NC0000272_Pigeon River Investigation NC WQ_19811030

Aft North Carolina Department of Ncturt- I
Resources &Community Dev�lopm tD
Wart: .uaity Division
OCT 30 1981
Western R� ional Office
4shevi!I North Carolina
PIGEON RIVER INVESTIGATION
1980
n
Division of Environmental Management
Water Quality Section
Monitoring and Technical Services Branch

Acknowledgements
The principal investigators involved in this evaluation were staff
members of the Monitoring and Technical Services Branch, Water Quality
Monitoring Unit.
We would like to acknowledge the support and assistance of the staff
of the Western Regional Office with special thanks to tor. Jack Wingate and
Mr. Jay Davies of the Division of Inland Fisheries and Mr. Doug Harned and
Mr. Joe Freeman of the Tennessee Valley Authority.
Cover: Hydropsychid caddisfly larva. Redrawn from Anker Odum, in; Wiggins,
Glen B. 1977. Larvae of the North American Caddisfly Genera (Trichoptera) .
University of Toronto Press
i

Pigeon River Report
1980
Table of Contents
Page
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Chemical-Physical Section , , , , , , , , , , , , , , , , , , , , 1
Chemical-Physical Station Locations . . . . . . . . . . . . . . . . . • 4
Dye Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Cross Sectional Study , , , , , , , , , , , , , . . . . , , 25
Chemical/Physical , , , , , , , , , , , , , . , , , 30
Model Development . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Introduction/Biological . . , , , , , , , , . , . . . . 71
Fisheries Investigation . . . . . . . . . . . . . . . . . . . . . . 72
Benthic Surveys , , , , , , , , , , , , , . . . . . 77
Bioassays . . . . . . . . . . . . . . .
Biological Station Locations , , , , , , , , , , , , , , , , , , , 90
Apendix I - Tissue Results , , , , , , , , , , , , , , , , , , , , 103
Appendix II - Benthos . . . . . . . . . . . . . . . . . . . . . . 125
Appendix III - Benthos , , , , , , , , , , , , , , , , , , , , , , 129
ii

LIST OF TABLES
TABLE PAGE
1. Station Locations - Physical/Chemical Study . . . . . . . . 4
2. Discharge Measurements on the Pigeon River and
Selected Tributaries . . . . . . . . . . . . . . . . . . . 8
3. Pigeon)River Time-of-Travel Study . . . . . . . . . . . . . 13
4. Intensive Survey Sampling Schedule . . . . . . . . . . . . 32
5. pH, D.O. , Temperature, Fecal Coliform, Solids and P&N
Series Data for Stations P-0, P-1, P-2, P-4, P-5 . . . . . 33
6. BOD5, Metals, Sulfate, Chloride, Conductivity and Color
Data for Stations P-0, P-1, P-2, P-4, P-5 . . . . . . . . 34
7. pH, D.O. ; Temperature, Fecal Coliform, Solids and P&N
Series Data for Stations P-6, P-7, R7A, P-8 . . . .. . . . 35
8. BOD5, Metals, Sulfate, Chloride, Conductivity and Color
Data for Stations P-6, P-7, P-7A, P-8 . . . . . . . . . . 36
9. pH, D.O. , Temperature, Fecal Coliform, Solids and P&N
Series Data for Stations P-9A, P-10, P-11, and P-11A . . . 37
10. BOD5, Metals, Sulfate, Chloride, Conductivity and Color
Data for Stations P-9A, P-10, P-11, and P-11A . . . . . . 38
11. pH, D.O., Temperature, Fecal Coliform, Solids and P&N
Series Data for Stations P-12, P-13, P-4A, P-5, P-9 . . . . 39
12. BOD5, Metals, Sulfate, Chloride, Conductivity and Color Data
for Stations P-12, P-13, P-4A, P-5, P-9 . . . . . . . . . 40
13. pH, D.O., Temperature, Fecal Coliform, Solids and P&N- Series
Data for Stations P-11B, P-12A, P-12B . . . . . . . . . . 41
14. BOD5, Metals, Sulfate, Chloride, Conductivity and Color
Data for Stations P-11B, P-12A, P-12B • • • • • • • • • • 42
15. Long Term BOD Data for Stations P-0, P-1, P-2, P-4, P-4A,
P-5, P-5A, P-6, P-7, P-7A . . . . . . . . . . . . . . . . 47
16. Long Term BOD Data for Stations P-8, P-9, P-9A, P-10, P-11,
P-11A, P-12, P-12A, P-12B . . . . . . . . . . . . . . . . 48
17. Long Term BOD Data for Station P-13 . . . . . . . . . . . . 49
18. 30-Day P7N Series for Stations P-0, P-1, P-2, P-4, P-5 50
19. 30-Day P7N Series for Stations P-6, P-7, P-7A, P-8, P-9A 51
20. 30-Day P&N Series for Stations P-10, P-11, P=11A, P-12, P-13 52
I

