EPA 430/9-75-019
ENVIRONMENTAL EFFECTS
OF SCHUYLKILL OIL SPILL II
(June 1972)
\s>
'3 U.S. ENVIRONMENTAL PROTECTION AGENCY
3 OFFICE OF WATER PROGRAM OPERATIONS
WASHINGTON, D.C. 20460
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EPA - 430/9-75-019
ENVIRONMENTAL EFFECTS OF SCHUYLKILL OIL SPILL II
June 1972
By
Division of Oil and Special Materials Control
Office of Water Program Operations
U.S. Environmental Protection Agency
Washington, B.C. 20460
December 1975
Under Contract
68-01-0781
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FOREWORD
Since 1971, the Environmental Protection Agency has supported a
program for studying the effects of oil pollution under special contractual
arrangements providing for a multi-disciplinary, fast response, field
survey team. This study was activated under such an agreement to
investigate the impact of a spill of six to eight million gallons of
sludge from ruptured dikes at a waste crankcase oil re-refinery plant
in the aftermath of Hurricane Agnes. The main section of this report
is devoted to detailed chemical and biological data on the distribution
and occurrence of hydrocarbon residues and heavy metals in the aquatic
environment. In the section entitled recommendations, the report
suggests use of cleanup techniques that are least damaging to vegetation,
and what corrective measures can be taken to prevent erosion.
Results from this and similar studies are intended to provide a better
understanding of the multiple pathways oil can follow when discharged
into the aquatic ecosystem. Furthermore, such investigations will
assist in the formulation of regulations, policies and procedures that
are most effective in the removal of oil from water.
This report is intended for use by government, industry, and other
interested parties. I want to'express my sincere thanks and appreciation
for all who participated in the successful completion of this project.
H. D. Van Cleave
Chief, Spill Prevention & Control Branch
Oil & Special Materials Control Division
Office of Water Program Operations
Washington, .D. C. 20460
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NOTICE
This report has been reviewed by the Oil and Special Materials
Control Division, EPA, and approved for publication. Approval does
not signify that the contents necessarily reflect the views and policies
of the Environmental Protection Agency, nor does mention of trade
names or commercial products constitute endorsement or recommenda
tion for use.
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ABSTRACT
The fate and effects of a spill of six to eight million gallons of
waste crankcase oil rerefined sludge into the Schuylkill River, Pa. ,
in June of 1972 have been studied. The spilled oil contained high con-
centrations of heavy metals and aliphatic and aromatic hydrocarbons.
The spill occurred during a flood, and riverbank trees were coated
with oil. Levels of lead were higher in downstream trees; however,
no direct permanent effects were noted. Levels of heavy metals in
river waters remained below those set by the U. S. Public Health
Service for drinking water supplies; however, higher concentrations
of lead and zinc were observed downstream.
Levels of lead in sediments were higher downstream. Concen-
trations of petroleum hydrocarbons in sediments were higher at down-
stream stations. Concentrations of lead in downstream benthic
macrofauna were higher. Immediately downstream from the spill,
there was evidence of environmental degradation not observed upstream
or further downstream.
Recommendations for handling of similar spills have been
formulated.
11
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TABLE OF CONTENTS
Page
SUMMARY 1
CONCLUSIONS 4
RECOMMENDATIONS 5
INTRODUCTION 6
MATERIALS AND METHODS 12
1. Description of Sampling Stations 12
2. Analyses of Vegetation 15
3. Physical and Chemical Analyses of River Water 15
4. Heavy Metals Analyses 15
5. Petroleum Hydrocarbon Analyses 18
6. Biological Analyses of River Biota 24
7. Observations of Shore Cleanup Impact and 27
Effectiveness
RESULTS AND DISCUSSION 28
1. Properties of Spilled Crankcase Oil Waste 28
2. Effects of the Oil Spill on Vegetation 28
3. Physical and Chemical Parameters of Schuyl- 41
kill River Water
4. Concentrations of Metals in Schuylkill River 42
Water
5. Heavy Metals in Sediments 42
6. Petroleum Hydrocarbons in Schuylkill River 46
Sediments
7. Heavy Metals in Benthic Macrofauna and Fishes 46
8. Petroleum Hydrocarbons in Fishes 48
9. Other Effects of the Oil Spill on River Biota 94
10. Cleanup Impact and Effectiveness 101
ACKNOWLEDGEMENTS 106
REFERENCES 107
111
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TABLE OF CONTENTS
(Continued)
GLOSSARY
APPENDICES
IV
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LIST OF FIGURES
FIGURE
NUMBER TITLE PAGE
1 M ap of Schuylkill River Area 8
2 Monocacy Sampling Stations 9
3 Douglassville Sampling Stations 10
4 Parker Ford Sampling Stations 11
5 Extensively Oiled Riverbank Vegetation 31
6 Oil-Coated Riverbank Vegetation Along the 32
Banks of the Schuylkill River in July, 1972
7 Oil-Coated Ornamental Evergreens 10 Days 34
After the Oil Spill
8 Oiled Evergreens 1 Year After the Oil Spill 35
9 Cross-Section of Oiled Oak Bark Magnified 37
613X
10 Concentrations of Lead in Schuylkill River 43
Water from 3 July to 4 August 1972
11 Concentrations of Lead, Zinc, Cadmium, 44
Copper, and Mercury in Schuylkill River
Sediments Collected in November, 1972
12 Relative Concentrations of Petroleum Hydro- 47
carbons in Schuylkill River Sediments
Collected in November, 1972
13 Infrared Spectrum of Cyclohexane Fraction 56
from Spilled Crankcase Oil Waste (SCOW)
Collected in July, 1972
14 Infrared Spectrum of Cyclohexane Fraction 56
from Downstream White Suckers Collected
in July, 1973
15 Infrared Spectrum of Cyclohexane Fraction 58
from Upstream White Suckers Collected in
July, 1973.
16 Infrared Spectrum of Cyclohexane Fraction 58
from Downstream Brown Bullheads Collected
in July, 1973
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LIST OF FIGURES
(Continued)
FIGURE
NUMBER TITLE PAGE
17 Infrared Spectrum of Benzene and Benzene/ 59
Ether Fraction from Downstream White
Suckers Collected in July, 1973
18 Infrared Spectrum of Benzene and Benzene/ 59
Ether Fraction from Upstream White Suckers
Collected in July. 1973
19 Infrared Spectrum of Benzene and Benzene/ 60
Ether Fraction from Downstream Brown
Bullheads Collected in July, 19^3
20 Infrared Spectrum of Benzene and Benzene/ 60
Ether Fraction from Downstream Crappies
Collected in July. 1973
21 Infrared Spectrum of Benzene Fraction from 61
Spilled Oil Collected in July, 1972
22 Infrared Spectrum of Benzene/Ether Fraction 61
from Spilled Oil Collected in July, 1972
23 Infrared Spectrum of Benzene Fraction from 62
Rerun of Column Chromatogram of Spilled
Oil Collected in July, 1972
24 Chromatogram of Cyclohexane Fraction from 64
Spilled Oil Collected in July, 1972
25 Chromatogram of Benzene Fraction from 65
Spilled Oil Twice Collected in July, 1972
26 Chromatogram of Cyclohexane Fraction from 66
Upstream White Suckers Collected in July, 1973
27 Chromatogram of Cyclohexane Fraction from £7
Downstream White Suckers Collected in July,
1973
28 Chromatogram of Cyclohexane Fraction from 68
Downstream Brown Bullheads Collected in
July, 1973
29 Chromatogram of Cyclohexane Fraction from 69
Downstream Crappies Collected in July, 1973
VI
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LIST OF FIGURES
(Continued)
FIGURE
NUMBER TITLE PAGE
30 Chromatogram of Benzene Fraction from 71
Upstream White Suckers Collected in July,
1973
31 Chromatogram of Benzene Fraction from 72
Downstream White Suckers Collected in
July, 1973
32 Chromatogram of Benzene Fraction from 73
Downstream Brown Bullheads Collected in
July, 1973
33 Chromatogram of Benzene Fraction from 74
Downstream Crappies Collected in July, 1973
34 Standard Polycyclic Aromatic Hydrocarbons 75
35 Chromatogram of Polycyclic Aromatic Hydro- 77
carbons each 0. 116 mg/ml in Benzene
36 Chromatogram of Benzene Fraction from 78
Upstream White Suckers Doped with Benzo (a)
Pyrene
37 Chromatogram of Benzene Fraction from 79
Upstream White Suckers Doped with 1,2-
Benzanthracene
38 Chromatogram of Benzene Fraction from 80
Upstream White Suckers Doped with Chrysene
39 Chromatogram of Benzene Fraction from 81
Upstream White Suckers Doped with Flouranthene
40 Chromatogram of Benzene Fraction from Up- 82
stream White Suckers Doped with Pyrene
41 Chromatogram of Benzene Fraction from Up- 83
stream White Suckers Doped with Pehenanthrene
42 Chromatogram of Benzene Fraction from Col- gg
um n Chromatogram of Harrison Lake National
Fish Hatchery Channel Catfish without TPM
Internal Standard and with 5 ppm added Hydro-
carbon
VII
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LIST OF FIGURES
(Continued)
FIGURE
NUMBER TITLE PAGE
43 Chromatogram of Standard Polycyclic 89
Aromatic Hydrocarbons with Triphrnylmethane
(TPM) Internal Standard
44 Chromatogram of Benzene Fraction from 90
Column Chromatogram of HarrisOn Lake
National Fish Hatchery Channel Catfish with
TPM Internal Standard and Zero ppm Added
Hydrocarbon
45 Chromatogram of Benzene Fraction from 91
Column Chromatogram of Harrison Lake
National Fish Hatchery Channel Catfish with
TPM Internal Standard and 2 ppm Added Hydro-
carbon
46 Chromatogram of Benzene Fraction from 92
Column Chromatogram of Harrison Lake
National Fish Hatchery Channel Catfish with
TPM Internal Standard and 5 ppm Added Hydro-
carbon
47 Chromatogram of Benzene Fraction from 93
Column Chromatogram of Harrison Lake
National Fish Hatchery Channel Catfish with
TPM Internal Standard and 10 ppm Added Hydro-
carbon
48 Chlorophyll £ Pheopigments of Schuylkill River 96
Water During July, 1972
49 Ranges-of Abundance of Three Dominant Zoo- 98
plankton Taxons Collected on 28 July and 29
November 1972 in the Schuylkill River
50 Ranges of Abundance of Two Dominant Macro- 99
faunal Taxons Collected on 29 November 1972
and 28 July 1973 in the Schuylkill River
51 Daily Oxygen Metabolism of Schuylkill River 102
Biota on 30 July 1972 at Monocacy Bridge
52 Daily Oxygen Metabolism of Schuylkill River 103
Biota on 30 July 1972 at Parker Ford Bridge
Vlll
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LIST OF TABLES
TABLE
NUMBER TITLE PAGE
Location and Characteristics of Schuylkill 14
River Sediment Sampling Sites
Constituents of Spilled Crankcase Oil Waste 29
Collected Near Douglassville Bridge in July,
1972
Heavy Metal Concentrations in Waste Crank- 30
case Oil Samples Collected and Analyzed in
1971 by the U. S. Environmental Protection
Agency
Heavy Metal Concentrations in Tree Leaves 38
Collected from M onocacy Farm in May, 1973
Heavy Metal Concentrations in Tree Leaves 39
Collected Near the Douglassville Bridge in
May, 1973
Heavy Metal Concentrations in Tree Leaves 40
Collected Near the Pottstown Bridge (Route 100)
in May, 1973
Comparison of Metals in Schuylkill River and 45
Potomac River Sediments
Levels of Aliphatic and Aromatic Hydrocarbons 84
in Schuylkill River Fish Collected July, 1973
IX
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LIST OF APPENDICES
APPENDIX
NUMBER
DATA FROM ANALYSES OF RIVER WATER
1. 24 Hour Temperature and Dissolved
Oxygen July, 1972 112
2, Biochemical Oxygen Demand, Chemical
Oxygen Demand, and M. O. Alkalinity
of Schuylkill River Water Above and
Below Spill Site in July, 1972 114
3. Hydrogen-ion Concentration in Schuyl-
kill River Water 12 July - 5 August 1972 116
II DATA FROM HEAVY METALS ANALYSES OF
RIVER WATER AND SEDIMENTS
1. Concentrations of Lead, Zinc, Cadmium,
and Copper in Schuylkill River Water
3 July 4 August 1972 119
2. Concentrations of Lead, Zinc, Cadmium,
and Copper in Schuylkill River Bottom
Samples Collected in July, 1972 127
in DATA FROM HYDROCARBON ANALYSES OF
SEDIMENTS
1. Chromatogram of Oil in Sediment Composite
Collected in November, 1972, at Control
Station M 131
2. Chromatogram of Oil in Sediment Composite
Collected in November, 1972, at Station D-l 132
3. Chromatogram of Oil in Sediment Composite
Collected in November, 1972, at Station D-2 133
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APPENDIX
NUMBER PAGE
III 4. Chromatogram of Oil in Sediment Composite
(cont. ) Collected in November; 1972, at Station D-3 135
5. Chromatogram of Oil in Sediment Sub sample
Collected in November, 1972, at Station D-3 136
6. Chromatogram of Oil in Sediment Composite
Collected in November. 1972, at Station D-4 137
7. Chromatogram of Oil in Sediment Composite
Collected in November, 1972, at Station D-5 138
8. Chromatogram of Oil in Sediment Composite
Collected in November, 1972, at Station P-l 139
9. Chromatogram of Oil in Sediment Composite
Collected in November, 1972, at Station P-2 140
10. Chromatogram of Oil in Sediment Composite
Collected in November, 1972, at Station P-3 141
11. Chromatogram of Oil in Sediment Composite
Collected in November, 1972, at Station P-4 142
12. Chromatogram of Oil in Sediment Composite
Collected in November, 1972, at Station P-5 143
IV DATA FROM HEAVY METALS ANALYSES OF
RIVER BIOTA
1. Concentrations of Lead, Zinc, Cadmium,
and Copper in Benthic Macrofauna Collected
in July, 1973 145
2. Concentrations of Lead, Zinc, Cadmium,
Copper, and Mercury in White Suckers
Collected in November, 1972; January and
July, 1973 146
3. Concentrations of Lead, Zinc, Cadmium,
Copper, and Mercury in Brown Bullheads
Collected in November, 1972; January and
July, 1973 147
XI
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APPENDIX
NUMBER PAGE_
IV 4. Concentrations of Lead, Zinc, Cadmium,
(cont. ) Copper, and Mercury in Crappies
Collected in November, 1972; January and
July, 1973 148
5. Concentrations of Lead, Zinc, Cadmium,
Copper, and Mercury in Bluegills Collected
in November, 1972, and January, 1973 149
6. Concentrations of Lead, Zinc, Cadmium,
and Copper in Schuylkill River Fishes
Collected 19 and 22 July 1972 150
7. Concentrations of Lead, Zinc, Cadmium,
and Mercury in Schuylkill River Fishes
Collected 23 and 29 July 1972 151
V HYDROCARBON IN FISHES
1. Extraction Data 153
2. Saponification Data 154
3. Column Chromatographic Data 155
4. Extraction and Saponification Results from
Harrison Lake National Fish Hatchery Fish 159
5. Column Chromatographic Data Harrison
Lake National Fish Hatchery Fish 160
6. Peak Area and Weight Correlations of Poly-
cyclic Aromatic Hydrocarbons Compared to
Triphenylmethane Internal Standard
7. Percent Recovery of Polycyclic Aromatic
Hydrocarbons from Harrison Lake National
Fish Hatchery Fish (2 ppm added Hydro-
carbon)
xn
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APPENDIX
NUMBER PAGE
V 8. Percent Recovery of Polycyclic Aromatic
(cont. ) Hydrocarbons from Harrison Lake National
Fish Hatchery Fish (5 ppm added Hydro-
carbon) 163
9. Percent Recovery of Polycyclic Aromatic
Hydrocarbons from Harrison Lake National
Fish Hatchery Fish (10 ppm added Hydro-
carbon) 164
VI DATA FROM BIOLOGICAL ANALYSES
1. Chlorophyll a_ Content of Schuylkill River
Water Above and Below the Oil Spill Site in
July, 1972 166
2. Zooplankton Abundance in Schuylkill River
Water Above and Below the Oil Spill Site in
July, November, and December, 1972, and
July, 1973 168
3. Benthic Macrofauna Abundance in Schuylkill
River Sediments in November - 1972, and
July, 1973 174
4. Counts of Bacteria in Schuylkill River Sedi-
ments (Organisms/g of Sediment) Above and
Below Oil Spill in July, 1972 184
5. Stomach Contents of Fishes Collected from
the Schuylkill River in Winter, 1972, and
Summer, 1973 185
Xlll
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SUMMARY
Six million gallons of rerefined waste crankcase oil sludge
spilled into the Schuylkill River near Douglassville, Pennsylvania, in
June of 1972. This report summarizes a study of both the immediate
and the long-term effects of the spill.
The spilled oil coated and caused extensive temporary damage
to vegetation along approximately 17 miles of riverbank. Most trees
and herbaceous species lost their leaves, thus the aesthetic value of
the riverbanks was impaired during the summer of 1972. Some oil-
coated branches were killed. Some dead branches have been invaded
by wood-rotting fungi that may in time damage the trees.
The spilled oil did not cause direct permanent damage to
deciduous species along the riverbank; however, many ornamental
evergreens have been seriously damaged and have lost their aesthetic
value.
Leaves on trees in the heavily affected downstream areas had
significantly higher lead levels than leaves from trees in the area
immediately upstream from the spill site in the summer of 1973. How-
ever, lead levels were not higher than levels in urban trees reported
in the literature.
Concentrations of the heavy metals, lead, zinc, cadmium, and
copper in Schuylkill River water downstream from the spill site in
July, 1972, were below permissible levels for drinking water supplies
set by the U. S. Public Health Service.
Lead and zinc levels in the Schuylkill River water were higher
in the downstream areas than at the immediately upstream site during
early July, 1972. In mid-late July, 1972, concentrations of lead and
zinc had generally decreased to background levels.
Lead levels in Schuylkill River sediments collected during
November, 1972, were significantly higher in the downstream areas
than immediately upstream.
Petroleum hydrocarbon concentrations in sediments collected
in November, 1972, from the downstream areas were significantly
higher than in sediments from the upstream station at Monocacy. Com-
parison of the gas chromatograms of oil in the sediments suggests that
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the spill was responsible in part for the high petroleum hydrocarbon
concentrations at downstream stations.
Lead concentrations in Diptera larvae and Oligochaete worms
collected in July; 1973, were three to seven times higher in the
immediately downstream area than in the immediately upstream area.
Heavy metals concentrations in fishes collected from the
Schuylkill River in July, 1972; November, 1972; January, 1973; and
July, 1973, were similar at both upstream and downstream sample
stations.
Aromatic and aliphatic hydrocarbon concentrations were simi-
lar in upstream and downstream fish collected in July, 1973, but are
markedly higher than concentrations in fish from a pure environment.
Zooplankton samples taken on 16 July 1972 and 14 July 1973
indicated no differences in taxon diversity between upstream and
downstream lengths of the river that can be attributed to the oil spill.
Macrofauna samples collected five and thirteen months after
the spill (29 November 1972 and 28 July 1973) indicated no differences
between upstream and downstream lengths of the river that can be
attributed to the oil spill.
Chemical oxygen demand (COD) during July, 1972, was greatest
in the length of the river downstream from the spill site between
Douglassville Bridge and Spring City Bridge. A substantially greater
amount of pheopigment level characterized Parker Ford, downstream
from the spill site, on 29 July 1972. Repspiration of the biotic com-
munity at Parker Ford was marginally greater on 30 July 1972 than
at the immediately upstream site. Bacteria (including hydrocarbon
oxidizers) consistently reached peak levels at the Parker Ford Bridge
station. Each of the above observations, taken separately, offers
only weak evidence of environmental differences among upstream and
downstream lengths of the river. Collectively, they present circum-
stantial evidence that the length of the river between Douglassville
Bridge and Spring City Bridge (0. 7 - 16. 5 miles below the oil spill)
was characterized by a degree of environmental degradation not evi-
dent immediately upstream or downstream.
Existence of numerous actual and potential sources of pollution
in the Douglassville Bridge - Spring City Bridge length of the river
preclude positive assignment of the oil spill as the cause of environmental
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degradation. However, the oil spill could quite plausibly have resulted
in both the high COD and pheopigment content that was observed in this
length of the river. These conditions, in turn, could be expected to
stimulate a buildup of bacterial decomposers which would cause the in-
creased community respiration that was detected by the diurnal oxygen-
curve technique.
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CONCLUSIONS
The rerefinery sludge temporarily, damaged deciduous trees
and other vegetation along the riverbanks by causing premature loss
of leaves and reduction of aesthetic values during the summer of 1972.
Recovery from this contamination by the summer of 1973 was evident.
Evergreen trees and ornamental evergreen shrubs were permanently
damaged by rerefinery sludge as evidenced by loss of needles from
affected branches.
Although flood conditions on the Schuylkill had an overriding
influence on many of the aquatic aspects of the study, environmental
degradation due to rerefinery sludge and associated heavy metals was
obvious as late as thirteen months after the spill.
Heavy metal concentrations in the river remained below those
concentrations listed as prohibitory for drinking water by the U. S.
Public Health Service.
Techniques used in the removal operation represented the best
practice available for the problems encountered. These techniques
included :
. Oil deposited on the land areas was physically removed.
Care was taken not to bury removed oil where contamination to ground
water or livestock might occur.
. Only trees, shrubs, and branches in the most heavily
polluted areas were removed in order to leave a root system to
prevent bank erosion.
. "Quick-cover", fast growing grass was used to prevent
erosion of river banks, following physical removal of oil.
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RECOMMENDATIONS
In the event of a spill of similar material near a stream or
river:
1. Immediately mobilize quick-response study teams
to analyze the impact of the spill.
2. Utilize cleanup techniques that do the least harm to
trees and vegetation including:
A. Remove oil from the ground using hand imple-
ments so as not to disturb root systems and cause erosion.
B. Remove only downed trees and heavily coated
brush without unnecessarily disturbing the soil.
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INTRODUCTION
On 22 June 1972 floods caused by heavy rains from Hurricane
Agnes inundated oil storage lagoons on the banks of the Schuylkill
River near Douglassville, Pennsylvania. The lagoons contained resi-
due from several years of operation of a petroleum rerefining plant
employing the vacuum distillation process. The plant rerefined waste
crankcase oil collected from service stations and garages. A by-
product of the rerefined process was a thick, tarry residue which could
not be economically reduced or used. An estimated 6-8 million
gallons was stored in the lagoons at the time of the flood.
The flooding river swept the oil from the lagoons and carried
it downstream. Because the flooded Schuylkill was far beyond its
usual boundaries, the oil coated trees, homes, and riverbanks as the
water receded. Riverbanks on both sides of the river were coated on
the average to a distance of 50 yards inland along 17 miles of the river.
A study of the effects of the spill has been conducted during the
year following the spill. The objectives of the study were to:
1. Evaluate the severity and extent of damage to vegetation
along the river,
2. Determine the health hazard due to heavy metal con-
tamination of drinking water supplies,
3. Determine the constituents of the oil and its fate and
effects in the river, and
4. Evaluate the impact and effectiveness of shore clean-up
operations and recommend procedures for handling similar spills.
To accomplish the objectives:
--The properties of the spilled crankcase oil waste were deter-
mined.
