RISK ASSESSMENT FOR CHIDRINA1ED PARAFFINS:
EFFECTS ON FISH AND WILDLIFS
Health and Environmental Review Division
Environmental Effects Branch
Toxicology Section
December 18, 1985
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. -. FREUMINAPY TJJSK ASSESSMENT ON CHLORINfflED n-EARAFFINS
EXECUTIVE SUMMARY
The following risk assessment is limited to 58 percent chlorinated, short
chain-length (Cio-13) tv-paraffins. Ihe chemical/physical, exposure, and
-toxicological data were obtained mostly frcm open literature and reports
submitted by the Chlorinated Paraffins Consortium. Predicted jresidue levels
for the three scenarios are frcm a contract report ty Versar inc. *hich used
used releases estimated tsy PEI Associates, Inc.* -, Sunmary of the important
information in this risk .assessment are as follows:
-» - o Production levels for 1983 was 67 million pounds to be used in a wide
variety of products. Releases from manufacture, reformulation, use,
•--,. .-and disposal are estimated to l>e 50 million pounds per year.
o Chloroparaffins are highly persistent, have low water solubility, sorb
readily to sediments and organic matter, have a high bioconcentration
potential and sane accumulation between trophic levels in the food web.
o Monitoring data indicate -that chloroparaff ins are present at sampling
-sites near two manufacturing plants .in the U.S. and are wide-spread
"*: contaminants in the united Kingdom.* ^-Monitoring data also support the
predicted environmental exposure levels made by Versar Inc. In some
cases, residue levels in sediments have even been underestimated.
o Chloroparaffins have little acute toxicity to fish, birds, and -mammals,
but they are highly toxic (less than 1 jng/1) to Crustacea and algae.
Chronic toxicity in most "test species occurred at levels less than 20
ug/1 for a wide array of reproductive parameters. Statistically signi-
ficant (P=0.05) chronic effects were reported at -levels as low as 2A
-to 3.1 Ajg/1 -for-four test species. All four studies failed to identify
a no-observed-«f f ect level (NOEL).
o Three scenarios were developed which are representative of -many sites?
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'large and snail rivers; low, high and tidal flows; fresh and estuarine
areas; and north/south gradients. Similar effects at other sites may
be expected.
o Environmental exposures predicted .in water in the -three scenarios either
approach or exceed the lowest chronic effect level (0.5 ug/1) leaving
.little or TK> margin for safety. The lowest effect level cannot be
identified due to an absence of NQEL's.in those four test species.
o Population reductions can be anticipated in all three scenarios among
-- aquatic species, including iish, zooplankton, Crustacea, molluscs, and
insect larvae. Benthic species may be expected to be directly affected
most by the higher chloroparaffin residues present in the sediments.
Depopulation reductions and loss of some benthic species can be expected
to adversely affect the availability of food to species higher on the
food web. Oyster reductions can also affect water quality, reduce
primary productivity, and cause losses in the two aquatic habitats.
Oyster reefs and seagrass beds are important habitats to commercial ly-
,- .important shrimp, blue crabs, and sport fishes in the Galveston Bay
area. Population reductions will also affect food availability-for
the numerous aquatic birds which feed on fish and benthic organisms.
o "Jteproduction on aquatic birds in Sugar Creek area may also be adversely
-affected isy chloroparaff ins in their food, which exceed the NOEL.
Residue levels in biota approach the NOEL for birds in the Galveston
Bay area, which is an important nesting and/or feeding area for many
aquatic birds, including at least four endangered avian species.
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o Under the scenarios presented, chloroparaffin releases do not pose a
toxicological barrier to migratory species moving through the area.
o The extent of the toxic effects on benthic species fron residues in
sediments and residues bioconcentrated in biota can not be evaluated
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without additional testing. Additional tests are also necessary to
determine the no-effeet-level for fish reproduction and chronic effects
on nysid shrimp and daphnids.
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A. Manufacture, Use, and Disposal
Chlorinated jv-paraffins are a class of chlorinated hydrocarbons having the
general formula CjjH(2x-y+2) Cly, They are obtained by chlorination of normal
paraffins (at least 98 percent linear) and wax fractions. The talk of the
manufactured products are based on €12» Cjs, and €24 feedstocks and are 40 to
70 percent chlorine. While a chlorinated n-paraf f in product may be clasif ied
fes Ci2» the actual composition is a range of chain lengths that average Ci2«
Chlorinated jv-paraf fins nay i>e liquids or solids with a wide range In
viscosity.
The capacity of U.S. manufacturers to produce chlorinated paraffins far
surpasses the past, present, or expected future demands for .the compounds.
During 1983, with -two of the «ight potential producing -plants closed, active
U.S. capacity was -217 million pounds, while demand was only 67 million pounds
(Long, 1984).
"There are over 200 camercial products that consist of pure chlorinated
iv-paraffins. They are used as extreme-pressure additives in lubrication oils
and metal cutting' oils, secondary plastinzers and flame xetardants in plastics,
softeners and flame retardants in rubber, plasticizers in paint, adhesives,
sealants,.and chalks (Long, 1984). Some uses are as fire and water retardants
in fabric finishing -and a constitutent in printing inks. The National
Institute for Occupational Safety and Health (NIQSH) has identified over 500
commercial products that contain chlorinated n-paraff ins as a constituent (PEI
.Associates, Inc., 1984).
B. Regulatory Status
Chlorinated n-paraff ins (35-64 % chlorine) were reccranended for testing by
the Interagency Ttestrng Committee (Federal Register, 1977) based on the following
information:
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1) 1972 production levels of 80 million pounds; - v
2) use of these materials on a wide variety of household and paint products,
*
as well as adhesives and flame retardants;
3) estimated release xates of 50 million pounds per year;
-4) degenerative-changes in the liver and spleen of mice exposed -to chloro-
paraffins in a chronic study;
5) concerns for human health effects on carcinogenicity, mutagenicity,
teratogenicity and other chronic effects in the absence of data; and
5) . the need for a critical .assessment of the biological -Significance of the
_ .. ~ occurrence of chlorinated n-paraffin residues in fish and the aquatic
environment.
The Environmental TTotection Agency announced in the Federal Register - *
(1982) that the EPA. would-not at that -time propose a section 4(a) rule to
require health or environmental effects testing of the chlorinated n-paraf fins.
That decision was based on the acceptance of a voluntary testing proposal made
by a consortium of international manufacturers of chloroparaffins. Environmental
fate jieeds included studies on solubility of four categories and an aerobic and
anaerobic biodegradatipn tests: Environmental toxicity tests proposed by the
Consortium are tiered tests (Federal Register, 19B2). Phase 1 tests are 30-60
day lethal and sublethal studies on mussels and rainbow trout for each of four
specified test compounds (see Appendix A). Phase ~2 tests on the most -toxic
compound identified in Phase 1 tests include chronic and bioconcentration tests
on aquatic invertebrates and fish. The American members of the Consortium also
agreed to conduct a avian reproduction study on mallard ducks. EPA received
the environmental toxicity studies from the Consortium in 1984 and the avian
reproduction study in 1985. All-of the studies have :been reviewed and evaluated
-for scientific soundness and effect levels. "The conclusions from that data
validation process have been integrated into an environmental hazard assessment
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(Rabert, 1985).
Information on releases and predicted environmental txncentrations for an
environmental exposure assessment were prepared by contractors. PEI Associates,
Inc. (1985) estimated the release levels from manufacture, reformulation, use,
and disposal. Versar Inc. (1985) then used those release estimates to prepare
a preliminary exposure assessment for three manufacturing and/or use sites
selected by EPA. Those three sites are the Schuykill River in Pennsylvania,
Sugar Creek in Ohio, and the Houston Ship Channel/fcalveston Bay, Texas.
III. ENVIRONMENTAL EXPOSURE ASSESSMENT
A. Environmental Pate
. Little environmental fate data are available on chlorinated ji-paraff ins.
The complex nature of the mixtures and the difficult analytical methods needed
to separate and quantify residues have limited the development of information.
Even much of the data that has been developed is of questionable quality.
Chlorinated n-paraffins are generally considered to be persistent. Chemical
degradation is generally considered insignificant. Chloroparaffins do-not
hydrolyze, oxidize, £>r otherwise react at significant rates under ambient
temperatures and relatively neutral conditions.
Data on biodegradation reported by Hildebrecht (1972), Zitko and Arsenalt
(1974 and 1975),-and the Consortium are all inconclusive. Some biodegradation
.of 58% chlorinated, short chain-length n-paraffins by microorganisms in a 5-day
biochemical oxygen demand (BOD) test was reported by Hildebrecht, but how much
has been strongly debated. Zitko and Arsenault (1974 and 1975) demonstrated
that microbial degradation in estuarine sediments is faster under anaerobic
conditions than aerobic, but poor recovery of sorbed residues (about 20%)
demonstrated by Raron (1976) and erratic data make quantification of degradation
rates difficult. Aerobic and anaerobic studies submitted by the Consortium
also indicate little evolution of gases (a measurement of biodegradation)
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for the four -tested mixtures. In general, it is -thought that dechlorination
preceeds degradation of the paraffin moiety, tut no information has been
reported on the identity, persistence, or toxicity of degradates or metabolites.
Water solubility data .submitted by the Consortium indicate that the chloro-
paraffin products have low solubility. Solubility ranges frcn 3.6 — 6.6 ug/1
(ppb) for the long chain-length mixtures (C2Q-30) ~t° 95 ~ 47° U9/1 ior t*16 short
chain-length mixtures (Cio-13)- Insolubility in vater also appears to Increase
vith increased chlorine content. The hydrophcbic nature of the chloroparaffins
Increases the likelihood that residues would readily adsorb to organic matter
and suspended particles in -both the water column and the sediments at the
water-sediment interface.
Campbell and McConnell (1980) found that sediments typically contained
1000- to 2000-fold higher residue levels than measured in the overlying water
column, Ramm (1978) found that spiked residues were tightly bound to sediments,
such that only about 10-20 percent were recovered by use of solvents. Harm
(1978) concluded from residue data on benthic biota (chironotud larvae and
worms) that chloroparaf fins residues are accumulated by some benthic organisms.
Chloroparaffins are generally considered to have a low vapor pressure
(about 1-2 x 10~6 mm Hg at .20 °C). Low volatilization of chloroparaf fins would
.indicate low dispersion capability, but residue concentrations in domestic fowl
and sheep wool-near manufacturing plants (Campbell and McConnell, 1980) suggest
seme airborne dispersion. The .range of chloroparaf fin vapor pressures are not
too dissimilar from PCB values, which indicates sane potential for atmospheric
transport to distant environments.
Little data exist which demonstrate mobility and transport of chlorinated
jt-paraffin residues from-sites-of manufacturing, reprocessing, use, or disposal.
Very low solubility in water and low vapor pressure would predict low mobility,
but monitoring data in the United Kingdom indicate widespread levels of low
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contamination in water, sediments, aquatic organisms, and even ccranercial fish
foods. Analyses of test organisms and food items used in the chronic tests
indicated low levels of short to intermediate chain length chloroparaffins in
rainbow trout (1.3-2.0 ppn), toussels (1.2 ppn), algae (1.8-2.6 ppn)* Artemia
(0.51-0.57 ppn), and fish food pellets (0.78-2.14 ppn) (Harland et al.f 1983).
How residues have spread to contaminate so many of these areas is not yet
aiderstood.
S. Environmental Exposure Levels
3he exposure estimates used in this risk assessment include: extensive
monitoring data collected in the United Kingdom by Campbell and McConnell
(1980); unpublished monitoring data submitted to EPA by Diamond Shamrock for
two sites; and the environmental concentrations estimated by Versar me. at the
three U.S. sites.
. Campbell and McConnell (1980) reported chloroparaffin residue levels found
in water and sediments from nunerous sites throughout the United Kingdom. In
general, residue levels show an increase in chlorinated rv-paraff ins ^as river .in
water as Jit passes from the uplands into .industrialized areas, and a decrease
when the river joins the sea. In the industrial areas, residue levels in the
sediments were 0.1-15.0 ppm, while concentrations in overlying waters ranged
from 0.5 to 6.0 ppb. Residues in marine and non-marine waters remote from
industrialized areas were frequently -found in either the sediments, -water, or
both. ' The highest residue levels found in a non-industrial area was in the
Sound of Taransay on the remote isle of Harris in the northwestern part of
Scotland. Residues in water were 2.0 to 4.0 ppb in water and less than the
limit of ijetection in the sediment « 0.05 ppm). Slightly lower concentrations
•were found at many remote areas throughout the country and Irish Sea. About
half of the sediment samples from the North Sea contained residues -ranging
from 0.05 to 0.3 ppn. Residue levels in sediment were about 103- to 104-fold
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higher than residues an the overlying waters. Short to intermediate chain-
J.ength chloroparaffins were usually found in sediments at higher concentrations
than the longer chain-length mixtures.
„ Biological samples from 5 aquatic species (plaice and pouting -- two benthic
fish species, pike - a predatory fish, nussels, and grey seal) collected in the
rivers and sea in the United Kingdom, indicated chloroparaf fin residues in all
species. Campbell and McOonnell also reported residues in seabirds (0.5 to 1.2
ppm) and seabird eggs (< 0.05 to 2 ppm).. Liver sanples in all three avian
species and over €6 percent of the eggs contained chloroparaf fins. Analysis of
human foodstuffs in the On i ted Kingdom indicated chloroparaf fin residues .in
dairy products (0.3 ppm), vegetable oils and derivatives (0.15 ppm), ..and fruits
and vegetables (0.025 ppn).-~ "While no residues were found in tissues of Welsh
.sheep grazed remote from chloroparaf fin production, sheep grazed in Weston Point
near a manufacturing plant contained 0.2 ppm in liver, 0.05 ppm on mesenteric
fat and kidney, and no residues found in the heart, lung, or perinephritic fat.
