But the toxicity of oils due
to their oily char.-mtcr should be generically similar.
On a re In Led topic, the last section of the document
discusses more wor'- on dissolution of chemicals from oily
wastes. I think this is worthwhile, but again I recommend e
generic approach. For example, rather than assume specific
chemicals to be present at certain concentrations in oily
wastes, the procedure should be a general method to
calculate dissolution of any chemical species from the oil.
The method could then be applied to a particular oily waste
using specific data on the constituents in that oil.
Overall, I was impressed with the literature research
that went into the proposed procedure and found it a very
credible piece of work. The complexity of oil transport
necessitates an incremental approach to model development..
and the proposed procedure ir; an appropriate and valrd first
step. Eventually, more compl-jx models may be desired, but
the general approach proposed in the draft procedure is
valid jmd usei'ul for screening analyses. Nonetheless, the
special properties of oil are incompletely accounted for in
the current approach and the approach is vulnerable to
criticism'if it is characterized as anything more than a
simple screening tool.
Comments on Document
I found the document that presents the procedure to b'i
confusing and difficult to follow. A particular confusion
is a failure to distinguish discussions that apply to
eventual future development of a sophisticated model and
those which apply to the formulae presented in the
procedure. Many concepts are presented that are not
actually used in the proposed procedure. To correct this
confusion a reorganization of the document is needed. One
suggestion for overall organization is the following:
o Introduction - objectives of the proposed
procedure with a specific discussion of use in the
RCRA permitting process
o Background - why oily waste is s problem requiring
the special attention of this procedure as a part
of landfill permitting
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o Criteria - water quality criteria, applicable to
oily waste (including 'the formal EPA criteria and
the API classification of oil thickness
visibility)
o Physical phenomena - a generic discussion that
catalogs the important physical, chemical and
biological phenomena affecting oily waste in the
environment
o Proposed procedure - presenting the proposed
procedure as a screening approach
o Future work - discussing technical areas needing
further study and planned future work, perhaps
proposing eventual development of a sophisticated
mo'lcl of oily vastfts
1 think an organisation sucn as this that clearly separates
the proposed procedure from physical phenomena that are
discussed but not actually included in the procedure would
make the document much easier to follow.
The language in the document is equivocal in many
places. Phrases likf> "it seems that", "it may be that", "it
is not clear how", c.:.:c. make the document seem ambiguous and
less well thought through than it is. Before releasing the
document for public romment, rhe tone of the document should
be strengthened by <• \ iminating the type of phrases listed
above.
The document also needs tc> be edited with respect to
references to criteria and regulations. The references to
regulations should include specific citations of the Code of
Federal Regulations or Federal Register. The references as
they are now are not specific end give an impression that
the procedure is only vaguely related to a regulatory
purpose„
The discussion of criteria would benefit from a review
by the criteria experts in the Criteria and Standards
Division. While I do not believe there are any errors in
the discussion as it is now, the document is not written
with the ususl terminology of v,-ater-cual i ty criteria. There
are also many raore recent references available on oil
tcxicity to aquatic species that should be included in the
discussion. I do not believe any of these would chance the
proposed proceSure, but would strengthen the document prior
to release for public comment.
-------
I hope these comments and the references I have
furnished will be helpful. I appreciate the opportunity to
participate in reviewing this approach to a very interesting
technical problem, and I look forward to following the work
as it progresses. If you have any questions on the above or
i£ I can supply further information, please call me at (617}
263—4857.
Sincerely,
Peter Shanahan, Ph.D., P.E.
cc: S. McCutcheon, EPA
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.it 217333-3812
March 7, 1988
Dr. Stc?vr.- C. HcCutchcH>n
USF.PA Flf-.-Athens
Athens, Gfl 3C6K3
I have begun thr> process of collecting the material I said I would
provide. Enclosed you will find a disk and the manuals for the FWS habitat
evaluation procedure (HEP) and the microcomputer version of the habitat
suitability index (HSI) models. With the report I left with you should be
able to figure out whnt is going on with the HSI models. We have found that
you will need the species reports available from Ft. Collins to select the
proper responses in the HSI analysis. I think you should be able to adapt at
HSI analysis as a add on to your proposed model although the run time of thi1
version is pretty slou. You might want to begin interacting with the people
at. Ft. Collins where KB I and HEP is centered. I am enclosing a copy of the
new HEP newsletter, you might want to request some of the new HSI models
listed in this issue. You might also want to contact the R&D people at the
Division of Biological Services) U ;i:HS in Washington. Also you might want t(
get a copy of Biological Report P-5'6), December 198 but
after ten years I am sure few of the same people are around now. Pleasa
share this report with Tom, he sai't he needed an approach to develop width
and depth for another project.