--the recovery of trees along the banks of the Schuylkill was
monitored during the summer of 1972 and during fall bud set and spring
1973 leaf formation. In the spring of 1973, the concentrations of heavy
metals in tree leaves downstream from the spill were determined and
compared to concentrationS( in leaves of trees from an upstream station
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--physical and chemical parameters of river water were moni-
tored at upstream and downstream stations. Biochemical oxygen de-
mand, chemical oxygen demand, alkalinity, temperature, dissolved
oxygen, and hydrogen-ion concentrations were determined during the
summer of 1972.
--concentrations of lead, zinc, cadmium, and copper in the
Schuylkill River water were determined on a daily basis from 3 July
1972 until 4 August 1972.
--concentrations of the metals lead, zinc, cadmium, and copper,
and of petroleum hydrocarbons were determined in Schuylkill River
sediment samples collected in November, 1972.
--concentrations of the heavy, metals lead, zinc, cadmium,
copper, and mercury were determined in macrofauna collected from
the river in winter 1972 and summer 1973.
--levels of polycyclic aromatic and aliphatic hydrocarbons were
determined in fishes from the Schuylkill River.
--other possible effects of the spill were monitored. Average
levels of total and active chlorophyll ji were measured in July, 1972.
Zooplankton were collected at stations upstream and downstream from
the spill,and major taxon diversity was determined. Benthic macro-
fauna were sampled upstream and downstream from the spill and ranges
of abundance of the dominant macrofaunal taxons determined. The
types and abundance of bacteria in Schuylkill River sediments were
determined during the summer of 1972. Using diurnal curve techniques,
community respiration, including that of the bottom community, was
determined during July of 1972.
--clean-up operations were monitored, and recommendations ^
were submitted to the EPA on a day-to-day basis during July, 1972.
Recommendations for the handling of similar spills are included in this
report.
This report summarizes work conducted under Basic Ordering
Agreement 68-01-0701, Delivery Order 1, a study of the immediate
effects of the spill and work under Contract 68-01-0781, a follow-up
study of the longer-term effects of the oil spill.
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P E.NNSYl_VAK.\\A
Figure 1. Map of the
Schuylkill River area
VALULY
STATE PARK
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Collection station
for fishes
Vegetation sampling
station
Seuitiit:nt sampling
stations
MONOCACY
SAMPLING SITE
MONOCACY
BRIDGE
CONTROL SAMPLING
SITE FOR
VEGETATION
Site of Spill
FIGURE 2. MONOCACY SAMPLING STATIONS
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Site of Spill
Vegetation Sampling
station
Sediment sampling
station
DOUGLASSVILLE
VEGETATION
SAMPLING SITE
UNIONVILLE
D3
JFIGURE 3. DOUGLASSVILLE SAMPLING STATIONS
10
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PARKER FORD BRIDGE
Collection station
for fishes
Sediment sampling
stations
FIGURE 4. PARKER FORD SAMPLING STATIONS
11
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MATERIALS AND METHODS
1. DESCRIPTION OF SAMPLING STATIONS
A. Vegetation
Bark and leaf samples were collected from sampling
stations on the banks of the Schuylkill River in heavily oiled areas near
Unionville and Pottstown Bridge (Route 100), and from a control station
on the southwest bank of the Schuylkill at Monocacy Farm, approximately
1/2 mile upstream from the site of the spill. These stations are shown
on Figures 1 through 3.
B. River Water
River water samples for heavy metals and physical and
chemical analyses were collected at Monocacy Bridge, Douglassville
Bridge, Parker Ford Bridge, Spring City-Royersford Bridge, and Falls
Bridge at Philadelphia. These bridge locations are shown on Figure 1.
C. Fishes for Petroleum Hydrocarbon and Heavy Metals
Analyses
Fishes were collected at stations in the Monocacy area
1. 3 miles upstream from the spill, Figure 2, and from the Parker Ford
area, Figure 4, 11 miles below the spill.
For the analysis of fish from a clean environment, channel cat-
fish were taken from Harrison Lake National Fish Hatchery located on
Route 5 between Williamsburg and Richmond, Virginia.
D. Sediment
Sediment samples for heavy metals and hydrocarbon
analyses were collected in the Monocacy area, 2. 1 miles above the oil
spill, in the Douglassville area 0. 4 and 2. 3 miles downstream from the
oil spill, and in the Parker Ford area 10.6 to 12.5 miles downstream
from the oil spill. Figures 2, 3, and 4 show the locations of these
sample stations. The characteristics of each station are shown in
Table 1.
E. Benthic Macrofauna
Benthic organisms for biological and heavy metals
analyses were collected at the sediment sampling stations discussed above.
12
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F. Zooplankton and Phytoplankton Pigment
Plankton were sampled from Monocacy Bridge and
Parker Ford Bridge. Locations of these stations are shown in Figure 1.
13
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TABLE 1 Location and Characteristics of
Schuylkill River Sediment Sampling Sites
IDENTIFICATION
DISTANCE FROM
SOURCE OF SPILL
(Miles)
CHARACTERISTICS
Monocacy
Monocacy
Douglassville
Dl
D2
D3
D4
D5
Parker Ford
PI
P2
P3
P4
P5
2. 1 above
0. 4 below
1. 0 below
1. 7 below
2. 1 below
2. 3 below
10.6 below
11.4 below
12. 0 below
12. 0 below
12. 5 below
Downstream edges of small
island
Downstream edge of small
island (1-3 ft. deep)
Downstream edge of island
(1-3 ft. deep)
Downstream of small islands
(1-3 ft. deep)
Behind snag (1-3 ft. deep)
Downstream of small islands
(1 ft. deep)
Downstream edge of large
island (2-4 ft. deep)
Over shoal area (2 ft. deep)
In mouth of creek (6 ft. deep)
Over shoal area (2 ft. deep)
Open river (5-6 ft. deep)
14
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2. ANALYSES OF VEGETATION
Ground and air surveys were made in July, 1972, to determine
the extent and severity of damage to trees. Follow-up surveys were
conducted in the fall of 1972 and the spring and summer of 1973. Indi-
vidual specimens of various species were selected within the upstream
(Figure 2) and downstream (Figure 3) sampling stations and marked
with plastic tape so that their recovery could be monitored during fall
bud-set and spring leaf formation. Sections of branches and bark from
oil-soaked trees within the sampling stations were removed and placed
in vials of fresh Formalin Acetic Acid and-Alcohol (FAA) killing and
preserving fluid (Sass 1958). Sections were allowed to stand in the
killing and preserving fluid for three weeks to become sufficiently rigid.
Freehand sectioning was used to obtain thin cross sections that were
stained, mounted, and examined to determine the extent and effects of
oil penetration.
3. PHYSICAL AND CHEMICAL ANALYSES OF RIVER WATER
Dissolved oxygen was determined in the field using the modified
Winkler micromethod with a LaMotte dissolved oxygen kit (Model EDO,
Code 7414). Hydrogen-ion concentration (pH) was measured in the
field with a LaMotte electrode kit (Model HA, Code 1901).
BOD, COD, and alkalinity were determined per Standard
Methods, 13th ed. Samples were collected in polyethylene containers,
refrigerated, and delivered to the laboratory within four hours of
collection.
4. HEAVY METAL ANALYSES
A. Leaves (Dry Ash Method)
Leaves from the spring 1973 growing season were taken
for analysis. They were stored in clean polyethylene bags until analysis.
To remove surface contamination, the leaves were washed: they were
wet in a 0. 1% ivory soap solution, rinsed once in tap water, and then
again in distilled water. Ten to fifteen leaves from each species were
composited and analyzed for lead, zinc, cadmium, and copper using a
dry-ashing technique. The procedure is:
Sass, J. E. 1958. Botanical Microtechnique. Iowa State Uni-
versity Press, Ames, Iowa, 228 p.
15
-------
(1) Dry leaves for two days at 85 °C.
(2) Grind sample to finely divided particles in
a Wiley mill.
(3) Weigh out 1 g of particles into a crucible for
dry ashing at 500 °C for one hour in a muffle furnace.
(4) Cool and dissolve ash in 5 ml of 12HC1 diluted
19:1.
(5) Take the sample to dryness by evaporating HC1
off on hot plate.
(6) Redissolve residue in 4 ml HC1 diluted 19:1.
(7) Filter solution through filter paper.
(8) Brin5 filtrate to 25 Ml in a volumetric flask with
distilled water.
(9) Set up standard curves for each element in ques-
tion, and analyze samples with atomic absorption spectrophotometer
(Perkin-Elmer Model 303).
B. River Water
Since the sensitivity of the atomic absorption method is
limited by the instrument, organic extractions and concentrations had
to be utilized for the metals cadmium and lead.
The procedure used was that of the Environmental Pro-
tection Agency as described in: Methods for Chemical Analysis of
Water and Wastes (1971).
The values for copper and zinc were obtained by direct
aspiration of the water since the permissible levels of these metals
for water supplies were above the sensitivity of the instrument.
C. Sediments
Composite samples from ten downstream stations
U. S. Environmental Protection Agency, 197)- Laboratory
Branch, Inter-Office Correspondence.
16
-------
(Figures 3 and 4) and one upstream (control) station (Figure 2) were
observed to determine if, and in what quantities, oil had been
deposited in the river. Ten to twenty (10-20) subsamples were
taken at each site with a .25 ft. Ekman dredge. Attempts were
made to sample the upper 2-3 inches of sediment. Samples were
stored in clean polyethylene bags.
The non-crystalline forms of lead, zinc, cadmium,
copper, and mercury were analyzed using atomic absorption techniques.
Since it is likely that the surface area of sediments affects the amount
of oil-metals accumulated, each subsample was wet sieved (U. S. stan-
dard sieve, No. 230, 63 micron openings) to assure that each composite
sample was similar in particle size distribution, thereby allowing a
better comparison among locations. The sieved subsamples were
than air dried and 1 g portions of each were combined to obtain the
composites.
The procedure for extracting lead, zinc, cadmium, and
copper is:
(1) Place 1, 000 g of samples in an acid-washed
Phillips beaker.
if possible).
(2) Add 5 ml of concentrated HNO- (Boxes Ultrex,
(3) Heat until solution begins to boil, being careful
not to lose sample by bumping.
(4) Allow sample to cool. Repeat Steps 2 and 3.
(5) After cooling, add 10 ml of distilled water.
(6) Centrifuge and save supernatent liquid.
(7) Set up standard curves for each element in ques-
tion and analyze with Varian AA-5 atomic absorption spectrophoto-
meter.
Analyses of replicate samples extracted by this method
showed a precision of - 8% for lead, -5% for zinc, - 3% for cadmium,
+ 7% for copper and 110% for mercury.
The method for mercury consisted of sulfuric acid-
potassium permangenate oxidation and a reduction step with hydro-
oxylamine sulfate-- stannous sulfate. The analyses were performed
17
-------
on a Coleman mercury analyzer which had been modified with a
quartz flow cell and recorder attachment. This method has been
utilized successfully on sediments elsewhere (Huggett, et al; 1971)-
D. Biota
Benthic organisms and fishes were analyzed for lead,
zinc, cadmium, copper, and mercury after digestion in concen-
trated nitric acid, as performed by Huggett, et al; (1973).
Replicate analyses of all biota were performed by atomic
absorption spectrophotometry using a Varian AA-5 instrument.
5. PETROLEUM HYDROCARBON ANALYSES
A. Sediment
The composite samples, each composed of ten to
twenty subsamples, from the ten downstream (Figures 3 and 4)
and one upstream (Figure 2) sample sites were extracted and
analyzed by flame ionization gas chromatography to obtain an
estimate of oil content.
The procedure of extraction and cleanup is given in
detail here, since in the problem of oil pollution gas chromatography
results are comparable only if obtained in the same manner.
(1) Place 5 g of each dried composite sample into
a clean 125 ml Erlenmeyer flask.
(2) Add 50 ml benzene-methanol azetrope (benzene
60. 4%, methanol 39. 6% ) and 50 ml n-heptane.
(3) Allow to stand twenty-four hours and then place
in an ultrosonic bath for fifteen minutes.
(4) After settling, decant heptane/azetrope solution
into glass tubes and centrifuge.
Huggett, R. J., M. E. Bender, H. D. Sloan. 1971. " Mercury
in sediments from three Virginia estuaries." dies. Sc. 12-4. 280.
Huggett, R. J. , M. E. Bender, H. D. Sloan. 1973. "Utilizing
metal concentration relationships in the Eastern oyster (crasostrea
virgmica) to detect heavy metal pollution." Water Res. 7:451-460.
-------
(5) Transfer supernatent liquid into 300 ml round-
bottom flasks and evaporate on a rotary vacuum dryer until disappear-
ance of the azetrope fraction (bottom layer disappears when temperature
of flask increases to 260 C).
(6) Pass the partially evaporated samples through a
chromatographic column consisting of activated alumina (AG-7, 100/200
mesh, 4.1% H2 O), eluted with 3 ml of heptane. Evaporate samples to
0.25 ml and inject portions into the gas chromatograph.
B. Petroleum Hydrocarbons in Fishes
The analytical procedure which was used to determine
the kinds and amounts of petroleum hydrocarbons in fish is .complex
and time-consuming, and some of the techniques reported below were
developed solely for this investigation.
The procedure reported below is that of a typical run on
a fish sample of upstream white suckers taken from the Monocacy area
(Figure 2), and each step was performed sequentially. Any variations
in sample sizes and weights of products obtained with other fish samples
(and spilled crankcase oil waste) are discussed in the Results and Dis-
cussion, page 48.
Samples were packed in dry ice and shipped in insulated
chests. The samples were thawed to remove flesh for heavy metals
analysis, then refrozen and kept in cold storage until analysis.
(1) General Laboratory Precautions
The following laboratory precautions were prac-
ticed to minimize error, contamination, and decomposition during the
analysis of hydrocarbons:
a. Samples were stored in either a dark cabi-
net or in brown bottles capped •with aluminum foil liners, since ultra-
violet radiation is known to decompose polycyclic aromatic hydro-
carbons.
b. The laboratory was equipped with General
Electric F-40-Go yellow fluorescent lamps to minimize ultraviolet
light.
19
-------
c. Observations of fluorescent zones during
chromatography, using a Gelman Camag ultraviolet lamp at 350 nano-
meters, were held to a minimum to avoid hydrocarbon decomposition.
d. Smoking was not permitted in the laboratory
to avoid possible contamination of samples.
e. All glassware (and grinding/blending equip-
ment) was detergent-washed, rinsed in water followed by acetone, and
dried under an infrared lamp or in the atmosphere. It was further rinsed
in fractionated benzene and dried under an infrared lamp prior to use.
(2) Solvent Purification
All solvents (except where specified) were purified
by fractionation of 2. 5 liter batches, under nitrogen, through a 22 x
2.3 (ID) cm column packed with cut glass tubing. The all-glass appara-
tus was assembled using ungreased ground joints and protected from
the atmosphere with a tube of anhydrous calcium sulfate. The first
250 Ml forerun and last 250 Ml pot residue of each batch were dis-
carded. Fractionated solvents were stored in metal foil-lined capped
brown bottles. Ethyl ether used in column chromatography was glass-
distilled from Burdick and Jackson Laboratories, Inc.
(3) Extraction of Oils from Fish
Materials used were fractionated benzene, Fisher
B-245(see previous Solvent Purification Section); anhydrous magnesium
sulfate, Fisher M -65, which was Soxhlet extracted forty-eight hours
with fractionated benzene before use, and dried under an infrared lamp.
Blending and extraction procedures are as follows:
a. Grind two to three fish specimens with a
standard meat grinder into a porcelain dish and tnix with a spatula.
b. Weigh, to the nearest gram, about 500 g
of ground fish into a one-quart stainless steel W aring blender, and
partially blend.
c. Add 7% by weight of benzene for the pur-
pose of aiding the grind, and blend until a "fish soup" after blending
to determine the losses of volatiles.
-------
d. Weigh the "fish soup" after blending to
determine the losses of volatiles.
e. Weigh 250 g of "fish soup" into a beaker
and immerse in ice.
f. Add 180 g of preextracted anhydrous
magnesium sulfate and stir until a solid mixture is formed.
g. Regrind blend in a Waring blender to a
powdery consistency (some lumpy material cannot be eliminated,
however), to give a "fish powder".
h. Weigh approximately 100 g of "fish powder"
sample into a Soxhlet thimble which has been previously extracted for
forty-eight hours with benzene.
i. Extract "fish powder" for twenty-four hours
in refluxing benzene.
j. Strip benzene extract of solvent at the
water pump on a hot water bath using a rotary evaporator by trapping
the benzene distillate in a filter flash assembly immersed in ice water,
and save the fish oil residue.
k. Repeat steps (h) and(j) with a fresh fish
powder sample and combine the oils obtained in step x.
Assuming the losses in volatile material from step (d)
to be the added benzene, the fraction of fish in the fish "soup" can be
calculated as:
fraction of
weight original ground fish
fish in =
final weight fish soup
fish "soup"
The percent fish in the final "fish powder "is then calculated as:
% fish in ^^ fish soup x wt. fraction fish in fish "soup"
fish + MgSO4 wt- fish SOUP + w*' MgSO4
21
-------
The extraction data for the samples processed are given
in Appendix V-l.
(4) Saponification of Oil Extracts.
Materials used were 6N KOH (Fisher USP) in
fractionated methanol; cyclohexane, Fisher C-556, fractionated;
benzene, Fisher B-245, fractionated; sodium chloride, Fisher S-271;
magnesium sulfate, Fisher M-65, preextracted forty-eight hours with
fractionated benzene.
Saponification procedures are as follows:
a. Mix extracted oil with 6N potassium hydrox-
ide and leave at room temperature for forty-eight hours.
b. Dilute mixture with water, transfer to a
500 ml separatory funnel, and extract twice with cyclohexane and
twice with benzene. Combine extracts.
The separation of the layers in this step
was difficult. The addition (and mixture) of solid sodium chloride in
the separatory funnel for as long as twelve to sixteen hours helped to
break the emulsions. In those cases where a clear cut separation of
the layers could not be achieved, the top hydrocarbon layer was separ-
ated with a pipette so that a clear hydrocarbon extract devoid of inter-
facial material was obtained for the next step.
c. Wash hydrocarbon extract with about 25%
its volume of IN sulfuric acid (twice) and water (twice).
d. Dry extract over anhydrous sulfate and
filter off the magnesium sulfate using a medium-porosity sintered
glass funnel (Pyrex #36060) washed with benzene.
e. Evaporate extract leaving a viscous oil to
be used for column chromatography.
The data, including volumes of 6N KOH,
volumes of water and solvents -used, etc. , are given in Appendix V-2.
(5) Column Chromatography of Saponified Extracts.
Materials used were aluminum oxide (alumina ),
basic, Type E, (activity I), Brinkmann Instruments, Inc. , without
22
-------
further purification; anhydrous magnesium sulfate, Fisher M-65,
preextracted forty-eight hours with fractionated benzene; cyclohexane,
Fisher C-556, fractionated; benzene, Fisher B-245, fractionated;
ethyl ether, glass distilled, Burdick and Jackson Laboratories, Inc. ;
chromatographic column (Fisher Porter) 5.0 cm ID fitted with a
fritted disk and stopcock, A. H. Thomas catalog Nos. 27Z6-Q82,
-R20, -R83, -S42.
Chromatographic procedures are as follows:
a. Mix saponified extract with four times its
weight of basic alumina, blanket with a little cyclohexane, and leave
for forty-eight hours at room temperature.
b. Assemble chromatographic column (5. 0
or 2. 0 cm inside diameter) with a fritted glas disc and stopcock at
its base, and partially fill with cyclohexane. Add alumina from the
top, stir in the cyclohexane, and allow to settle. Add anhydrous
magnesium sulfate equal to 10 percent of the weight of alumina, stir,
and allow to settle.
c. Place slurry of alumina/sample/cyclo-
hexane (from a) in the chromatographic column and open the stopcock
to allow the cyclohexane to approach the level of the top of the sample
(save eluate).
d. Collect the following three fractions from
the column:
-- cyclohexane fraction
-- benzene fraction
-- 90:10 benzene; ethyl ether fraction
e. Strip cyclohexane fraction at the water
pump on a hot water bath.
f. Combine benzene and benzene-ethyl
ether fraction and strip solvent at the water pump.
g. Reserve the non-volatile hydrocarbon
residues from (e) and (f) for infrared and gas chromatographic
analysis.
The data for the coltmn chromatographic
step are given in Appendix V-3.
23
-------
(6) Infrared and Gas Chromatographic Analysis
Infrared spectra of all hydrocarbons were deter-
mined as smears between salt plates on a Bausch and Lomb Schimadzu
Spectronic 250 infrared spectrophotometer. After analysis, the sam-
ples were reisolated from the salt plates by washing with fractionated
benzene. The benzene solvent was stripped a': the water pump to leave
the hydrocarbons which were subsequently analyzed by gas chromato-
graphy.
Gas chromatography of the cyclohexane eluate
was performed on a Varian Aerograph Model 2720 using 7' x 1/8" 1. 5
percent OV-17 on Chrom.osorb G 100/120 DMCS for the cyclohexane
fraction. All runs were programmed from 50-293°C at 8°/min using
N2 carrier gas at 22 psig. Injector and detector temperatures were
2l6oC and 270°C, respectively.
Gas chromatography of the aromatic hydrocar-
bons from benzene-benzene/ethyl ether eluate was performed on the
same instrument using a 7' x 1/8" 4. 5 percent SE-52 on Chromosorb
G 100/120 DMCS at 50-293° at 8°/min using N2 carrier gas. For gas
chromatography of hydrocarbons from benzene-benzene/ether fraction
obtained from the Harrison Lake fish samples and standard hydro-
carbon mixture, the isothermal hold period was set at 300°C.
The benzene-eluted compounds from column
chromatography of the Harrison Lake samples were each treated with
a known quantity of triphenylmethane just before gas chromatography.
The infrared spectra are given in Figs. 13-23,
and gas chromatograms are given in Figs. 24-41. Gas chromatograms
pertaining to Harrison Lake fish are shown in Figs. 42-47.
6. BIOLOGICAL ANALYSES OF RIVER BIOTA
A. Chlorophyll a
Chlorophyll a samples were filtered in the field on GF/C
filters and shipped in darkened ice containers to the laboratory where
they were frozen and kept darkened until analysis. They were analyzed
24
-------
by standard spectrophotom etric techniques (Lorenzen, C. J. ,
1966 & 1967) that measure pigment fluorescence within two days
of field collection. Since most petroleum products also emit
fluorescence, tests were performed to determine if presence of
oil in the river would bias chlorophyll a_ readings. Oil from the
Berk Associates plant was added to three water samples (collected
from an area not contaminated by the oil spill) at concentrations of
.4 percent and compared to three controls lacking oil. Although
total chlorophyll a levels were similar between treated and control
samples, active and dead chlorophyll a concentrations in the oiled
samples averaged 64% higher (7,4 as compared to 4. 5 mg'/l) and 32
percent lower (10. 4 as compared to 15.3mg/l), respectively, than
in the controls. Thus, spectrophotometric techniques may tend
to overestimate the ratio between live and dead pigments below the
oil spill. This bias is probably minimal due to the relatively low
oil levels found in the river (measured in ppm) as compared to the
amounts added in these tests.
B. Zooplankton
Zooplankton samples were collected with a #12-mesh
metered net (2-ft diameter), preserved in 10 percent formalin, and
subsampled to determine organism abundance.
C. Benthic Macrofauna
2
Macrofauna were collected with a . 25 ft Ekman dredge,
preserved in 10 percent formalin, and washed onto a 1. mm screen
prior to separation. Organisms in the more important taxons were
identified down to the generic level.