TABLE PAGE
21. 30-Day P&N Series for Stations P-4A, P-5A, P-9, P-11B,
P-12A, P-12B . . . . . . . . . . . . . . . . . . . . . 53
22. 30-Day P&N Series for Station P-12B . . . . . . . . . . 54
23. 91-Day P&N Series forStations P-1, P-2 . . . . . . . . 55
24. Measured Point-Source Flows for Calibration and
Allocation Models . . . . . . . . . . . . . . . . . . 61
II

LIST OF FIGURES
FIGURE PAGE
1. Map of the Total Study Area with Station Locations 5
2. Map of the Canton Area with Station Locations . . . . . 6
3. Map of the Clyde Area with Station Locations . . . . . . 7
4. USGS Flow Gage on Pigeon River at Canton . . . . . . . . 9
5. USGS Flow Gage on Pigeon River near Hepco . . . . . . . 10
6. Pigeon River Flow Model . . . . . . . . . . . . . . . . 11
7. Dye Concentration Curve at Station P-4 . . . . . . . . . 14
S. Dye Concentration Curve at Station P-5 . . . . . . . . . 15
9. Dye Concentration Curve at Station P-6 . . . . . . . . . 16
10. Dye Concentration Curve at Station P-7 . .. . . . . . . . 17
11. Dye Concentration Curve at Station P-8 . . . . . . . . . 18
12. Dye Concentration Curve at Station P-10 . . . . . . . . . 19
13. Dye Concentration Curve at Station P-11 . . . . . . . . 20
14. Dye Concentration Curve at Station P-11A . . . . . . 21
15. Dye Concentration Curve at Station P-12 . . . . . . . . . 22
16. Dye Concentration Curve at Station P-13 . . . . . . . . . 23
17. Pigeon River Dye Study - Average Velocity vs Distance . . 24
18. Conductivity Cross-Sections taken on 14 May 1980 . . . . 26
19. Conductivity Cross-Section Taken at the R.R. Bridge Below
Champion Outfall on August 14, 1980 . . . . . . . . . . . 27
20. Conductivity Cross-Sections Taken on 26 August 1980 . . . 28
21. Temperature Cross-Sections Taken on 26 August 1980 . . . 29
22. Pigeon River D.O. Profile . . . . . . . . . . . . . . . 43
23. Pigeon River PAN Series . . . . . . . . . . . . . . . . 44
24. Pigeon River 5-Day BODS . . . . . . . . . . . . . . . . 45
25. Pigeon River 90-Day Long Term BODS . . . . . . . . . . . 46
III

List of Figures - continued
FIGURE PAGE
26. Organic Nitrogen Calibration . . . . . . . . . . . . . . 63
27. Ammonia-Nitrogen Calibration . . . . . . . . . . . . . . 64
28. Oxidized Nitrogen Calibration . . . . . . . . . . . . . . 65
29. CBOD Calibration . . . . . . . . . . . . . . . . . . . 66
30. Dissolved Oxygen Calibration . . . . . . . . . . . . . . 67
31. Champion Allocation, D.O. = 6 mg/l . . . . . . . . . . . 68
IV