I have begun my search for pool/riffle information. To thot end I am
enclosing a copy of another Stall and Yang report which touches on the issue
and a copies of several papers on riffles and pools. I also looked through
my collection of reprints and am enclosing a paper by Keller and Melhorn
which is directly related to the pool-riffle question) and a section from
Richard's book on pool-riffle spacing. This is a big topic and these papers
only scratch the surface. I think it will be enough to further thinking on
stream impact assessment.
-------
I am received the copies of your overheads on Friday and will work to
finalize a short critique paper bas«d on those materials and our phone
conversation. If you have any questions} please call (517)333-0997.
Nith best regards*
Edwin E. Herricks
Associate Professor of
Environmental Biology
ccsBrian Bicknell
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APPENDIX II
1986 "Gold Book" Criteria for Oil and Grease
The following criteria are reproduced from Quality Criteria for Water
1986 (U.S. EPA Rep. 440/5-86-001 with updates 1 & 2, 1987). Tables 6 and 7
referred to in the criteria document are reproduced from the "Red Book "
Quality Criteria for Water 1976 (U.S. EPA 1976).
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CRITERIA:
OIL AND GREASE
For domestic water supply: Virtually free from
oil and grease, particularly from the tastes
and odors that emanate from petroleum products.
For aquatic life:
(1) 0.01 of the lowest continuous flow 96-hour
LC50 to several important freshwater and
marine species, each having a demonstrated
high susceptibility to oils and
petrochemicals.
(2) Levels of oils or petrochemicals in the
sediment which cause deleterious effects to
the biota should not be allowed.
(3) Surface waters shall be virtually free from
floating nonpetroleum oils of vegetable or
animal origin, as well as petroleum-derived
oils.
INTRODUCTION:
It has been estimated that between 5 and 10 million metric
tons of oil enter the marine environment annually (Blumer, 1970).
A major difficulty encountered in the setting of criteria for
oil and grease is that these are not definitive chemical
categories, but include thousands of organic compounds with
varying physical, chemical, and toxicological properties. They
may be volatile or nonvolatile, soluble or insoluble, persistent
or easily degraded.
RATIONALE:
Field and laboratory evidence have demonstrated both acute
lethal toxicity and long-term sublethal toxicity of oils to
aquatic 'organisms. Events such as the Tamp_ico Maru wreck of
1957 in Baja, California, (Diaz-Piferrer, 1962), and the No. 2
fuel oil spill in West Falmouth, Massachusetts, in 1969
-------
(Hampson and Sanders, 1969), both of which caused immediate death
to a wide variety of organisms,' are illustrative of the lethal
toxicity that may be attributed to oil pollution. Similarly, a
gasoline spill in South Dakota in November 1969 (Bugbee and
Walter, 1973) was reported to have caused immediate death to the
majority of freshwater invertebrates and 2,500 fish, 30 percent
of which were native species of trout. Because of the wide
range of compounds included in the category of oil, it is
impossible to establish meaningful 96-hour LC50 values for oil
and grease without specifying the product involved.
However, as the data in Table 6 show, the most susceptible
category of organisms, the marine larvae, appear to be intolerant
of petroleum pollutants, particularly the water soluble
compounds, at concentrations as low .as 0.1 mg/L.
The long-term sublethal effects of oil pollution refer to
interferences with cellular and physiological processes such as
feeding and reproduction and do not lead to immediate death of
the organism. Disruption of such behavior apparently can result
from petroleum product concentrations as low as 10 to 100 ug/L
(see Table 7).
Table 7 summarizes some of the sublethal toxicities for
various petroleum pollutants and aguatic species. In addition to
sublethal effects reported at the 10 to 100 ug/L level, it has
been shown that petroleum products can harm aquatic life at
concentrations as low as 1 ug/L (Jacobson and Boylan, 1973).
Bioaccumulation of petroleum products presents two especially
important public health problems: (1) the tainting of edible,
-------
aquatic species, and (2) the possibility of edible marine
organisms incorporating the high boiling, carcinogenic polycyclic
aromatics in their tissues. Nelson-Smith (1971) reported that
0.01 mg/L of crude oil caused tainting in oysters. Moore et al.