D. Bacteria
Sediment samples for bacteria analysis were placed in
sterile petri dishes in the field and transported in ice to the laboratory
where several decimal dilutions were prepared by placing 11 g of mud
sample into 99 ml of sterile buffered dilution water. The mixture was
Lorenzen, C. J. 1966. "Method for the Continuous Measure-
ment of Invivo Chlorophyll Concentration," Deep Sea Research, Vol. 13,
pp. 223-227.
Lorenzen, C. J. 1967. "Determination of Chlorophyll Pheo-
Pigments: Spectrophotometric Equations, " Limnol. Oceanography,
12:343-345.
25
-------
shaken twenty-five times and transferred (11 ml) to each successive
99 ml dilution bottle. Bacteriological counting procedures were
as follows:
(1) Standard plate count. Estimation of viable aero-
bic, mesophilic, heterotrophs was made by spreading 0. 1 ml portions
of diluted samples on plates of tryptone slucose extract agar using
sterile glass rods. Colony counts were made after five days at 25°C.
(2) Hydrocarbon oxidizers. Bushnell-Haas medium
was prepared from ingredients and solidified with 1. 5 percent agar
(Oxoid brand lon-agar No. 2). B-H medium is a mineral-salts base
without carbon source and supposedly does not support bacterial
growth unless a suitable carbon source is added. For counts of hydro-
o
carbon oxidizers, spread plates of suitable dilutions were prepared on
B-H agar and inverted with 0. 1 ml of kerosene added to the lid. In a
few instances, additional plates were prepared, and 0. 1 ml of sterile
dodecane was pipetted to the surface of the inoculated, non-inverted
plates.
(3) Casein hydrolyzers. Spread plates of nutrient ,
agar containing 10 percent (v/v) of sterile skim milk were made, and
colonies showing zones of clearing (hydrolysis) were counted.
(4) Amylolytic organisms. Nutrient agar containing
0.2 percent of soluble starch was used to prepare spread plates. After
flooding with iodine solution, colonies surrounded by clear zones were
counted.
(5) Fermentative bacteria. Tubes containing 10 ml
of purple broth base (BBL) plus 0. 5 percent glucose were inoculated
in triplicate with 1. 0 ml of appropriate dilutions. These showing acid
production (yellow indicator) were scored positive and used to deter-
mine mpn values from standard tables.
(6) Sulfate reducing bacteria. From the initial 1:10
dilution of mud sample, 1. 0 ml portions were transferred to 9 ml of
sulfate reducer agar API (Difco) at 450°C in screwcapped tubes.
Serial decimal dilutions were made in the molten agar. After twenty-
one days at 25°C in an anaerobic jar, tubes showing blackening were
scored positive and MPN values determined.
26
-------
E. Dissolved Oxygen and Community Respiration
Oxygen measurements were taken throughout the twenty-
four hour daily cycle and used to estimate gross primary productivity
and community respiration according to the diurnal-curve method of
Odum (1956). The single-curve modification was employed. Correc-
tions for diffusion were obtained by assuming the coefficient of gas
transfer (K) to be 2.0 g/m2/hr at 0 percent saturation (estimated from
Odum's table 1). Community respiration was determined by extra-
polating the diffusion-corrected hourly predawn oxygen decrease
(measured in ppm) to the twenty-four hour daily cycle and multiplying
by river depth. Gross primary production was calculated by measuring
the area between the diffusion-corrected rate-of-change curve and a
horizontal line drawn through the predawn hours and multiplying by
river depth. Depth at both sampling stations was about 1 m.
F. Food Habits of Fishes
Fishes were captured by hook and line and net. Stom-
achs were extracted, slit along one surface to allow rapid preservation
of contents, wrapped in gauze stripping, and shipped in 10 percent
formalin to the laboratory.
7. OBSERVATIONS OF SHORE CLEANUP IMPACT AND
EFFECTIVENESS
Cleanup operations were monitored by direct observation for
the first five days and recommendations submitted on a daily basis
during July, 1972. Hosing operations removed oil from sight but put
it into the river where the effects where the effects may be more seri-
ous.
Booms properly and rapidly deployed in reaches of the river
with currents less than 2 knots will .permit containment of the oil for
pickup by vacuum trucks or other oil collection systems.
Burning of oil-covered debris and recovered oil was not con-
sidered judicious since burning releases lead and other heavy metals
in their most harmful vapor form.
Pools of oil along the shore line were observed requiring clean-
up since several were running into the river.
Odum, H. T. 1956. "Primary Production in Flowing Waters,
Limno. Ocean. 1: 102-117.
27
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RESULTS AND DISCUSSION
1, PROPERTIES OF SPILLED GRANKCASE OIL WASTE
The spilled oil had a specific gravity of 0. 97. A sample of
spilled crankcase oil waste (SCOW) collected from the riverbank near
Unionville in July of 1972 contained 33 percent petroleum hydrocarbon,
51 percent water, 13 percent insoluble residue, and 3 percent water
soluble remainder by difference. Direct distillation of the SCOW up
to 185°C yielded approximately 0. 5 percent organic volatile material.
Visual inspection of the spilled oil suggested that it contained
mostly tars and aliphatics. The oil sample contained 48 percent ali-
phatic hydrocarbons and 4. 5 percent aromatic hydrocarbons.
The spilled oil contained high concentrations of the heavy
metals lead, zinc, cadmium, and copper (Table 2). An analysis of
oil samples from the storage pits, conducted by the Environmental
Protection Agency in 1971 (Table 3), also indicated the presence of
heavy metals.
2. EFFECTS OF THE OIL SPILL ON VEGETATION
A, General
A survey, taken on 1 and 2 July 1972, of oiled river-
bank areas from the spill site to Valley Forge revealed that trees along
both banks of the Schuylkill River were extensively coated with spilled
oil (Figure 5) to a height of approximately 20 to 25 feet above the
normal river level (Figure 6) with the trees in the Douglassville area
most heavily coated. No variation in oil thickness at different tree
heights was noted. However, the upper,, uncoated foliage did not show
symptoms of damage.
4
The riverbank tree community had sustained consider-
able damage by the force of the river water which pushed the trees
over and, in some cases, uprooted them. This type of mechanical
damage occurred all along the river and was not related to the oil-
coating problem. It was observed during an air survey on 1 July that
the foliage of some uprooted trees in the river was trapping and col-
lecting the floating oil. Since the foliage would probably release oil
into the river over a period of weeks, it was recommended that these
oil-coated and uprooted trees by removed to a disposal site.
28
-------
TABLE 2 Constituents of Spilled Crankcase Oil Waste
Collected Near Douglassville Bridge in July, 1972
HEAVY METALS
1
Lead
Zinc
Cadmium
Copper
% Solids:
16,300 ppm 1 6%
1,960 ppm t 2%
5. 1 ppm i 6%
87 ppm t 2%
11.1%
HYDROCARBONS
Water
Hydrocarbon Oil
Insoluble Residue
Water Soluble Remainder
51%
33%
13%
3%
POLYCHL.QRINATED BIPHENYLS
Test: negative, sensitivity 0. 5 ppm
1
Mean of replicate analyses.
29
-------
TABLE 3 Heavy Metal Concentrations in Waste
Crankcase Oil Samples Collected and Analyzed in 1971
by the U. S. Environmental Protection Agency
Element
(mg/kg of oil)
Zinc
Cadmium
Arsenic
Boron
Phosphorous
Iron
Molybdenum
Manganese
Aluminum
Beryllium
Copper
Silver
Nickel
Cobalt
Lead
Chromium
Vanadium
Barium
Strontium
Sample
14604
1,800
10
50
5
50
2, 500
20
58
430
0.1
210
1
10
10
10,000
16
22
360
64
Sample
14612
2, 100
9
45
18 '
1, 700
2,200
18
63
560
0. 1
190
0.8
8
0.8
19, 000
28
18
740
2.7
Sample
14631
165
5
25
25
970
128
10
5
85
0.05
18
0.5
5
9.9
5,200
3
22
24
5.8
Sample
14634
350
16
80
8
950
96
30
64
66
0.1
41
2
16
31
6,600
10
48
1,600
3.3
30
-------
Figure 5 Extensively Oiled Riverbank Vegetation
31
-------
Figure 6. Oil-coated riverbank vegetation along the banks of the Schuylkill
River in July, 1972
-------
Many tree species at the Douglassville Bridge sampling
station were developing new leaves from the oil-coated branches as
early as 8 July 1972. This indicated that the growing points had not
been killed by the oil and that biological recovery was progressing in
spite of presence of oil on the soil, foliage, and trunks. Herbaceous
plants on the riverbank were beginning to show signs of recovery.
A winter survey was made on 3 January 1973 of the trees
along the riverbank at Douglas sville Bridge, Unionville, Parker Ford,
and other points to examine the terminal and lateral buds of several
mixed stands of trees. Longitudinal and cross-section of buds and
small twigs were made on the scene and examined for evidence of tissue
necrosis. Internode lengths of the trees were also examined and com-
pared to the previous season's growth. There was no evidence that
the buds of the oil-soaked trees were dying nor was there any obvious
indication of decreased growth rates. Dormant buds on the trees were
plentiful and appeared to be normal. Some dead trees were still
coated with oil. However, they were relatively few compared to the
population of trees examined. Some trees had a few dead, oil-coated
branches. It was expected that these dead branches would become in-
fected with wood-rotting pathogenic fungi which would invade the main
trunk and eventually kill the tree.
Additional checks on the recovery of the deciduous tree
community were made during the spring and summer of 1973. The
results of these surveys were basically the same. No unusual symp-
toms of permanent damage were found. During the summer survey,
some dead branches were found; and there .was evidence of invasion by
wood-rotting fungi. In general, however, the trees and herbaceous
species in affected areas showed excellent recovery.
There was one exception to the remarkable recovery of
the tree community. Evergreens and other ornamental species in the
yards of private residences along the river had been severely damaged.
Damaged trees included conifers, such as pines, hemlocks, firs, and
spruces. Other evergreen species that suffered damage were yews
and junipers (Figures 7 and 8). The growing pattern of evergreens is
much different than that of the deciduous trees. Deciduous trees were
able to shed their damaged leaves. In contrast, conifers shed their
needles very slowly and are unable to rid themselves of damaged
tissue that can cause harm to affected branches. Many oil-soaked
evergreens in private residences have lost their aesthetic value and
are probably irreparably damaged.
33
-------
00
Oil
Level
Figure 7. Oil-coated ornamental evergreens 10 days after the oil spill
-------
Figure 8. Oiled evergreens 1 year after the oil spill
-------
B. Penetration of Oil Through Bark
Freehand, stained sections of oak, maple, and sycamore
tree bark revealed that oil which was tenaciously attached to the outer
bark did not appear to penetrate beneath the surface to any great degree
(Figure 9). Penetration was probably prevented by the cork layer.
Oak and maple have relatively thick cork layers compared to sycamore.
However, the bark of sycamore is exfoliative and falls off in time.
C. Heavy Metals in Tree Leaves
Plants have been shown to accumulate metals from their
surroundings. One potential long-term effect of this spill was viewed
as the uptake of toxic concentrations of heavy metals from the oil-
coated soil or through the bark. Thus, a study of heavy metal accumu-
lation was conducted. Based on the analyses of the oil (Tables 2 and 3),
the metals selected for study were lead, zinc, cadmium, and copper.
The study was designed to detect trends of abnormally high accumula-
tions of heavy metals derived from the oil which may have correlated
with any observed symptoms of phytotoxicity. Sampling was concen-
trated on those species representative of the mixed deciduous forest
along the banks of the Schuylkill.
Data from the heavy metals analysis of the leaves col-
lected at Monocacy, Douglassville, and Parker Ford in May, 1973, is
presented in Tables 4, 5, and 6.
A non-parametric sign test (Snedecor and Cochran 1967)
was applied to the pooled data of seven pairs of species at Monocacy
Farm and Douglassville Bridge. Lead values were significantly greater
at the 95 percent confidence level in affected leaves from the Douglass-
ville Bridge area. The levels of other metals at oiled and control
stations were not significantly different.
The statistically significant difference in lead concen-
trations between Monocacy Farm and Douglassville Bridge is probably
not important in terms of well-being of the trees. Considerably higher
amounts of lead are known to occur in many plant species. Smith
(1973) reported difficulty in establishing "normal" levels of lead even
after sampling trees in relatively unpolluted areas and comparing
values to published concentrations obtained from similar areas. He
Snedecor, G. W. , and W. G. Cochran. 1967. Statistical
methods: Iowa State University Press, Ames, Iowa. 593 p.
Smith, W. H. 1973. "Metal contamination of urban woody plants.
Envir. Sci. Tech. 7:631-636.
36
-------
Figure 9. Cross-section of oiled oak bark magnified
613X
3?
-------
OJ
00
TABLE 4 Heavy Metal Concentrations in Tree Leaves
Collected from Monocacy Farm in May, 1973
Heavy Metal Concentration (ppm)
1
No. of Trees
Species
Maple
Oak
Oak
Sassafras
Sycamore
Elm
Black Walnut
Sampled
12
7
7
6
8
4
3
Lead
5. 0
6. 0
5. 0
3. 0
4. 0
5. 0
6.0
Zinc
26.0
28. 0
21. 0
29. 0
20. 0
73. 0
24. 0
Cadmium Copper
* 0.4
* 0.4
* 0. 6
* 0.5
0.8 0.5
* 0. 8
* 0. 5
Mean of replicate analyses for each element from the pooled sample.
ij.
than 0. 5 ppm.
-------
OJ
TABLE 5 Heavy Metal Concentration in Tree Leaves
Collected Near the Douglas sville Bridge in May, 1973
Species
Maple
Oak
Oak
Sassafras
Sycamore
Elm
Black Walnut
Heavy Metal Concentration (ppm.)
o. of Trees
Sampled
12
6
1
3
1
8
7
Lead
11. 0
8. 0
9. 0
4.0
6. 0
10. 0
8. 0
Zinc Cadmium
32. 0 *
32. 0 *
25. 0 *
25.0
20. 0 *
25.0 *
27. 0 *
Copper
0.4
0. 8
0. 8
0.6
0.8
0.4
0.6
Mean of replicate analyses for each element from the pooled sample.
#
''~Less than 0. 5 ppm.
-------
TABLE 6 Heavy Metal Concentrations in Tree Leaves
Collected Near the Pottstown Bridge in May, 1973
Heavy Metal Concentration (ppm)
No. of Trees
Species
Oak
Oak
Sycamore 5 5.0 30.0 * 0.6
Mean of replicate analyses for each element from the pooled sample.
"""Less than 0. 5 ppm.
vTo. of Trees
Sampled
4
2
Lead
6. 0
6.0
Zinc
22. 0
24.0
Cadmium
*
*
Copper
0. 5
0.4
-------
cited literature describing lead concentrations in unpolluted environ-
ments as approximating 1 ppm. Baumhardt and Welch (1972) reported
lead concentrations from 3.6 to 27.6 ppm in symptomless corn leaves.
Concentrations of lead in grasses along two highways ranged from 20
to 60 ppm (Chow 1970). Warren and Delavault (in Campbell and Mergard
1972) suggested that "normal" lead concentrations be considered to be
0. 1 to 2. 5 ppm. On the other hand, Mortvedt et al (1972) reported
apparently healthy radish plants growing at concentrations of 2. 3 ppm
to 12, 000 ppm lead. Lead levels in trees along the Schuylkill are not
abnormally higher than concentrations reported in other investigations
(Chapman 1966, Gauch 1972, Lounamaa 1956, Smith 1973). Similarly,
Jones's (in Montvedt et al 1972) normal range for zinc is 25 to 150 ppm
with zinc toxicity not occurring below 400 ppm.
3. PHYSICAL AND CHEMICAL PARAMETERS OF SCHUYLKILL
RIVER WATER
Water temperature at Monocacy and Parker Ford Bridges
(Appendix 1-1) ranged from 21°C to 28°C during July, 1972. Oxygen
levels (Appendix 1-1) varied from lows of around 4. 5 to 7. 0 ppm in the
Baumhardt, G. R. , and L. F. Welch. 1972. "Lead Uptake and
Corn Growth with Soil-Applied Lead, " J. Envir. Qual. 1:92-94.
Chow, T. J. 1970. "Lead Accumulation in Roadside Soil and
Grass," Nature 225:295-296.
Campbell, I. R.,and E. G. Mergard. 1972. Biological Aspects
of Lead; An Annotated Bibliography, Part I and Part II. E.P.A. Pub-
lication No. AP-104.
Mortvedt, J. J. , P. M. Giordano, and W. L. Lindsay (eds).
1972. 'Micronutrients in Agriculture, Soil Soc. Amer. , Inc., Madi-
son, Wisconsin. 666p.
Chapman, H. D. (ed. ). 1966. Diagnostic Criteria for Plants
and Soils, Div. Agr. Sci. , University of California, Berkeley. 793 p.
Gauch, H. G. 1972. Inorganic Plant Nutrition, Dowden,
Hutchinson, and Ross, Inc., Stroudsberg, Pa. 488p.
Lounamaa, J. 1956. "Trace Elements in Plants Growing Wild
on Different Rocks in Finland, " Ann. Bot. Soc. Vanamo 29:1-196.
Smith, W. H. 1973. "Metal Contamination of Urban Woody
Plants," Envir. Sci. Tech. 7:631-636.
41
-------
early morning to 5. 5 to 8. 0 ppm (about 62 to 91 percent saturation at
22°C) during midday. No differences were noted between upstream
and downstream stations.
Alkalinity (Appendix 1-2) ranged from 50 to 84 ppm with no
apparent differences among upstream and downstream stations. Nor-
mal alkalinity in fresh water rivers and streams is about 0 to 200 ppm.
Daytime hydrogen-ion concentrations in July and August, 1972,
(Appendix 1-3) were 7. 0 to 7. 8 with maximum values usually occurring
at the Valley Forge Bridge station. The presence of the highest values
at Valley Forge suggests a downstream increase in primary producti-
vity that is characteristic of many streams and rivers.
Biochemical oxygen demand (BOD) measurements taken during
the summer of 1972 (Appendix 1-2) ranged from 0.4 to 4. 2 ppm. High-
est levels were usually observed in the Douglassville Bridge - Parker
Ford Bridge length of the river (0. 7 to 11. 7 miles below the oil spill).
Chemical oxygen demand (Appendix 1-2) was between 5. 38 to
15,44 during July and August, 1972. Maximum COD usually occurred
in the length of the river between Douglassville Bridge and Spring City
Bridge stations (0. 7 to 16.4 miles below the oil spill).
4. CONCENTRATIONS OF METALS IN SCHUYLKILL RIVER WATER
Lead and zinc levels were generally highest directly below the
oil spill (Douglassville-Parker Ford Bridge stations) until about mid-
July, 1972 (Appendix II-l). Concentrations had dropped to background
levels during the remainder of July. An increase in concentration was
noted in August at Parker Ford. This trend is shown for lead in Fig-
ure 10. No differences in copper or cadmium levels were noted among
stations sampled (Appendix II-l).
5. HEAVY METALS IN SEDIMENTS
Sediment's in the Schuylkill River were analyzed for lead, zinc,
cadmium, and copper during the summer of 1972. During November
of 1972 sediments were analyzed for lead, zinc, cadmium, copper, and
mercury.
Data from the summer of 1972 is presented in Appendix II-2.
The summer 1972 survey was conducted to determine if there were
areas of oil or metals contamination from the spill. No such areas
were found. The winter 1972 sampling was concentrated in areas where
sediment deposition was expected.
42
-------
FIGURE 10. CONCENTRATIONS OF LEAD IN SCHUYLKILL RIVER WATER
FROM JULY 3 TO AUGUST 4 1972
x x Monocacy Bridge
• • Parker Ford Bridge
345 6 7 8 9 IO II 12 13 14 15 16 17 18 19 20 21 2g 23 24 25 26 27 28 29 30 31
July
-------
FIGURE II. CONCENTRATIONS Of LEAD , ZINC , CADMIUM ,
COPPER AND MERCURY IN SCHUYLKIIL RIVER
SEDIMENTS COLLECTED IN NOVEMBER 1971
1400
1300
From Spill
44
-------
Data from the winter analyses is presented in Figure 11. The
existence of many possible sources of pollution in the river between
Douglassville and Parker Ford preclude assignment of the spill as the
cause of the increased metals levels. Data from the November, 1972,
analyses are tabulated in Appendix II-3).
Concentrations of all heavy metals were analyzed by "t" tests,
or modifications of this procedure (Guenther, 1964) if heterogeneity of
variances existed between samples, to determine if levels below the
oil spill were greater than those observed in the Monocacy area. Only
lead levels were significantly higher below the spill. The calculated
t value was 3. 71 as compared to a tabled value of 2. 05 at the . 95 con-
fidence level extrapolated to 4. 5 degrees of freedom. However, the
significance was due to one extremely high lead level (1,400 ppm)
observed below the spill.
Table 7 compares concentrations of lead, zinc, and copper in
the Schuylkill with concentrations of the same metals reported by
Houser (1972) in the Potomac River.
TABLE 7 Comparison of Metals in Schuylkill River
and Potomac River Sediments
Schuylkill Potomac
Lead (ppm) 619. 0 52. 7
Zinc (ppm) 823. 0 348. 1
Copper (ppm) 234. 1 70. 2
Concentrations of these metals in the Schuylkill are signifi-
cantly higher. It is realized that the Potomac is estuarine while the
Schuylkill is fresh water. However, data presented by Hugget, et al
(1972), for fresh water portions of the Rappahannock also suggest that
Guenther, W. C. 1964. Analysis of Variance, Prentiss-
Hall, Inc. , New Jersey. 23 p.
Huggett, R. J. , M. E. Bender, H. D. Slone. 1972. Final
Report to the Corps of Engineers, Norfolk Dist. Analysis of dredge
spoils from th'e James and Elizabeth Rivers.
45
-------
the Schuylkill has unusually high background levels of heavy metal
pollution. Levels of zinc and copper in the Schuylkill at the control
(Monocacy) site are ten times higher than in the Rappahannock.
6. PETROLEUM HYDROCARBONS IN SCHUYLKILL
RIVER SEDIMENTS
Gas chromatograms of oil from sediment composites collected
in November, 1972, from above and below the spill (Appendix III-l
through III-1Z) show very high unresolved backgrounds.
The relative amounts of petroleum hydrocarbons in the sediment
composites were computed using data on instrument attenuations,
volumns injected, and the areas under the chromatograms. Relative
concentrations at downstream stations as compared to Monocacy (con-
trol station) are shown in Figure 12. The underlying assumption was
that hydrocarbons in the unresolved backgrounds of each chromatogram
were of similar nature. In general, downstream stations show a much
higher concentration of petroleum hydrocarbons than the upstream
control stations. Levels were especially high directly below the oil
spill. However, the upstream control stations exhibited the same
types of oils, although at lower concentrations, as observed at the
other stations.
One subsample of a composite collected 1. 7 miles below the
spill was highly contaminated with oil, as evidenced by smell and
visible sheen when mixed with water. Since the sample apparently
contained the most oil, it was extracted and analyzed separately
(Appendix III-5). By comparing this with the other analyses, it was
noted that it contained twenty-five times as much oil as the control
composite.
7. HEAVY METALS IN BENTHIC MACRQFAUNA AND FISHES
Lead concentrations in mixed samples of Diptera larvae and
Oligochaeta worms (mostly Tub if ex) collected at benthos sampling
station D-2 were a factor of 3-7 higher than samples taken above the
oil spill (Appendix IV-1). Other metals exhibited no noticeable differ-
ences.
Levels of metals in fishes collected above and below the spill
are presented in Appendices IV-2, IV-7. No significant differences
due t^ the oil spill can be detected.