Monitoring data from the lower Grand River at a Diamond Shamrock manufac-
turing plant near Plainsville* Ohio indicated significant levels of chloro-
paraf fin residues m water, sediments, benthic biota, and plant roots (Ramm,
1977). Residues found in water were about 2 {0.5-3) ppb with the highest
concentrations located at the two sampling sites located just above and below
the discharge point. Residues in the sediments were considerably higher-at-the
two sampling sites downstream from the discharge point (both 3.1 to 12.6 ppm)
than the site just above (0.8 ppm). No residues were detected in several
species of fish, crayfish, clams, and tadpoles collected at one or^nore of the
sites. Chironomids and/or worms contained residues at all four sites with the
highest residues occurring -at the *ite just downstream from the discharge
point* Residues-were also found in the roots of potomogeton at all four sites,
but the residue levels did not correlate-to sediment levels. The author
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concluded that there was no evidence of residue uptake by many of these species,
but that the strong evidence of accunulation existed in Insect larvae and worm
samples. The observation was made by the author that "Ihe abundance of insect
larvae, especially in the lower river, was relatively low compared to that of
other similar rivers we have investigated,*
A pausible interpretation of the irregular pattern of residues in water and
sediments would be that the manufacturing plant is a major source of residues in
the river. The high residue levels in the sediment indicate adsorption from
discharges over a prolonged period, while the similarity in residue levels in
the water above and below the discharge point was caused by either an occasional
reverse flow up the river :the short distance to the nearby jipstrearo sampling
site possibly due to low flow in the river and high discharge rates or storm
surges from lake Erie.
Samples taken at the Diamond Shamrock manufacturing site in Houston, Texas
on the Patrick Bayou also indicated widespread chloroparaffin contamination of
sediments and biota CRamm, 1978). Only one out of five water samples contained
residues <1~5 ppro) .above the level of detection at 1 ppb. All 26 sediment
samples contained residues which ranged .Iran 0.15 to 10.0 prnu Residues found
in biota were 0.10 to 0.52 ppm in whole crabs, 0.2 to 0.42 ppxi in whole
killif ish, and 0.15 ppn in vegetation. While recovery levels for spiked samples
were moderate for biota samples (70 to 85 percent), recovery ±n sediments was
quite low (10 to 20 percent). "While measured sediment levels ranged from 0.2
- 10.O ppm, the low recoveries for spiked sediments would suggest that the
actual sediment concentrations are more probably in the range 1 -^50 ppn."
"Versar Inc. (1985) predicted environmental concentrations in water,
sediments, and biota for various segments of three aquatic areas near select
manufacturing, reformulating, and/or use sites identified by EPA. The three
sites were the Schuykill River near Oonchohocken, Pennsylvania; Sugar Creek
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,*
near Dover, Ohio; and the Houston Ship Channel /Upper Galveston Bay, Texas. The
release estimates used in the modelling effort by Versar Inc. were obtained
from tiie report from PEI Associates, Inc. (1984). In the absence of release
data on chlorparaffins, PEI Associates made simple assumptions and used flat '
percentage estimates based on production volumes and use estimates in manufac-
turing, reformulating, packaging, cleaning, and spills. No release estimates
were made for disposal* Releases from cleaning were 10 percent, 1.0 percent
from packaging, and 0.01 percent from spills (0.1 percent spilled and 90 percent
pick up with absorbents).
~3he residue concentrations of Oilorowax 500-C and Chlorowax 70 predicted
in water, sediment, and biota by Versar Inc. are summarized in Appendix A.
Given the difference in physical/chemical properties of these two chlorinated
n-paraffins, they assumed that these residue estimates would bracket environ-
mental concentrations for all other chloroparaffin products. Residue estimates
were made for both controlled and uncontrolled releases. Controlled releases
assume removal of some residues during wastewater treatment. Residues in
water and sediments were each computed as dissolved, sorbed, and total residues.
The assumption that residue concentrations in interstital water would be the
same as residues in the water column provides a minimal value. One might
expect residue levels in interstitial water to be higher than these estimated
levels based on equilibrium kinetics-with sediment concentrations. How much
higher is not known.
C. Summary of Environmental Exposure
Chloroparaffins are relatively Insoluble in water. Residues in water
readily sorb to suspended solids and tightly bind to sediments. Although
chloroparaff ins appear-to toe relatively non-volatile, residues have been found
at sites that indicate atmospheric transport. Environmental monitoring in the
United ICingdom,'Ohio, and Texas indicate widespread, low-level contamination
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in water* .sediments, aquatic plants and animals, human foodstuffs, and human
tissues. Residues in the low parts per million were found to contaminate the
test organisms and their food sources. While environmental residue levels
were generally found highest near .industrialized areas and diminish when .the
rivers reach the sea, monitoring samples .indicate high residue levels in water
and sediments in some remote areas. Residue levels in sediment are about 1000-
fold higher than concentrations in overlying water. Recovery of residues from
spiked samples indicate poor recovery (10 to 20 percent). 'Residues Jn .benthic
organisms and "berrthic fish were higher than residue levels in organisms found
in the upper water column.
Modelling of residue releases, transport, and environmental distribution
at three manufacturing/use sites indicate widespread, low-level contamination
'. of large areas. Comparison of the predicted chloroparaf f in residue levels -at
three sites (a river, creek, and estuary) indicated the highest environmental
concentrations of chloroparaffin would occur in Sugar Creek, followed by the
the Houston Ship Channel/Gal veston Bay area, lexas. Ihe lowest chloroparaf fin
residue levels occurred in the Schuylkill Biver, Pennsylvania are probably due
to continous flushing and a comparatively high mean stream flow-rate in-the
river (2,940-cfs). Estimated residue levels in the sediments followed the same
site order.
IV. ENVIRONMENTAL HAZARD ASSESSMENT
-A. Phase I ana II — Consortium Testing
Information on environmental effects of chlorinated it-paraffins from .both
Consortium sponsored studies and available literature were reviewed in depth by
,>
EEB iRabert, 1985). The results of the Consortium's Phase I and II testing are
summarized in Appendix B. Phase I -testing consisted of 60-day toxicrty tests
conducted on rainbow trout and bay mussels to identify the aost toxic mixture of
four selected chloroparaf fin groupings. - The groupings included the following
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combinations of chlorination and chain length: intermediate chlorination (58%)
and short chain-length (Cio-iah intermediate chlorination 452%) and intermedi-
ate chain-length (Cj^ij); and one low (42%) and one high (70%) chlorinated,
Jong chain-length (020-30) mixture. The results of the Phase _I tests indicated
that the 38% chlorinated short (Cio-13^ chain-length n-paraffins were more toxic
than the other three tested chloroparaffin formulations. However, the testing
matrix fails, to indicate if it is the most toxic of all chlorinated paraffin
combinations. The other mixtures are not without observed chronic effects.
Dhguantified abnormal behavior were reported for all formulations, especially
upon mussel filtration (feeding) activity. The effects indicate that chronic
effects are "likely to exist for all •formulations. Bioconcentration factors
reported in the studies indicate that residues of all^four formulations will
X
'accumulate in biological tissues. The extent of bioconcentration _in Phase I
tests could not be ascertained due -to -the insufficient sampling. Consequently,
the BCF values reported for the tested -formulations in Phase I tests-must be
considered both preliminary and minimal values.
Phase "IT chronic tests on 58% chlorinated, short chain-length n-paraffins
indicate significant (P - 0.05) chronic adverse effects in the range of 2.4 to
20 ug/1 for rainbow trout, sheepshead minnow embryo-larvae, mussels, daphnids,
mysid shrimp, and -the marine alga. These effects generally include chronic
lethality, altered growth, and reduced reproduction. Shortcomings identified
in most of~the studies precluded identification of the lowest effect level
concentration as well as the percent of the adverse effect* Analysis of the
.aquatic data indicate that adverse effects occurred at the lowest concentration
S
... tested (0.5 ug/1) and that testing at lower levels may produce additional
significant adverse effects below 1 ug/1.
B. Toxicological Effects of 58% Chlorinated (€10-13 Vij-Paraf fins
Tn the absence of surf icent toxicological data on other chloroparaffin
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formulations, all further discussion of the toxicolgical effects shall be
limited^to the 58% chlorinated, short chain-length (010-13) n-paraffins
tested in Phase II and whatever other environmental data are available on that
formulation.
. 1. Acute Toxicity
. „ Acute effect levels of chloroparaffins on some aquatic species must be
interpreted with caution for some test species. The water solubility of Cjj
is only about 0.095 "to (U47 ppm, therefore -all toxicity values greater than
that concentration are suspect, for example, all 96-hour fish I/SO values are
-greater than 100 ppm (Table 1). Thus, -the absence of acute toxicity in some
species is simply a function of too short a time period for the ma")) amount of
chloroparaffm available in the water to penetrate the organism. Further
evidence that uptake rates are slow on some species is indicated by mortality
and toxicological effects reported in both the Phase I .and Phase II tests on
rainbow -trout and mussels. Consequently,-the greatest concerns for this kind
of chemical are usually .chronic effects.
Table 1 contains what limited data are available .on the acute effects for
short chain-length (Cio-13) chloroparaffin formulations. Of these test species,
the most acutely sensitive species to chloroparaff ins are daphnids and mysid
shrimp which were both affected by the 58% chlorinated, short chain-length
n-paraff ins at similar concentrations (the 96-hour-LC50 .values are 18 ug/1 and
less than 14 ugA« respectively). Other acutely sensitive aquatic invertebrate
species included the oopepod Nitocra spinipes with a LC50 value of 100 ug/1,
followed by the relatively insensitive chironcmid midge, greater than 162 ug/1.
The two species of algae tested reacted very differently from each other
when acutely exposed ±o 58% chlorinated short rhain-length jv-paraff ins. The
/marine algae Skeletonema costaton was the--more sensitive species with a 96-hour
EC50 of 42.3 (27.3 - 93.1) ug/1 for growth (cell oountK The effect of the test
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- material on growth rate of the marine algae was transient and by Day 10 no
difference in growth rates were apparent when compared to controls. The highest ,-._
f
reduction in growth .rate occurred during the first-two days and produced *" hr
EC50 of 31.€ (20.7— 37.6) ug/1. Toxicant effects on the .freshwater green
algae* Selenastrurn capricomutum, differed f ran the marine algae in that its
growth reduction was produced by higher test concentrations and the greatest . ..
effect occurred at the end of the JO-day study. The lowest reported EC50 for
-the green algae was 1,310 <880 —- 4,060) ug/1 at 10 days, which was derived by
extrapolation from the 45 percent reduction found at the highest test level,
"1,200 ug/1. Increasing differences in growth rates compared to controls an the ,
latter days of the study indicate that longer exposure would probably produce
lower effect levels for green algae. How much lower-is unknown. Still another
factor affecting the interpretation of these'Static test results is the loss of
50 to 80 percent of the residues from the water column. Analyses of water and
algae samples on Day 10 indicated that the balance of the residues had sorbed
to the algal cells. Increase in the number of algal cells during the growth
phase of this test has had the effect of distributing some residues to the new
cells and thereby reducing the concentration per cell, whole the longer-term
toxicity in these tests might indicate toxic effects m algal populations in
flowing water, these toxicity values would underestimate toxicity for algal
populations in standing waters which would accumulate additional discharges,
such as lakes, ponds, and estuaries.
The rat LD50 value of greater than 21.5 g/kg indicates minimal acute
toxicity to mammals. No acute oral LD50 or 1X30 data were available on birds.
2. -Oircnic Toxicity
Chronic effects were reported on all Phase i-«nd Phase II test species for
most chlorinated paraffin formulations tested (Appendix!)). Chronic effects on
sheepshead minnow larvae, rainbow trout, mussels, daphnids, mysid shrimp, and
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marine algae indicated high sensitivity to chloroparaffins. All of these *
species indicated effects at measured concentrations below 20 ug/1. Due to
*
various testing inadequacies found in each study, it Is impossible to determine
the actual HATC level inmost studies. Statistically significant (P=0.05)
effects probably occur at concentrations even lower than those reported. No
>. observable effect levels (NOEL) were not identified in the following studies:
mysid shrimp (0.6 ug/1 -s- adult mortality), sheepshead minnow (2.4 ugA - body
length), daphnids (2.7 ug/1— number of young and offspring/female), and
rainbow trout (3.1 ug/1 - mortality). Data indicate that chronic effects are
more dependent on the duration of exposure than the test concentration for
chloroparaf fins. It would appear that simply prolonging the exposure will
elicit toxic effects, irrespective of the test concentration. For example,
50 percent of the rainbow trout exposed to 3.1 ugA for 168 days in a fciocon-
centration test began dying 64 days into the depuration period, while the
same species exposed to a slightly higher test level (3.4 ugA) for the same
time period in a growth study displayed no significant growth effects. The
•* absence of growth effects is unusual, since it is considered one of the most
sensitive, toxicological endpoints.
Adverse effects reported for chloroparaffins include chronic mortality,
significantly (P * 0.05) increased and/or reduced growth, abnormal behavior,
reduced filtration (feeding) activity, reduced offspring per female, offspring
survival, reduced insect hatchability, reduced insect emergence, and reduced
cell growth in algae. The maximum acceptable toxicant concentration (MAIC)
levels for these effects were identified as < 2.4 ugA for the sheepshead
minnow, < 2.7 ugA for daphnids, and < 3.2 ugA for rainbow trout. At the
lowest concentration tested {0.5 ugA)» mysid shrimp -mortality *ras 30 and 40
-percent compared to 10 to 30 percent in controls and 25 and 30 percent in the
in
acetone controls. Whether and how much of the mysid mortality at the level of
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0.5 ug/1 vas'-induced by the toxicant is difficult to tell. The erratic mortal-
ity data may have resulted .from toxicity of other contaminates -in the food
»
source. The food source, Artemia, contained 0.6 ug/g chloroparaffins and
1.4 ug/g PCBs and organochlorine pesticides, mostly DDT.
Chronic effects reported-in chloroparaffin studies submitted by the
Consortium are listed in Table 2 in order of increasing measured test concen-
trations. Reproductive effects, other than growth, weretiot found .in either of
the ±wo .sheepshead minnow studies (2.4 to 54.6 ug/1 and 36.2 to 620.5 ug/1).