(1973) reported that concentrations as low as 1 to 10 ug/L could
lead to tainting within very short periods of time. It has been
shown that chemicals responsible for cancer in animals and man
(such as 3,4-benzopyrene) occur in crude oil (Blumer, 1970). It
also has been shown that marin.e organisms are capable of
incorporating potentially carcinogenic compounds into their body
fat where the compounds remain unchanged (Blumer, 1970).
Oil pollutants may also be incorporated into sediments.
There is evidence that once this occurs in the sediments below
the aerobic surface layer, petroleum .oil can remain unchanged and
toxic for long periods, since its rate of bacterial degradation
is slow. For example, Blumer (1970) reported that No. 2 fuel
oil incorporated into the sediments after the West Falmouth spill
persisted for over a year, and even began spreading in the form
of oil-laden sediments to more distant areas that had remained
unpolluted immediately after the spill. The persistence of
unweathered oil within the sediment could have a long-term effect
on the structure of the benthic community or cause the demise of
.specific sensitive important species. Moore et al. (1973)
reported concentrations of 5 mg/L for the carcinogen 3, 4-
benzopyrene in marine sediments.
Mironov (1967) reported that 0.01 mg/L oil produced deformed
and inactive flatfish larvae. Mironov (1970) also reported
inhibition or delay of cellular division in algae by oil
-------
concentrations of 10~4 to 10-1 mg/L. Jacobson and Boylan (1973)
reported a reduction in the chemotactic perception of food by the
snail, Nassarius obsoletus, at kerosene concentrations of 0.001
to 0.004 mg/L. Bellen et al. (1972) reported decreased survival
and fecundity in worms at concentrations of 0.01 to 10 mg/L of
detergent.
Because of the great variability in the toxic properties of
oil, it is difficult to establish a numerical criterion which
would be applicable to all types of oil. Thus, an application
factor of o.oi of the 96-hour LC50 as determined by using
continuous flow with a sensitive resident species should be
employed for individual petrochemical components.
There is a paucity of toxicological data on the ingestion of
the components of refinery wastewaters by humans or by test
animals. It is apparent that any tolerable health concentrations
for petroleum-derived substances far exceed the limits of taste
and odor. Since petroleum derivatives become organoleptically
objectionable at concentrations far below the human chronic
toxicity, it appears that hazards to humans will not arise from
drinking oil-polluted waters (Johns Hopkins Univ., 1956; Mckee
and Wolf, 1963). Oils of animal or vegetable origin generally
are nontoxic to humans and aquatic life.
In view of the problem of petroleum oil incorporation in
sediments, its persistence and chronic toxic potential, and the
present lack of sufficient toxicity data to support specific
criteria, concentrations of oils in sediments should not approach
levels that cause deleterious effects to important species or the
-------
bottom community as a whole.
Petroleum and nonpetroleum oils share some similar physical
and, chemical properties. Because they share common properties,
they may cause similar harmful effects in the aquatic
environment by forming a sheen, film, or discoloration on the
surface of the water. Like petroleum oils, nonpetroleum oils
may occur at four levels of the aquatic environment: (a) floating
on the surface, (b) emulsified in the water column, (c)
solubilized, and (d) settled on the bottom as a sludge. Analogous
to the grease balls from vegetable oil and animal fats are the
tar balls of petroleum origin which have been found in the marine
environment or washed ashore on beaches.
Oils of any kind can cause (a) drowning of waterfowl because
of loss of buoyancy, exposure because of loss of insulating
capacity of feathers, and starvation and vulnerability to
predators because of lack of mobility; (b) lethal effects on fish
by coating epithelial surfaces of gills, thus preventing
respiration; (c) potential fishkills resulting from biochemical
oxygen demand; (d) asphyxiation of benthic life forms when
floating masses become engaged with surface debris and settle on
the bottom; and (e) adverse aesthetic effects of fouled
shorelines and beaches. These and other effects have been
documented in the U.S. Department of Health,. Education and
Welfare report on Oil Spills Affecting the Minnesota and
Mississippi Rivers and the 1975 Proceedings of the Joint
Conference on Prevention and Control of Oil Spills. . . -
-------
such oils result in deleterious, environmental effects described
in this criterion. Thus, it is recommended that surface waters
shall be virtually free from floating nonpetroleum oils of
vegetable or animal origin. This same recommendation applies to
floating oils of petroleum origin since they too may produce
similar effects.