Introduction
The Pigeon River, in North Carolina, is used as a water supply for
Champion Paper Company near Canton, North Carolina, and at times, the
entire flow of the river is diverted through the plant. After treatment,
wastewater from the paper mill is discharged to the river. The effluent
is characterized by elevated levels of color, dissolved solids, tannin
compounds, and temperature not normal in streams located in this section
of the State. Based upon previous investigations and data review,
it is possible that the original loading (BOD) from the mill is suf-
ficiently high to have depressed instream oxygen levels to or below the
water quality standards limits in North Carolina and perhaps in Tennessee.
The uncharacteristically high color, dissolved solids and temperature may
also be affecting biological productivity of the river and thus not providing
for the intended uses of the river according to water quality standards.
The Pigeon River from Canton, North Carolina to its confluence with the
French Broad River in Tennessee is adversely affected by the industrial
discharge from Champion International Paper Corporation. The use potential
of the river is thereby restricted for water supplies and recreational
activities. This situation has resulted in a cooperative agreement between
TVA, EPA, NCDEM and the State of Tennessee to assess the impact of the water
temperature, color, dissolved solids, and BOD on water quality and biological
productivity of the Pigeon River. As a part of this agreement the Technical
Services Branch of NCDEM performed a time-of-travel tracer study and an
intensive physical/chemical water quality study to calibrate a DO - BOD Model.
This model will be used to determine allocation limits for BOD5 and effluent
DO for Champion Paper's NPDES permit. The NPDES permits of the towns of
Clyde and Waynesville will also be reviewed at this time.

The Pigeon River originates in western North Carolina in Haywood
County at the confluence of the West and East Forks of the Pigeon River.
It then flows north for 69 miles to its confluence with the French Broad
River at Lake Douglass, 5 miles north of Newport, Tennessee. One of the
main physical features of the river is Waterville Lake, which was
constructed in 1929 by Carolina Power & Light for hydroelectric Power.
The lake has a capacity of 8.27 billion gallons and is located 20 miles
below Canton. Except under high flow conditions, the entire flow of the
river is diverted through a hydroelectric tunnel to Waterville, Tennessee,
thus bypassing almost 8 miles of riverbed.
The reach of the Pigeon River from Canton to the headwaters of Water-
ville Lake was the main concern of this study. This segment includes five
major tributaries: Beaverdam Creek, Richland Creek, Crabtree Creek, Jonathan's
Creek and Fines Creek. It has an average slope of 15.3 ft/mile and a drainage
area at Canton of 133 square miles and at Hepco of 350 square miles. The
sampling stations are shown on Table No. 1 and in Figures 1 through 3. There
are 12 river, 6 tributary and 3 effluent stations.
The Pigeon River is seriously affected by Champion Paper Corporation in
Canton. During low flow conditions up to 90% of the river may be diverted
through the plant and discharged as effluent. This effluent is characterized
by high levels of color, dissolved solids, and elevated temperatures. The
Champion discharge also has a small percentage of domestic waste present.
Other significant dischargers to the river are the towns of Clyde and Waynes-
ville. The town of Clyde has a secondary treatment plant with a design
capacity of .128 MGD and is entirely domestic. The town of Waynesville has
a secondary treatment plant with a design capacity of 6 MGD and receives
domestic and industrial waste. One of the industries which discharges into
the Waynesville Plant is a tannery, A. C. Lawrence Company, which adds an
2

additional amount of color to the river.
Continuous flow data for the Pigeon River from the 24th through
the 31st of August was obtained from the USGS gage stations at Canton
and Hepco. The Canton station is located 0.3 miles above station P-1
while the Hepco station is located 2 miles upriver from station P-13.
This data is presented in Figures 4 and 5. Discharge measurements
taken during the intensive sampling runs on the tributaries are reported
in Table 2. A flow model of the total river segment showing points of
water uptake, discharges, and tributary confluences is presented in
Figure 6.
3