The two studies indicated a statistically significant IP « 0.05) increased
growth at low test concentrations (2.4 - 71.0 ug/1) and significant decreased
growth at the highest test level (620.5 ug/1),. The pattern of growth enhance-
ment and growth reduction were repeated at similar test levels in rainbow
trout studies. 'The similarity between the growth curves for the two species
drawn from tJata in two separate tests on each of these species adds confidence
to the validity of this unusual dose-response curve. No significant differences
in susceptibility were found between the various early life stages in rainbow
trout or sheepshead minnow. Some differences in fish species sensitivity to
chloroparaffins were indicated toy the absence of or only slight sublethal
effects reported in bluegill and channel catfish studies.
The absence of .reproductive effects found in the sheepshead minnow study
should be interpreted with caution. First, Jthe exposure period for these two
studies were only 28 and 32 days long and adverse effects, especially.in fish,
are slow to manifest themselves, probably due to slow residue uptake. Second/
these abbreviated reproduction studies began by introducing embryos to the test
concentrations, rather than exposing adults to the chemical for weeks prior to
spawning. -It is generally-understood that embryos will not-sorb residues f ran
water readily, therefore, the developing embryos were TiotTnetabolicallyexposed
to toxicant concentrations-to the same degree that it would if -the female had
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18
deposited residues on the yolk. Given the significant male mortality reported
in the mysid chronic -study, it would appear that the differential mortality
between the sexes resulted -when females deposited sane of their body burden of
chloroparaffin residues into their eggs, a situation known to occur in birds,
fish, and other organisms with DDT.
, Growth studies on cannon mussels exposed to the same short chain-length
chloroparaffin indicated reduced growth rates at concentrations greater than
.2.3 ug/1 and less than 9.8 ug/1 (53 percent reduction in -both tissue and shell
length). Toxicant levels reducing mussel growth are less "than the concentra-
tions reported to reduce growth in sheepshead minnow (greater than 280 ug/1 and
less than €20 ug/1) and in rainbow trout (greater -than 350 ug/1 and less than
1,070 ug/1).
Chronic effects on both crustaceans were found at similar concentrations.
The number of daphnid offspring per female was reduced by 44 percent at 277
ug/l» the lowest test concentration. ~In mysid shrimp, a 33 percent reduction
in offspring/female occurred at 7.3 ug/1. Chironomid midges, another aquatic
invertebrate, was not as sensitive as the above two crustaceans, but adverse
reproductive effects -on midge larvae were reported for hatching, emergence, and
eggs per mass at concentrations of either "78 or 121 ug/1.
Reproductive effects of 58% chlorinated, short chain-length n-paraffins on
mallard -ducks included statistically significant effects on eggshell thickness
and percent viable embryos per egg set at 1000 ppra. The no observed effect
level found in the avian reproductive test was 166 ppm.
3. Bioconcentration
s
Long-term bioconcentration studies on mussels and rainbow trout exposed to
.58% chlorinated, short chain-length ji-paraffins demonstrated high BCF levels in
whole organists-ranging from 24,800 to 40,900 and 3,550 to 5,260, respectively.
"While the data for some organs were erratic and never .stabilized, equilibrium
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19
between water concentrations and whole organism residue levels were reached in
about 45 to 80 days in missels and about Day 90 in rainbow trout. Depuration
'half-life rates for the whole organisms were reported as 9.2 to"19.8 days in
•the missel and 18.7 to 19.8 days in the rainbow trout. Of the tissues measured
the highest residues occurred in the digestive organs of both species. BCF
levels in the mussel's digestive gland/stomach ranged from 104,000 to 226,000.
In rainbow trout, initial residue levels were highest In the liver and viscera
with BCF values of 11,430 to 15,970, but the levels in the liver declined in
the latter half of the study to 2,770 to 3,930. BCF values found in flesh or
carcass were considerably .lower (1,330 to 5,040). Declining residues in trout
liver give the impression that the active elimination of -the C14 residues may
occur via-metabolic breakdown of the chloroparaffins.
Itie bioconcentration study on mussels exposed to nominal concentrations of
2.35 and 10.1 ug/1 of 58% chlorinated short chain-length paraffins indicate BCF
values of 40,900 and 24,BOO, respectively for the whole animal. Compared to
the gonad and residual tissues, the digestive gland had the highest residue
levels with BCF values of 104,000 and 226,400 at levels of 2.35 and 10.1 ug/1,
respectively. Whole animal residues attained equilibrium at the highest
exposure level at about Day 42, which also corresponded to the onset of low
level mortality that persisted throughout the 91-day exposure and through Day
125 (34 days into the depuration period). As discussed earlier, mortality
also occurred in the rainbow trout bioconcentration study during the depuration
phase. However the trout deaths began after 64 days of elimination and ceased
on Day 69, leaving only two surviving fish at the lowest test lever. Based on
a comparison of chloroparaffin uptake from water and food in the literature,
the contamination of the fish food source at B.B5 to :2.2 ppm could not be
considered responsible forrthe late mortality during'.the depuration phase. T^e
BCF values reported in the two'bioconcentration studies agree well with results
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20
reported on -the sanre test material in the 60-day t.oxicity tests submitted on
the mussel and rainbow trout (Table 3). These levels, however, are consider-
ably higher than x:hloroparaffin values previously reported in the literature.
The BCF values are in^close agreement with'BCF levels Teported_foi? the same
mussel species exposed to DDT (4,550-49,600) and fCB (7,200-26,600) by Geyer
et al. (1982).
Data in the two 10-day algal studies indicate low level accumulation of
chloroparaffin residues directly front the water (Table 4K The algal residue
data in Table 4 -indicate a general increase in the "BCF value as the test con-
centration increases. The -low BCF -estimates (£1 to 7.6) compared to BCF
values for the same exposure period on mussels (10,099 - 11,915) and rainbow
trout (1,500 -1,654), indicate that the uptake is probably passive sorbtion
of the hydrophobic-residues to the cell wall rather than active transport.
t
-"Depuration rates for chloroparaffins in whole mussels and fish are slow.
The half-life -for depuration in the whole organisms were reported to be 9.2
to 19.8 days in the mussel and 18.7 to 19.8 days in the rainbow trout. f
=
_4. Bicroagnification
Estimation of BCF values resulting from dietary uptake of chloroparaffins
was made from residues analyses results reported for Phase II studies. The
dietary SCF estimates for mussels and rainbow trout are 0.46 and 1.5, respec-
tively. Algae fed to the missels in the bioconcentration study contained 2.6
ug/g wet weight. The food pellets used during the latter part of the rainbow
trout study contained 0.85 ug/g short-intermediate chloroparaffins. Residue
contributions from these contaminated food to the whole body residues would
account*for-11.8 to 13 percent in rainbow trout^-and 0.5 to 1.2 percent in "whole
-mussels.
While one anight expect residues in food to compliment -residue uptake from
water or sediments, their overall contribution to whole body .residues As rela-
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21
lively small. Test data reported in the literature by other researchers also
indicate that chloroparaffin uptake fran water are greater than fran food
sources. The real significance of dietary uptake of chloroparaffin is a trans-
port mechanism for exposure of organisms that -would not bioconcentrate residues
directly fron water.
C. Summary of Environmental Effects
Acutely, the 58% chlorinated short chain-length
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22
be exposure tine and concentration. While the effect of -best-concentration is
an obvious factor, the effect of exposure duration, to the extent necessary to
show toxicity in the chlorinated paraffins, is highly unusual. As -seen on the
rainbow trout bioconoentration study,.168 days exposure and an additional 64
days t3f post-exposure depuration passed before significant mortality occurred.
Very few chemicals demonstrate such prolonged development of chronic effects,
and even fewer chemicals produce delayed mortality so late into the depuration
phase. This delayed -mortality is reminiscent of toxic -effects caused by the
mobilization of stored T5DT/DDF residues during periods of stress, such as
starvation, migration, reproduction, and residue concentration in developing
- embryos.
The ±wo sheepshead minnow studies are not adequate to test the effects of
-chloroparaffins on fish reproduction. "First, the 28- and 32-day studies were
not of suffioent duration for chloroparaffin toxicity to manifest itself.
Second, the exposure in -the fish reproduction studies began with embryos,
thereby, failing to measure the effect of residues stored in egg yolk.
^n ±he rainbow trout and mussel bioconoentration studies, the BCF values
were reported as 3,550— 5,250 and 24,800 — 40,900, respectively. These levels
of bioconcentration are of considerable concern, especially when combined *tith
persistence, -such as has been indicated for chloroparaffins. Distribution of
chloroparaffin residues in .tissues appear to be similar for species as diverse
as mussels, fish, quail, and mice. Residue levels tend to be highest in those
tissues with high cell turnover rates and/or a high metabolic capacity. BCF
values in mussels are similar to levels reported for DDT and PCB. Depuration
half-life rates for chloroparaffins in whole mussels and fish are slow (9.2 .to
19.8 days and 18.7 to 19.B days, respectively)^
Uiomagnification of choroparaff irr irom food sources appears "to contribute
considerably less chloroparaffin to-tissues than bioconcentration from water.
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23
Biomagnification is of special concern because it provides a residue transport
mechanism to organisms that would not otherwise bioconcentrate residues
directly from water. Biomagnification is also .sign ificant, because residues -
usually accumulate in those species at the top of .the food web, which have low
reproductive capability. .,
In general, one might expect biomagnification effects to be greatest Jin
species feeding on benthic organisms which are exposed to higher chloroparaffin
concentrations in the sediments than are found in water column. Consequently,
chloroparaff in residues entering the aquatic environment, aught be expected to
•be found in most, if not all organisms, especially those species at the top of
the food web.
^ Insuf f ioent data are available, however,vto .correlate body residue levels
with toxicolcgical effects. While no data is currently available to correlate
hazard from tissue residue levels,-concern for bioraagn if action remains r>ecause
residues may accumulate -in species at higher trophic levels in the food web.
Mortality data reported m missel and rainbow trout Moconcentration studies
.Indicate that adverse effects do not necessarily cease when--exposure ends.
Both species experienced mortality during the depuration phase. .All, but two,
rainbow trout died at the lowest concentration withm one week, 64 days into
the depuration period. Tbtal rainbow trout mortality occurred during the same
time period at .the highest level.
Chloroparaff in data indicate little toxic ity to terrestrial species.
Acute oral LD60 data to rats of greater than 21.5 g/kg indicate low acute
concerns for mammals. Chronic effects on mammals is currently under review
and can not be addressed at this time. -Chronic effects on avian reproduction
Included statistically significant tP « 0.05) effects on mallard eggshell
thickness and percent viable embryos per egg set at 1000 ppm (NOEL 166 ppm),
Ihe breadth of toxic effects in a wide variety of species from various
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24
environments in combination of high BCF values, slow depuration, high toxicity,
persistence,:and the widespread distribution of these chloroparaffin residues
in ±he environment indicate that chlorinated paraffins pose a potential threat
to a wide variety of organisms, especially aquatic species. Because this wide
array of adverse effects occur in aquatic species at such low concentrations,
at or below analytical detection limits, all chloroparaffin releases to the
environment are of considerable concern with .respect to fish and wildlife
safety.
*V. ENVIRONMENTAL TUSK ASSESSMENT
A. Scenarios
The three environmental risk scenarios discussed below are based on the
toxicological effects data identified in,laboratory studies, some limited field
monitoring data at chloroparaffin manufacturing sites, and environmental
residue concentrations predicted by Versar Inc. for three manufacturing/use - -
sites selected by EPA to represent a variety of exposure parameters. The three
-sites include a large river, a small river/creek, and an estuary. A summary of
the predicted environmental concentrations (PEC) in water, sediments, and baota
at one or more locations at each of these sites are listed in Appendix A.
Versar Inc. predicted environmental concentrations for both Chlorowax 500-C
(Cio-12) and Chlorowax 70 (C20-3Q) *or ^^ controlled .and uncontrolled
releases. No assessment of Chlorowax 70 can be made at this time, because the
environmental effects data needed to make a risk assessment .are only available
for the shorter chain length compounds. .Therefore, the evaluation of adverse
environmental effects on fish and wildlife will be limited to anticipated
effects from the 58% chlorinated short chain-length (Cjn-12) ^-paraffins.
This risk assessment is largely a comparison of predicted environmental
r concentrations in Appendix *-and the toxicological effects listed in Table 2.
Chronic exposures are assumed at the predicted concentrations from .frequent or
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25
continuous releases. It also assumed that interstitial water concentrations „ =
are higher than water column concentrations, that residues sorbed to sediments
are bioavailable, and that dissolved and total residues in water are at least
partially, if not, ccnpletely available as exposure levels to organisms.
Toxicological effects on the surrogate test species are extrapolated to local
flora and fauna species and limited conclusions are made on the effect of
species interactions. Jtesidue levels in various organisms-are estimated from
data in Tables 3 and 4, using BCF values for the closest -test concentration.
Interpretation of residue levels in whole animals is limited considerably,
because data correlating body residue levels to mortality and other effects
are missing.
1. Schuykill River* Pennsylvania
The predicted chloroparaffin residue levels in the Schuylkill River are
presented in Table 5 for water, sediment and various trophic levels of ±>iota.
While the predicted water concentrations of 0.26 and 0.5 ug/1 are too low to
produce any acute toxicity according to available data, these water concentra-
tions may i* expected to cause significant adverse chronic effects in .some of
the more sensitive aquatic invertebrates and fish. The lowest chloroparaffin
test concentration (0.6 ug/1) produced 30 and 40 percent mortality in mysid
shrimp. How much of that mortality is due to chloroparaf fin toxicity is hard
to distinguish from the 10 to 30 -percent mortality seen in controls and the 25
to 30 percent mortality in the acetone controls. The test results from other
species (rainbow trout, sheepshead minnow, and daphnids) do not preclude
adverse effects at 0.5 ug/lr and possibly 0.26 ug/1. No observable effect
levels were below the lowest test levels for each .of these four species.
Larval growth (length) in sheepshead oninnow was significantly affected at
2.4 ug/1. "The number of daphnid young were reduced 43.6 percent at 2.~7 ug/1.
Aid at 3.1 j?pb rainbow trout mortality was 50 percent.