(QUALITY CRITERIA FOR WATER, JULY 1976) PB-263943
SEE APPENDIX C FOR METHODOLOGY
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-------
„• REFERENCES CITED IN TABLES 6 and 7
I Allen, H., 1971. Effects of petroleum fractions on the early development
of a. sea urchin. Marine Pollution Bulletin. 2:138.
^ ATEMA, J. and L. Stein. 1972. Sublethal effects of crude oil on
£• the behavior of the American lobster. Technical Report
Woods Hola OceanogtapUic Inst.\ No. 72-72,
*• * •' V
, The
SST ri°f °U Pollution °" littorri comities.
Institute of petroleum, London. 250 p.
r BARRX, M. and P. Yevich, 1971. Incidence of cancer in the soi't-
shcll clam, Hja arenatin. Final report of State of Maine
(Dept. Sea and Shore fisheries)" to U. S. Air Force. Contract
Ho. F. 33600-72-C-OS40. 32p.
-i . . *A
^ Bellan. G.'i et^al_.. 1972. The sublcthal effects of a detergent on the
reproduction, development, and settlement in the polychactous annelid
Capitclla capitata. Marine Biology, 14:133,
t ' .' .
"7 Blumer, M.» e^al_.. 1071. A small oil spill. Environment, 13:2.
,,i T «-ic-(ii 197.T. Tnlcr.ict.lon
'
97 p.
Cf Brockson. R. W. andH.T. Bailey, 1973. Uw.piralory response of juvcnil
Chinook salmon and striped basp exposed to benzene, a water-soluble
component of crude oil. In: Proceedings, Joint Conference on Preven-
tion and Control of Oil Spills, Amer. Pet. Inst., Washington. D. C.
1C Brown. D. H. 1972. The effect of Kuwait crude oil and a solvent cmul-
sificr on the metabolism of the marine lichen, Lichina pygmaca.
Marine Biology, 12:309.
| ( CAIRNS AND SCHEIER, 1950. . • • .
GIIPMAN, W.- A. and P. S. Caltsoff. 1949. Effects of oil mixed
. vita carbonized sand on aquatic animals. Spec. Sclent
V. '.He.. B. S. FiBh Wildl. Scrv. 1. 52 p. P icicnC.
-------
bioassay oC oil refinery effluents in Oklahoma. In
Trans. 2nd Rcm. Blol. Prol-. VfatCT _?oj.l: . R. A. Taft
San. Enp. Center, Cincinnati, Ohio, Tech. Rep. "WGO-3:
27G-2S5. - .........
'-.'.-"••
ENVIRONMENTAL PBOTKCTION AGENCY. 1971, ' Waste Oil Study. Report
to Congress. 401 p. • ' '
»,— Gardner, G.R., et_al., 1973. Analytical approach in the evaluation
of biological effects. Jour. Fish. Res. Bd. Canada, 35:3185.
Gilfillan, E.G.. 1973. Effects ol seawater exracts of crude oil on
carbon budgets in two species of mussels. In: Proceedings. Joint
Conference on Prevention and Control of Oil Spills. Amer. Pet.
\ . • ' '• .
Inst. , Washington, D.C. :
/7 Gordon, D. C. and N. J. Prouse. (wljLIW. The effects of three
different oils on marine phytoplankton photosynthesis". -Marine Biol.
Jacobson, S. M. and Eoylan. 1073. Effect of seawatcr soluble fracxiun
of kerosene on chemotaxis in a marine snail, Nassarius obsoletus.
Nature. 241:213. .- > '' ' . •....;:. • ' '
J<3 KARINEN, J. F. and S. D.- Rice. • 1974. Effects of Frudhoe Bay "crude
' oil on molting tanner crabs, Chionoecctes bairdi. Marine
Fisheries Review. -36:31.
/^O Kauss, et^ai., 1972. Field and laboratory studies of the effects of crude
oil spills on phytoplankton. In: Proceedings, 18th Annual Technical
Conference, Environmental Progress in Science and Education.
O I Kittredgc, J. S.. 1073. Effects of water-soluble component of oil
polluUon on chomorcccption by crabs. Fisheries Bulletin.
7, l_ Krebs. C.T., 1973. Qualitative observations of the marsh fiddler
(Uca Pugnax) populations in Wild Harbor March following the
September. 10C9 oil spill. National Academy of Sciences. Washington.
D.C.. Unpublished manuscript.