46
-------
FIGUREI2. RELATIVE CONCENTRATIONS OF PETROLEUM HYDROCARBONS
IN SCHUYLKILL RIVER SEDIMENTS COLLECTED IN
NOVEMBER 1972
12
-o
o
o
89
8
_o
«J
c
o
i2
-2
0.85
3.02
1.61
-I
Spill Site
2 3
Miles From Spill
10
12
13
-------
The extensive use of Diptera larvae as food by several species
of fish (Appendix V 1) suggested that this food link could serve as a
pathway by which metals could be accumulated in the fishes.
8. PETROLEUM HYDROCARBONS IN FISHES
The overall sequential analytical procedure used to search for
the possible presence of petroleum hydrocarbon residues in fish is
given in the Materials & Methods Section, page 20, and is diagrammed
below:
WHOLE FISH
V
1) grind in meat grinder.
2) blend in a Waring blender with 7. 4% by
weight of benzene,
"FISH SOUP"
blend in a Waring blender with approximately
70% weight percent of anhydrous magnesium
\ / sulfate,
'FISH POWDER"
V
1) Soxhlet extract 24 hours with refluxing
benzene,
2) evaporate benzene,
EXTRACTED OIL (Appendix V-l, V-4)
1) saponify oil in 6N methanolic KOH
48 hours at room temperature,
2-) dilute with water and extract with cyclo-
hexane and then with benzene (simple
extraction),
3) wash the combined organic extracts with
V
IN H2SO4, dry, and evaporate solvent,
TOTAL HYDROCARBONS FROM SAPONIFICATION
(Appendix V-2, V-4)
(Continued)
48
-------
TOTAL HYDROCARBONS FROM SAPONIFICATION (Continued
from previous page)
1) apply to a basic alumina
column for column chromato-
graphy,
2) elute with cyclohexane, leaving
any fluorescent material on the
column,
3) elute the fluorescent material
i. with benzene followed by
ii. 90/10 benzene/ethyl ether
combine 1) and ii),
4) evaporate solvent from the above
two fractions
A)
CYCLOHEXANE-ELUTED
ALIPHATIC HYDROCARBONS
(VERY WEAKLY FLUORES-
CENT) (see Appendix V-3,
V-5)
1) infrared analysis
2) flarne ionization
GC analysis
IRs: Figs. 14-16
GCs: Figs. 26-29
B) BENZENE-BENZENE/
ETHER-ELUTED ARO-
MATIC HYDROCARBONS
(STRONGLY FLUORES-
CENT)(see Appendix V-3,
V-5)
1) infrared analysis
2) flame ionization
GC analysis
IRs: Figs. 17-20
GCs: Figs. 30-33, 42,
46-47
GC = Gas Chromatogram
IR = Infrared spectrum
This procedure was applied to two sets of fish samples:
1) fish obtained from the Schuylkill River in July, 1973, in
the region of the oil spill,
2) fish (presumably free of oil contamination) from Harri-
son Lake National Fish Hatchery, designated in this report as "HLFH"
fish (see Subsection J, p. 86). In order to test the above analytical proce-
dure, some "HLFH" samples were deliberately tainted with known amounts
of polycyclic aromatic hydrocarbons in the initial blending step of the
analysis, and finally the composite benzene-benzene/ether fraction
from column chromatography was analyzed by GC.
49
-------
The procedure,with some modification, was also applied to a
sample of the spilled crankcase oil waste (SCOW), collected from the
river in July, 1972. The GCs and IR spectra from this analysis, after
column chromatography, are listed:
IR cyclohexane fraction: Fig. 13
IR benzene and benzene/ether fractions: Figs* 21-22
GC cyclohexane fraction (SCOW); Fig. 24
GC benzene/ether fraction (SCOW): Fig. 25
The above procedure was adopted because it combined the
merits of published procedures and provided as much information as
possible in the fewest analytical steps. These steps included:
1) separation of the benzene soluble oils from the fish
2) separation of the hydrocarbons from these extracted oils
3) separation of the hydrocarbons into two classes,
i) the saturated aliphatic hydrocarbons, and
ii) the polycyclic aromatic hydrocarbons
A similar type procedure was applied to the spilled crankcase
oil waste (SCOW) to determine if any intelligible comparisons could be
made between the hydrocarbons isolated from the fish vs_. those isolated
from SCOW.
The polycyclic aromatic hydrocarbons were of special interest
in view of the known carcinogenic properties of some of these com-
pounds. The notable early work of Cahnmann and Kuratsune (1957)
describes the isolation and identification of these polycyclic aromatics
in oysters which were taken from waters slightly contaminated by oil
pollution. Their procedure involved a direct liquid-liquid extraction
step on 5 kg of shucked oysters blended in methanol followed by saponi-
fication of the extract with methanolic potassium hydroxide. About
Cahnmann, H. and M. Kuratsune. 1957. "Determination of
Polycyclic Aromatic Hydrocarbons in Oysters Collected in Polluted
Water," Anal. Chem. 29:1312.
50
-------
twenty-one chromatographic columns were prepared using various
adsorbents to isolate the polycyclic aromatics, many of which were
identified by their characteristic ultraviolet absorption spectra. A
list of these polycyclic aromatics appears in Fig. 34. This procedure
applied to fish in the Schuylkill River would be very time-consuming
and might limit the number of fish samples which could be examined.
On the other hand, facile and rapid methods of analysis such as
direct gas chromatography on oils extracted from fish (or on SGOW)
would render little conclusive information due to the extreme chemical
complexity of any petroleum product. The suspected waste oil is
theoretically able to be comprised of multi-thousands of hydrocarbons.
However, it should be noted that the work of Zafiriou, Blumer,
and Myers (1972) provided "fingerprint" gas chromatographic compari-
sons of spilled crude oils with crudes from the spill source and were
able to correlate them in many cases.
The examination of kerosene-like materials in the Australian
mullet was pursued by Connell (1971), and the procedure included ex-
traction of fish flesh with ethyl ether followed by steam distillation to
separate the steam volatile hydrocarbons. The isolated hydrocarbons
were subjected to gas chromatography, and the chromatograms com-
pared to the chromatograms from oily river sediments and commercial
kerosene. Similar studies were conducted on edible shellfish by Blumer,
Souza, and Sass (1970) in which shucked shellfish were extracted with
refluxing methanol, and the methanol extracts (and solids precipitated)
extracted with pentane. Further separations were achieved with column
chromatography followed by fingerprint gas chromatography. Compari-
son of the chromatograms obtained with those of a No. 2 fuel oil (acci-
dentally spilled in the area before shellfish examination) revealed
similarities in some cases.
Zarifiou, O. , M. Blumer, and J. Myers. 1972. Correlation
of Oils and_pil Products by Gas Chromatography. National Technical
Information Service Report PB-211-337 UNPUBLISHED MANUSCRIPT.
Connell, D. W. 1971. "Kerosene-like Tainting in the Australian
Mullet, " Marine Pollution Bulletin^ 12 (2): 188.
BHmer, M. , G. Souza, and J. Sass. 1970. "Hydrocarbon
Pollution of Edible Shellfish by an Oil Spill, " Biol. 5:195.
51
-------
In the present study of the spill in the Schuylkill River, the
material spilled might well be composed primarily of a complex mix-
ture of hydrocarbon materials. However; the material spilled was the
waste product from the rerefining of waste crankcase oil. Thus, the
expected tarry and intractible residues would undoubtedly differ in
composition from a crude oil or a given kerosene fraction.
A. Blending and Extraction of Fish Samples (and SCOW)
The above published procedures for extracting oils from
fish (and SCOW) may not be applicable to the present problem. For
example, steam distillation of ether extracts from Schuylkill River
fish may separate hydrocarbons; but the suspected contaminating
material (SCOW) might be composed of high molecular weight hydro-
carbons of low-vapor pressure. Because of the low-steam volatility
of high molecular weight hydrocarbons, separation of these materials
by this technique will be incomplete.
The blending of Schuylkill River fish with magnesium
sulfate and subsequent Soxhlet extraction of the fish powder with re-
fluxing benzene is a modification of a procedure published by the
Patuxent Wildlife Research Center. In this process,fowl were ground
and blended with anhydrous sodium sulfate, and the resulting free-
flowing powder was subsequently extracted with refluxing petroleum
ether. The use of anhydrous sodium sulfate failed with Schuylkill River
fish, because the refluxing benzene resulted in liberation of water from
the sample which clogged the flush tube in the Soxhlet apparatus com-
pletely inhibiting the extraction process.
The use of benzene vs. pentane or petroleum ether as
an extracting solvent was preferred due to the known insolubility (or
partial solubility) of some polycyclic aromatics in these solvents.
The essential data from the extraction are outlined in
Appendix V-l and the process is described on page 20. Some heat
was developed in the blending process, and corrections were made for
weight losses due to evaporation. Thus, the column labelled "Actual
Sample Extracted" in Appendix V-l represents a corrected value. The
selection of twenty-four hours reflux time was based on weight studies
of the amount of organic material extracted vs_. time. These studies
revealed that all the organic material was extracted in eighteen hours.
The weight percent of the total oil extracted, based on weight of starting
fish, varied from 2. 8 to 5. 9 percent. The oils extracted from HLFH
fish samples on forty-eight hours benzene extraction gave variations
ranging from 4. 9 to 7. 2 percent (Appendix V-4).
52
-------
B. Saponlfication
The purpose of the saponification step was to further
refine the fish oil obtained from the extraction step by converting the
relatively non-polar materials (e. g. , fat or lipid) to relatively polar
materials (fatty acid salts and glycerol).
These polar and water soluble products can then be more
easily separated in the next steps. The polar compounds were removed
in the extraction of the water-diluted saponification mixture with hydro-
carbon solvent followed by column chromatography. Other organic
compounds that may be present such as aldehydes, organic acids,
ketones, esters, and proteins are also sensitive to treatment with
methanolic potassium hydroxide, but hydrocarbons in general are inert.
A saponification step was used by Cahnmann and Kuratsune (1957) in
their determination of polycyclic aromatic hydrocarbons in oysters.
The percent recoveries of oil from the saponification
step varied from 17. 8 percent in the downstream brown bullhead
sample to 64. 3 percent in the upstream crappie sample, based on the
oils obtained from the original extraction (Appendix V-2).
The saponification step was the most difficult step in
the analysis. Samples emulsified badly on extraction of the diluted
saponification mixture with cyclohexane and benzene. The separation
of layers was accomplished to some extent by the addition of solid
sodium chloride. Even with the addition of salt, the clean-cut separa-
tion of layers, devoid of interfacial material, was not achieved. Some-
times the interface was not well defined. Despite these difficulties,
clean organic layers containing the sought-after hydrocarbons devoid
of interfacial material were separated. It is possible, however, that
some of the hydrocarbon material was left behind in the interfaces.
Another difficulty was the gelation of some of the cyclo-
hexane/benzene extracts after separation from the aqueous saponifica-
tion mixture. The upstream brown bullhead extract gelled very badly
after magnesium sulfate filtration. The gel completely clogged the
chromatographic column in the next step of the analysis. Thus, the
analysis for upstream brown bullheads had to be abandoned. During
the analysis of the downstream crappies, gelation occurred before the
filtration through magnesium sulfate, which increased the time required
to perform the normally simple laboratory operation.
Cahnmann, H. and M. Kuratsune. 1957. "Determination of
Polycyclic Aromatic Hydrocarbons in Oysters Collected in Polluted
Water," Anal. Chem. 29:1312.
53
-------
The apparent high yields of oil from the upstream
crappies seemed to be largely a gel-like material, which was not re-
vealed until the column chromatographic step. Then only plastic,
brittle, gel-like materials were eluted from the column, as opposed
to the oils usually observed, and these could not be analyzed.
The spilled crankcase oil waste extract was saponified
to eliminate any interfering acidic substances. All saponification data
are contained in Appendix V-2.
C, C olumn Chr omatojgrjyjhy
The purpose of this step was to separate the hydro-
carbons from other polar materials and also to separate the aliphatic
from the aromatic hydrocarbons for analysis by infrared and gas
chromatography.
The three principal eluting solvents which were used, in
sequence, were cyclohexane, benzene, and 90/10 benzene/ethyl ether.
The last two eluates were combined to give a benzene-benzene/ether
fraction. The principal criteria for the volumes of eluting solvents
used was the observation of fluorescent material on the alumina column.
Thus, the cyclohexane fraction was largely free of fluorescent material
while the benzene-benzene/ether fractions were heavily fluorescent.
Not all fluorescent material was eluted from, the alumina column even
when using a benzene/ethyl ether solvent combination.
The column chromatographic data are given in Appendix
V-3. The upstream crappies, eluted only solid gels, while the chroma-
tographic columns of the upstream brown bullhead became so badly
clogged no solvent would pass through it, even under pressure. Con-
sequently, these analyses were abandoned.
Except for the upstream brown bullheads, all column
loadings were in excess of 33:1 alumina-.oil sample. The lowest column
loading (20:1 alumina: oil sample) was used for the badly clogging up-
stream brown bullhead samples.
Column chromatography data for downstream and up-
stream suckers are compared in Appendix V-3. Here the percent
solids recovered based on starting material is 1. 8 vs^ 0,, 77 for cyclo-
hexane eluates and 1. 1 vs. 0.48 for benzene and benzene /ethyl ether
eluates in downstream and upstream suckers, respectively.
54
-------
D. Infrared Analysis
Infrared analyses (as smears between salt plates) were
performed on all materials from column chromatography except for
the upstream brown bullheads, the upstream crappies and the cyclo-
hexane fraction from the downstream crappies. Analyses were aban-
doned if there was insufficient sample for a suitable spectrum. After
spectral analysis, the samples were recovered by solvent washing from
the salt plates and analyzed by gas chromatography.
The infrared spectra of all cyclohexane fractions, Figs.
13-16, from column chromatography were essentially identical and
showed the predominant presence of aliphatic hydrocarbons both in the
waste oil and fish. There were some small unidentified peaks from
12. 2 to 13. 8 11 in the spectrum from an unusually thick sample of down-
stream brown bullheads.
All spectra of the benzene 4- benzene/ethyl ether frac-
tions from fishes, Figs. 17-20, were essentially identical and are
strongly indicative of aromatic hydrocarbons. A relatively small
amount of hydrocarbon residue was recovered from the downstream
crappies during the extraction, saponification, and column chromato-
graphy steps. Therefore, the infrared spectra of this sample was not
as clear as the others and minor differences were not discernible.
The spectrum for the "benzene" fraction of SCOW from
column chromatography is given in Fig. 21. While it was indicative of
aromatic hydrocarbons, its peaks were not as well resolved as the
corresponding spectra of fish, and it was not identical to the spectra of
the "benzene" eluates from fish. The spectrum of the 90:10 benzene:
ethyl ether fraction given in Fig. 22, showed that other material, prob-
ably having a carbonyl ( > C=0) group, was eluted from SCOW. An
attempt was made to further purify the benzene fraction from SCOW by
rechromatography on alumina. The benzene-eluted material from
rechromatography is given in Fig. 23. No further purification seemed
to be achieved in this rechromatograph step, since no essential dif-
ferences were observed on comparison of the spectra (Figs. 22 and 23).
E. Gas Chromatography
The purpose of gas chromatography was to separate and
estimate the components in the "cyclohexane" and "benzene-benzene/
ethyl ether" fractions. These fractions were recovered from column
chromatography of the SCOW and fish extracts after saponification.
55
-------
f4
i c^ --
5 ' 4 . • 7
'-^l—y^L^-^L!.^:r.r:,:,L^ ,
£
f
FIGURE 13. INFRARED
SPECTRUM OF CYCLOHEXANE
FRACTION FROM SPILLED
CRANKCASE OIL WASTE
(SCOW) COLLECTED IN
JULY, 1972
2CC~;ITCD 1605
WAVENUVScR CM"'
T403
ntxr
1000 £Ti
PHASE SMlAft. THICKNESS.
SAMPLE CVUONfcANf SOLVENT_tfOfF REFERENCE..
fMcoov S«OK;
CONCENTRATION ' SCAN TIME J1.JMW
| DATE
j OPER
'JMUS..J ®-*^~
„«./) PA'T NO. 201-77775
ATOR-T.B JWY P5INTE
NTED IN JAPAN
1
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9C
-sd
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S^6C
<
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30
20
10
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!• 3
• •- - - i '
1 : !
-C- . . :
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". !•! ;:!
-
: : . •
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. . -.1
.
i
i
-,
/
4
5
',•', -I-'-1
" ' '' ' _-
.—--*
^ 6 '"-^ 7 89
.
FIGURE 14. INFRARED
SPECTRUM OF CYCLOHEXj
FRACTION FROM DOWN-
" STREAM WHITE SUCKERS
COLLECTED IN JULY, 1
i
i)
.
i i
11 I i
;
*.*.
^j
24
;
-T
.j r
00
|
^^
1 "
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973
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:
If '''•
I !.•
V
10 11 12
.
Vy
Srt
1 .; "
. :" : - ! ":
i - :
i - . :
" i - - - .
. - - j . . .
tT Pi
nip*
., 1600 iOJ 1200 10
i
/
Mt
tt
o"0 —
S. — '
.
131415
1 1 1
N
V
. 1
' i
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A
650
:-:•-.= cvtWHIXhB^ sCivENT_A/OA/^
FMCTVfw. ^Q CONCENTRATION
REFERENCE
SCAN TIME l\Ml^_1
flUPHaTI* KK(QKO> • PAH NO. 201-77775
Wdi**' OPERATOR_fJO^51 . PRINTED IN JAPAN
-------
The technique has developed in practice to the extent
that a present-day working organic chemist cannot function without a
gas chromatograph. If the peaks observed in the gas chromatogram
of a complex mixture are well resolved, the analyst has an opportunity
to:
1) tentatively establish,but not prove,the
presence of a given component by adding known compounds to the
sample, rerunning the chromatogram, and observing peak height
enhancement,
2) establish the definite absence of a given
component in the original sample by the same technique as 1) and
observe extra peaks in the chromatogram of the sample doped with
known compounds (assuming no background) or
3) conclusively identify a compound from
the gas chromatograph by trapping the effluent gas from each peak
after the component passes the detector, thereby isolating the com-
ponent to study other physical properties. This latter technique can
be applied where a) the sample is not destroyed by the detector,
b) relatively large amounts of samples are available, and c) a rela-
tively large column is used.
In the case of complex mixtures, the gas chromatogram
may show only poorly resolved peaks against a large "background. " If
the chromatograms of two samples of multi-component mixtures have
identical peaks of similar relative intensity, the samples are presumed
to be identical. This "fingerprint" technique has been studied with
some success in efforts to identify the source in crude oil spills. That
success is due to the fact that different crude oils, while extremely
complex in their chemical composition, show significant differences in
their gas chromatograms.
The application of fingerprint gas chromatography to
identify hydrocarbons in marine life has been applied with some success
by Blumer et al. (1970) and by Connell (1971). Connell obtained finger-
prints on extracts of the Australian mullet and compared these to sub-
stances isolated from river sediments.
Blumer; M. , G. Souza, and J. Sass. 1970. "Hydrocarbon
Pollution of Edible Shellfish by an Oil Spill, " Biol. 5:195.
Connell, D. W. 1971. "Kerosene-like tainting in the Australian
Mullet, " Marine Pollution Bulletin. 12 (2): 188.
57
-------
' S
SA
SU.
; SOLVENT NONt __ REFERENCE ________ flUPJt/*"*
CONCENTRATION __ SCAN TIME H-flil^ CftR&ON
,^ DATEjf/«na ...
OPERATOR J".(
PA!T N0. 201-77775
PRINTED IN JAPAN
2
100
C 50
S
-HH C1
4 ^
-4+1-1
9 10 11 12131415
I
FIGURE 16. INFRARED
.; SPECTRUM OF CYCLO-
HEXANE FRACTION FROM !
— DOWNSTREAM BROWN 1
i BULLHEADS COLLECTED i
-; IN JULY, 1973
SPECTRUM NO
'"WAVENUMBER CM*1
PHASE SMffAR THICKNESS ~** REMARKS
SCXVENT.A/CA/fi REFERENCE T".
CONCENTRATION SCAN TIMEi.
DATE
PART NO !
OPERATOR T'-Q-K*t^ PRINTED IN JAPAN
-------
2 5-
..I ,
^l-L-M-l-U-i--
...lii!:'!.; i
1 '
i i
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§50
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z
rTt~r
4000" ,'oOOOJ'" J200 " 2oCO~~ ' 2~GOU2Cu
SPECTRUM NO PHASE &1HHAH THICKNESS
* R(«TlW'EtJT- •"»*" REFERENCE
".0 CONCENTRATION SCAN Tlv
FIGURE 17. INFRARED
SPECTRUM OF BENZENE AND " '
BENZENE/ETHER FRACTION
FROM DOWNSTREAM WHITE
r SUCKERS COLLECTED IN
JULY,19/3
REFERENCE
SCAN TIME
; J
FIGURE 18. INFRARED .X-
SPECTRUM OF BENZENE
:AND BENZENE/ETHER
FRACTION FROM UPSTREAM
WHITE SUCKERS COLLEC-
TED IN JULY, 1973
ooo' ~i"s jo reoo"
WAVENUMBER CM''
-------
9 10 11 I 2 1 3 M 1 5
FIGURE 19. INFRARED
j SPECTRUM OF BENZENE
.AND BENZENE/ETHER
FRACTION FROM DOWN-
STREAM BROWN BULL-
HEADS COLLECTED IN
JULY, 1973
___ THICKNESS _ REMARKS
REFERENCE I
SCAN TI'"
PAH NO 201-777
OPERATOR f.&.U? PRINTED IN UP,
-60
Z
<4C
FIGURE 20. INFRARED SPECTRUM OF
BENZENE AND BENZENE/ETHER FRAC-
TION FROM DOWNSTREAM CRAPPIES
COLLECTED IN JULY, 1973
PHASE 3MKnK... THICKNESS _. —.
SOLVENT A/0A/JT REFERENCE ._ *".
CONCENTRATION SCAN TIME £& Ml^J.
-------
*•?
FIGURE 21. INFRA-
RED SPECTRUM OF
BENZENE/ETHER FRAC
TION FROM SPILLED
OIL COLLECTED IN
_ JULY, 1972
I'll;-:
PHASE
SOLVENT. AtONf
CONCENTRATION
^c'XT
V/AVENUV.B5R CM'1
THICKNESS REMARKS
REFERENCE
SCAN TIKE H Mlf>/_
T5oo~J
DATE _
OPERATOR
SuO oiO
03 *-Ti——V—..
PART NO 201 • 77775
', PRINTED IN JAPAN
5 50
—4-1972
FIGURE 22. INFRA-
RED SPECTRUM OF
BENZENE/ETHER
FRACTION FROM
SPILLED OIL COL-
LECTED IN JULY, 7
_
$*••- = 6fPVZI«*/«TMfH SOLVENT
CONCENTRATION
DATE ^11\M13
S'*
REFERENCE WO»MTf%
SCAN Tl VE |l M|M CflR6«AC
-------
FIGURE 23. INFRARED
SPECTRUM OF BENZENE
FRACTION FROM RERUN
OF COLUMN CHROMATO-
GRAM OF SPILLED OIL
COLLECTED IN JULY,
1972
DATE 7S
fl' fARI N° 2<"'77775
OPERATOR'T-SiJUlV PRINTED IN JAPAN
62
-------
The spilled crankcase oil waste was an extremely com-
plex mixture as indicated by the large unresolved backgrounds in the
chromatograms of the waste oil (Figs. 24 and 25).