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26
Adverse effects on mussels at 2.3 ug/1 included a 7.7 percent reduction
the tissue growth rate which was not considered statistically significant ^tP =
0.05) and mortality slightly Jugher than controls (7% versus 5%). ~3he effects
of chloroparaffin residues in sediments at 440 ppb en -the sensitive life stages
such as reproduction and larval survival when setting on contaminated sediments
- have not been studied and are unknown for mussels, clams, and other benthic
organisms. This residue level is considerably higher than the 10 ug/1 concen-
• tration causing 33 percent mortality in the missel BCF study and the 9.3 ug/1
causing more than 50 percent growth reduction In the shell and tissue weight,
A ccnplete life-rycle test on fish with longer exposures, so that residues are
present in the egg yolk, is also likely to cause significant adverse effects
at lower test xxxicentrations in water. However, additional-testing to identify
no effect levels or MATCs may present a problem in measuring exposure concen-
trations, because the limit of detection for chloroparaffins is about 1 ug/1.
-Table 5 lists the predicted chloroparaffin residue levels in aquatic
organisms from the Schuykill River. Bioconcentration and biomagnification of
chloroparaf fin residues from water-only exposure %«ould range fron 0.03 ug/g in
water column species to 30.7 ug/g in predators upon benthic species. Maximum
residue levels in biota predicted by Versar Inc. was similar (33 ug/g). These
residue levels .are considerably less than the 166 ppn no effect level seen an
the mallard reproduction study. Consequently, nor direct effects en avian
reproduction are anticipated from chloroparaff in residues released at this
site. Population reductions may affect the availability of food for aquatic
birds, especially wading birds which feed en benthic species. ^
, Based upon the BCF value of 36,OOOX for rainbow trout, the chloroparaf fin
levels -that bioconcentrated directly from the water in planktonic and nektonic
species, would range~ from 0.94 - 1,8 ug/g. These ^species would include mostly
planktonic unicellular and small colonial algae and other non-swutming organ-
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27
isms, and nektonic species like daphnids and rotifers and filter-feeding fishes
such as shiners, alewife, shad, and herring. Biomagnification of "residues in
nektonic primary carnivore's, such as bass and possibly brown trout, would
contain residues-ranging from 1.4 to 2.7 ug/g (based on a 1.5-fold -accumulation
factor derived from residues found in the rainbow trout controls in the BCF
study). Biese residue levels of 1.8 ug/g are, in fact, similar to the chloro-
paraffin contamination levels present in -the food fed rainbow trout in the BCF
study.
Bioccncentration of chloroparaffin in benthic organisms, such as aquatic
• insect larvae of chironomid midges, mayflies, and stoneflies, clans, worms, and
other benthic invertebrate filter feeders and detritus feeders, are estimated
to be between 10,6 ^and 20.5 ug/g Abased on a BCF value of 40,900X for missels).
Benthic carnivores* such as sunfishes, catfish, bullheads, goldfish, carp,
minnows, and suckers, feeding on these benthic species would be expected to
accumulate residue levels of 16.0 to 30.7 ug/g.
Monitoring data from a manufacturing site on the Grand River in Ohio,
s
indicated some possibly adverse effects on aquatic insect larvae at similar
chlorparaffin concentrations measured in the water at Site I tJownstream from
the release point (Ramm, 1977). Possible adverse effects were indicated by the
authors in their observation that, "The abundance of insect larvae, especially
in the lower river, was relatively low compared to that in other similar rivers
we have investigated.* Verification of this reduction due to chloroparaffin
levels is not possible since no sediment toxicity data are available from
which chronic toxicity to benthic organisms can be correlated to chloroparaffin
residue levels in the sediments. Measured residue levels in sediments (3.1 —
12.6 ppst) and benthic chironomid larvae ^nd worms (7.29 ppm) were about 10-fold
higher than predicted for'that water concentration in Table 5. Barely detect-
able levels of chloroparaff ins found in some .fish tissues may simply indicate
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28
-±hat the sampled fish are recent immigrants and nest-long-term residents. The
absence of measurable residues in fish samples may have been due -to either
chronic ±oxicity and/or reduction in food availability reported as reduced
larval insect populations.
Results from the available chronic studies are too erratic to wake any
predictions on the interactions between species and between trophic levels.
New chronic tests would be needed for daphnia, mysids, and a complete life
cycle study on fish, -in order -to quantify the adverse effects of chloroparaffin
residues at -the exposure levels predicted -for these uncontrolled releases. :No
adverse effects are anticipated on birds or avian reproduction from predicted
.residues in biota at 33 ug/g.
Predicted residue levels from controlled releases .(bottom of Table 5) in
the Schuykill River are lower than any levels which might be expected to cause
adverse chronic effects.
• Predicted chloroparaffin residue levels in -the Schuykill River from
uncontrolled releases are sufficiently low that no acute toxicity effects are
anticipated on any aquatic species and 'these concentrations would not form a
toxic barrier to migration of species through the area. Predicted reside
levels in the water approach the lower end of test levels producing adverse
chronic effects in several test species, therefore adverse effects might -be
expected in sensitive aquatic species. Monitoring data-from the Grand River
with chloroparaff in concentrations in sediments similar to predicted levels in
the Schuykill River indicated reduced larval insect populations. Since labor-
atory tests indicate that the insect larvae are not the most sensitive species
to chloroparaff ins, population reductions may be anticipated on other benthic
organisms. Population reductions in these insect larvae and other important
bentMc organisms might be -expected :to affect the availability of food for many
aquatic species occupying higher trophic-levels, including important sport
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29
fish species,-ducks, and wading birds such as herons.
- 2. Sugar Creek, Ohio
Chloroparaffin residue levels in Sugar Creek, Ohio exceeded adverse effect
levels in the aquatic segments of the creek both above and below -the confluence
with the Toscarawas River. The mean stream flow rates in the two segments of
the creek were 330 cfs in the first segment and 1740 cfs in the second segment
below the confluence. The predicted water concentrations of 0,4-to 4.1 ug/1
' are too low to produce any acute toxicity according to available data and as
such would not be expected to act as a toxic barrier to movement of aquatic
organisms through the contaminated segments.
Chronic effects, however, would be expected in some of the more sensitive
aquatic invertebrates and fish from these residue concentrations in water in
both segments of the river. Below the confluence with the Tuscarawas River
the residue levels are" similar -to estimated concentrations in -the Schuykill
River in Pennsylvania. Since the fauna would be similar in the two areas,
chronic effects similar to those predicted, for the Schuykill River would be
expected.
Since estimated Chloroparaffin residues in water (4.1 ug/1) in the segment
above the confluence are clearly greater than measured test concentrations
causing chronic effects -in several test species, adverse chronic effects would
be expected on aquatic organisms. ~Ihe reported .adverse effects below 4.1 ug/1
include mysid shrimp mortality and a 20.8 percent reduction in the -number of
mysid young, 43.6 percent reduction in young daphnids and young daphnids per
female, 50 percent mortality in rainbow trout, and increased growth in both
rainbow trout and sheepshead minnow.- 3he 4.1 ug/1 estimate also correlates
well with the 3 ppm measured concentration at Site II, the discharge point from
a manufacturing *site on the Grand River-anTfiio. ^Adverse effects tioted "during
the sampling period Included reduced larval insect populations, in fact, the
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30
only aquatic invertebrates sampled were a crayfish (normally a relatively
insensitive species) and chironoraids. Organisms in -the other sampling sites
variously also'included clans, snails, tadpoles, and worms.
Table 6 lists the estimated chloroparaff in residue levels in aquatic
organisms from Sugar Creek. Bioconcentration and bioroagnification of chloro-
paraff in residues in the upper segment from water-only exposure would range
from 7.56 - 14.8 ug/g in water column species to 128.6 - 251.5 ug/g in
carnivores upon benthic species. Maximum residue level in biota predicted by
•\fersar Inc. vas similar (274 ug/g). These residue levels are slightly higher
than the 166 ppn no effect level seen in the mallard reproduction study, but
- considerably less than than the chronic level of 1000 ppm causing eggshell
thinning and embryo viability in mallard ducks. Consequently, adverse chronic
effects on avian reproduction might be possible from chloroparaffin residues
released at this site -for fcirds feeding on predators upon benthic organisms
and, possibly but not likely, for birds feeding directly on benthic species.
Based upon the BCF for rainbow trout (36,OOOX), the chloroparaff in residue
levels that bioconcentrated directly fron the water in planktonic and Jiektonic
species, would range from 7.6 to 14.8 ug/g. These species would include mostly
planktonic unicellular and small colonial algae and other non-swimming organ-
isms, and nektonic species such as small mobile crustaceans like daphnids and
rotifers and filter-feeding fishes such as shiners, alewife, shad, and herring.
Biomagnification of residues in nektonic primary carnivores, such as bass
and possibly brown trout, would contain residues ranging from 11.3 to 22.1 ug/g.
These residue levels are equal to or greater than residues levels measured in
rainbow trout'BCF study when 50 to 100 percent mortality occurred during
depuration.
Bioconcentration of chloroparaffin in benthic organisms, such -as aquatic
;-insect larvae of chironomid midges, mayflies, and stoneflies, clams, worms, and
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31
other benthic invertebrate filter feeders and detritus feeders, are estimated
to be between 85.9 and.167.7. ug/g. In fact, the residue levels measured an
. chironcnud larvae at the discharge point *ere 93.4 ppro. Benthic carnivores,
such as sunfishes, 'catfish, bullheads, goldfish, carp,-rockbass, white bass, .
minnows, and suckers, feeding en these benthic species would be expected to
accumulate residue levels of 130 to 250 ug/g. ~The hardly detectable residues
in seme fish species of this trophic level cause one to question whether the
sampled fish were residents or whether any resident fish could survive chronic
exposure. All of the bioconcentraticn tests conducted en fish indicate accumu-
lation of chloroparaffins from either water or dietary exposures.
Predicted chloroparaffin residue levels in Sugar Creek from uncontrolled
*.:„ releases are sufficiently .low that no acute toxicity effects are anticipated on
- any aquatic species and these concentrations vould not form a toxic barrier to
migration of species through the area. Predicted residue levels an the water
exceed the lower end of test levels producing adverse chronic effects in several
test species, therefore adverse effects might also be expected in sensitive
,aquatic species =SUCK as fish, daphnids, and small crustaceans. .Monitoring data
from a manufacturing site on the Grand River in Ohio, indicated adverse effects
on some aquatic insect larvae at similar chlorparaffin concentrations measured
in the water at Site II adjacent to the release point iRamm, 1977). Population
losses -in sensitive species will reduce the availability of food to aquatic
species In higher trophic levels, including aquatic birds such as ducks and
wading birds. In addition, avian reproduction might be affected by feeding
on aquatic organisms* since the chloroparaf fin residues in the food web are
predicted to be higher than the chronic no effect level.
While insufficient
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32
Results iron sediment toxicity tests would most likely also indicate adverse
effects on reproduction and settling capability in freshwater clans and other
benthic species. Sediment toxicity results might also explain the-absence of
-clams in the sampling' at Site II in the Grand River.
Controlled releases into "Sugar Creek might be expected to cause chronic
adverse effects on aquatic species. While chloroparaff in levels -in ±he water
column are not likely to impact'organisms, sediment levels of 130 ppb may
reduce populations of benthic species and affect the availability of food for
*ll other aquatic species.
3. " Houston Ship Channel/Galveston Bay, Texas
The Houston Ship Channel enters the northwestern part of Galveston Bay
near the mouth of the'San Jacinto River (Figure 2). The shipping channel then
turns south along sane islands that partially separate it from a series of
interconnecting embayments to the east. These bays from north to south are
Burnet, Scott, Tabbs, and the tipper San Jacinto Bays. TitJal flow and water
circulation in these estuarine areas are such that while chloroparaffin
residues are greatest in the channel itself* the .residues are also spread into
these highly productive, estuarine embayments.
The U.S. Department of the Interior, Fish and Wildlife Service (1982) on
,±heir Gulf Coast ecological inventory maps Indicate that the Galveston .Bay area
is a breeding and nursury area for many species of birds, fish, and aquatic
invertebrates. Many of these species are important either as a connercial
fishery or as a sport fishery. The Houston Ship Channel is a nursery area for
such sport and ccramercially-important fish and Crustacea, as sheepshead, drum,
southern flounder, white shrimps-brown shrimp, and blue crabs.' The adjacent
San Jacinto Battleground Historic Park As inhabited by dabbling ducks, red-
* -shouldered hawks, gulls,-terns,'herons, and egrets.
Scott -Bay east -of ±he Houston Ship Channel is indicated as habitat for
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33
herons, egrets', roseate spoonbills, and olivaceous cormorants. Tabbs Bay to
the south is a nursery area for white and brown shrimp, blue crabs, and
commercial -and/or sport fish species including drum, sheepshead, and southern
flounder. -
The shallow shore veas in the upper Calves ton Bay are a vast nursery for
commercially-important white and brown shrinp, blue crabs, and ccnnercial and/
or sport fish species: drum, sheepshead, and southern flounder. The upper
Calves ton Bay area ds -also a breeding area for olivaceous cormorants, the
white-faced ibis (an state endangered species), gulls, terns, herons, egrets,
and a breeding and nursery area for eastern oysters. Other aquatic birds,
like great blue herons, Louisiana herons, snowy egrets,-roseate spoonbills,
and black skiimters, live and breed on the small islands and along the edge of
the upper bay.
Predicted chloroparaffin residue levels in the Houston Ship Channel and
the adjacent estuarine areas approach or exceed the lower limits of -anticipated
effect levels in -at least ten out of the eleven segments modeled by Versar Inc.
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34
no effect levels in the chronic tests.
Table 7 lists predicted chloroparaffin residue levels in aquatic organisms
in the Houston Ship Channel tthe first four segments), -adjacent embayments, and
Galveston Bay. Bioconcentration and biomagnification of chloroparaffin from a
water-only «q?osure are estimated to range fron fl.29 - 5 ug/g in plankton/hekton
species to 4.9 - 85.9 ug/g ia first-level carnivores upon benthic species.
Higher residue levels might be found in second-level carnivores and in other
species near the top of the estuarine food web. The maximum residue level in
biota predicted by Versar Inc. was siinilar (100 ug/g).