TABLE 1
Station Locations
Physical/Chemical Study
August 25 - August 28
Distance (Miles)
From Champion
Discharge Station Location
- 6.07 P-0 Pigeon River below the confluence of the two forks
.05 P-1 200 feet upriver of Champion Paper outfall
0 P-2 Champion outfall
.15 P-3 RR Trestle
.40 P-4 Pigeon River at N.C. Hwy 215
P-4A Beaverdam Creek at N.C. Hwy 215
.50 P-4B Pigeon River at confluence of Beaverdam Creek
1.9 P-5 Pigeon River at bend at River Mile 61.2
- P-5A Thickety Creek at SR - 1550
3.75 P-6 Pigeon River at bend at River Mile 59.3
5.35 P-7 Pigeon River at SR - 1642 (Clyde)
5.80 P-7A Clyde WWTP
7.35 P-8 Pigeon River at SR - 1533
- P-9 Richland Creek at SR - 1519
8.2 P-9A Waynesville WWTP
9.2 P-10 Pigeon River at SR -1625
10.5 P-11 Pigeon River at SR - 1649
12.75 P-11A Pigeon River at confluence with Crabtree Creek
- P-11B Crabtree Creek 100 yards above mouth
14.2 P-12 Pigeon River at SR - 1363 (Ferguson Bridge)
P-12A Jonathans Creek 100 yds below Iiwy 276
- P-12B Fines Creek at SR - 1338
19.2 P-13 Pigeon River at SR - 1396 (Hepco)
4

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TABLE 2
DISCHARGE MEASUREMENTS
On the Pigeon River and Selected Tributaries
REACH: Pigeon River
R
ion Velocity Are Cross-Sectionaler Location Date Time ft/sec (FT ) Width Discharge
P-1 100 ft. upriver of
Champion outfall 800514 1140 1.1 132 108 170
P-1 200 ft upriver of
Champion outfall 800828 1035-1100 .39 10.73 40.5 5.04
P-4A Beaverdam Creek 800826 1510-1525 .615 at H 215 3.97 12.0 2.73
P-5A Thickety Creek g00826 1555
at SR-1550 •39 1.71 6.5 .70
P-9 Richland Creek 800826 1650
at SR-1519 1.78- 20.29 26.5 40.00
P-9 Richland Creek g00827 1400
at SR-1519 1.67 18.42 27.0 33.30
P-1lB Crabtree Creek
100 yds above mouth 800826 1750 .33 1 18.55 29.0 6.19
P-11B . Crabtree Creek 800827 1455 .37
100 yds above mouth 19.72 29.0 6.57
P-12A Jonathan Creek g00826 1849-1970 1.02
100 yds below Hwy 276 30.95 52.0 36.28
P-12A Jonathan Creek
100 yds below Hwy 276 800827 1550-1617 1.02 31.14 52.0 35.73
P-12B Fines Creeko 800826 2000 .62
of SR-1338 9.52 9.52 6.09
P-12B Finesree o f
SR
of SR 800827 1635-1646 .69
-1338 10.31 14.50 6.59

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Dye Study
On August 25, 1980 a dye study was conducted on a 19.66 mile stretch
of the Pigeon River from P-2, Champion outfall, to P-13 the SR-1396 bridge.
The study was divided into two segments because of an estimated time-of-
travel of two days. The first was from P-2 through P-10, a 9.12 mile reach,
and the second was from P-10 through P-13, a 10.54 mile reach.
Four liters of Rhodamine WT, a red fluorescent dye tracer, were slug
injected at each dose site. Samples were then taken at the downstream
stations from mid river by hand samplers. Samples were run on a Turner
Model 111 Fluorometer to determine peak and total dye concentrations. This
information was then used to establish time intervals for slug sampling
during the water quality sampling runs.
The results are presented in Table 3. The first segment, P-2 through
P-10, had a time of travel of 23 hours and 30 minutes and a velocity of
.57 feet/second. The second segment P-10 through P-13 had a time-of-travel
of 21 hours and 10 minutes and a velocity of .73 feet/second. The
total time-of-travel was 44 hours and 40 minutes with a velocity of .65
feet/second. The dye curves for the various stations are shown on figures
7 through 16. A velocity vs distance relationship is presented on Figure 17.
li