In this study two sets of gas chromatograms were
determined on refined extracts from fish and waste crankcase oil.
1) the. cyclohexane fraction from colttmn
chromatography on alumina using a 6' by 1/8" OV-17 column pro-
grammed from 50-293°C at 8°C per minute.
2) the benzene (actually benzene + benzene/
ethyl ether) fraction from column chromatography on alumina using a
7' by 1/8" SE-52 column programmed from 50 to 293°C at 8°C per
minute.
Both of these columns were methyl phenyl silicone gum
rubber columns. The OV-17 column was used by the Virginia Institute
of Marine Science (Gloucester Point, Virginia) for analysis of crude oiJLs,
while the SE-52 column was used specifically for the analysis of poly-
cyclic aromatic hydrocarbons by Chatot et al. (1969).
F. Cyclohexane Fractions
Gas chromatograms were obtained on cyclohexane frac-
tions from column chromatography of spilled crankcase oil waste
(Fig. 24), upstream white suckers (Fig. 26), downstream white suckers
(Fig. 27), downstream brown bullheads (Fig. 28),and downstream
crappies (Fig. 29). These samples were chromatographed by a pre-
baking process in which the sample was placed in a small aluminum
foil cup and baked for five minutes inside the injection port of the
instrument before the temperature program was started.
While the infrared evidence (page 55) clearly illus-
trated the presence of aliphatic hydrocarbons in all cyclohexane frac-
tions of SCOW and fish, the gas chromatograms (Figs. 24, 26-29)
indeed illustrated their expected complexity. All samples showed a
broad, undefined background ranging from approximately 140 C to
270°C. However, no consistent fingerprint pattern was evident on
comparing the relatively small peaks superimposed on the prominant
background.
Chatot, G. , Jequier, W. , Jay, M. , and Fontanges, R. 1969.
"Study of Atmospheric Polycyclic Hydrocarbons: Problems Connected
with Coupling of Thin Layer Chromatography with Gas Phase Chroma-
tography, " Journal Chromatography 45:415.
63
-------
'J"> LO •*?- Tf CO CM CO r- O CO O> ;. -—- -—- —
>- FRACTION FROM SPILLED
!— OIL COLLECTED IN JULY,
-,_ 1972
-------
^ to p— en ^f. to »~ •«£. cr> t— to o ^ g>^ 01
p— co to ^ C7 csi CM »~ ooo^oicor— to
CM CVIOJ CJ evJOJCvJCOCJOJi— T-T—T— r-
I I I I I I I a I fl I B B I 1 I
FIGURE 25. CHROMATOGRAM
; OF BENZENE FRACTION FROM
"I-'-; SPILLED OIL - TWICE
--;--7 COLLECTED IN JULY, 1912
"1—<
1 s.0
xo
CMOOLO
-------
— -<•» — IO O> O
"Tor r- LO m
! OJ CM CVI CVJ
-L-rt
CJ O> O O f— tO fM
«— ' cn en
-------
O
T
o
us
CJ
r— en iti~*tcn r- t-j r- c\j t— CM «-
OJ f— r-r-o CT cr> c^ r- r— coca in
CSJ <\J CvJcvJCvJt— f— v-r- r~ r- r~ r-
o
o
in
i I I
..._ t_.;_..!_ _r_L LJ-L \-\.\-
r i • i i i r~rt~?"1 "n~
I I
i . , I : • j o o
-! —f- ;--j-.-.-. '—J. —j T-O
I i : , 1 xcnio
FIGURE 27. CHROMATO-
GRAM OF CYCLOHEXANE
FRACTION FROM DOWN-
STREAM WHITE SUCKERS
COLLECTED IN JULY,1973
CO
-------
00
i:r;r ; r r; i :r
. FIGURE 28. CHROMATO-
' GRAM OF CYCLOHEXANE
FRACTION FROM DOWN-
WrA- *
-------
FIGURE 29. CHROMATOGRAMi
OF, CYCLOHEXANE FRACTION
FROM DOWNSTREAM CRAPPIES
j—j- T-r-| COLLECTED IN JULY, 1973 i
__ : ' VAKIMV
o J : SofrEi -272.0
us i Cfif^ 1.5% OV-iT
-------
G. Benzene-Benzene/Ether Fractions
In contrast to the cyclohexane fractions, the gas chroma-
tograms from the "benzene" fraction of fish showed very well resolved
peaks with much less background. A typical example was seen in the
chromatogram of the upstream suckers (Fig. 30). This chromatogram
showed at least twenty-one well resolved peaks, thus offering an excel-
lent chance for peak matching studies with authentic samples of poly-
cyclic aromatic hydrocarbons.
A peak to peak analysis of the chromatograms from the
benzene fraction of fish will not be detailed here. The chromatograms
of the downstream suckers (Fig. 31), downstream brown bullheads
(Fig. 32), and downstream crappies (Fig. 33) samples all showed re-
markable similarity with many matching peaks. Admittedly, many of
these peaks varied in intensity, but their retention times were quite
reproducible.
While the gas chromatogram of the benzene fraction
from rechromatographed SCOW (Fig, 25) showed many well-resolved
peaks, it also contained a very large undefined background. As dis-
cussed above, this was due to the complexity of the spilled material.
The pattern differed from those of fish. Many peaks matched, but
there were many others of questionable identity.
H. Peak Matching Studies by Chromatography
Peak matching studies of the benzene eluate from up-
stream white suckers (Fig. 30) were conducted. This chromatogram
was compared with chromatograms of the same sample spiked with
individual polycyclic aromatic hydrocarbons. A list of these aromatics,
their structures and sources are given in Fig. 34. These hydrocarbons,
except for phenanthrene, were found in oysters by Cahnmann and Kurat-
sune (1957).
The chromatogram of the mixture of these polycyclic
aromatics is given in Fig. 35, which was obtained from a standard
solution containing 0. 116 mg/ml of each aromatic. The location of
Cahnmann, H. and M. Kuratsune. 1957. "Determination of
Polycyclic Aromatic Hydrocarbons in Oysters Collected in Polluted
Water," Anal. Chem. 29:1312.
70
-------
en m t~ 10 u-j
OJCVJeMCSJCJ
CJC-JCSJCVICVJt>J 1-
~**s
1._
FIGURE 30. CHROMATOGRAM
OF BENZENE FRACTION FROM
UPSTREAM WHITE SUCKERS
COLLECTED IN JULY, 1973
IENTJTIVE PEAK ASSIGNMENTS
l7~~PHENANTHFEf.'E
3! PYRENE
4. CHRYGENE /^D/OP
3ENZANTHRACENE
5. BENZO-A-PYPENE
LO C_»
10 - — O i <
I — \- CC
oa-r z «;
«-<_>(—
X O CO
CD CO LO
LO r~
CO
a.
-u» —
LklO
ZCL
-------
o ----- COOOr- Cl '~ OCO pj
-, i cncoeo r— 10 in r~ -*n cj
IV
O> CO CO f— to IO
.j . !. J ..~~~..~,
ll_ _' _ :
" o ,
- o
O- I
OJCJ
{ f
1 CO
I
i- FIGURE 31. CHROMATOGRAM
J_ OF BENZENE FRACTION FROM
! DOWNSTREAM WHITE SUCKERS
COLLECTED IN JULY, 1973 _ ;__. _.i_
or- :c
o • z\
10 O —I"!
-------
•O
OJ
en CM to OLD
j) oo r* r^ t£>
CM CM OJ CJ CM CJ
. i i i i I:
FIGURE 32. CHROMATOGRAM OF ;
BENZENE FRACTION FROM DOWN- :
STREAM BROWN BULLHEADS
COLLECTED IN JULY, 1973
I ILL i i !_:„„
-------
'i FIGURE 33. CHROMATOGRAM
OF BENZENE FRACTION FROM
DOWNSTREAM CRAPPIES
COLLECTED IN JULY, 1973 -+-^—i--'^-i -IR--—j--^.-"7,
— z a: I
i — -—!..
o sr Xi •
«- !_.„ . _ p(Tj. eir/z.6a.
0 i i :• ,
i ! cfi4fT-'£
• —-z.v>\ --i——'*->-,--r-
LU UJ , . ! i , I ]
. -CQ-t-^-J— —!-f--(-i
-! • : |.j V
i a
-------
Figure 34. Standard polycyclic aromatic hydrocarbons
Name
Chrysene
Flouranthene
Chemical Structure
Supplier
Aldrich Chemical
Co., 95%
Aldrich Chemical
Co., 99.9+%
Pyrene
Phenarithrene
Aldrich Chemical
Co., zone refined
99.9+%
Purified sample
prepared by author
Benzo (g,h,i)
perylene
Aldrich Chemical Co.
Benzo (a)
pyrene
Aldrich Chemical Co.
1,2-Benzanthracene
K & K Laboratories,
Inc.
75
-------
these aromatics as specified on the chromatogram in Fig. 35 was
accomplished in a separate study by spiking the mixture with individual
standards.
It is to be seen from Fig. 35 that chrysene and 1, 2-
benzanthracene were not resolved on an SE-52 column. Furthermore,
the heavy polycyclics (benzo-a-pyrene) and benzo (g,h,i) perylene did
not emerge from the column until after the temperature program to
293°C was completed.
Tentative assignments of these polycyclic aromatics are
given on Fig. 30 for the upstream white suckers, and the gas chroma-
tograms, listed below, supporting these tentative assignments are
given in Figs. 36-41.
Known hydrocarbon compounds (Fig. 34) were added to
samples of upstream white suckers to tentatively establish the presence
of these hydrocarbons in the fish residues by peak enhancement.
Fig. 35 Polycyclic aromatic hydrocarbons each
0. 116 mg/ml in benzene
•»
Fig. 36 Upstream white suckers + benzo (a) pyrene
Fig. 37 Upstream white suckers + 1,2-benzan-
thracene
Fig. 38 Upstream white suckers + chrysene
Fig. 39 Upstream white suckers + fluoranthene
Fig. 40 Upstream white suckers + pyrene
Fig. 41 Upstream white suckers + phenanthrene
Possibly a benzo (g,h, i) perylene peak was observed in
Fig. 47 at 17. 5 cm from the isothermal hold period.
I. Kinds and Levels of Hydrocarbons in Fish
The data given to ascertain the kinds and levels of petro-
leum hydrocarbons in Schuylkill River fish must be treated with caution.
The weights of hydrocarbons obtained from column chromatography,
given in Table 8, can only be judged in the context of considerable vari-
ation in the results of the analytical process, particularly in the sapon-
ification step.
76
-------
FIGURE 35. CHROMATO-
GRAM OF POLYCYCLIC
J _ . . , , _
AROMATIC HYDROCARBONS j-*- -
EACH 0.116.MG/ML IN '.
BENZENE
.T-.--i--/ /--I
! i I i hi
-------
CO
C?> r~
-------
-- FIGURE 37. CHROMATOGRAM
OF BENZENE FRACTION FROM
— UPSTREAM WHITE SUCKERS
DOPED WITH 1,2- BENZAN
THRACENE
-------
CO
o
till. II I I I
FIGURE 38. CHROMATOGRAM OF ;
BENZENE FRACTION FROM UP-
STREAM WHITE 'SUCKERS DOPED !
WITH CHRYSENE f~^ ~*-
| . r .r-----..! : .-! r • r
i L_J [_ 1 .. •_.-_•_ L _(
-------
00
•'1
,11 *~*~ a
: I t.. i : > I • [«« tM«\jrucvicjtvjc>jcvj «MOJ r-i
-~-; ~- : i ! I I I r 1 I ' | II [II
-;'-4--i-t-
rrt-h-;-
"l^i^^'-'i •. • i :-"r"-i .v~i'-1."]-."r
.!-:--^--?---i-i-'N^.
;-)•; i ::r::T:!::H'!' !
: FIGURE 39. CHROMATOGRAM
OF BENZENE FRACTION FROM
UPSTREAM WHITE SUCKERS i
DOPED WITH FLOURANTHENE
-------
00
_.« r—rocs csi CNJIO o CM eo -^. o
i •—| 1 o> r- r- u> u> u>-*r ^- to
-------
00
CU PJ CVICM CJCJCJCJOJCM CM I—
;_':i_l.._. co | I II II II 1
FIGURE 41. CHROMATOGRAM OF
& £ BENZENE FRACTION FROM UPSTREAM
—-I4l £S~ WHITE SUCKERS DOPED WITH
PEHENANTHRENE
rtn-i-ttm-h-
-------
oo
TABLE 8 Levels of Aliphatic and Aromatic Hydrocarbons
in Sch ylkill River Fish Collected July, 1973
Sample
Spilled oil (SCOW)
White suckers
downstream
White suckers
upstream
Brown bullheads
downstream
Brown bullheads
upstream
Grappies
downstream
Crappies
upstream
115
116
Aliphatic
Starting
Sample (g)
93
110
113
116
112
Hydrocarbons I
(mg)
575*
25
24
15
lydrocarbon.1
(mg)
90*
15
15
9
Aromatic Aliphatic
Hydrocarbo
(ppm)+
10
*From 1, 196 g oil extract at saponification step
*#Analysis abandoned due to clogged chromatographic column
***Only solid gel products on column chromatography
+Based on starting sample (fish or spilled oil)
481,000
227
212
129
70
Aromatic
Hydrocarbons
(ppm)+
45,300
136
133
78
87
-------
In the analyses of the Schuylkill River fish, the infrared
spectra of either the cyclohexane or the benzene-benzene/ether frac-
tions showed qualitative reproducibility in the analyses that could be
completed to this stage. All spectra indicated to a large degree the
absence of absorptions corresponding to hydroxyl, primary and secon-
dary amino, and carbonyl functional groups. This means that typical
organic substances such as fats, amino acids, proteins, alcohols,
carboxylic acids and esters, simple sugars and polysaccharides were
largely absent in the final fractions from column chromatography.
The infrared spectra of the cyclohexane fractions of
Schuylkill River fish and SCOW, along with the GC data, indicate the
predominant presence of a complex mixture of saturated aliphatic
hydrocarbons. The average level of aliphatics in Schuylkill River fish
was 160 ppm (Table 8) v£. our average level of 13 ppm for cyclohexane
eluted residues obtained from similar analytical treatment of HLFH
fish (Subsection J, page 86, and Appendix V-5).
The infrared spectra of the fluorescent benzene-
benzene/ether fractions indicated the possible presence of polycyclic
aromatics. The weak absorptions at 3000-3100 cm (absent from
the cyclohexane eluates) suggested carbon to hydrogen bonds of the
olefinic and/or aromatic type. The absorptions at 650-1250 cm"
were characteristic of the complex absorption of polycyclic aromatics.
Furthermore, the presence of saturated aliphatic structures was also
indicated by the absorptions at 2800-3000 cm" , 1440 cm" and
1380 cm" . It was not determined whether these absorptions indicated
the presence of saturated aliphatic hydrocarbons, or if the saturated
aliphatic radicals were bonded to other kinds of structures. Even
simple methyl (-CHo) derivatives would show these absorptions. The
gas chromatographic data, including the peak matching studies with
polycyclic aromatics (Fig. 34) previously identified as being in oysters
by Cahnmann and Kuratsune, indicated the presence of these materials
in the benzene-benzene/ether fraction of Schuylkill River fish.
Cahnmann, H. and M. Kuratsune. 1957. "Determination of
Polycyclic Aromatic Hydrocarbons in Oysters Collected in Polluted
Water," Anal. Chem. 29:1312.
85
-------
J. Studies of Fishes from Harrison Lake
National Fish Hatchery
1. Test of Analytical Procedure for Polycyclic
Aromatic Hydrocarbons
To provide data on fish from a relatively clean
environment and to check if the polycyclic aromatics can be deter-
mined by the analytical method used, samples of channel catfish were
taken from the Harrison Lake National Fish Hatchery and tainted wit>>
benzene solutions of polycyclic aromatics (Fig. 34) at the initial
blending stage of the procedure. Four analyses were conducted with
the added hydrocarbons at levels of zero, two, five, and ten ppm of
each hydrocarbon. Two minor modifications were made in the pro-
cedure: 1) the fish powder was extracted 44-48 hours instead of 24
hours (no appreciable change in variation of oils extracted occurred,
Appendix V-4), and 2) the saponification time period was reduced
from 48 hours to 24 hours, which seemed to result in less troublesome
gel formation.
The Harrison Lake fish are designated as "HLFH
fish. " The fish hatchery itself is located in Virginia at the head of
Herring Creek which empties into the James River about four miles
from the hatchery. The waters used by the hatchery all come from
Harrison Lake which is about 190 acres in area (approximately 70
acres of open water) with no industry on its shores. Its clear waters
are bordered by about 150 yards of woodland, and motorboat traffic is
minimal since no public boat ramps or motorboat services are avail-
able. The traffic is basically limited to five horsepower engines
which must be carried manually.
The percent yields of non-volatile residues from
the extraction and saponification processes are given in Appendix V-4,
and the yields of non-volatile residues from the cyclohexane and ben-
zene/benzene-ethyl ether fractions from column chromatography are
given in Appendix V-5.
2. Gas Chromatographic Studies on Benzene-
Eluted Residues from Harrison Lake Fish
The residues from the benzene-benzene/ether
fraction (Appendix V-5) were subjected to vapor phase chromatography
86
-------
A typical chromatogram is given in Fig. 42, which was determined on
fishes with 5 ppm added polycyclic aromatic hydrocarbon. Except for
a large peak after the isothermal hold period, all peaks corresponded
to those from the chromatogram of the standard aromatic hydrocarbon
mixture (Fig. 43). Except for the addition of triphenylmethane (TPM)
internal standard, the chromatogram of the benzene-benzene/ether
residue from Harrison Lake fish with no added polycyclic aromatic
hydrocarbons showed no peaks corresponding to these hydrocarbons
(Fig. 44). All gas chromatograms of the benzene-benzene/ether frac-
tions eluted from the Harrison Lake fish containing added polycyclic
aromatic hydrocarbons showed similar patterns (Figs. 42 and 45-47).
3. Percent Recoveries of Polycyclic Aromatic
Hydrocarbons from HLFH Fish
The percent recovery of polycyclic aromatic
hydrocarbons from the Harrison Lake fish, which were purposely
treated with known amounts of these hydrocarbons during the blending
stage of the analysis, was determined. The method used involved the
addition of a known quantity of an internal standard to the benzene-
benzene/ether fraction from column chromatography prior to the gas
chromatographic analysis.
To determine weight relationships from the
internal standard, a solution of known amounts of the polycyclic aro-
matic hydrocarbons was mixed with a known amount of triphenylmethane
internal standard. The chromatogram of this mixture is given in Fig.
43. From this chromatogram the area ratio for each hydrocarbon
peak vs, the peak for TPM standard was determined, and the area
ratio divided by the known weight ratio for each peak was also deter-
mined. The area ratio/weight ratio listed for each hydrocarbon in
the table (Appendix V-6) represented a correction factor to be applied
later to the analysis of benzene-benzene/ether eluted compounds from
column chromatography.
Calculations of the percent recovery of the
hydrocarbons from HLFH fish are summarized in Appendices V-7 to
V-9. No calculations were made on the benzene-benzene/ether eluted
material from HLFH fish with zero ppm added hydrocarbons. From
the calculations in Appendices V-7 to V-9, the percent recovery of
hydrocarbons ranged f om 27 - 43 percent for fishes doped with 2 ppm
hydrocarbon, 54 - 106 percent for fishes doped with 5 ppm hydro-
carbon, and 43 - 78 percent for fishes doped with 10 ppm hydrocarbon.
87
-------
CO
00
FIGURE 42. CHROMATOGRAM ;
OF BENZENE FRACTION FROM
r^ i -r - COLUMN CHROMATOGRAM OF
HARRISON LAKE NATIONAL
-I-- FISH HATCHERY CHANNEL
H-—Jf-j-' CATFISH WITHOUT TPM
i^-^-riT INTERNAL STANDARD AND
H-: WITH 5 PPM ADDED HYDRO- ur
-==—r-;-h CARBON
-------
CO
FIGURE 43. CHROMATOGRAM
-S--H-H—;-: OF STANDARD POLYCYCLIC ARO-
MATIC HYDROCARBONS WITH
TRIPHRNYLMETHANE - TPM -
INTERNAL STANDARD
-------
FIGURE 44. CHROMATOGRAM OF:
BENZENE FRACTION FROM COL- .
UMN CHROMATOGRAM OF HARRI- ,
SON LAKE NATIONAL FISH
HATCHERY CHANNEL CATFISH
WITH TPM INTERNAL STANDARD
AND ZERO PPM ADDED HYDRO-
CARBON
I • c/J= -
-------
•>
' I • I J I'M | i ! J
; -I FIGURE 45. CHROMATOGRAM OF
M—1--| BENZENE FRACTION FROM COL-
i -'--) UMN CHROMATOGRAM OF HARRI-
-!-_! SON LAKE NATIONAL FISH
HATCHERY CHANNEL CATFISH
WITH TPM INTERNAL STANDARD — r|
M j AND 2 PPM ADDED HYDROCARBON
• I.!
; ]
1 i
-- ' - 4 . -
1 1 i
1 I
j -
4-
-
i
!
_.i.
I
,
,_.
1-
-
[
1
_ 1 _
^—
-------
IN)
_._
J-i-i- FIGURE 46. CHROMATOGRAM
OF BENZENE FRACTION FROM -
COLUMN CHROMATOGRAM OF
---,—{—r HARRISON LAKE NATIONAL —
^--!-[- FISH HATCHERY CHANNEL
——+- CATFISH WITH TPM INTERNALr
rrT-f: STANDARD AND 5 PPM ADDED ^
-t-r HYDROCARBON
J 1-P\—j- -'[-4 — i-- ' i—! :r_l— -L- ; ; L !
___ __,
:! -1 -i :-i- i -"-.- !
-------
FIGURE 47. CHROMATOGRAM -,
OF BENZENE FRACTION FROM - !•
COLUMN CHROMATOGRAM OF -!
HARRISON LAKE NATIONAL -f
FISH HATCHERY CHANNEL CAT-
FISH WITH TPM INTERNAL
STANDARD AND 10 PPM ADDED
HYDROCARBON
J.11
-r- -I- f
-------
The chromatograms clearly show that the analy-
tical procedure is useful for detecting levels of polycyclic aromatics
at the one ppm concentration level.
9. OTHER EFFECTS OF THE SPILL ON RIVER BIOTA
A. General Trophic-Level Interactions Among
Schuylkill River Biota
The river ecosystem is composed of four basic compon-
ents: abiotic substances, producer organisms, consumer organisms,
and decomposer organisms. Abiotic materials, such as water, carbon
dioxide, nitrogen, and phosphorous, are assimilated by two main types
of producer s- -phytoplankton and algae attached to substrata on the
river bottom. Members of this first trophic level are, in turn, grazed
upon by the major components of the second trophic level--zooplankton
and bottom-dwelling types of herbivores. These organisms are then
preyed upon by the secondary consumers or primary carnivores that
constitute the third trophic level--small adult fishes and the young of
most fish species. Tertiary consumers (secondary carnivores), which
are usually large fishes, prey upon the secondary consumers. Decom-
posers (aquatic bacteria and fungi) break down the excretory products
and dead remains of both producers and consumers into abiotic sub-
stances, thus completing the trophic cycle.
Additional trophic pathways are usually superimposed
upon the basic structure described above. Some organisms (omnivores)
feed upon a number of trophic levels. For example, brown bullheads
captured in the Schuylkill River had been feeding on small fish, dip-
teran larvae, and algal mats. It has also been suggested that members
of the upper-trophic levels can directly utilize certain abiotic sub-
stances. Some organisms switch trophic levels as they mature and
become physically able to ingest larger food items, and other organ-
isms utilize trophic components of other ecosystems (for example,
crappies observed in this study had been feeding upon flying insects).