Based upon the bioconcentration factor (BCF) for rainbow trout~(36,OOQX)» -
the chloroparaffin residue levels-that bioconcentrate directly from the water
to planktcnic and nek tonic species, would range front 0.29 to 5.0 ug/g. These
species would include mostly planktonic unicellular and small colonial algae,
diatoms, copepods, small shrimp, a multitude x>f larval stages-of crustaceans,
molluscs, polychaetesi fish, etc. that utilize water^currents to distribute
their young, and filter feeding fish such as shad, silversides, menhaden,
sardines, and-anchovies present in Galveston Bay system. Biomagnification of
^
these residues in first-level nektonic carnivores, such as ^acks, would contain
residues .ranging from 0.4 to 7.6 ug/g.
Bioconcentration of chloroparaffin in benthic filter feeders, such as
oysters, mussels, clams, and setae polycheate worms, are estimated to be 3.3 to
57.3 ug/g. Bicmagnification of .residues from these benthic organisms in
predatory molluscs, sheepshead, drums, and stingrays, would range from 4.9 to
85.9 ug/g.
Biomagnification.of sediment residues in benthic fish such as mullet,
^pinfish, and catfish, and .benthic -invertebrates such as detritus feeders,
crabs, shrinp, im/sids, amphipods,' polychaete worms, whelks, and other benthic
invertebrates, are -estimated as t).2 to 2.0 ug/g. Predators upon -these benthic
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35
organisms/ -such as seatrout, spot, croakersf killifish, and flounder, might be
expected to contain 0.3 to 3.0 ug/g.
Monitoring data collected at a manufacturing site on the edge of the
Houston" Ship Channel {Figure 2) reported chloroparaffin residues in-sediments
somewhat-higher-than the 1.3 ug/g predicted levels in the upper segment of the
Houston Sup Channel (Raram, 1978). The residues at Stations H and I in the
channel ranged from 1.5 to €.0 ppn, when corrected for poor analytical recovery.
The highest residue level (50 ppm) occurred at Station D where the discharge
from Patrick Bayou enters the shipping channel. Oat of five water samples, the
only sample found to contain chloroparaff ins was from Station F.
A possible explanation for the lack of correlation between residue levels
in the water and sediment samples and "the location of the various sampling
sites might ±>e flue to increased insolubility of chloroparaffin in saline water.
Solubility levels of organic chemicals are typically lower in saltwater than
-freshwater. Station F, source of-the single ^jositive water sample, was located
in a snail ditch near two outfalls from the manufacturing site and as such
probably discharges freshwater, thereby, being less saline compared ±o-the
other stations located in Patrick Bayou and the shipping channel. The measured
level at Station F was 1.5 ppb, reported to be at the edge of the detection
limit (1.0 ppb). At "the other sampling sites, residue levels in water .below
the detection limit could have been due to reduced solubility due the higher
salinity. Mo data are available that Indicate the difference in solubility
between fresh and saltwater.
Three out of the four stations having the highest chloroparaff in residues
in sediments were located where water salinity were highest. Station D which
had the highest residue level, was located at the point where salinity would
increase dramatically-as the Bayou discharged into the shipping channel.
Stations P and T were located at the higher saline sites in the shipping channel.
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36
High residue levels ^t Station A, the fourth cite, could be attributed to poor
flushing. Station A was located upstream from two outfall points at the manu-
facturing site. Transport of chloroparaffin residues to this site would be
dependent on incoming tidal tsurrents in the bayou -to the sampling site further-
est up the bayou. "The residues would readily sorb to the organics, settle into
the sediments, and persist, because flushing at that station would be.less than
flushing at any sanpling site.
Chloroparaffin residues were also measured in a few biological samples from
five stations.' The sanples included -whole crabs, killifish, and vegetation.
The residue levels in the killifish and crabs ranged from 0.20— 0.42 ppn to
0.10 to 0.52 ppm, respectively. The highest residue levels were found in the
xxabs collected at Station C, the station nearest Station D, which had the
highest residue levels in sediments.- Residue levels in crabs decreased as the
distance of Stations B and J increased from station €„ Of Stations,B and C,
the only sites at which fish were sampled, the highest chloroparaffin residue
levels were found at Station B, the station nearest the two outfall points in
Patrick Bayou. No biological-samples were reported..from the four sampling
-stations with the~highest sediment residue levels. Although no prediction was
made for residue levels in the Patrick Bayou from which to estimate residues in
•"biota, these residue .levels are about 10-fold below residue levels estimated
for the shipping channel (2.0 ug/g). As in the case of the Grand River, low
residue levels in highly mobile species such as these crabs and killifish,
probably indicate that these individuals were not long-term residents in the
area. '
The highest estimated chloroparaffin residue levels, i.e./those in carni-
vores upon benthic species are slightly less than the 166 ppm no effect Jlevel
seen in the mallard reproduction study. Consequently, adverse chronic effects
are unlikely on avian-reproduction, based on these residue estimates. However,
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37
given the fact -that predicted sediment values have been consistently lower than
levels monitored at similar sites by Ramro (1977 and 1978), the model used by
Versar Inc. -may be consistently underestimating releases and/or partition into
sediments.' These sediment predictions would also affect estimates of residues
:dn biota.
In the absence of toxicity data correlating residue levels in sediments to
toxic effects in benthic organisms, it is impossible to assess probable adverse
effects on the nearly 200 benthic raacroinvertebrate gp^ctes listed in Galveston
Bay by Shidler 0960). Holland et al. U973) listed 32 benthic species at
Station 22 alone in -the upper Galveston Bay. Gillard (1974) delineated four
characteristic henthic assemblages in the area of Tabbs Bay and upper Galveston
Bay. - - >
Residue levels predicted in the Houston Ship Channel range from 1,300 ugAg
(ppb) in the upper channel to 950 ug/kg in the lower channel. "These levels-were
less than the "1,500 to 6,000 ppb residues-measured in the upper ship channel.
Residues levels in the upper enbayments and Galveston Bay ranged from 140 to
^40 ug Ag
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38
resuspended' anto the water column on particles ty less sensitive, benthic
organisms like polychaetes turning over sediments as they feed.
The oyster is the most conroercially, and perhaps, ^ecologically-important
benthic organisms to be -found in the Calves ton Bay system. Commercially, the
bay provides 50 to 90 percent of the entire Texas oyster fishery. Besides the
areas open to the public, 658 acres are privately leased as of 1972, the last
year for which data was found. Ecologically* the oyster is Jmportant in the
sedimentation of anorganic particulate matter from the water column and the
reduction of water-turbidity below the critical levels. Water clarity affects
the depth of light penetration into the water and consequently, the amount of
-primary productivity (the base of the food web), by phytoplankton, benthic
algae, and seagrasses. /Turbidity also determines how deep-vegetation such-as
seagrasses can-grow. Oyster reefs and seagrass beds, which are both dependent
on healthy oyster populations, provide the two most important aquatic habitats
in the bay. - The seagrass t>eds are -nursery areas -for many fish species like
young sheepshead, seatrout, southern flounder, red drum, croaker, and kingfish,
shrimp, and many other invertebrates. Galveston Bay .has -the highest conmercial
yields of any Texas bay and often leads an production of brown and white shrimp
and blue crabs. Galveston Bay has the-most heavy fishing pressure of any Texas
bay system and the oyster reefs are prime habitat for many sport fish such as
adult sheepshead, black and red drums, and Atlantic croaker. Oysters are also
important for production of pseudofeces which provide the basis for additional
food chains. .- Sediment toxicity tests are needed before the predicted residue
levels in sediments can be evaluated for adverse effects on benthic species,
including-oyster spat setting andjBurvival.
Of the-349 avian species reported from the Galveston Bay area, .about 120
plus aquatic avian species might be expected to be directly exposed to chloro-
paraffin residues in their food. If chloroparaffins are to affect any avian
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39
species in the Galveston Bay area, those-species roost-likely to be affected
would be benthic feeders such as the roseate -spoonbill, ibises (including the
state-endangered whiter-faced ibis), herons, egrets, "the federally-endangered
wood stork, bitterns, -rails, least curlew, icons sandpipers/ plovers, oyster-
catcher, ducks, grebes, and-mergansers. Upper trophic-level, fish-eating bird
species, like the federally-endangered brown pelican and bald eagle, the white
pelican, and osprey, might also be at risk. .Additional reproduction tests on
other avian test species may indicate If any of these, avian species might be
adversely affected by chloroparaffin releases into the Galveston TJay system.
Current avian reproduction studies do not indicate a margin of safety for the
upper-trophic level birds in the Galveston Bay area based on the predicted
chloroparaffin levels in aquatic biota. • ~
Residue levels fron controlled releases into the Galveston Bay system have
been predicted to range from 0.004 to .0,12 ug/1 in water, -from 10 to 100 ug/kg
in sediments, and from 0.02 to 4.91 ug/g in biota. These residues in water are
sufficiently low that even at the highest level 0.12 ug/1, chronic effects are
£
unknown at this time. The effect of the.residue .levels in sediments and biota
are less certain. Chloroparaffin.residues in rainbow trout measured during
the depuration period were only 0.9 to 3;0 ug/g wet weight, when 50 percent
mortality occurred in the 3 ug/1 test level. While it is possible that residue
levels in biota -may reach lethal levels in sate species and reduce seme popula-
tions under controlled releases, it is doubtful that chloroparaffin residues
would bioaccumulate sufficiently to directly affect avian reproduction.
The potential for adverse effects in the Houston Ship Channel/Galveston
Bay area frcm uncontrolled releases is great. The bay is the most productive
bay system an Texas for commercial oysters, shrimp, and blue crabs. The oyster
reefs and seagrass beds are the-two most important aquatic habitats for young
and adult fish, and both habitats are dependent on healthy oyster populations.
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40
Galveston Bay has the heaviest fishing pressure of-any Texas bay system. The
important sport fish include seatrout, sheepshead, drum, and southern flounder.
"Predicted chloroparaffin .concentrations in water-are sufficiently high that
chronic adverse effects may be anticipated in species such as fish,'zooplarikton,
shrimp,-mussels and oysters. Population reductions in these species will alter
availability of food for many higher trophic-level species, including numerous
aquatic avian species nesting and feeding in the Galvestion Bay system.
Population reductions in oysters would not only affect the commercial
value of the crop, but oyster losses over sane critical limit could alter water
quality in the bay. . Increased turbidity in the water due to oyster losses will
reduce primary productivity, the base of the food web, and reduce the amount of
areas on the bay where -seagrass beds can grow. Deduction in oyster reefs and
seagrass beds would affect the two most important habitat areas in the bay for
young and adult sport fish, conmerically-important shrimp and blue crab.
- Predicted chloroparaffin residues in "the sediments are sufficiently high
to anticipate population reductions m sensitive benthic organisms. Population
losses would affect availability of food to sane species higher in the food
web, including numerous aquatic bird species nesting and feeding in the bay.
unknown are the adverse effect levels of chloroparaffins in sediments on
recruitment ~and larval settling of benthic species. -Predicted residue levels
faioconcentrated and/or bioraagnif ied in biota exceed levels measured in rainbow
trout at a time when 50 percent of the remaining fish died. _The effect of
*
these residue levels on survival or reproduction are unknown for many aquatic
species including fish. Predicted residues from uncontrolled releases approach
-the no effect level for .avian species and leave no margin of safety.
B. Direct Effects
1. Acute "Itacicity
Under the conditions described in the three scenarios, chloroparaffin
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41
releases'are not likely to acutely affect any aquatic manuals, birds, fish, or
other aquatic species.~ Absence of acute toxicity in fish and mamnals appears
to be largely related to relatively low water solubility and low uptake rates.
Consequently, chloroparaffin releases predicted by Versar Inc., are not likely
to form a toxic barrier for migratory species through the contaminated area.
Based on the manmalian acute oral toxicity data and avian dietary levels in
the reproduction test, bioconcentration of chloroparaffin in biota will not
contain an acutely lethal dose. While chloroparaffins are highly acutely toxic
to Crustacea, algae, and zooplankton species, it is doubtful they would pose
an acute -hazard to fish or wildlife.
" 2. Chronic Toxicity
Chloroparaftin testing has indicated high chronic toxicity to several
test species. Six out of the eight test species showed chronic effects below
20 ug/1. No observed effect levels (NOEL's) were below test concentrations in
four of these test species, including the rainbow trout, sheepshead .minnow,
rnysid shrimp, and daphnids. Higher mortality on males than females an the
mysid shrimp test suggested that males are more sensitive to chronic exposures
than females. The cessation of mortality in the daphnid ±est after Day 6
suggests that the difference in mortality between sexes may be due to reduction
in body burdens via deposition 6f chloroparaffins into the yolk of their eggs.
Since male mysids -have no such pathway to dispose of chloroparaffin, residues
continued to increase until lethal levels were-reached. Transfer of residues
to egg yolks has been confirmed by published data showing chloroparaffin
residues in seabird eggs. s
The reproductive effect of chloroparaffins residues deposited in eggs was
tested in chronic tests on daphnids,"mysid shrimp,-chironomids, and-mallard
ducks. -Qratussion of stored residues in eggs in the sheepshead study started
with embryos raises concerns about adverse effects an early fish developmental
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42
stages,. Also given the slow uptake -rate of chloroparaffins, the 26- to 32-day
exposures were not of sufficient duration to measure the full extent of chronic
toxicity.
Chronic exposure ±o the chloroparaffin levels predicted_in the water and
-sediments -at the three scenarios is expected to reduce the species diversity in
the receiving waters of all three sites. Predicted concentrations in water
either exceeded or approached the test concentrations that affected both fish
species, mysid shrimp, and daphnids. Additional tests at lower concentrations
are necessary ~to evaluate the level ~of effect for all four species. Sorption
of chloroparaff ins to sediments at 1,000 to 10,000 -tines the water level,
suggest that sensitive benthic organisms are also likely to be effected.
However, sediment toxicity data are not available ~to correlate residue levels
in sediments with -toxic effects.