-------
Kuhnhold. W. W. . 1970. .The influence of crude oils on fish fry. In:
Proceedings, FAO conference. Rome, Italy.
,. c.'. .Mr. E.»dedelacr«lssanoed,onealgue
Pla,c,onlqn, m presence „,„„ ^^^^^ utmae pw ^
Sci. (Paris) 265 (Ser. D):489."
a.
•if
•".<- '«• Products on tte d«velopmw of
naffish. Vop. tthtiol. 7(3).557. -V
O. C. . ,,ro. The
o, w B,ack
on flora and
Conference on
Agriculture
of the United Nations, Rome.
.MOORE, .S. F., R. L.Dwyer.and S. N. Katz. 1973. A preliminary
•'.-•-. assessment of the environmental vulnerability of tiachias
';' Bay, Maine to oil supertankers. Report No. MITSG 73-6. 162 .p.
MORROW, J. E. 1974. Effects of crude oil and some of its components
on young coho and sockcye ealiuon. Publication EPA-C60/3-73-016.
'.:••' v. s. E. p. A.
*$ ( NELSON-SMITH, A. 1973. Oil pollution aild mnrinc ccoloCy.' Plenum
press. 'New York. 260 p.
Nuzzi' K. . 1973. Effects of water soluble extracts of oil on phyto
... plankton, In: Proceedings, Joint Conference on Prevention and
Control of Oil Spills. Amer. Pet. Inst. . Washington, D.C.
2 17
-------
environment, unem. ind., 1:14.
*2"t/ PICKERING, Q. H. and C."Henderson. 1966. .Acute toxlcity of some
7 important petrochemicals to fish. Wat'sr Poll. Contr. - Fed.
J. 38 (9);1419-U29'.. ..... ' • .:-,.
« — Rice, S. D.. 1973. Toxicity and avoidance tests with Prudhoe Bay oil
and pink salmon fry. Proceedings of joint conference on prevention
of oil spills. Wash.. D. C. , pp. 667-670.
• i ' i * ' • * - '
steel* D'L> and B'J< CoPeland> 1967. Metabolic responses
of some estuarine organisms to an industrial Affluent
control. Mar. Sci. Univ. Texas 12:143-159
Strand, J. W., et^al.. 1971. Development of toxic ity test procedure •
for marine phytoplankton, p. 279-286. In_: American Petroleum
Institute. Proceedings of a joint conference oh prevention and control
of oil spills, Washington. D. C.
Calif. W6 p.
*f Ted, J.H. 1972. An introduction to environmental ethology
Woods Hole Oceanographic Institution. Ref. 72-42. Woods
ffole Mass. Unpublished manuscript. . '
Vaughan, B.E. 1973. Effects of oil and chemically disparsr.d
oil on selected marine biota -.a laboratory study. "
*
Richland, Washington, Battelle Pacific Northwest Laboratories
120 p. .
Wells. P.G., 1972. Influence of Venezuelan crude oil on lobster
larvae. Marine Pollution Hull., 3:105. •• '•
218
-------
Waber,C.G..19G8,
Wilson, k. W. . 1970. The toxicity of dU-spiH dispersants to the
embryos and larvae of some marine fish. fa. Proceedings, ' -i
FAO Conference, Rome. Italy. '
Wohlschlog, D.E. and j.N. Cameron. 1967. Assessment of low level
Stress on the respiratory metabolic uf the pinfish (layodon
rhomboldes). Inst. Mar. Sci. Univ. Texas 12:160-171
Sift fc
-------
APPENDIX III
PARAMETERS EXPECTED IN THE DATA BASE FOR HAZARDOUS CHEMICALS
DEVELOPED FOR THE OFFICE OF SOLID WASTES
Parameters in the Data Base - WASTBASE
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WASHINGTON OFFICE
110 17th St.. I(W, Suite 220
WASHINGTON, O.C. 20006
202 833-3608
1/15/87
Agnes Ortiz
EPA
OSW WH-562B
401 M Street, S.W.
Washinqton, D.C. 2046O
Dear Ms. Ortiz:
Here is a list of the variables contained in the data set
WASTBASE. for use with the dBASE III menu system WASTE BASE. The
following chemical parameters: molecular weight; acid— and base-
catalyzed and neutral hydrolysis; half-life for volatilization . -
from'water; Henry's law constant; Octanol-Water partition
coefficient; water solubility: and vapor pressure are present in
the data set. The number and percentage of records for which
non-blank, non-zero values for these parameters•exist are given
along with variable definitions.