In many lakes and ponds, the most abundant types of
producers and primary consumers are phytoplankton and zooplankton,
respectively. However, in relatively shallow bodies of water, such as
the Schuylkill River, the bottom community (attached algae, benthic
invertebrates such as Oligochaeta and Diptera larvae and pupae, bac-
terial flora) plays a more dominant role.
94
-------
Major food items of species of fish collected during
the winter of 197Z-73 and the summer of 1973 were: white suckers --
Diptera larvae and pupae; brown bullheads -- Diptera larvae and pupae,
small fish; crappies -- Diptera larvae and pupae, aquatic insects;
bluegills -- small fish (Appendix VI-5). The importance of planktonic
and benthic life forms of Diptera to the trophic needs of these fish
species is apparent. The families Psychodidae, Tendipedidae, and
Ceratopogonidae were the most widely represented groups of dipterans
observed in stomach contents.
Stomach contents of white suckers, brown bullheads,
crappies, and bluegilrs gave no indication of differential food habits
that could be attributed to the oil spill.
B. Chlorophyll a^
Average levels of total and active chlorophyll a.
(Appendix VI-1) increased from Monocacy Bridge station to Valley
Forge Bridge station on 16 and Z9 July 1972. This tends to substan-
tiate the hypothesis of increased downstream primary productivity as
suggested by pH measurement. Average levels were higher at all
stations on Z9 July than on 16 July.
Comparison of the ratios between pheopigment (inactive
chlorophyll a) and total pigments indicated a substantially greater
amount of "dead" material at Parker Ford Bridge (11.7 miles below
the oil spill) on 16 July than at either Monocacy Bridge or Valley
Forge Bridge (Figure 48). A slightly greater amount of pheopigment
was observed at Parker Ford Bridge on 29 July than at the other
stations.
Duplicate pigment measurements at the same sampling
station generally indicated an acceptable degree of precision in sam-
pling and spectrophotometric methods. The reason for the large
differences between duplicate samples taken on 16 July at Valley
Forge Bridge is unknown.
C. Zooplankton
Zooplankton samples taken on J6 July, 19 July, 28 No-
vember, 1 December 1972, and 14 July 1973 (Appendix VI-2) were
generally similar at upstream and downstream stations. Members of
the groups Cladocera (water fleas), Copepoda (copepods), and Tendi-
pedidae (midges) were dominant forms throughout much of the study.
95
-------
50-r
<
_l
I
O.
O
cc
o
I
o
o
LJ_
D
2
UJ
5
e>
o!
o
LU
Q.
I
O.
O
ec
O
I
o
40-
30-
20-
10-
MILES FROM OIL SPILL
1.7
16 JULY 1972
29 JULY 1972
LOCATIONS
MONOCACY
BRIDGE
0 SPILL SITE
11.7
PARKER FORD
BRIDGE
25.0
VALLEY FORGE
BRIDGE
FIGURE 48 CHLOROPHYLL a PHEOPIGMENTS OF SCHUYLKILL RIVER WATER DURING JULY 1972
-------
Ranges of abundance of these groups shortly after the oil spill
(Figure 49) did not indicate differences between upstream and down-
stream stations that can be attributed to the oil spill. All three taxons
exhibited greater abundance at Parker Ford Bridge station than at the
upstream control station (Monocacy Bridge).
Major taxon diversity fluctuated between 6 and 10 during
the study. Most taxons exhibited sharply reduced numbers during
fall and winter. Lesser numbers of Cladocera, Copepoda, and Tendi-
pedidae were observed in the summer of 1973 than during the summer
of 1972.
D. Benthic Macrofauna
Larvae of the families Hydropsychidae (net-building
caddis flies) and Psephenidae (water pennies) decreased in abundance
in the area of the river directly below the oil spill and did not increase
to their former production levels during the summer of 1972. Both
groups are tolerant of rapid stream velocities and were collected in
Perkiomen Creek, a small tributary emptying into the Schuylkill
River between Phoenixville and Norristown, during and after the
flooding caused by Tropical Storm Agnes. Therefore, it is likely that
their scarcity in the Schuylkill was caused by the presence of oil
rather than by the flood conditions. The food-gathering nets of many
caddis fly larvae were visibly coated with oil. This may have reduced
feeding efficiency. Water penny larvae breathe by ventral abdominal
gills which rest directly against the rock surfaces upon which the
animals attach. Any oil adhering to the rocks could conceivably have
interfered with normal respiratory processes.
Quantitative sampling efforts directly after the oil spill
were unsuccessful because of high-water conditions and lack of
familiarity with the more suitable habitats of the river. Macrofauna
samples collected on 29 November 1972 and 28 July 1973 (Appendix
VI-3) exhibited no apparent variation among stations that can be attri-
buted to the oil spill.
Ranges of abundance of the two dominant macrofaunal
taxons (Figure 50) indicate that Oligochaeta (represented primarily
by sludge worms of the genus Tubifex ) were more abundant at both
the Monocacy stations (above the oil spill) and the Parker Ford sta-
tions (10. 6 to 12. 5 miles downstream from the spill) than at the
Douglassville stations (0. 4 to 2.3 miles directly below the spill), and
that numbers of Tendipedidae observed at the Monocacy and Douglass-
ville stations did hot differ greatly. Parker Ford stations were not
97
-------
vO
oo
160-
140-
120-
d 10°'
Z
1 80-
z
o
0 60-
40-
20-
MILES FROn/lOILSPIl
11 COPEPODA
JCLADOCERA
"N" TENDIPEDIDAE
•
T
1
•
»
i
F
f
•
/
/
/
/
x
/
/
»
"P
X
X
X
±
.L 1.7 * 11.
0 SPILL SITE
•
I
•.
I
.
»
^
•
•
7 25.0
LOCATIONS MONOCACY PARKER FORD VALLEY FORGE
BRIDGE BRIDGE BRIDGE
FIGURE 49 RANGES OF ABUNDANCE OF THREE DOMINANT ZOOPLANKTON TAXONS COLLECTED
ON 28 JULY AND 29 NOVEMBER 1972 IN THE SCHUYLKILL RIVER
-------
vO
40,000 -j
30,000-
£T
6
z
S 20,000 -
CO
Z
o
cc
o
10,000-
TT
M TENDIPEDIDAE
1^ OLIGOCHAETA
TT
\
\
s TT
\ ^
^
\ ^
\ ^
^ jT- s NO SAMPLE ^
$ \ 4 s FROM28JULY1973P^
p \ ^ s J
l^ ^"^ "J ^ TT
MILES FROM OIL SPILL f I | II
2.1 ' 0.4 2.3 10.6 12.5
0 1 1 < 1
T~ 1 1
LOCATIONS MONOCACY DOUGLASSVILLE PARKER FORD
STATION STATION STATION
SPILL
SITE
FIGURE 50. RANGES OF ABUNDANCE OF TWO DOMINANT MACROFAUNAL TAXONS COLLECTED ON 29 NOVEMBER 1972
AND 28 JULY 1973 IN THE SCHUYLKILL RIVER
-------
sampled on 28 July 1973. Tendipedidae were commonly encountered
at the other sampling stations on that date. Since both Tubifex_ and
Tendipedidae are biological indicators that are resistant to most forms
of pollution (Rounsefell and Everhart, 1953), the most likely result of
the oil spill on the bottom community might be expected to be elevated
numbers of both taxons in relation to other organisms directly below
the spill at the Douglassville stations. This was not the case.
Major.taxon diversity at the sampling sites ranged
from 0 7 during the study (Appendix VI-3). Oligochaeta were more
abundant than Tendipedidae on 29 November 1972. This relationship
was reversed on 28 July 1973 presumably due, in part, to the onset
of the midge reproductive season.
E. Bacteria
Bacteria counts of river sediment were taken on 17, 23,
and 30 July 1972 and are shown in Appendix VI-4. On each collection
date, the greatest numbers of casein splitters, glucose fermenters,
and sulfate fermenters were found at the Parker Ford Bridge station.
The generally low counts of glucose fermenters could indicate little
recent addition of carbohydrate-like pollution to the river. Similarly,
low numbers of sulfate fermenters may be due to relatively aerated
conditions in the river bottom or to inactivation of the samples by air
after sampling.
Contamination of the agar medium prevented estima-
tion of the important hydrocarbon oxidizers on 17 and 23 July. How-
ever, on 30 July these bacteria were at least twice as abundant in the
Parker Ford Bridge area than at the other stations.
Standard plate counts (Table 23) also revealed highest
bacteria counts in the Parker Ford Bridge area on all sampling dates.
F. Community Metabolism
Suitability of oxygen data (Appendix 1-1) for treatment
by diurnal-curve techniques was determined. Data collected on 16
and 29 July 1972 were not usable since normal predawn decreases in
Rounsefell, G. A. and W. H. Everhart. 1953. Fishery Science:
Its Methods and Applications. J. Wiley and Sons, London. 444p.
100
-------
oxygen concentrations, from which estimates of community respira-
tion are derived, did not occur.
Oxygen data for 30 July 1972 and diurnal-curve analysis
are presented in Figures 51 and 52. Community respiration and gross
primary production were slightly higher at Parker Ford Bridge than
upstream at Monocacy Bridge. Community respiration at both sam-
pling stations was relatively high as compared to several river sys-
tems described by Odum (1956 , Table 2). Both P/R ratios were just
over 1. 0, indicating an autotropic river system in which in-situ pri-
mary production slightly exceeds community respiration.
Biochemical oxygen demand (BOD) measurements
taken during the summer of 1972 (Appendix 1-2) ranged from 0.4 to
4.2 ppm. Highest levels were usually observed in the>Douglassville
Bridge - Parker Ford Bridge length of the river (0. 7 to 11.7 miles
below the oil spill).
The importance of the bottom community in the
Schuylkill is evidenced by comparing biochemical-oxygen-demand of
the river water to estimates of community respiration obtained by the
diurnal-curve techniques. BOD, which measures respiration of only
the planktonic flora and fauna of the river, was only 0. 4 to 4.2 ppm
oxygen over a five-day period. However, total community respiration,
including that of the bottom community, as determined by diurnal-
curve techniques, was approximately 25 ppm oxygen during a single
24-hour cycle.
10. CLEANUP IMPACT AND EFFECTIVENESS
A. A major portion of the oil swept from the pits of Berk
Associates was filtered from the rising flood waters by land vegeta-
tion or deposited on the river's banks and proximal areas. Apparently
only a small amount of oil was carried directly into the river basin.
It is likely that much of the oil that was carried into
the river basin combined with the heavy silt and clay load that charac-
terized the flooding river and was rapidly carried downstream toward
Delaware Bay. No large masses of oil were observed during bottom
Odum, H. T. 1956. "Primary Production in Flowing Waters,
Lim.no. Ocean. 1:102-117.
101
-------
JRE] 51. p.
AHY
OXYGEN METABOLISM 0F I
RlVE'R
MOlNOCKcY BRJn>GE~l7 MZI^
3.
-------
FIGURE 52. DAILY OXYGEN METABOLISM OF SCHUYLKILL RlVER
BIOTA ON '30 JULY 1972 AT PARKER FORD ?R1D''E
11.7 MIL^S BELLOW
0600 1300, 11800
Time of Day (hr)
-K4
+.3
—K2-
-Kt
- O
r -.t
a.
— -3
n
/ ; r F
1—
I
I t |__!|_ II
Diffusion coijected !
060O 1200 1800
Time of Day (hr)
Z400
Community "Respiration (g/m /day] = 25.20
Gross Primary Production (g/nti^/day) - 27.50
P/R ratio f= 1.09
103
-------
sampling operations. Most of the silt and clay particles upon which
hydrocarbon and heavy metals precipitate were washed away by the
flood waters. Only a sand-pebble substratum remained. Chemical
analysis of heavy metal and hydrocarbon concentrations of the bottom
indicated that there was some oil contamination of the river bottom
below the spill.
Cleanup of the river bottom was considered unnecessary
due to the high cost. The inefficiency of the operation would have only
served to redistribute much of the oil that had been deposited on the
river bottom.
B. Oil that was deposited directly on land had to be physi-
cally removed. Heavy metal constituents of the oil were likely to
persist through time. Workmen had to avoid accidental oral intake of
the oil (Physical contact with the metals' components is not a problem).
Burning of oil will vaporize heavy metals and result in a potential
hazard to workmen and to the surrounding environment. Burning
should never be attempted. Vaporization of low-boiling aromatic
hydrocarbon (another component of the oil) caused a noticeable "oily"
smell in the affected area. Toxic materials will evaporate and be
oxidized and decomposed with time. However, they are considered a
health hazard to men subjected to chronic exposure through inhalation.
Care was taken not to bury removed oil where contamination to ground
water or livestock might occur.
C. Oil deposited on vegetation (leaves, grasses, etc. )
adhered tightly to the plants after a period of consolidation. Rainfall
or falling of leaves into the river resulted in only small amounts of
heavy metals and remaining hydrocarbons (most toxic hydrocarbons
had already been evaporated or decomposed) going into solution.
Hence, periodic precipitation and gradual fall of leaves into the river
unlikely caused major human health problems. Any hosing of vegeta-
tion during a short time period or before low-boiling aromatic hydro-
carbons had evaporated or decomposed would have resulted in a more
acute problem of river pollution than doing nothing. Primary cleanup
operations performed for the removal of vegetation resulted in the
following:
1) Only trees, .shrubs, and branches in the most
heavily polluted areas were removed in order to leave a root system
to prevent bank erosion.
2) "Quick-cover," fast-growing grass was used to
prevent erosion.
104
-------
3) Angled booms were placed at strategic locations
along the river to collect floating leaves and oil slicks. Booms were
placed in slowly moving sections of the river and kept in operation
until most oil-covered leaves had dropped from the banks. Angled
booms also directed floating oil to the bank at water velocities of less
than 2 knots. Trucks were permanently at locations to suck leaves
and oil from the junctions of the booms and riverbank.
105
-------
ACKNOWLEDGEMENTS
Ocean Science and Engineering, Inc. , gratefully acknowledges
the hard work and dedication of the scientists and technicians who
contributed to this study.
Mr. Charles R. Mainville was the Program Manager.
Dr. Charles R. Curtis, Associate Professor of Plant Pathology
at the University of Maryland, conducted the investigations of the ef-
fects of the spill on vegetation.
Techniques for the analysis of hydrocarbons in vertebrate
fishes were developed by Professor Trevor Hill of the College of
William and Mary. Dr. Hill was assisted in his work by Messrs.
William S. Eck, Robert Huggett, and Gerry Lasser.
Mr. Robert Huggett of the Virginia Institute of Marine Science
performed the heavy metaos analyses of the oil, sediments, and or-
ganisms.
Biological analyses and water-quality investigations were
performed by Dr. Curt D. Rose, Head of the Shellfish Division of the
University of Maryland's Center for Environmental and Estuarine
Studies. Dr. Rose was assisted by Messrs. Rodgers Huff, Joseph
Ustach, Bud Millsaps, Dan Terlizzi, and Don Meritt.
Messrs. Michael Clark, Larry Kingsbury, and Roy L. Rice of
OSE performed much of the field work during the program.
106
-------
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Anon. , Methods of Analysis for Chlorinated Pesticide Residues.
Patuxent Wildlife Research Center.
Baumhardt, G. R. , and L. F. Welch. 1972. "Lead Uptake
and Corn Growth with Soil-Applied Lead, " J. Envir. Qual. 1:92-94.
Blumer, M. , G. Souza, and J. Sass. 1970. "Hydrocarbon
Pollution of Edible Shellfish by an Oil Spill, " Biol. 5:195.
Cahnmann, H. and M. Kuratsune. 1957. "Determination of
Polycyclic Aromatic Hydrocarbons in Oysters Collected in Polluted
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Campbell, I. R. , and E. G. Mergard. 1972. Biological Aspects
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Chapman, H. D. , and P. F. Pratt. 1961. Methods of Analysis
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Chapman, H. D. (ed). 1966. Diagnostic Criteria for Plants
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Chatot, G. , W. Jequier, M. Jay, and R. Fontanges. 1969.
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Connell, D. W. 1971. "Kerosene-Like Tainting in the Aus-
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Chow, T. J. 1970. "Lead Accumulation in Roadside Soil and
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Gauch, H. G. 1972. Inorganic Plant Nutrition. Dowden,
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107
-------
Huggett, R. J. , M. E. Bender, H. D. Slone. 1972. Final
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Huggett, R. J. , M. E. Bender, H. D. Slone. 1^71. "Mercury
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Huggett, R. J. , M. E. Bender, H. D. Slone. 1973. "Utilizing
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Huggett, R. J. , M. E. Bender. 1972. "Trace Metals in the
Rappahannock River Sediments," Chesapeake Research Consortium
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Hunt, R. H. , and M. J. O'Neal. 1967. Encyclopedia of Chem-
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Lorenzen, C. J. 1966. "A Method for the Continuous Measure-
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227.
Lorenzen, C. J. 1967. "Determination of Chlorophyll Pheo-
Pigments: Spectrophotometric Equations," Limno. Ocean. 12:343-
345.
Lounamaa, J. 1956. "Trace Elements in Plants Growing Wild
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Mortvedt, J. J. , P, M. Giordano, and W. L. Lindsay (eds).
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Wisconsin. 666 p.
Odum, H. T. 1956. "Primary Production in Flowing Waters, "
Limno. Ocean. 1:102-117.
Rounsefell, G. A., and W. H. Everhart. 1953. Fishery
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Sass, J. E. 1958. Botanical Microtechnique. Iowa State
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Smith. W. H. 1973. "Metal Contamination of Urban Woody
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108
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Snedecor, G. W. , and W. G. Cochran. 1967. Statistical
Methods. Iowa State University Press, Ames, Iowa. 593 p.
U. S. Environmental Protection Agency. 1971. Laboratory
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Zarifiou, O. , M. Blumer, and J. Myers. 1972. Correla-
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MANUSCRIPT.
109
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GLOSSARY
Common Name
Birch
Black walnut
Bluegill
Brown bullheads
Channel catfish
Crappies
Elm
Golden shiver
Hickory
Maple
Net building caddis flies
Oak
Sassafras
Sycamore
Tree of heaven
Tuliptree
Water pennies
White suckers
Wild cherry
Biological Name
Betula sp.
Juglans nigra L.
Lepomis macrochirus
Ictalurus nebulosus
Ictalurus punctatus
Pomoxis sp.
Ulmus sp.
Notemigonus crysoleucas
Carya sp.
Acer sp.
Hydropsychidae
Quercus sp.
Sassafras albidium
Platanus occidentalis L.
Ailanthus altissima
Liriodendron tulipifers L
Psephenidae
Gatostomus commersoni
Prunus sp.
110
-------
APPENDIX I DATA FROM ANALYSES OF RIVER WATER
111
-------
Appendix 1-1. Twenty-four (24) hour temperature and dissolved
July 1972
oxygen
Above Spill
Monocacy
Time
0025
0630
0930
1230
1530
2020
Monocacy
Time
0100
0640
0950
1310
1905
Temp.
24
24
25
27
27
25
Temp.
23
23
24
23
24
16 July
Dissolved C>2
(ppm)
5.2
5. 7
5.9
6. 1
6.2
6.2
29 July
Dissolved 03
(ppm)
5.2
6.2
6.3
7.5
7.6
1972
Time
0000
0600
0900
0200
1600
1830
1972
Time
0030
0625
0925
1245
1235
Below Spill
Parker
Temp.
26
25
25
27
28
28
Parker
Temp.
23
23
24
24
24
Ford
Dissolved C>2
(ppm)
5.3
5.8
5.8
6.3
6.4
6.4
Ford
Dissolved Q?
(ppm)
5.7
7.0
7. 1
7.6
8.0
112
-------
Appendix 1-1. (continued)
Above Spill
Monocacy
Time
0000
0600
0900
1200
1500
1800
2100
2400
Temp.
21
21
21
21
21
21
21
21
30 July
Dissolved O^
(ppm)
4.9
4.4
4.5
4.9
5.8
5.6
5.6
5.2
1972
Time
0030
0630
0930
1230
1530
1830
2130
2430
-L^ \_. JL- \-/ " LJ^JLJ-J-
Parker Ford
Temp.
23
23
23
23
23
23
23
23
Dissolved C>2
(ppm)
B.I
4.4
4.4
4.7
5.7
5. 5
5.5
5. 0
113
-------
Appendix Ir2. Biochemical oxygen demand, chemical oxygen demand, and
M.O. alkalinity of Schuylkill River water above and
below spill site in July 1972
Station
Above Spill
Monocacy
Below Spill
Douglassville Br.
Parker Ford Br.
Spring City Br.
Rt. 113 Br.
Valley Forge Br.
Falls Br. (Phila.)
Above Spill
Monocacy
Below Spill
BOD (ppm-5 day)
3 July 1972
1.1
0.9
1.5
1,5
1.3
1.4
1.3
11 July 1972
1.0
COD (ppm)
6.71
7.38
9.40
15.44
10.07
15.10
10.74
5.59
M.O. Alkalinity
(ppm CaCOi)
50
54
53
56
52
52
55
Douglassville Br. 0.9 5.38
Par' er Ford Br. 0.4 10.40
Valley Forge Br. 0.8 4.97
114
-------
Appendix 1-2. (continued)
18 July 1972
Above Spill
Monocacy Br. 0.6 9.27 70
Below Spill
Douglassville Br. 0.9 10.50 68
Par'.er Ford Br. 0.7 16.10 72
Valley Forge Br. 0.5 9.67 67
25 July 1972
Above Spill
Monocacy Br. 1.8 7.56 73
Below Spill
Douglassville Br. 2.7 11.10 82
Parkerford Br. 1.8 7.96 85
Valley Forge Br. 1.6 11..10 76
1 August 1972
Above Spill
Monocacy Br. 1.9 8.97 68
Below Spill
Douglassville Br. 4.2 11.30 78
Parkerford Br. 1.7 6.24 76
Valley Forge Br. 1.3 6.63 78
115
-------
Appendix 1-3. Hydrogen-ion concentration in Schuylkill River water
12 July - 5 August'1972
Date
July 12
July 13
July 14
July 15
July 16
July 17
July 18
July 19
July 20
July 21
July 22
July 23
July 24
July 25
July 26
July 27
July 28
July 29
July 30
July 31
Above Spill
Monocacy
7.4
7.4
7.2
7.4
--
7.0
7.1
7.2
7.2
7.1
7.2
7.2
7.3
7.2
7.2
7.2
7.2
7.2
7.2
7.2
Stations
Douglassville
:'.4
7.3
7.2
7.4
7.5
7.0
7.1
7.2
7.1
7.2
7.2
7.2
7.3
7.2
7.2
7.2
7.2
7.2
7.2
7.2
Below Spill
Par'-er Ford
7.4
7.4
7.2
7.4
7.4
7.0
7.0
7.0
7.2
7.1
7.2
7.2
7.4
7.2
7.2
7.2
7.2
7.2
7.2
7.2
Valley Forge
7.5
7.7
7.3
7.4
7.7
7.3
7.2
7.2
7.2
7.1
7.2
7.3
7.8
7.6
7.2
7.3
7.2
7.6
7.8
7.6
116
-------
Appendix 1-3. (continued)
Date
Monocacy
August 1
August 2
August 3
August 4
August 5
7.2
7.3
7.2
7.1
7.2
Stations
Douglassville Parker Ford
7.2 7.2
7.2 7.2
7.1 7.2
7.2
7.5
Valley Forge
7.4
7.4
7.3
7.3
—
All readings were taken during the day and, therefore, represent
maximum daily values.