Evidence" of population reductions in aquatic organisms was reported in a
monitoring study of -the Grand River that indicated insect larval populations
lower than seen in similar Ohio rivers. It is unclear whether the paucity of
biological samples and species at sampling sites were coincidental with high
residue levels measured in the sediments in the Grand River and Houston Ship
Channel or indicative of areas depopulated by chloroparaffins. Toxic effects
front sediment residues could .be even greater than indicated. Based on measured
-residues that were higher than predicted iniJoth the Grand River and Houston
Ship Channel, it-may be necessary to modify the model used by Versar Inc. to
predict higher chloroparaff in residues in sediments.
3. Bioconcentration *
' Data indicate that chloroparaff ins are Jbioconcentrated from water and are
biomagnifled from one trophic level to another in the food web/ Itesidue levels
in biota exceed the no effect level in the avian study and may pose a risk to
avian reproduction in Sugar Creek area, and possibly the Houston Ship Channel/
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43
Galveston Bay area. "While predicted residue levels in the upper segment of
Sugar Creek exceeded the mallard reprcductaon *JOEL of 166 ppn, ±he residues are
-not close to the 1000 ppro effect level. The importance of the Houston Ship
Channel and-Calveston Ttey to-a wide range of aquatic'birds and four endangered
species might require additional evaluation of data and reconsideration of all
assumptions.
Except "for evaluation of risk to avian reproduction, insufficient toxicity
data are available to correlate toxic effects -from either tissue residues or
dietary levels. Fifty and one hundred percent mortality in the remaining
rainbow trout between Cay 64 and €9 of the depuration period at two test
concentrations, indicates that death may occur long after exposure from water
has ceased and even after a considerable loss of residues, v Jtesidue levels in
rainbow trout sanpled during that period of mortality were lower than residue
levels predicted in fish in all three scenarios. Therefore, predicted residue
levels in fish and other might be expected to have adverse effects, including
death.
C. Indirect Effects
1. Short-term Effects
Chloroparaffin releases predicted by Versar inc. are not expected to cause
any short-term indirect effects.
2. Long-term Effects
indirect advei.se effects from Chloroparaff Ins may be from two general
sources, reduction in the availability of food to higher organisms and loss
of productive habitats. The effect of reduced food availability are obvious
(reduced growth, lower reproductive potential, and possibly malnutrition and
death), but the effects from habitat loss are generally even more devastating.
"The most devastating indirect effect that chloroparaffins could have is
probably the loss of oysters on Galveston Bay. Oyster losses could result in
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44
increased turbidity in water, reduced primary productivity in phytoplankton,
benthic algae, and seagrasses (basis of an extensive food chain in estuaries),
and losses in productive habitats-including the oyster-reefs and seagrasses
beds which are-nursery areas for many juvenile and adult fish, shrimp, and
blue crabs. Without oysters filtering particulate natter out of the water
column below sane critical level, light penetration in the water would be
highly restricted and subsequently, the productive volume of bay would i>e
reduced by the -turbidity. Population reduction in filter feeding species may
also affect water quality such that other species cannot survive.
A second irerjor .indirect effect -from chloroparaffins would be reduction in
benthic faunal diversity as anaerobic conditions in the sediments increase.
the loss of sensitive burrowing benthic organisms from toxic-sediments reduces
the amount of sediment turnover and subsequent oxygenation of the sediments.
VJhen oxyen can -no longer diffuse readily into the pore water, the sediments
become anaerobic as organisms consume the limited amount of oxygen, die and
decompose, the anaerobic level slowly rises toward the surface of the sediments
driving out even the chemically non-sensitive species for lack of oxygen* In
freshwater and estuaries, clams are important both as filter feeders and as
borrowers. Predicted chloroparaf fin levels in sediments may be toxic to clams.
The absence of sampled clams at the Grand River site which had the highest
chloroparaf fin residue levels in sediments may be indicative of toxic effects.
ttule the effects of these two examples may be the most far-reaching, losses
of other populations can have unpredicted effects other than simply the loss of
that species from the ecosystem and/or food chain. '
Disruption of the food web from the loss of chemically-sensitive species
and other species displaced by anaerobic sediments will affect many species in
both freshwater and estuaries. Benthic organisms in the Galveston Ray area
form a large .portion of-the diet of many species of cuiiier daily-important
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45
fish,-as well as toenthic-fceding birds such as roseate spoonbills, and the "v
endangered white-faced ibis and wood stork. -Reduction in fish populations from
either loss of food or chemical-sensitivity will affect other species of fish
and fish-eating birds such as the osprey, herons, egrets, and-the-endangered
bald eagle and brown pelican.
VI, CONCLUSIONS
. About 67 million pounds of chloroparaffins are manufactured per year for a
wide array of uses. Releases -from manufacture and uses are estimated .to be 50
million pounds per year. Chloroparaf fins are persistent in the environment and
widespread contamination is indicated by monitoring in the united Kingdom and
around two manufacturing sites in the U.S.. Chloroparaf fins are relatively
^ insoluble in water and sorb readily to sediment at levels 1,000 to 10,000 tunes
- higher than overlying water. Residues bioconcentrate at levels from 10,000 to
40,000 in aquatic species and can also furhted Monagnify in the food web (1.5-
fold) . Chloroparaf fins have been measured in many benthic tirganisms and benthic
fish species contain higher residue levels than the fish higher in the water
£
column. Residues have been found in seabirds and their eggs; in terrestrial
crops, and in human foodstuffs.
Analysis of uncontrolled chloroparaf fin releases from manufacturing and
use sites in three distinct aquatic areas, the Schuylu.ll River in Pennsylvania,
Sugar Creek in Ohio, and the Houston ship Channel/fcalveston Bay area in Texas,
indicate that chronic toxicity levels are approached or exceeded for several
test species in all three environments. Monitoring studies adjacent to the
Houston Ship Channel and in the Grand River in Ohio indicate .that predicted
residue levels in water, sediments, and benthic biota from releases are real is-
tic, if not too low for sediments.
" Predicted chloroparaf fin levels in all three scenarios are sufficient in
water and sediments that chloroparaffins are expected to have adverse chronic
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46
effects on a wide range of sensitive, local aquatic species. Biological data
reported in the monitoring studies at two manufacturing sites suggested that
population reductions occurred in sane benthic species. Oiironomid larvae were
reported to be less numerous than seen in other comparible rivers in the state.
KnS the absence of biological samples at -the ^our sampling stations in Patrick
Bayou and the Houston Ship Channel where the highest residue levels were found
in sediments could be either a coincidence or. indicative that benthic species
%iere not present. The monitoring study reported only residue levels and gave
no details about biological sampling. Measured residues in the highly motile
species at levels lower -than predicted compared to chironomid data, suggest
that the motile species were not permanent -residents.
Absence of chronic no observed effect~levels 4NOEL) in four-test species
(rainbow trout, sheepshead minnow, daphnia, and mysid shrimp) at concentrations
close to predicted environmental levels suggest that chronic effects will occur
In-each scenario. Much higher residue levels in the sediments suggest that
chronic effects -will also occur in benthic species. The level of these adverse
effects are unknown due to poor -test results an the studies and the absence of
sediment toxicity tests. Comparison of chronic toxicity levels of chironomid
larvae with other test species, suggest that, if the less sensitive, chironomid
population was reduced by these residue levels in sediment, than all other more
sensitive benthic populations would also be affected. Oysters and clams are
two sensitive benthic organisms which can affect the aquatic environment well
beyond simple reduction in food availability like many species. Populations
reductions in oysters could reduce water quality, inhibit primary production
by phytoplankton fthe base of food web), and destroy the two most productive
habitats in Galveston Bay estuary. ± Population reductions-in sediment-burrowing
species .like clans affect sediment porosity and dissolved oxygen penetration
into sediments, which causes sediments to become anaerobic and uninhabitable
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• 47
for most benthic infauna.- flenthic population reductions would affect food
availability for a wide array of aquatic species including wading birds like
.the roseate spoonbill, and the endangered white-faced ibis and wood stork, and
fish-eating birds like the herons, -egrets, osprey, and endangered .bald eagle
and brown pelican in the Galveston Bay area. Predicted residues in Sugar Creek
%»ere sufficiently high to exceed the NOEL for avian reproduction. - Widespread
. utilization of the Galveston Bay area by aquatic t»irds also •warrants close
- scrutiny for possible Atoxic effects. Predicted chloroparaff in levels in the
biota of Galveston Bay indicate no margin of safety for aquatic birds. No
adverse effects are anticipated In migratory species (fish, -birds, or inverte-
brates) which traverse any of the three release sites.
While insufficient data are -available front existing tests to quantify
chloroparaff in effects on fish reproduction, sediment toxicity to benthic
. species or toxic effects on settling of planktonic larvae of benthic species,
monitoring data indicate that predicted residue levels will adversely affect
aquatic species in all three scenarios. Although predicted chloroparaffin
levels may be highest in Sugar Greek, the complexity, sensitivity, and produc-
tivity of the Galveston Bay area make it the most ecologically and economical ly-
-Jmportant of the three scenarios. Chloroparaff in levels measured in rainbow
trout when 50 percent mortality occurred during the depuration period, indicate
that adverse effects can ~be anticipated from predicted residue levels in biota
•at-three sites. Any correlation between internal residue levels and their
effects are uncertain, isecause the mechanism(s) of chloroparaffin toxicity and
metabolically-active site of concern is unknown. ,,
In the absence of predicted environmental releases and residue levels, no
effort has been made here to evaluate the .risk posed by the disposal of chloro-
-paraffms. Monitoring data in United Kingdom indicate that^flhile chlorinated
Tj-paraffin residues are usually highest near manufacturing sites, residues
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48
were found at remote sampling sites. 'The source of these remote residues are
thought to have occurred from disposal. Chronic exposure to these levels
would be expected to adversely affect sensitive species. However, the absence
of measurable residues an the study does not mean adverse chronic effects will
not occur, because the limit of detection in water is too high to adequately
monitor either test concentrations or environmental samples.
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49
VII. REFERENCES
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Gillard, R. M. 1974. Distribution, abundance and species diversity of macro-
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Geyer, H., P. Sheehan, D. Kotzias, 15. Freitag, and F. Korte. 1982. Prediction
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Hildebrecht, C. O. - Biodegradability study on chlorinated waxes." Lab. Hep. No.
50-0405-001. Environlab, Inc., Plainsville, Ohio. 1972.
Holland, J. S., N. J. Maciolek, and C. H. pppenheimer. 1973. Galveston Bay
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Howard, P. H., J. Santodonato, and J; Saxena. Investigation of selected
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Linden, E., B.-E. Bengtsson, O. Evanberg, and G. Sundstrom. 1979. The acute
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water organisms, the bleak (Alburnus alburnus) and the harpacticoid
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Long, J. W. Existing chemical market review on chlorinated paraffins.
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Rabert, «W. S. "."Hazard assessment for chlorinated n-paraff ins: Effects on
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Ramon, A, E. An investigation of chlorowax in the lower Grand River. Final
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mental Resource Associates, Inc., JJetter dated August 15, 1977.
Ramro, A. E. Final report to Mr. Jack Borror, Diamond shamrock Corporation,
concerning the analytical results of chlorowax determinations made on
samples collected in Houston, Texas, between August 8—12, 1977. Environ-
mental Resource Associates, Inc., Letter dated November 21, 1978.
Shidler, J. 1960. Preliminary survey of invertebrate species. Texas Parks and
Wildlife Department. Job Rep. No. MO-l-R-2. 15 p.
Tarkpea, M., E. Linden, B.-E. Bengtsson, A. Larsson, and 0. Svanberg. 1981.
Products control studies at the Brackish Water Toxicology laboratory 1979-
1980. Swedish Environmental Protection Board, Brackish Water Toxicology
Laboratory, Nykoping. Report NBL 111 (in Swedish), p. 45. "In; Svanberg,
O. (ed.). Chlorinated paraffins: A review of. environmental behaviour and
effects. Swedish Environmental Protection Board, Report SNV PM 1614.
U.S. Department of the Interior. 1982. Gulf Coast ecological inventory. U.S.
Dept. Int., Fish Wildl. Serv.,
* j .,
Versar Inc. Prelminary "Exposure Assessment for chlorinated paraffins: Final
report. EPA Contract No. 68-02-3969, Task No. 46. Prepared for Exposure
Evaluation Division, Office of Toxic Substances, U.S. Environmental
Protection Agency, Washington, D.C., August 5, 1985.
Wolfe, L. *,., W. M. Pulich, and J. A. Tucker. 1974. Checklist of the birds of
Texas. Texas Ornithological Society. 128 p.
Zapotosky, J. E., P. C. Brennan, and P. A. Benioff. Environmental fate and
ecological effects of chlorinated paraffins. Argonne National Laboratory,
Div. Environ. Impact Studies. Prepared for Environmental Assessment
Branch, Office of Toxic Substances, U.S. Environmental Protection Agency,
Washington, D. C. , April 1981.
Zitko, ~V. and E. Arsenault. tSilonnated paraffins: Properties, uses, and
polution potential. Fish. Mar. Res. Dev., Tech. Rep. 491. 38 p. 1974.