ACIDH\DK:
— APP8:
APP9
BASEKYDR
_-»-CA
CANCER
Half-life forJacid-catalysed hydrolysis,
unless otherwise noted;
<15 non-zero values: 2.S« of compounds).
Flag indicating appearance of substance in 4O CFR part
appendix VIII.
Flag indicating appearance on groundwater monitoring
."Appendix IX'JL- ^-_ ^^-fn r ^n ,i4i-r** T~~ M~' V\r"
±«—houi'a
* CA3NO:
CHARACT:
._*• COMPOUND:
CYN:
DESCRIP1
DESCRIP2
DESCRIP3
unless otherwise looted;
(58 non-zero values; 3.6*O.
Maximum concentration of substance in a waste under
"California list" (FR vol. 51 no. 1O2).
Flag indicating carcinogenicity.
Chemical Abstracts Service Registry name (9th
Collective Index>.
CAS Registry number1.
Chnr3crLeriatic for which substance is listed.
Common name of substance used in some regulatory
documents.
Indicates presence of cyanide moiety and form (free or
bound) . ' • ...
For F and K waates, first 20O characters of
description given in 40 CFR part 261, subpart C
Second 2OO characters of description.
Third 2OO characters of description.
DEVELOPMENT PLANNING AND RESEARCH ASSOCIATES, INC.
200 Research Drive P.O. Box 727 Manhattan. Kansas 66502 Telephone 913-539-3565
Cable: AGRI
Telex 7045
-------
Ma. Qrtii
O1/1S/87
Page 2
FN1ST3RD
FN2ND3RD:
FN3R03RD:
GEOUPA:
GROUPB
GROUPC
HFLF:
HLAW:
HORG :
LOG KOW:
METAL:
HOLEWT:
NAME:
NEUTHYDR:
PCB:
REFNO:
REGLEVEL:
RELIST:
RL1ST3RD:
RL2ND3RD:
RL3RD3RD:
Flag indicating .assignment of substance to first third
of schedule for land disposal restriction under the
final rule
Indicates assignment to group C of first third of
schedule for land disposal, restrictions under proposed
relisting.
Half-life, for volatilization from water at STP;
(137 non-blank values; 23*i> . .
Henry's law constant (unitless):
(137 no-zero values: 23H).
Element symbol for halogen present in substance.
Log of the Octanol-Water partition coefficient
(unitless);
<137 non-zero values: 23«).
Element symbol for toxic metal in substance.
Molecular weight of substance:
(344 non-blank values: S7?s.
Common name used in other regulatory documents. U
•__.,. r^Mrc- Cgr-oJ^-t"cx^ir\^T -.. ^. *'
ror hydrolysis a-mrer—ireiutrF5L^e.uii\3.utriort-a,
hou-r-s unless otherwise noted;
(64 values; 1O.6%).
Flag indicating that substance is a poly-chlorinated
bipheny1.
Number by which published data source is indexed ir,
CIS.
Threshold concentration, in mg/1, of a substance in a
leachate of a waste obtained by the Toxicity
Characteristic Leaching Pocedure (TCLP; FR vol. 51 no,
114)
A list oi" F and K wastes of which substance is a
constituent, taken £rotn the document presenting the
proposal for relisting the shcedule for land disposal
restrictions. •. •
Flag indicating assignment to first third under-•'"'.'•
proposed relisting. • '•' • ••
Flag indicating assignment to second third under
proposed relisting. - • \ "
Flag indicating assignment to third third under
proposed relisting. •„ ..
-------
Ms. Ortir.
O1/1S/87
Page 3
SOLTEMP:
SOLUB:
SOLUNITS:
SORTK:
SORTKEY:
VPRES3:
VPTEMP:
WASTCODE:
WSTREAM:
Temperature at which solubility meaaureraent was taken,
Solubility in water;
(137 non-zero values; 23«>.
Units for solubility measurement.
String beginning with first alphabetic character of
COMPOUND; Uey by which substances are sorted in some
published lists.
Corresponds to SORTK, but based on NAME rather than
COMPOUND.
Vapor Pressure at one atiixosphere;
112 non-zero values; 2*O .
Temp.eratur& of vapor pressure measurement.
EPA Hazardous Waste Number <4O CFR part 261).
Corresponds to RELIST, but based on 4O CFR part 261
appendix VII.
Data quality assurance is continuing for all variables.
Yours tfruly
Karl A. Anderson
Analyst
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