117
-------
APPENDIX II DATA FROM HEAVY METALS ANALYSES
OF RIVER WATER AND SEDIMENTS
118
-------
Appendix II-l. Concentrations of lead, zinc, cadmium,and copper in
STATION
3 July
Monocacy Farm Bridge
Douglassville Bridge
Parker Ford Bridge
Spring City/Royersford Br.
Route 113 Bridge
Valley Forge Bridge
Falls Bridge
4 July
Monocacy Farm
Douglassville Bridge
Parker Ford Br., Sample 1
Parker Ford Br., Sample 2
Spring City/Royersford Br.
Route 113 Bridge
Valley Forge Bridge
Falls Bridge
5 July
Monocacy Farm, Sample 1
Monocacy Farm, Sample 2
Douglassville Bridge
HEAVY METAL
Lead
0.015
0.014
0.014
0.011
0.039
0.033
0.018
0.004
0.038
0.023
0.040
0.003
0.024
0.010
0.009
0.004
0.003
0.086
Zinc
0.01
0.025
0.01
0.03
0.070
0.03
0.025
0.01
0.05
0.04
0.02
0.01
0.04
0.02
0.01
0.03
0.03
0.05
CONCENTRATION (ppm)
Cadmium
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
Copper
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0,05
0.05
0.05
0.05
0.05
119
-------
Appendix II-l. (continued)
STATION
5 July (contd)
Parker Ford Bridge
Route 113 Bridge
Valley Forge Bridge
Falls Bridge
6 July
Monocacy Farm, Sample 1
Monocacy Farm, Sample 2
Douglassville Bridge
Parker Ford Bridge
Spring City/Royersford Br.
Route 113 Bridge
Valley Forge Bridge
Falls Bridge
7 July
Monocacy Farm, Sample 1
Monocacy Farm, Sample 2
Douglassville Bridge
Parker Ford Bridge
Spring City/Royersford Br.
Route 113 Bridge
Valley Forge Bridge
Falls Bridge
HEAVY METAL CONCENTRATION (ppm)
Lead
0.004
0.046
0.016
0.011
0.002
0.002
0.040
0.029
0.011
0.005
0.016
0.012
0.004
0.002
0.041
0.015
0.019
0.018
0.019
0.015
Zinc
lost
0.04
0.01
0.01
0.02
0.02
0.01
0.03
0.04
0.02
0.04
0.01
0.05
0.02
0.06
0.07
0.08
0.05
0.01
0.04
Cadmium
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
Copper
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
O.'OS
0.05
0.05
0.05
120
-------
Appendix II-l. (continued')
STATION
8 July
Monocacy Farm, Sample 1
Monocacy Farm, Sample 2
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
9 July
Monocacy Farm
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
10 July
Monocacy Farm
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
11 July
Monocacy Farm
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
12 July
Monocacy Farm
Douglassville Bridge
HEAVY'METAL CONCENTRATION (ppm)
Lead
0.006
0.004
0.018
0.010
0.028
0.005
0.015
0.013
0.015
0.002
0.008
0.005
0.006
0.002
0.010
0.010
0.014
0.002
0.006
Zinc
0.04
0.02
0.05
0.03
0.07
0.010
0.06
0.06
0.01
0.010
0.037
0.010
0.012
0.018
0.031
0.018
0.010
0.010
0.031
Cadmium
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
Copper
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
121
-------
Appendix II-l. (continued)
STATION
12 July (contd)
Parker Ford Bridge
Valley Forge Bridge
13 July
Monocacy Farm
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
14 July
Monocacy Farm
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
15 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
lt> July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
HEAVY METAL CONCENTRATION (ppm)
Lead
mmnmu 1
0.017
0.016
0.003
0.006
0.008
0.006
0.005
0.013
0.010
0.011
0.002
0.007
0.005
0.002
0.005
0.003
0.005
O.OOb
Zinc
0.018
0.010
0.004
0.016
0.029
0.004
0.009
0.026
0.016
0.009
0.015
0.029
0.015
0.011
0.011
0.009
0.015
0.018
Cadmium
0.002
0.002
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
Copper
0.05
0.05
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
122
-------
Appendix II-l. (continued)
STATION
17 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
18 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
19 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
20 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
21 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
HEAVY METAL CONCENTRATION (ppm)
Lead
0.003
0.003
0.003
0.003
0.002
0.016
0.002
0.003
0.001
0.003
0.003
0.002
0.003
0.003
0.002
0.002
0.001
0.002
0.003
0.003
123
Zinc
0.007
0.007
0.007
0.009
0.013
0.012
0,014
0.014
0.013
0.011
0.013
0.012
0.013
0.012
0.013
0.011
0.012
0.014
0.013
0.012
Cadmium
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
Copper
0.03
0,03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
-------
Appendix II-l. (continued)
STATION
22 July
Monocacy Bridge
Douglassville B ridge
Parker Ford Bridge
Valley Forge Bridge
23, 24, 25 July
Samples lost in shipment
26 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
27 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge .Bridge
28 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
HEAVY METAL CONCENTRATION (ppm)
Lead
0.002
0.002
0.002
0.002
0.006
0.009
0.005
0.008
0.008
0.006
0.006
0.007
0.005
0.006
0.007
0.007
Zinc
0.011
0,013
0.014
0.013
0.005
0.007
0.005
0.005
0.004
0.004
0.005
0.009
0.003
0.002
0.009
0.011
Cadmium
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0^001
0.001
Copper
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
124
-------
Appendix II-l. (continued)
STATION
29 July
Monocacy Bridge
Douglaasville Bridge
Parker Ford Bridge
Valley Forge Bridge
30 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
31 July
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
1 August
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
2 August
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
HEAVY METAL CONCENTRATION (ppm)
Lead
0.007
0.006
0.006
0.034
0.007
0.006
0.008
0.008
0.009
0.006
0.009
0.009
0.001
0.001
0.003
0.001
0.005
0.005
0.007
0.006
Zinc
0.007
0.007
0.009
0.008
0.008
0.008
0.007
0.004
0.009
0.005
0.007
0.017
0.013
0.012
0.012
0.012
0.007
0.009
0.012
0.007
Cadmium
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.011
0.001
0.001
0.001
0.003
0.001
Copper
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
125
-------
Appendix II-l. (continued)
STATION
3 August
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
4 August
Monocacy Bridge
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
5 August
Monocacy Bridge
Parker Ford Bridge
IffiAVY METAL CONCENTRATION (ppm)
Lead
0.007
0.007
0.012
0.012
0.005
0.007
0,022
0.012
0.006
0.007
Zinc
0.015
0.015
0.012
0.009
0.009
0.009
0.006
0.012
0.012
0.009
Cadmium
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
Copper
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
J.03
0.03
126
-------
Appendix II-2. Concentrations of lead, zinc, cadmium,, and copper in
STATION
1 July
12.4 miles below spill
12.4 miles below spill
11.72 miles below spill
11.72 miles below spill
2 July
2.35 miles below spill
2.35 miles below spill
3.75 miles below spill
5.75 miles Itoelow spill
6.75 miles below spill
6.75 miles below spill
8.75 miles below spill
8.75 miles below spill
10.7 miles below spill
19.90 miles below spill
19.90 miles below spill
22.25 miles below spill
22.25 miles below spill
4 July
Parker Ford Bridge
Parker Ford Bridge
Route 113 Bridge
Loi Lead
32.5.
154.0
14.2
16.9
61.7
3.7
1.3
17.5
19.7
16.9
11.9
28.8
171.0
38.5
37.6
44.1
26.2
5.1
9.3
22.1
Zinc
259
218
426
353
133
70
51
169
161
177
119
158
225
235
300
309
233
135
230
274
Cadmium Copper
0.2 45.1
0.2 32.6
0.4 30.0
0.4 47.5
0.2 494.0
0.2 25.0
0.2 22.7
0.2 31.4
0.2 35.8
0.2 35.1
0.2 38.1
0.2 36.4
0.2 33.3
0.2 27.3
0.2 32.0
0.2 40.5
0.2 29.1
0.2 34.9
0.2 23.7
0.2 28.6
127
-------
Appendix II-2. (continued)
STATION
5 July
Route 113 Bridge
9 July
Monocacy
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
11 July
Monocacy Farm
Douglassville Bridge
Valley Forge Bridge
15 July
Douglassville Bridge
Parker Ford Bridge
Valley Forge Bridge
Loi
Lead Zinc Cadmium Copper
161.0 310
16.707, 304 373
10.087. 372 312
12.427. 124 162
9.907. 32.1 62,1
26.317. 2210.0 656
0.2
1.7
2.1
1.5
5.71%
39.2 144
1.2
2.6
3.1
33.5
395.0
14.1
13.5
9.2
416
101
192
38
1.3
0.2
0.2
0.2
145.0
22.5
38.4
11.9
161
113
42.7
25.9
193
22.0
128
-------
Appendix II-3. Concentrations of lead, zinc, cadmium, copper and
mercury in Schuylkill River bottom sediments
collected in November, 1972
ppm Dry Weight
Sample Station
Monocacy*
Monocacy - 1
Monocacy - 2
Monocacy - 3
Monocacy - 4
Monocacy - 5
Douglas sville - 1*
Douglassville - 2*
Douglassville - 3*
Douglassville - 4*
Douglassville - 5*
Parker Ford - 1*
Parker Ford - 2*
Parker Ford - 3*
Parker Ford - 4*
Parker Ford - 5*
Lead
500
426
445
413
435
458
530
450
1400
690
780
550
460
70
570
690
Zinc
930
820
640
576
602
698
920
920
650
700
510
840
1200
130
940
1420
Cadmium
3.9
3.9
2.8
2.5
2.2
2.9
3.9
1.8
3.1
2.6
2.3
6.3
8.0
0.2
8.2
9.3
Copper
290
240
277
248
242
266
260
140
190
240
190
240
310
51
350
370
Mercury
0.013
0.010
0.021
0.008
0.016
0.027
0.009
0.295
0.016
0.115
0.045
0.081
0.090
0.130
0.087
0.490
* Composite
1 Mean of replicate analyses
129
-------
APPENDIX III DATA FROM HYDROCARBON ANALYSES
OF SEDIMENTS
130
-------
cj LO o r- ^t i— co o> c\j cj
to LO-^-TJ- cvjcv T— o en en ot
OJ OJ CJ CXI CJ CJ CJ r- r- *—
APPENDIX III-l. CHROMATOGRAM
OF OIL IN SEDIMENT COMPOSITE
COLLECTED IN NOVEMBER, 1972,
AT CONTROL STATION M
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APPENDIX III-2. CHROMATOGRAM
OF OIL IN SEDIMENT COMPOSITE
COLLECTED IN NOVEMBER, 1972,
AT STATION D-l
i/j/' ; IT 'i i itn I
-------
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APPENDIX III-3. CHROMATOGRAM
OF OIL IN SEDIMENT COMPOSITE
COLLECTED IN NOVEMBER,1972,
AT STATION D-2
-------
Page 134 intentionally left blank.
134
-------
APPENDIX III-4. CHROMATOGRAM
OF OIL IN SEDIMENT COMPOSITE
COLLECTED IN NOVEMBER, 1972,
AT STATION D-3
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s fill i i i r
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_ . APPENDIX III-5. CHROMATOGRAM
l_ [. i OF OIL IN SEDIMENT SUBSAMPLE
COLLECTED IN NOVEMBER, 1972,
AT STATION D-3
-------
APPENDIX Ill-b. CHROMATOGRAM
OF OIL IN SEDIMENT COMPOSITE
COLLECTED IN NOVEMBER,, 1972,
AT STATION D-4
!. - it'll- "irilllZI^ I -. - ;^?>'-
FT-\—-7T.r.Trrti n
-------
00
! APPENDIX III-7. CHROMATOGBAM
OF OIL IN SEDIMENT COMPOSITE
.__L-L\'_U- COLLECTED IN NOVEMBER, 1972,
AT STATION D-5
-------
CO o ,— pr, U3 CO CO I*- f~ ' /) O t~ r- «~ OCXJ O T- _ I- - -
^ en on r*- ^ lOio^f co cj CM r- o O o>or» f* to u> j
CNJC\JCMCVJCVJ CJCJCxJ CJ C>J CJCMOJIM «—f— »— T~ T~ i
u. ill" I I irii iri li I I ; 1~T' >T
: t • ' ! I i . ' '„ : ; _|_J_4_'_J_SL_!^: _J.J
o •
o
if>
', : ";^iPf7
""" "
! APPENDIX III-8. CHROMATOGRAM
1 j OF OIL IN SEDIMENT COMPOSITE
_ ' COLLECTED IN NOVEMBER,,1972j
: "f AT STATION P-l
-------
APPENDIX III-9. CHROMATOGRAM j
OF OIL IN SEDIMENT COMPOSITE
—j ^ . COLLECTED IN NOVEMBER,1972,
- i-' •- i-AT STATION P-2
-------
; -- n «- 1-
OT °° "
; ocvj <<*• un CM o •<*• t^ ^ — : — " ~ ° r ? ', —
31OlO-4-COOJOJt- O0> CO r— UJ.lrt •* : O ; | , 1. ;
JCMCVJCJCJOJOJCJ CMr- f— f—f~T— r- . _.. , .' T— , • __ '
I \ I I I ! i | i i i - 1 1 1 ' i J I ; ;
! • -. ' \ ! \. - ., . j :v ! .. - - '.-,'..
_ !. . i i. _ --- ._ .:
o
00
* /'-I i
APPENDIX III-10. CHROMATOGRAM
; OF OIL IN SEDIMENT COMPOSITE
COLLECTED IN NOVEMBER, 1972y
- AT STATION P-3
-------
CT> OJ
cr> en
v—
AT STATION P-4
[NJ
o
o
-------
Lo
APPENDIX 111-12. CHROMATOGRAM
OF OIL IN SEDIMENT COMPOSITE
COLLECTED IN NOVEMBER,1972,
AT STATION P-5
_U .i8.L.u_ J_Lli _.,_^_U Li
-------
APPENDIX IV DATA FROM HEAVY METALS ANALYSES
OF RIVER BIOTA
144
-------
Appendix IV-1. Concentrations of lead, zinc, cadmium, and copper
in benthic macrofauna collected in July, 1973
Sample
M(a)
M(b)
M(c)
M(d)
M(e)
M(-f)
D2(a)
D2(b)
D2(c)
D3
D3
Lead
49. 3
51.1
51.4
79. 1
10.9
49. 3
143. 0
362.0
16.9
24.2
49.8
ppm
Zinc
102. 0
107.0
99.5
99.4
43.3
68. 7
65.4
68.9
31.0
38. 6
33. 1
(whole body,
Cadmium
0. 1
0. 1
0. 1
0. 1
0. 1
0. 1
0. 1
0. 1
0. 1
0. 1
0. 1
wet weight)
Copper
29.7
31.5
35. 0
73.9
71. 1
21.8
19.9
9. 1
19.8
7- 0
23. 2
Mercury
*
*
*
*
*
*
*
*
*
*
*
*Not abundant enough for mercury analysis.
145
-------
Appendix IV-2. Concentrations of lead, zinc, cadmium, copper, and
mercury in white suckers collected in November., 1972,
January and July, 1973
Sample
Organ
ppm (wet weight)
Monocacy
Nov. 1972
Fish 1
Fish 2
July 1973
Fish 1
Fish 2
Parkerford
Jan. 1973
Fish 1
Fish 2
July 1973
Fish 1
Fish 2
Liver
Liver
Flesh
Flesh
Flesh
Flesh
Flesh
Flesh
Lead
<0.4
/ 0. 4
/O. 4
<0.4
<0.4
<0.4
0.7
0. 5
Zinc
21.8
21. 3
4.0
3.2
15.9
20. 5
5.4
4.6
Cadmium
0. 5
0. 2
<0. 1
<0. 1
0. 1
<0. 1
^0 1
<0. 1
Copper
3. 24
3.83
0. 05
0. 05
0. 60
0. 33
0. 10
0. 13
Mercury
:::
0. 18
0. 14
0. 12
0. 09
0. 13
0. 16
146
-------
Appendix IV-3. Concentrations of lead, zinc, cadmium, copper, and
mercury in brown bullheads collected in November, 1972,
January and July, 1973
Sample Organ
Monocacy
Nov. 1972
Fish 1
Fish 2
July 1973
Fish 1
Fish 2
Fish 1
Parkerford
Jan. 1973
Fish 1
Fish 2
July 1973
Fish 1
Fish 2
Fish 1
Fish 2
Liver
Liver
Flesh
Flesh
Liver
Liver
Liver
Flesh
Flesh
Liver
Liver
Lead
0.4
0.4
0.4
0.7
0.4
0.4
0.4
0.4
0.4
64. 2
1.4
ppm (wet weight)
Zinc
21.7
22.0
2. 1
2. 5
22. 0
23.9
21.9
2.7
3. 2
31. 0
20. 0
Cadmium Copper
0.7
0. 1
0. 1
0. 1
0.5
4. 1
0. 2
0. 1
0. 1
1. 3
0. 5
6.3
45. 9
>
0.05
0. 20
0.05
12.6
87.3
0. 05
0. 11
53
0.05
Mercury
0. 18
0. 19
_ *. •
0.07
0. 05
— — —
147
-------
Append ix IV-
Concentrations of lead, zinc, cadmium, copper, and
mercury in crappies collected in November,1972,
and July, 1973
Sample Organ
Monocacy
Nov. 1972
Fish 1
Fish 2
July 1973
Fish 1
Fish 2
Parkerford
July 1973
Fish 1
Fish 2
Liver
Liver
Flesh
Flesh
Flesh
Flesh
Lead
0.4
0.4
0.4
0.4
0.4
0.4
ppm (wet weight)
Zinc
17.4
17. 1
3.8
4. 1
3. 0
11. 1
Cadmium Copper
0. 1
0. 1
0. 1
0. 1
0. 1
0. 1
9.48
1.84
0. 05
0. 05
0. 05
0.05
Mercury
0.09
0. 11
0. 11
0.08
148
-------
Appendix IV-5. Concentrations of lead, zinc, cadmium, copper, and
mercury in bluegills collected in November, 1972,
and January,1973
Sample Organ ppm (wet wei
Monocacy
Nov. 1972
Fish 1
Fish 2
Parkerford
Jan. 1973
Fish 1
Fish 2
Flesh
Flesh
Liver
Liver
Lead Zinc Cadmium
0.4 10.4 0.1
0.4 15.6 0.4
0.4 15.8 0.4
0.4 19.4 0.4
ght)
Copper
1.79
7.65
0.77
1.35
Mercury
0. 10
0. 07
149
-------
Appendix IV-b.
Concentrations of lead, z±-nc, cadmium,and copper in
JS.chuvlkill River fishes collected 19 and 22 July, 1972
Sample Organ Metal Concentration
Monocacy
19 & 22
July
Parkerford
19 & 22
July
Brown bullhead
Brown bullhead
Blue gill
Shiner
Blue gill
Composite 3
Samples 8. 0,
7. 2, 7. 8 cm
Flesh
Flesh
Flesh
Flesh
Flesh
Lead
1. 3
2. 0
2. 3
2.6
4.4
Zinc
1.0
1.0
3.0
7.9
3.4
Cadmium
0. 1
0. 1
0. 1
0. 1
0. 1
ppm
Copper
0.5
0. 3
0.4
0.4
0. 6
150
-------
Appendix IV-7. Concentrations of lead, zinc, cadmiumjand mercury
^ in Schuylkill River fishes collected 23 and 29 July, 1972
Sample
Org
an
Monocacy
23 & 29
July
Parkerford
23 & 29
July
Blue gill
Brown bullhead
Brown bullhead
(Composite)
Blue gill
Blue gill (Comp. )
Blue gill (Cornp. )
Flesh
Flesh
Flesh
Flesh
Flesh
Flesh
Lead
0.9
0.3
0. 2
0.5
1.0
1.0
Cadmium
0. 38
0. 10
0. 07
0. 06
0. 10
0. 08
Copper
0. 5
0.2
0. 6
0.1
Mercury
0.741
0. 776
0. 162
0. 330
0. 104
0. 241
151
-------
APPENDIX V HYDROCARBON IN FISHES
152
-------
Ul
OJ
Appendix V-l. Extraction Data
Sample/ Wt.
Sample MgS04 sample Extraction
description extracted (g) extracted (g) time (hr)
% Oil
Wt. oil (based on
product (g) sample*)
Spilled Crankcase
Oil Waste (SCOW)
White suckers
(downstream)
White suckers
(upstream)
Brown bullheads
(downstream)
Brown bullheads
(upstream)
Crappies
(downstream)
Crappies
263
201
206
200
201
201
200
93
110
113
116
112
115
116
48
24
24
24
24
24
24
39.
3.
6.
3.
5.
4.
5.
5
37
65
21
32
68
44
42.6
3.06
5.88
2.77
4.75
4.07
4.61
(upstream)
* Original fish or SCOW
-------
Appendix V-2 Saponification Data
. from
iction (g)
1.
3.
6.
3.
5.
4.
5.
20
37
65
21
32
68
44
6N
KOH (ml)
30
84
166
80
133
117
136
H20
added (ml)
30
168
398
160
266
234
272
Solvent
(ml) *
30
68
142
64
106
94
108
Oil
product (g)
0.
1.
3.
0.
3.
1.
3.
94
38
11
57
27
70
50
%
oil prod . **
78.
41.
46.
17.
61.
36.
64.
4
0
8
8
6
3
3
Spilled Crankcase
Oil Waste (SCOW)
White suckers
(downstream)
White suckers
(upstream)
Brown bullheads
(downstream)
Brown bullheads
(upstream)
Crappies
(downstream)
Crappies
(upstream)
* Volume used in separatory funnel extraction, 2X
with cyclohexane followed by 2X with benzene.
** Based on .oil sample from first column
-------
Appendix V-3. Column Chromatographic Data
(Cyclohexane Elutions)
Sample (g)
Alumina (g)
MgS04 (g)
Column
diameter (cm)
Volume cyclo-
hexane solvent
(ml)
Aliphatic
hydrocarbons
(mg)
Aliphatic
hydrocarbons
(% based on
above sample)
Spilled White White Brown
Crankcase suckers suckers bullheads
Oil Waste (downstream) (upstream) (downstream)
0.94
47
4.7
1.38
124
12.4
3.11
124
V
12.4
0
23
2
.57
.3
2.0
450
575
5.0
550
25
5.0
550
24
61
1.
0.8
2.0
300
15
2. 6
155
-------
Appendix V-3 (Cont.) Column Chromatographic Data
(Cyclohexane Elutions)
Sample (g)
Alumina (g)
MgSCU (g)
Column
diameter (cm)
Volume cyclo-
hexane solvent
(ml)
Aliphatic
hydrocarbons
(mg)
Aliphatic
hydrocarbons
(% based on
above sample)
Brown
bullheads
(upstream)
3.27
66
6.6
2.0
Grapples
(downstream)
1. 70
116
11.6
5.0
600
Crappies
(upstream)
3.50
116
11.6
5.0
600
307**
.5
8.8**
* Column clogged with gel, analysis abandoned
**
Solid gel eluted
156
-------
Appendix V-3 (Cont.) Column Chromatographic Data
(Benzene-Benzene/Ether Elutions)
Sample (g)
Alumina (g)
MgS04 (g)
Column
diameter (cm)
Volume benzene
solvent (ml
Spilled White White Brown
Crankcase suckers suckers bullheads
Oil Waste (downstream) (upstream) (downstream)
0.94
47
4.7
1.38
124
12.4
3.11
124
12.4
0.