Zitko, V. and E. Arsenault. Fate of high-molecular weight chlorinated paraffins
in the aquatic environment. 169th Nat. Meet. Aner. Chen. Soc., April 6-11,
1975. - "
-------
Table 1. Acute environmental LC50 values for short (Cio-13> chain-length
chloroparaffins (58% chlorination unless indicated otherwise)
Test Species
Fish:
Bluegill Sunfish
(Lepomis macrochirus)
Channel Catfish
(Ictalurus punctatus)
Tathead Minnow ~
(Pimephales promelas)
Rainbow trout
(Salmo gairdneri)
Bleaks
(Alburnus alburnus)
Witaclor 49 49% Cl
Witaclor 55EN 56% Cl
Witaclor 63 €3% Cl
Chlorparaffin
Huls 70C 70% Cl
Witaclor 71P 71% Cl
Aquatic Invertebrates:
Waterflea
(Daphnia magna)
Duration
(hours)
- 96
- 96
-96
96
96
96
96
96
,96
48
96
Test Concentration
(mg/l)
> 300
> 300
> 100
> 300
> 5,000
>. 10,000
> 5,000
> 10,000
> 5,000
0.046 *
0.018
"Reference **
_ ~
Johnson and Pinley (1980)
Johnson and Finley (1980)
Johnson and Finley (1980)
Johnson and Finley (1980)
-
Linden et al, (1979)
Linden et al. (1979)
Linden et al. (1979)
Linden et al. (1979)
Linden et al. (1979)
Chloroparaffin Consortium
Chloroparaff in Consortium
Mysid Shrutp 96
(Mysidopsis bahia)
Copepod
(Nitocra spinipes)
Witaclor 49 49% Cl 96
'Cereclor 50LV 49% Cl 96
Cereclor 70L 701jCl 96
Chlorparaffin
huls 70C 70% Cl 96
Midge larvae 48
(Chironanus tentans)
Algae;
Marine Diatom 48
(Skeletonema costaturn) -96
Freshwater Green Alga ' 96
(Selenastrum * 168
capricornutum) " 240
< 0.0141 * Chloroparaffur Consortium
0.06 - - Tarkpea et al. (1981)
0.10 Tarkpea et al. (1981)
< 0.3 .Tarkpea et al. (1981)
-< 5 Tarkpea et al. (1981)
> 0.162 Chloroparaffin Consortium
0.0316 Chloroparaffin Consortium
0.0423 Chloroparaffin Consortium
3.69 " Chloroparaffin Consortium
1.55 Chloroparaf fin .Consortium
-1.310 . Chloroparaffin Consortium
* Revised value based on best estunate from raw data.
"** Citations may be found In the Hazard Assessment Document
-------
Table 2. Chronic environmental toxicological effects in order of increasing
•test concentrations.
*
Test Level - Test Species "lexicological Effect
(ug/1)
0.6 Mysid Shrimp 35 % adult mortality (controls 20-27.5%)
(Chronic - 28 days)
1.2 Mysid shrimp t 45 % adult mortality (controls 20-27.5%)
(Chronic - 28 days) 14.7 % reduction in nunber of young
2.1 Daphnia magna no effect
(Semi-static - 14 days)*
"2.3 Common Mussels 2.6 % increase in growth rate of shell
(Growth - 84 days) 7.7 % reduction in growth rate of tissue
(dry weight)
2.35 Ccmnon Mussel 7 % mortality (5 % control mortality)
(BCF - 147 + 98 days)
, 2.4 -Mysid Shrurp * 42.5% adult mortality (controls 20-27.5%)
(Chronic - 28 days) 2.0 % reduction in number of young
2.4 Sheepshead Minnow 3.8 % increase in body weight
Study 1-28 days) * 4." ° increase in body length
2.7 Daphnia magna * 43.6 % reduction in number of offspring
(Chronic - 21 days)t 43.9 % reduction in offspring/female
„ 3.1 teinbow Trout * 50.0 % mortality
- XBCF - 168 +
€4-69 days)
3.4 Rainbow Trout 0.02% increase in body weight
(Growth - 168 days) 0.7 % increase in body length
3.5 Daphnia magna NOEL
(Semi-static - 14 days)
3.8 Mysid Shrimp 32.5 % adult mortality (controls 20-27.5%)
(Chronic - 28 days) 20.8 % reduction in number of young
4.1 Sheepshead Minnow * 14.9 % increase in body weight
(Study 1 - 28 days)* 3.7 % increase in body length
-4.5 Marine Diatom 0.9 % increase in cell density
Skeletonema costatum 0.8 % increase in growth rate
(Acute - 2 days)
5.0 " "Daphnia magna 16.4 % reduction in number of offspring
(Chronic - 21 daysl 13,0 % reduction in offspring/female
9.9 % mortality in offspring
-------
Table 2. (cant.).
Test Level lest Species "Tbxicological Effect
(Study - Exposure)
5.0 -^ Mysid Shrimp , "20 % mortality
-.- - (Acute - 4 days)
6.2 Daphnia magna 6.9 % reduction in young/female
(Semi-static - 14 days)
6.4 Sheepshead Minnow * 31.3 % increase in body weight
(Study 1-26 days)1* 3.5 % Increase in body length
6/7 Skeletonema costatum 5 % - reduction in growth rate
(Acute — 2 days) 2.4 % Increase in cell density
7.1 Mysid Shrimp no mortality
(Acute - 4 days)
7.3 Mysid Shrimp 30 % adult mortality (controls 20-27,5%)
-.(Chronic — 28 days) 27.4 -§ reduction in number of young
^ ' . * ' * 32.6 % reduction an offspring/female
8.9 Daphnia magna * 36.6 % mortality
(Chronic - 21 days) 66.1 % reduction an number of offspring
* 49.9 % .reduction an offspring/female
.9.3 Ccranon Mussel ~ * 52.fi % reduction in growth rate of shell
(Growth - 84 days) "* 53 .R % reduction in growth rate of tissue
(dry weight)
•>
"Daphnia magna r ~* 50.0 % adult mortality
(Semi-static - 78.9 % reduction in number of offspring
14 days) - t 59.8 % reduction in offspring/female
•t t- 29 — 57 % increase in the number of days to
first release of young from brood
10.1 Common Mussel "* 33 % -mortality (5 % control mortality)
(BCF— 91 + 84 days)
12 Daphnia magna * 50.0 % mortality
(Chronic - 21 days)
12.1 Skeletonema costatum 12 % reduction in growth rate
(Acute - 2 days) f 14.3 % reduction in cell density
13 Cannon Mussel " t occasional reduction -in foltration
(Phase 1-60 days) -activity
13.7 Mysid shrimp * 50 % mortality
(Acute - 4 days)
-------
Table 2. (cont.l.
Measured
Test Level
(ug/1)
Test Species
(Study - Exposure)
Toxicological Effect
J4-3 -Bainbow Trout
~(BCF - 168 +
64-69 days)
100 % mortality in remaining population
14,9
16.3
17.2
19.6
22.1
23.8
24.0
31.6
Mysid Shrimp * 40 ^
(Acute - 4 days)
Daphnia magna ' * 100 ?
.. (Chronic - 21 days)
, Tteinbow trout * .25.4 *
(Growth- 168 days) 6.2 *
Skeletonema costatum* 30.0 S
(2 days) * 44 *
Sheepshead Minnow '* .27.5 *
(Study 1-28 days)* 7.2 *
Mysid Shrimp " * 95 3
(Acute - 4 days)
Mysid Shrimp . * 100 1
(Acute - 4 days)
Marine Diatom" * 50 <
Skeletonema costatum
i mortality
t mortality
\ increase in body weight
t increase in body length
t reduction in cell density
t reduction in growth rate
t increase in body weight
t increase in body length
i mortality
i mortality
i reduction in growth (cell count)
(2 days)
33 Hainbow Trout -t 33.3
(Phase I - €0 days)t 37.9
t 34.2
36.2 Sheepshead Minnow * 21.3
(Study 2 --32 days)* 7.4
43.1 Marine Diatom * 47
Skeletonema costatum* 34.2
(2 days)
44 Common Mussel t
(Phase I - 60 days)- ~ .
54.8 Sheepshead Minnow * :"31.°7
4Study 1-28 days)* 6.4
€1 * Midge - larvae ;" 19.3
(Chirononus -tentans) 6^1
(Chronic - 49 days)
% mortality
% -increase in body weight
% increase in -body length
% increase in body weight
% increase in body length
% reduction in rate growth
% reduction in cell density
occasional reduction in filtration
^activity
% increase in body weight
% increase in body length
- 21.7 % reduction in emergence
— 9.4 % reduction in filial eggs/
egg mass
-------
Table 2. (cent.).
Test Level Test Species Ibxicological Effect
(ug/1) (Study - Exposure)
71.0 Sieepshead Minnow "* 15.1 % increase in body weight
(Study 2—32 days)* 5.6 % increase in body length
71 Common Mussel t 50.0 % mortality
(Phase 1-60 days)
78 Midge - larvae * 60.0 * reduction in parent egg hatch
(Chironomus tentans) 16.9 % reduction in emergence
(Chronic — 49 days) 10.5 % reduction in filial eggs/egg mass
: 100 Sainbow Trout -~t. 13.3 % mortality
(Phase 1—60 days)t 13.5 % ancreaso in body weight
~t €.7 % increase in body length
100 Copepod "50 % mortality
_ Nitocra spinipes
(4 days)
110 Green Algae 16 % reduction in cell density
(Selenastrum
capncornatum)
(Acute - 3 days)
121 Midge - larvae * 100 % reduction in emergence
(Chironomus tentans)
(Chronic - 49 days)
130 Demon Mussel X 96 % mortality
(Phase I - ^a days)
161.8 Sheepshead Minnow 13.0 % increase in body weight
(Study 2 - 32-days)* -3.4 % increase in body length
- 162 Midge — larvae ~* _100 - % - reduction on emergence
(Chironomus tentans)
(Acute - 2 days)
220 ' Green Algae "" * 23 % reduction in cell density
(Acute - 3 days)
279.7 Sheepshead Minnow 1.9 % increase in body weight
(Study 2—32 days) 1.9 % increase in body length
350 Rainbow Trout " t 58.6 % /mortality
(Phase I - 60-days) - 3.1 \ decrease in body weight
- JL.9 % decrease in body-length
390 - Green Algae * J.8 - % -reduction in cell density
..(Acute — 4 days)
-------
Table 2. (cent.).
Measured
Test Level
-------
Table 3* Bioconcentration data in order of increasing exposure concentrations
ty species
Test Level " Test Species
(ppb) (Study - Exposure)
BCF Value " Residue Levels (range)
(pern)
Mussel
.2.35
10.1
13
,-44
71
130
Fish
3.1
14.3
.33
100
350
1,070
3,050
•o. JIIBIL i_ L •_• LI i « 1 m rtrtf\ " "i "^^ t ^i* ^ o^ \
UUtiiuun Mussel 40,900 . . 122 (7o-lB7j
{BCF - 147 days)
Cannon Mussel "24,800 ~ 249 (144-365)
(BCF - 91 days)
Cannon Mussel 25,292 329
(Phase 1-60 days)
Cannon Mussel * 16,427 723
(Phase 1-60 days)
Cannon Mussel 5,785 411
(Phase 1-60 days)
Cannon Mussel '12,177 1,583
(Phase 1-60 days)
Rainbow Trout 3,600 JJ.O (8.3-15.6)
. (BCF - 168 days
Rainbow Trout ' 3,300 75.2 (62.6-87.3)
(BCF— 168 days)
Rainbow -trout "7,155 "236
(Phase 1-60 days)
Rainbow trout ' 7,816 782
(Phase 1-60 days)
Rainbow trout 3,723 1,303
' (Phase 1-60 days)
.Rainbow trout .2,642 .2,827
(Phase 1-60 days)
Rainbow trout - 1*173 3,577
(Phase 1-60 days)
-------
Table 4. Comparison of 10-day bioconoentration estimates for four aquatic
species
~3test "Species
Test Level* ~B£F Value Residue Level-
istuoy — Exposure; IPPDJ (Km;
Marine Diatom
Skeletonema costatum
(Acute - 10 days)
-
Freshwater Green Alga
Selenastrum capncomutum
(Acute - 10 days)
Common Mussel
(Mytilus edulis)
(BCF- 10 day est.)
Rainbow Trout
(Salmo gairdneri )
(BCF - 7 and 10 days)
1,4
2.5
6.6
6.8
12.1
^17.8
35
:*2
79
100
150
140
2.35
10.1
3.1
14.3
£_1.1 < 0.0016
~~
< 1 - < 0.0025
- - 2.4 0.0224
5.5 . O.0372
4.0 0.0479
3.5 0.0622
1.5 . 0.051
1.9 0.118
3.2 0.251
4.1 0.410
-4.7 07710
7.6 1.060
ril,915- . -28 (24-32)
-
10r099 102 (87-117)
1,500 . 4.65 (3.4-5.9)
1,654 '23.65(19.2-28.1)
* -Water concentrations used -to conpute the BCF value in algae were measured
- -concentrations on Day 10 (the same day residues in -the algae were measured)
-------
Table 5. Chlorpparaf f in residue levels (ug/g) in ±>iota due to bioconcentration
and biomagnification in the Schuykill River near Conchohocken, Pa.
Source of Bioconcentration (BCF) " Biomagnification
- Exposure Plankton Filter U.5X BCF or PEC)
& Nekton Feeders Detritus First-level- "Benthic
(3,600X) (40,900X) Feeders Planktivores Carnivores
Hater
Dissolved Cug/1)
0.26 0.94 10.« - 1«4 16.0
Total (ug/1)
0.50
1.8
20.5
2.7
30.7
Sediment 1ugAg)
440 1,600*
18,000*
0.66
Controlled Releases
Water
Dissolved (ug/1)
0.009
0.003
.0.04
0.005
0.06
Ttotal (ug/1)
0.02
0.07
0.82
0.11
1.2
Sediment (ugAg)
20
72*
0.03
* No known biological component for residue level.
-------
Table 6. Oiloroparaffm residue levels (ug/g) in biota due to bioconcentration
- and biomagnification in Sugar Creek near Dover, Ohio
Source of
Exposure
Bioconcentration (BCF)
Plankton Filter
& Nekton Feeders
(3t600X) (40,900X)
Bicroagnification
(1.5X BCF or TEC)
Detritus First-level " Benthic
Feeders Planktivores Carnivores
Uncontrolled Releases
Water
Dissolved (ug/1)
2.1
Total (ug/g)
4.1
0.7
Sediment (ugAg)
3,600 _13
600 2
Controlled Releases
Water
Dissolved (ug/1)
0.07
0.01
Ibtal (ug/1)
0.14
0.03
Sediment (ugAg)
130
20
7.56
1,44
14.8
2.5
,000*
,200*
=
0.25
0.04
0.52
0.11
468*
72*
85.9
16.4
1 167.7
28.6
.147,200*
24,500*
2.9
0.41
5.7
1.2
-5r320*
820*
-. 11.3 128.8
2.2 24.5
-22.1 251.5
^X8 42.9
-5.4
0.9
0.38 4.3
0.05 0.6
0.79 8.6
0.16 1.8
0.20
0.03
No known biological component for residue level.
