7351

• UCREFRP Catalog Number: 7351
• Author: Woodward, D. F., E. E. Little and L. C. Smith
• Title: Toxicity of Five Shale Oils to Fish and Aquatic Invertebrates
• USFW Year: 1987
• USFW - Doc Type: Archives of Environmental Contamination and Toxicology
• Copyright Material: YES

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port important sport fisheries and natural resource
areas for recreation. In addition, four native fishes
of the area-Colorado squawfish (Ptychocheilus
lucius), humpback chub (Gila cypha), bony tail
(Gila elegans), and razorback sucker (Xyrauchen
texanus)-are in danger of extinction, and the U.S.
Fish and Wildlife Service is charged with their pro-
tection (Wydoski et al. 1980). An evaluation of the
sensitivities of endangered species, as well as stan-
dard test organisms, to potential contaminants is
critical in an assessment of risks associated with
the transportation of shale oils.
The objectives of this research were to initiate a
data base that would aid in the development of
shale oil resources by providing information needed
in hazard assessment and protection of endangered
fish and aquatic organisms in the impacted area,
Chemical characterization, lethal toxicity concen-
trations, sublethal effect concentrations, and
methods to relate laboratory findings with current
environmental monitoring techniques are included
in this data base for different oil shale products.

Methods

Test Organisms

The oil shale development area contains both a cold water and
warmwater fishery, Therefore, separate coldwater and warm-
water tests were performed. The warmwater test species were
the Colorado squawfish, selected because of its endangered and
protected status, and the fathead minnow (Pimephales pro-
melas), selected because of its general use as a standard test
species (ASTM 1980). The cutthroat trout (Salma clarki) was
selected as a test species in the cold water tests because it is a
native to Rocky Mountain streams and lakes and is easily ob.
tained (Lee et al. 1980). Colonized multiple-plate artificial sub-
strate samplers (Merritt and Cummings 1978) were used in the
cold water test to evaluate effects on structure of aquatic inverte-
brate communities. Baseline surveys on macroinvertebrates
were conducted before oil shale exploitation began in Colorado
(Erman 1981). Therefore, identifying taxonomic groups sensitive
to shale oiL contaminants and common to the development area
would be useful in assessing impact after a spill.
Colorado squawfish were obtained from the Dexter (New
Mexico) National Fish Hatchery, fathead minnows from our lab-
oratory culture, and cutthroat trout from the Jackson (Wyoming)
National Fish Hatchery. Before coldwater tests, multiple plate
samplers were allowed to colonize for 4 to 6 weeks in Flat Creek
on the National Elk Refuge, Jackson, Wyoming. Each artificial
substrate sampler was made up of eight 7,6-cm square tiles
spaced 0.64 cm apart. Warmwater tests were conducted in
spring water at 20 :!: 10C; pH was 8.4, alkalinity 196 mg/L (as
CaC03), and hardness 175 mg/L (as CaC03). Coldwater tests
were conducted at 10 :!: 10C; pH was 7.5, alkalinity 149 mg/L,
and hardness 158 mg/L. All fish were acclimated to the respec-
tive test waters for at least 10 days before tests were started,

D. F. Woodward el al.

Test Oil and Exposure Apparatus

Three crude shale oils were evaluated: Geokinetics, Paraho, anJ
Tosco; one hydrotreated crude, Paraho HDT; and one refined
product used for jet fuel, Paraho JP-4. Paraho crude, Parah"
HDT, and Paraho JP-4 were obtained from the Oak Ridge 1\,.
tional Laboratory, Department of Energy, Oak Ridge, Ten
nessee; Geokinetics crude from Geokinetics, Inc. (Vernal
Utah); and Tosco crude from Tosco Corporation (Golden, Col,,:
rado). Laboratory flow-through tests were conducted on tl>"
WSF of these oils for 96 hr, using the apparatus and procedure::
of Woodward el aJ. (1981, 1983), A 100 mg/L mixing ratio of l'
to water was selected to simulate a spill. The WSF in the fin"
separation tank made up the oil concentration in the highest c\
po sure , and was also diluted four successive times by 50r; 1,
provide four additional exposure solutions that were 50. 25. I:
and 6% of the first. Warm or cold spring water used in the d,i.,
tion also served as the experimental control solution, The Walc'
soluble fraction in the final separation tank ranged from U (,
6.5 mg/L depending on the oil. Duplicate exposure tanks or 4," :
volume were maintained under identical conditions for each, '
the six solutions. Each tank received I L of new exposure \\,."
at 5-min intervals. For the warmwater test, the two duphu
sets of tanks contained Colorado squawfish and fathcJ
minnows. In the cold water test, one set of tanks contained ,;
throat trout and the other contained the plate samplers COIOnlir
with aquatic invertebrates.

Chemical Analyses

Water-soluble fractions were prepared from each of th,' I"
shale oils by combining 0.5 g of oil and 350 ml of tap walel H.
each of two 500 ml Erlenmeyer flasks. Flasks were capped ""
shaken for 16 hr on an Eberbach shaker. After settling for ~ t
250 ml were siphoned from below the surface of each tltsk .."
combined in a I ,OOO-ml separatory funnel for extraction \\'
three 25-ml portions of methylene chloride. Befor,~ anal\"" .
internal standard of predeuterated naphthalene. pyrene, rt"
anthrene, perylene, anthracene, and benz(a)anthracenc ".
added, and the sample was reduced to I to 8 ml under a Sll<.'
of nitrogen. Samples were analyzed directly by gas chrom.""
raphy (GC) and mass spectrometry (MS) with computer u..".
analysis (DS). A model 4000 Finnigan MS with INCOS d..;.
system was used with electron impact ionization at 55 ekn"~
volts. Samples of I fl.l were injected onto a fused silica ,",Jr:
tube (60 m x 0.25 mm DB-5, J&W Scientific) by the on.""",'
technique, The temperature program follows: 50T. hold' "
50C/min to 2700C; 10C/min to 3000, hold 10 min. The ga... 1:.1"
was helium at 10 psi. The analytical procedure used In t~J
determinations required the development of an exten...ive (;( \'
search library specifically for these samples which entaJlnJ .',
ysis and interpretation of several hundred individual..",..,
nents of these mixtures. The interpretations \\-ere nl.lllc :
marily by using the National Bureau of Standards m,," ,"
trum library of over 30,000 spectra. Quantitations wele nl.','
the internal standard method. Relative response facWl' .
determined for a number of specific aromatic and aliphall.~ ,.~
pounds, and these factors were used for other member' \.:
compound classes. Quantitations of compounds nol ham, ,~
propriate standards were made by assigning a respon\c !;.,
based on inspection of the mass spectra of these compou:>,'
Total oil in water was determined for each of the 51\ IC" ~"

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