23
2.
57
3
2.0
200
Volume benzene/
ether* solvent
(ml) 200
Aromatic
hydrocarbons
(mg)** 107
Aromatic
hydrocarbons
(% based on
above sample) 11.4
5.0
400
150
15
5.0
250
150
15
2.0
300
200
1.1
.5
1.6
* 90/10 v/v benzene/ether
** From combining benzene-benzene/ether fractions
157
-------
Appendix V-3 (Cont.) Column Chromatographic Data
(Benzene-Benzene/Ether Elutions)
Sample (g)
Alumina (g)
MgSCU(g)
Column
diameter (cm)
Volume benzene
solvent (ml)
Volume benzene/
ether* solvent
(ml)
Aromatic
hydrocarbons
(mg)**
Aromatic
hydrocarbons
(% based on
above sample)
Brown
bullheads
(upstream)
3.27
66
6.6
2.0
***
***
***
Crappies
(downstream)
1.70
116
11.6
5.0
350
150
10
Crappies
(upstream)
3.50
116
11.6
5.0
500
200
214+
* **
0.6
6.1
* 90/10 v/v benzene/ether
** From combining benzene-benzene/ether fractions
*** Column clogged with gel during cyclohexane elutions
+ Solid gel eluted
158
-------
Appendix V-4. Extraction and Saponification Results From Harrison Lake National
Fish Hatchery Fish
Sample
HLFH-1
HLFH-2
HLFH-3
HLFH-4
(1)
HLFH*
fish ex-
tracted (g)
246
254
226
80
(2)
ppm
added
hydrocarbon
0
2
5
10
(3)
Percent
oil from
extraction
based on
(1)**
5.3
7.2
5.9
4.9
(4)
Oil
saponi-
fied (g)
4.89
8.00
8.00
3.96
(5)
Oil obtained
from saponi-
fication (g)
.44
.38
. 44
.29
(6)
Percent
oil from
saponif i cat ion
based on (4)
8.9
4.7
5.6
7.2
* HLFH: Harrison Lake National Fish Hatchery
** Extractions conducted on fish/MgSOi, mixtures 44-48 hrs. in refluxing benzene
-------
Appendix V-5. Column Chromatographic Data Harrison Lake National Fish
Hatchery (HLFH) Fish
Sample
HLFH-1
HLFH-2
HLFH-3
HLFH-4
Oil fr;om
saponif i-
cation for
chroma-
tog raphy
(g)
.44
.38
.44
.29
Added
Hydro-
carbon
(ppm)
0
2
5
10
Non-volatile
residue from
cyclohexane
elution (mg) *
1
2
2
1
Non-volatile
residue from
benzene
elution (mg) **
3
4
6
5
Residue
from
cyclohex-
ane elution
(ppm)
11
13
12
17
Residue
from
benzene
elution
(ppm)
33
40
45
66
* Column eluted with cyclohexane (425 ml)
** Column eluted with 650 ml benzene + 350 ml 90/10 benzene/ethyl ether (v/v)
-------
Appendix V-6 Peak Area and Weight Correlations of Polycyclic Aromatic Hydrocarbons
Compared to Triphenylmethane Internal Standard
Chromatograph sample: 1)
2)
Chromatogram: Fig
Peak
number
1
2
3
4
5
Aromatic
hydrocarbon
Phenathrene
Fluor an thene
Pyrene
Chrysene/1 ,2
benzanthracene
Benzo (a) pyren
10.0 ml standard hydrocarbon (HC) mixture (1.16 mg each
hydrocarbon) +
1.50 ml (1.63 mg) triphenylmethane (TPM) in benzene
. 55
Peak area**
X10~2 (mm~2)
3.3
3.4
3.3
6.3
e 3.0
Area HC^- Wt HCr
area TPM wt TPM
.72 .71
.74 .71
.72 .71
1.4 1.4
.65 .71
Area ratio
HC/TPM^
wt ratio
HC/TPM***
1.0
1.0
1.0
.92
TPM
Benzo (ghi)
perylene
TPM
2.5
4.6
.54
.71
.76
** Height (mm) x width at 1/2 peak height (mm)
*** Values used as correction factors in Appendix V-7, -8, -9
-------
tv
Appendix V-7. Percent Recovery of Polycyclic Aromatic Hydrocarbons from Harrison Lake
National Fish Hatchery Fish (2 ppm Added Hydrocarbon)
Chromatograph sample: 1) Benzene eluate from column chromatography (4.4 mg. solids) +
2) 0.70 ml. benzene solvent +
3) 0.30 ml. (0. 33 mg) triphenylmethane (TPM) in benzene
Chromatogram :
Hydrocarbon (HC)
Phenanthrene
Fluoranthene
Pyrene
Chrysene/1,2
ben z anthracene
Benzo (a) pyrene
Fig, 58
Area HC v
area TPM
.18
.31
.28
.59
.21
Corr. *
factor
1.0
1.0
1.0
1.0
.92
Wt. EC r
wt . TPM
.18
.31
.28
.59
.23
HC (mg)
.059
.10
.092
.19
.075
Theor**
HC (mg)
.22
.22
.22
.44
.22
Percent HC
recovery
27
45
42
43
34
Benzo (ghi)
perylene
.26
.76
34
.11
.22
50
* See last column, Appendix V-6
** Based on known quantities (2 ppm) of each added hydrocarbon to ground fish before
blending, and subsequently processed (extraction - saponification - column
chromatography)
-------
Appendix V-8. Percent Recovery of Polycyclic Aromatic Hydrocarbons from Harrison Lake
National Fish Hatchery Fish (5 ppm Added Hydrocarbon)
Chromatograph sample: 1) Benzene eluate from column chromatography (6.1 mg solids) +
2) 1.00 ml benzene solvent +
3) 0.80 ml (0.87 mg) triphenylmethane (TPM) in benzene
Chromatogram:
Fig. 59
Hydrocarbon (HC)
Phenanthrene
Fluoranthene
Pyrene
Chrysene/1,2
ben z anthracene
Benzo (a) pyrene
Area HC v
area TPM
.42
.60
.58
1.0
.42
Corr*
factor
1.0
1.0
1.0
1.0
.92
Wt HC ^
wt TPM
.42
.60
.58
1.0
.46
HC (mg)
.37
.52
.50
.87
.40
Theor**
wt HC (mg)
.68
.68
.68
1.4
.68
Percent HC
recovery
54
76
74
62
59
Benzo (ghi)
perylene
.63
.76
.83
72
.68
106
* See last column, Appendix V-6
** Based on known quantities (5 ppm) of each added hydrocarbon to ground fish before
blending, and subsequently processed (extraction - saponification - column
chromatography)
-------
Appendix V-9. Percent Recovery of Polycyclic Aromatic Hydrocarbons from Harrison Lake
National Fish Hatchery Fish (10 ppm Added Hydrocarbon)
Chromatograph sample:
Chromatogram :
Hydrocarbon (HC)
Phenanthrene
Fluor an thene
Pyrene
Chrysene/1,2
benzanthracene
Benzo (a) pyrene
1) Benzene
2) 0.90 ml
3) 0.60 ml
Fig. 60
Area HC v
area TPM
.65
.86
.89
1.5
.49
eluate
benzene
from column
solvent +
chromatography (5.3 mg
(0.65 mg) triphenylmethane
Corr*
factor
1.0
1.0
1.0
1.0
.92
Wt HC v
wt TPM
.65
.86
.89
1.5
.53
Wt
HC (mg)
.42
.56
.58
.98
.34
solids) +
(TPM) in benzene
Theor**
wt HC (mg)
.80
.80
.80
1.6
.80
Percent HC
recovery
53
70
73
61
43
Benzo (ghi)
perylene
.73
.76
.96
62
.80
78
* See last column, Appendix V-6.
** Based on known quantities (10 ppm) of each added hydrocarbon to ground fish before
blending, and subsequently processed (extraction - saponification - column
chromatography)
-------
APPENDIX VI DATA FROM BIOLOGICAL ANALYSES
165
-------
Appendix VI-1. Chlorophyll-a_ content of Schuylkill River water above
and below the oil spill site in July/1972
Chlorophyll A (micrograms /liter)
Date Station1 Total Active Pheopigment (Dead)
16 July 1972
ABOVE SPILL
Monocacy Bridge 3.78 2.78 1.00
3.41 2.63 0.78
Average 3.60 2.71 0.89
BELOW SPILL
Parker Ford Bridge 8.48 6.72 1.76
11.70 4.39 7.31
Average 10.09 5.56 4.54
Valley Forge Bridge 7.66 6.27 1.39
14.19 11.39 2.80
Average 10.93 8.83 2.10
29 July 1972
ABOVE SPILL
Monocacy Bridge 6. 15 4. 80 1. 35
Average 6. 15 4. 80 1. 35
BELOW SPILL
Parker Ford Bridge 10.46 8.13 2.33
10.46 7.73 2.73
Average 10.46 7.93 2.53
166
-------
Appendix VI-1, (continued")
Chlorophyll A (micrograms /liter)
Date Station Total Active Pheopigment (Dead)
29 July 1972
BELOW SPILL
Valley Forge Bridge 14.19 10.58 3.61
11.45 9.24 2.21
Average 12.82 9.91 2,41
Duplicate samples were usually taken at each station.
167
-------
oo
Appendix VT-2. Zooplankton abundance in Schuylkill River water above and below the oil spill in
July, November, and December, 1972, and July, 1973
16 July 1972 29 July 1972
Above Spill Below Spill Above Spill Below Spill
STATION:
Taxons
Monocacy "Parker Ford Valley Forge Monocacy Parker Ford Valley Forge
Peritricha
Protozoa
Coelenterata
Nemertina 4
(ribbon worms)
Rotifera
Nematoda
(round worms)
Nematomorpha
(hair worms)
Bryzoa
(moss animals)
Pelecypoda (bivalve 2
mollusk) larvae
100 +
100 +
100 +
3
3
100 +
100 +
18
12
3
100 +
-------
VI -2
16 July 1972
Above Spill Below Spill
29 July 1972
Above Spill ___ Below Spill
STATION:
Monocacy Parker Ford Valley Forge Monocacy Parker Ford Valley Forge
Taxons
Oligochaeta
(segmented worms)
Tardigrada
(water bears)
Cladocera 61
(water fleas)
Ostracoda 9
Copepoda 13
Amphipoda 1
Hydracarina 9
(water mites)
Hemiptera 1
(true bugs)
Odonata (dragon
and damsel fly) larvae
Trichoptera (caddis 1
fly) larvae
92
il
80
48
13
5
10
30
24
21
100+
-------
Appendix .VI-2. (continued)
16 July 1972
Above Spill Below Spill
29 July 1972
-Above Spill Below Spill
STATION:
Taxons
Monocacy Parker Ford Valley Forge
Bridge Bridge Bridge
Ephemeroptera
(May fly) larvae
Tendipedidae
Monocacy Parker Ford Valley Forge
Bridge Bridge Bridge
(midge) larvae 4
Culicidae
(mosquito) larvae
Coleoptera 3
(beetles)
Unidentified 8 15 1
Major taxon 10 7 7
68 149
5
10
5 5
~9 6
95
3
12
To
diversity
-------
Appendix _VT-2. (continued)
28 November 1972
1 December 1972
14 July 1973
STATION:
Above Spill Below Spill Above Spill Below Spill Above Spill Below Spill
Monocacy Parker Ford Monocacy Parker Ford Monocacy Parker Ford
Taxons
Peritricha
Protozoa 1
Coelenterata <. 1
Nemertina 6
(ribbon worms)
Rotifera 7
Nematoda
(round worms)
Nematomorpha < 1
(hair worm,s)
Bryzoa < 1
(moss animals)
<1
<1
11
<1
11
1
4
-------
Aj3pend ix VI -2 . (cont inued )
28 November 1972 1 December 1972 14 July 1973
Ab_oy_e Spill BeJ^ow^SpJll AboyjejSpill Below Spill Above Spill Below Spill
STATION: Monocacy Parker Ford Monocacy Parker Ford Monocacy Parker Ford
Taxons
Pelecypoda (bivalve
mollusk) larvae ^1
Oligochaeta 2
(segmented worms)
Tardigrada
(water bears)
Cladocera 5
(water fleas)
Ostracoda
Copepoda 1
Amphipoda
Hydracarina
(water mites)
Hemiptera
(true bugs)
13
-------
Appendix. VI-2. (continued)
28 November 1972 1 December 1972 14 July 1973
Above Spill Below Spill Above Spill Below Spill Above Spill Below Spill
STATION: Monocacy Parker Ford Monocacy Parker Ford Monocacy Parker Ford
Taxons
Odonata (dragon 1
and damsel fly) larvae
Trichoptera (caddis
fly) larvae
^ Ephemeroptera , 9 < 1 83 46
co (May fly) larvae
Tendipedidae
(midge) larvae
Culicidae 1
(mosquito) larvae
Coleoptera
(beetles)
Unidentified
Major taxon 99 99 8 10
diversity
Oil droplets were observed in this sample
-------
Appendix VI-3. Benthic macrofauna abundance in Schuylkill River sediments in November^ 1972,
and July, 1973 _______
STATION: Above Spill Monocacy (Replicate 1) Monocacy (Replicate 2j Monocacy (Replicate 3)
Organisms/m2 Type 1, 2 Organisms/rr?^ Type Organisms/m^ Type
Taxons
Nematoda 86 43
(round worms)
Gastropoda (snails) 43 (4)
Pelecypoda 86 (1) 43 (1) 43 (1)
(bivalve mollusks)
Oligochaeta 15,566 (l)+(2)+(5) 7,912 (1) (2) 5,461
(segmented worms)
Hirudinea (leeches) 43
Odonata (dragon-
damsel fly) larvae
Tendipedidae (midge) 129 86
larvae and pupae
Ceratopogonidae (biting
midge) larvae and pupae
Other Diptera larvae 215 (1)
and pupae
Fish larvae
Major taxondiversity 5 35
-------
Appendix VI-3.
29 November 1972
STATION: Below Spill Parker Ford 1
Organisms/m Type
Taxons
Parker Ford 2
Parker Ford 3
Organisms/m2 Type Organisms /m Type
Nematoda
(round worms)
Gastropoda (snails) 301
Pelecypoda 172
(bivalve mollusks)
Oligochaeta 3, 314
(segmented worms)
Hirudinea (leeches)
Odonata (dragon-
damsel fly) larvae
Tendipedidae (midge) 43
larvae and pupae
Ceratopogonidae (biting
midge) larvae and pupae
Other Diptera larvae 43
and pupae
Fish larvae
Major taxon diversity 5
(D(2)(4)
(1)
No
Organisms
11,621
301
43
(1)
-------
Append ix VI-3. £co_nt_irmed)
29 November 1972
cr-
STATION: Below Spill Douglas sville 1
Organ! sms/m.2 Type
Taxons
Nematoda
(round worms)
Gastropoda (snails)
Parker Ford 4
Parker Ford 5
Pelecypoda
(bivalve mollusks)
Oligochaeta 43
(segmented worms)
Hirudinea (leeches)
Odonata (dragon-
damsel fly) larvae
Tendipedidae (midge)
larvae and pupae
Ceratopogonidae (biting
midge) larvae and pupae
Other Diptera larvae 43
and pupae
Fish larvae
(1)
ganisms/m^ Type
129
301 (l)+(3)(4)
43 (2)
?, 123 (D+(2)+
Orgamsms/m^
86
43
6,327 (1
(1)
129
129
301
43
258
(1)
86
(2)
UH(4)
(1)
Major taxon diversity
-------
Appendix VI-3. (£ont_inued_)
29 November 1972
STATION: Below Spill Douglassville 2 Douglassville 3
Organisms/m.2 Type Organisms/m.2 Type
Taxons
Douglas sville 4
Organisms/m.2 Type
Nematoda
(round worms)
Gastropoda (snails)
Pelecypoda
(bivalve mollusks)
Oligochaeta
(segmented worms)
Hirudinea (leeches)
Odonata (dragon-
damsel fly) larvae
*
Tendipedidae (midge)
larvae and pupae
Ceratopogonidae (biting
midge) larvae and pupae
Other Diptera larvae
and pupae
Fish larvae
Major taxon diversity
12,986
43
989
43
(l)+(2)+ 1,851
12v
43
43
5
(1)
(1)
-------
Appendix VI-3. (continued)
29 November 1972
STATION: Below Spill Douglas sville 5
Organisms/m^ Type
Taxons
00
Nematoda 43
(round worms)
Gastropoda (snails)
Pelecypoda
(bivalve mollusks)
Oligochaeta 4,433
(segmented worms)
Hirudinea (leeches) 43
Odonata (dragon-
damsel fly) larvae
Tendipedidae (midge) 129
larvae and pupae
Ceratopogonidae (biting 43
midge)larvae and pupae
Other Diptera larvae
and pupae
Fish larvae
Major taxon diversity 5
(1)
-------
Appendix VI-3. (continued)
28 July 1973
STATION: Above Spill Monocacy (Replicate 1) Monocacy (Replicate 2) Monocacy (Replicate 3)
Organisms/m2 Type Organisms/in^ Type Organisms/m2 Type
Taxons
Nematoda 43
(round worms)
Gastropoda (snails)
Pelecypoda
(bivalve mollusks)
Oligochaeta 688 (l)+(2)+ 301 (l)+(2)+ 1,419
(segmented worms) (3) (3)(6) (3)
Hirudinea (leeches)
Odonata (dragon-
damsel fly) larvae
Tendipedidae (midge) 1,290 4,601 1,643
larvae and pupae
Ceratopogonidae (biting
midge)larvae and pupae
Other Diptera larvae
and pupae
Fish larvae
Major taxon diversity 2 32
-------
Appendix -VI-3. (continued)
28 July 1973
STATION: Above Spill Monocacy (Replicate 4) Monocacy ( Replicate 5)
Organisms/m2 Type Organisms/m.2 Type
Taxons
Nematoda 86
(round worms)
Gastropoda (snails)
Pelecypoda
(bivalve mollusks)
"H- Oligochaeta 1,634 (l)+(2)+ 2,838
o (segmented worms) (3) (3)
Hirudinea (leeches)'
Odonata (dragon-
damsel fly) larvae
Tendipedidae (midge) 3,096 1,032
larvae and pupae
Ceratopogonidae (biting
midge) larvae and pupae
Other Diptera larvae
and pupae
Fish larvae
Major taxon diversity 2 2
-------
Appendix VI-3. (continued)
28 July 1973
STATION: Below Spill Douglas sville Br. (Replicate 1) Douglassville Br. (Replicate 2)
Organisms/m2 Type Organisms/m^ Type
Taxons
Nematoda 86
(round worms)
Gastropoda (snails)
Pelecypoda
(bivalve mollusks)
_, Oligochaeta 5,246 (l)+(2)+ 2,666
2 (segmented worms) ' (3)(4) (3)
Hirudinea (leeches)
Odonata (drag-on-
damsel fly) larvae
Tendipedidae (midge) 1,677 4,472
larvae and pupae
Ceratopogonidae (biting
midge) larvae and pupae
Other Diptera larvae
and pupae
Fish larvae
Major taxon diversity 2 3
-------
oo
Appendix VI-3. (continued)
28 July 1973
STATION: Below Spill Douglas sville 2 Douglas sville 4
Organisms/m^ Type Organisms/m Type
Taxons
Nematoda
(round worms)
Gastropoda (snails)
Pelecypoda
(bivalve mollusks)
Oligochaeta 7,482
w (segmented worms)
Hirudinea (leeches)
Odonata (dragon-
damsel fly) larvae
Tendipedidae (midge) 3,870 1,030
larvae and pupae
Ceratopogonidae (biting 86
midge) larvae and pupae
Other Diptera larvae
and pupae
Fish larvae
Major taxon diversity 1 3
-------
A£jgendix VIr3. (continued)
Type of macrofauna present is described by the following
codes:
Gastropoda: (1) Ferissia; (2) Physa; (3) Lymnaea; (4) Gyranlus(? )
Pelecypoda: (1) Pisiclium; (2) Musculium
Oligochaeta: (1) Tubifex; (2) Limnodriluso; (3) Peloscolex;
(4) Nais; (5) Lumbriculidae; (6) Bnchytraeidae
Hirudinea: (1) Glossiphoniidae
Other Diptera larvae
and pupae: (1) Psychodidae
o
Abundance within taxons is indicated by "+" signs.
183
-------
Appendix VI-4. Counts of bacteria in Schuylkill River sediment (organisms/g of sediment)
above and below oil spill in July, 1972
00
STATION:
ABOVE SPILL
Monocacy
BELOW SPILL
Parker Ford Br.
Valley Forge Br.
ABOVE SPILL
Monocacy
BELOW SPILL
Parker Ford Br.
Valley Forge Br.
ABOVE SPILL
Monocacy
BELOW SPILL
Parker Ford Br.
Valley Forge Br.
Hydrocarbon
Oxidizers
No results.
Agar was
contaminated.
No results.
Agar was
contaminated.
5.0 x 105
1.0 x 106
2. 4 x 105
Casein
Splitters
17
4.5 x 106
1. 0 x I07
3.9 x 106
23
6. 0 x 105
2.8 x 106
no sample
30
2.9 x 106
9. 7 x 106
8. 0 x 105
Starch
Splitters
July 1972
6.8 x 106
4. 2 x 107
1. 3 x 106
July 1972
3. 5 x 105
5.6 x 106
no sample
July 1972
3. 1 x 106
9.0 x 106
3. 9x 106
Glucose
Fermenters
(MPN)
2.4 x 105
4. 6 x 106
9.6 x 105
1.5 x 105
1.5 x 106
no sample
4. 6 x 105
4. 6 x 105
1.5 x 105
Sulfate
Fermenters
(MPN)
1.5 x 102
2.4 x 103
3. 0 x 101
9.0 x 101
4. 6 x 103
no sample
4. 3 x 102
2.4 x 103
9. 0 x 101
-------
Appendix VI-5. Stomach contents of fishes collected from the Schuylkill
River in winter 1972 and summer 1973 .
Species
White sucker
Brown bullhead
Crappie
Bluegill
Winter 1972-73
Above Spill Below Spill
No. of Stomachs Contents No. of Stomachs Corients
6 100 - Diptera pupae 1 100 - Diptera pupae
8 Empty 4 Empty
1 1 unidentified fish 1 1 Diptera larvae
4 Empty vertebrate hair
mud
1 3 Diptera larvae
2 Diptera pupae
Mud
None captured
2 1 unidentified fish
1 1 unidentified fish
1 water boatman
(Coroxlidaej
2 Empty
3 Empty
3 1 unidentified fish
2 Empty
None captured
185
-------
Appendix VI-5(continued)
Species
White sucker
Summer 197-3
Above Spill Below Spill
No. of Stomachs Contents No. of Stomachs Contents
Gravel
Brown bullhead
Grapple
1 unidentified organic 1
material
3
1
1
4
Gravel
Empty
45 Diptera larvae
100 Diptera larvae
Empty
2
1
11 Diptera larvae 2
25 D iptera larvae
unidentified organic 1
material
1 Diptera larvae
insect appendage
unidentified organic
material
& Diptera pupae
4 Diptera larvae
Insect appendage
Fish remains
Empty
Empty
Fish scales
Fish bones
Mud
Fish skeleton
Algae mat
unidentified
fish (13mm)
Empty
Fish scales
insect appendage
fish scales
Insect appendage
Empty
186
-------
Appendix VI-5. (continued)
Note: Most Diptera larvae observed in fish stomachs were members
of the family Psychodidae. Diptera pupae were not further
identified. It is probable that many were members of the
families Tendipedidae and Ceratopogonidae.
187
------- |