-------
Table 7. Residue estimates (ug/g) in biota due to bioconcentration and biomag-
nification in the Houston Ship ChanneI/Galveston Bay .area* Texas from
uncontrolled chloroparaffin releases
'?- Source of
Exposure
Water
Bioconcentration (BCF) Bicnagnification
Plankton . Filter U.5X BCF or PEC)
& Nekton " Feeders Detritus First-level Benthic
(3,600X) (40,900X) Feeders Planktivores Carnivores
Dissolved (ug/1)
0,76
0.67
0.60
0.56
~ 0.35
0.51
0.39
0.33
0.26
0.24
€.08
Total (ug/1)
1.4
1.3
1.2
-. 1.1
1.0
1.0
0.8
0.6
0.5
0.4
0.2
Sediment (ugAg)
1,300
1,200
1,000
950
940
870
700
570
450
420
140
2.7
2.4
2.2
2.0
2.0
1.8
1.4
1.2
0.9
0.9
0.3
5.0
-4.7
4.3
4.0
3.6
3.6
2,9
2.2
1.8
1.4
0.7
4,680*
4,320*
3,600*
3,420*
3,380*
3,130*
2,520*
2,050*
1,620*
1,510*
500*
31.1
^7.4
24.5
22.9
22.5
20.9
. 16.0
13.5
*- 10.4
.'- 9.8
3.3
57,3
53.2
49.1
45.0
40.9
*- 40.9
~ 32.7
24.5
20.5
16.4
8.2
53,200*
49,100*
40,900*
38,900*
38,450*
35,600*
. 28,600*
V 23,300*
- ' 18,400*
17,200*
5,730*
"4.1
3.6
3.2
3.0
' 3.0
2.8
2.1
, 1.8
1.4
1.3
0.43
7.6
"7.0
-6.5
5.9
5.4
5.4
4.3
3.2
2.7
2.2
1.1
2.0
1.8
1.5
1.4
1.4
1.3
1.1
0.9
0.7
0.6
0.2
46.6
- 41.1
36.8
34.4
33.7
31.3
23.9
20.2
16.0
14.7
4.9
85.9
79.8
73.6
67.5
61.4
61.4
49.1
36.8
30.7
24.5
12.3
3.0
2.8
2.3
2.1
2.1
2.0
1.7
1.4
U.l
1.0
.0.3
JJo known biological conponent for residue level.
-------
Table 8. "Residue estimates {ug/g) in biota due to bioconcentration and bicmag-
nification in the Houston Ship Channel/Galveston Bay area, Ttexas from
controlled chloroparaffin releases
Source of
Exposure
Water
Dissolved (ug/1)
0.06
0.03
0.03
0.02
0.02
0.02
0.02
0.01
0.01
fl.Ol
0.004
Total (ug/1)
0.12
0.06
0.05
0.05
0.05
0.04
0.03
0.03
0.02
0.02
'0.007
Sediment (ugAg)
100
50
_ 50
40
40
40
30
30
-20
20
10
Bioconcentration (BCF) Bionagnification
. Plankton Filter (1.5X BCF or PEC)
' & Nekton Feeders Detritus First-level Benthic
(3,600X) (40,900X) Feeders Planktivores Carnivores
0.22
0.11
0.11
0.07
0.07
0.01
0.07
0.04
0.04
0.04
0.01
0.43
0^22
0.1B
n.is
0.18
0.14
J).ll
0.11
0.07
0.07
0.03
360*
180*
180*
144*
144*
144*
108*
" 108*
-72*
-72*
36*
2.4
1.2
1.2
0.82
0.82
0.82
0.82
0.41
0.41
0.41
-' 0.16
-4.91
2.45
2.0^
2.05
2.05
1.64
1.2
1.2
0.82
0.82
0.28
4,090*
2,040*
2,040*
1,640*
1,640*
1,640*
1,230*
1,230*
820*
820*
410*
0.32
0.16
0.16
- o.ii
0.11
0.11
o.u
0.05
, . 0.05
0.05
0.02
0.77
0.32
0.27
0.27
0.27
0.22
0.16
0.16
0.11
0.11
0.04
~0.2
-Q.OB
0.08
0.06
0.06
0.06 "
0.04
0.04
0.03
0.03
0.02
3.7
1.8
-1.8
1.2
1.2
. 1.2
1.2
0.6
0.6
0.6
0.02
7.4
3.7
1.1
3.1
- 3.1
0.2
1.8
1.8
1.2
1.2
0.4
No known .biological ccrponent for residue level.
-------
fir-i&VfTr:•"•>'. ..-•
m
•4-1
0)
en ro
Sm
Q
r-t
•P u
2 §1
e
lu
5
U-i
O
8
U-i
O 4J
*t t•?»«. ,r t
-------
-DIT7ALL
DIAMOND SHAMROCK
PMPBCJY
«
Figure 2. Map of sampling stations at Diamond Shamrock Manufacturing Plant
on Patrick Bayou adjacent to the Houston Ship Channel in Texas.
-------
•1. Mi M Mil
HI lit IHi
4 MI j
(tn ttn mi ntt My MM
fctat M •MM** ItMnf
MI tin m mi ntt IM m
iltif »M.«iMlfc* IMbt
f
H(^ \*HM MM m», MM
-------
Figure 3. ~-
-------
APPFNDIX A. Chloroparaffin residue levels in the Schuykill River near
Conchohocken, Pennsylvannia predicted by Versar Inc. (1985) based on
uncontrolled and controlled release estimates.
Predicted Chlorowax 500-C Residue Levels
Segment Location
Water _1,344
System self-purification time is roughly 27 months.
Controlled Residues
Below Discharge Point 0.000001 0.002 0.0005
System self-purification time is roughly .27 months.
0.3
-------
APPENDIX A (cant.). Chloroparaffin residue levels in Sugar Creek near Dover,
Ohio predicted by Versar Inc. (1985) based on uncontrolled and
controlled release estimates.
' Predicted Chlorowax 500-C .Residue Levels
Sequent Location
Uncontrolled Releases
Discharge Point
Below Confluence
Water (ug/1)
Dissolved Total
2.1 4.1
- 0.4 0.7
Pediment (ppm)
•total
3.6
0.6
- ~Biota <
(pptn)
274
49
System self-purification tune J.s roughly 4 months.
Controlled Releases
Discharge Point 0.07 . 0.14 " 0.13 10
Below Confluence 0.01 ~ 0.03 0.02 ,1.7
System self—purification tune is roughly 4 months.
Predicted Chlorowax 70 Residue Levels
* '
Segment 'Location
Uncontrolled Residues
Discharge Point
Below Confluence
- Water (ug/1)
Dissolved Total
0.06 7b
D.01 14
Sediment (ppm)
Total
20.5
3.9
Biota
(ppm)
10,550
2,003
System self-purification tune is roughly.18 months.
Controlled Residues
*
Below Discharge Point ~0.00001 0.015 0.004 2.1
Below Confluence 0.000002 0.003 0.0008 0.4
System self-purification time as roughly ISanonths.
-------
1SPPENDIX A (cent.). ~Chloroparaffin residue levels in the Houston Ship Channel/
Galveston Bay area, Texas predicted by Versar Jnc. (1985) based on
' uncontrolled release estimates.
Segment location
Predicted Chlorowax 500-C Residue Xevels
Water (ug/1) Sediment (ppro)
Dissolved • Total Total
Biota
(ppn)
Uncontrolled Releases
Houston Ship Channel 0."76
(west of mouth of
San Jacinto River)
Houston Ship Channel
(west of Scott Bay)
Houston Ship Channel
(west between Scott
Bay and Tabbs Bay)
Houston Ship Channel '0.56
(between Tabbs Bay
. and Morgans Point)
1.4
1.3
1.1
0.95
Upper most part of the 0.006
Houston Ship Channel
San Jacinto River
and Galveston .Bay
Lower Houston Ship
Channel and other areas
100
D.67
0.60
1.3
-1.2
1.2
1.0
87
"78
72
Barbours Cut
San Jacinto River
Scott Bay
Tabbs Bay
Galveston Bay
Upper San Jacinto Bay
Bumet Bay
System self-purification
Uncontrolled Releases
0.55
0.39
0.51
0.33
0.26
0.24
0.08
tine
1.0
0.8
1.0
0.6
0.5
0.4
0.2
is roughly .28 months
Predict^ Chlorowax 70
0.94
0.68
O.R7
0.57
0.45
0.42
0.14
Residue Levels
71
51
66
43
34
32
10
8.7 2.4 Ir233
^
0.003 - , . 3.8-4,0 1.1 545-571
0.006 ~7.4-~7.5 .' 2.1 _-lf065-lf074
Syston self-purafication tune as roughly 74 months.
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APPENDIX A (cent.). Thloroparaffin residue levels In the Houston Ship Channel/
Galveston Bay area, Texas predicted by Versar Inc. (1985) based on
controlled release estimates.
Segnent Location
Predicted Chlorowax 300-C Residue Levels
Water (ug/1) Pediment (ppm) Biota
Dissolved Total Total , - (pan)
Controlled Releases
Houston Ship Channel
(west of mouth of
San Jacinto River)
Houston Ship Channel
(west of Scott Bay)
Houston Ship Channel
(between Scott Bay
and Tabbs Bay)
Houston Ship Channel
(between Tabbs Bay
and Morgans Point)
Harbours Cut
San Jacinto River
Scott Bay
Tabbs Bay
Galveston Bay
Upper San Jacinto Bay
Buznet Bay
0.06
0.02
0.12
0.05
0.10
0,04
8.0
0.03
D.03
0.06
0.05
0.05
0.05
3.9
3.5
3.2
0.02
D.02
0.02
0.01
0.01
0.01
0.004
0.05
0,03
0.04
0.03
0,02
0.02
0.007
0.04
- 0.03
0.04
0.03
0.02
0.02
0.01
3.7
2.0
2.9
1.9
1.5
1.4
0.5
purification tine is roughly 20 months.
Houston Ship Channel
San Jacinto River
and Galveston Bay
Lower Houston Ship
Channel and other areas
0.000002
0.0000006
0.000001
0.003
0.0007-8
O.D001
0.0008
^
,0.0002
,0.0004
0.4
0.1
0.2
System self-purification tune is roughly 53 months.
-------
APPENDIX ft. Results o£ Phase II testing of 58 % Chlorinated Short-Chain Length
additional species.
H-Paraffins on
Test Species
Test Type
LC50
Overall MATC
MATC MATC
Hatchability Survival
(percent) (percent)
MATC
% Growth Rate1
Length Weight
Sheepshead Minnow
Cyprinodon variegatud
Bnbryo-ldrvae
(Study « 1)
(Study * 2)
> 2.4 < 4.1-55 ugA > 55 UgA > 55 ug/1 > 2.4 - > 2.4
(increased growth) (77-95) (68-90, 53 ug/1 <4.1-55 Ug/1
., 88 -100) (4 -7 % (14 - 31 *
r increase) increase)
< 36-71 < 162 ug/1
(increased growth)
, > 280 < 620 ug/1
(reduced growth)
> 620 ug/i > 62rt Ug/1 < 36- 71 < 36- 71
(80 - 95) (65.8- 90.7, < 162 Ug/1 < 162 ug/1
75.8-100) (5 - 7 % (15 - 21 %
increase) increase)
> 280 - . > 280 -»
, . < 620 Ug/1 < 620 ug/1
(9 % red.) (31% red.)
Waterflea
Daphnia tnagna
Lite-cycle 530 ug/1*
46 ppb
(48-hr EC50)
12 ug/1* s o.-» ug
> 8.9 < 16.3 ug/1 (66 * red. in
(6-21 day EC50) total reprod.)
•'" < 2.7 ug/1* < 2.1 ug/1*
(reduced young (44 % red.
per female) offspring
< 8.9 ugA* /female)
• - *
i
Mysid Shrimp Life-cycle
Mysidopsia bahia
Midge Life-cycle
Chironcmus tentans
14.1 ug/1*
< 14.1 ug/1
(96-hr LC50)
> 16? ug/1
(4B-hr TC50
no deaths)
> 7.3 < 13.7 ug/1* > 5.0 -
> 0.6 < 1.2 ug/1 < 7.3 ugA
(sign, parental
mortality)
(33 % red,
offspring
/female)
> 60 < 78 ug/1
(red. hatching)
> 60 -
< 78 ug/1
(60 * red.
hatching)
> 5.0 - > 8.4 ug/1*
< 8.9 ug/1* (1 * red.)
(37 I dead
offspring
not sign.)
> 0.6 - > 7.3 ug/1 > 7,3 ug/1
< 1.2 ug/1 ( I % ( 0.4 % -
(40-50 % increase) reduction)
parental
deaths) '
>,78 - < 78 ug/1 < 78 ug/1
< 121 ug/1 (10 % (1 %
(no red. in red. In
emergence) eggs/mass) hatch)
Data value cart hot he used with confidence.
-------
APPENDIX B (cont.)
fesk Species
Type
LC50
MATC
: 1,310 ug/1*
>,1,200 ug/1
(10-day ECSO)
Cell Growth
(particle count)
Green Algd Acute
Selenastnjm <•'
capricornatum
'3,690 Ug/i*
y 1,200 ug/1
(96-hr EC50)
> 390 < 570 ug/i
(35 % reduction
in growth)
> 390 < 570 ug/1
(35 % reduction
in cell growth)
Marine Alga
Skeletonewa
costatun
Acute
il.fi ug/1
(48-hr EC50)
,42.3 ug/1
(96-hr BC50)
j
> 69.fi ug/i
(10-day FC50)
> 12. 1 < 19.6 ug/1
1 (44 % reduction
in growth on Day ?)
> 19.6 < 43.1 ugA
(Day 4 - 34 * red.)
>, 69. B
(Day 10 - ho sign.)
> 12.1 < 19.6 ug/1
(44 % reduction
in growth on Day 2)
> 19.6 < 43.1 ug/i
(Day 4 - 34 % red.)
> 69.8 Ug/i
(Day ib - no sign.)
* Data can not be used with confidence.
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