1[S1lLli J
REACH: Pigeon River Time of Travel Study
Dist.
from Stream
Travel Cum. Veloc- Injec- Dis-
Sta.
Peak Time, Time, ity, Length, tion, charge, Slope
N0. Location Date Time hrs. hrs. ft/sec. mi. mi . cfs ft/mi .
P-2 Champion outfall 800825 0745 Dye Dose
P-4 NC Hwy 215 800825 0817 32 min 32 min .96 .35 .35
4 hr
P-5 Bend at R.M. 61.2 800825 1205 3 hr 48 min 20 min .58 1.50 1.85
P-6 Bend at R.M. 59.3 800825 1645 4 hr 40 min 9 hr .58 1.85 3.70
P-7 SR - 1642 (Clyde) 800825 2050 4 hr 5 min 13 hr 5 min .57 1.58 5.28
P-8 SR-1533 800826 0210 5 hr 20 min 187 hr 25 min .55 2.00 7.28
P-10 SR-1625 800826 0715 5 hr 5 min 23 hr, 30 min 53 1.84 9.12
SUB-TOTAL 23 hr .57 9.12
30 min
s.
P-10 SR-1625 800825 0730 DYE DOSE
P-11 SR-1649 800825 0945 2 hr 15 min 2 hr 15 min .87 1.34 1.34
P-11A Pigoen River just up- 800825 1505 5 hr 20 min 7 hr „62 2.25 3.59
river of Crabtree Cr 35 min
10 hr
P-12 SR-1363 800825 1820 3 hr 15 min 50 min .64 1.42 5.01
P-13 SR-1396 800826 0440 10 hr 20 min 21 hr .78 5.53 10.54
170 min
SUB-TOTAL �0 hr min .73 10.54
TOTAL 44 hr 65 19.66
40 min

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A
Conductivity _
Cross-Sectional Measurements
Conductivity and temperature cross-sections were taken at downriver
stations to determine the extent of the mixing zone of the Champion
effluent under average and low flow conditions. The Pigeon River at
Canton has an average flow of 324 CFS (52 year average) and a 7/10 low
flow of 52 CFS. On May 14, 1980 the Pigeon River had a flow of 237 CFS.
Conductivity cross-sections were taken at Station P-3, 200 feet downstream
of P-3, and Station P-4. The results are graphed in Figures 18 and 19 and
show that mixing was almost complete by Station P-4. The conductivity
ranged from 950 umhos to 1025 umhos with a 14% increase from the lowest
. s
to highest value.
Conductivity and temperature cross-sections were taken at a flow of
81 CFS on August 26, 1980 at stations P-3 and P-4. These results are pre-
sented -in Figures 20 and 21. They indicate that the mixing was almost
complete at station P-4. At P-4 there was only a 9% difference between the
highest and lowest conductivity values of 4000 umhos to 4400 umhos.
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1 1 11 1

Chemical/Physical
On August 26, 1980 the physical/chemical intensive sampling runs
were started. There were four slugs begun every four hours using the
times determined in the dye study. The sampling schedule for the river
stations is presented in Table 4. The tributary stations were sampled
twice on consecutive days and Station P-0 was sampled once, as a check
on the main upriver station, P-1. The parameters taken in the sampling
runs were D.O., Temperature, pH, Solids, BODS, BODlt, Fecal Coliform,
Metals, Sulfate, Chlorides, Color, Conductivity, and a P&N series.
Sulfate, Chlorides, Color, Conductivity, and Metals results are
shown in Tables 6, 8, 10, 12 and 14. The metals sampled were Chromium,
Cadmium, Copper, Iron, Lead, Nickel, and Zinc. Chromium, Cadmium, Copper,
Lead and Nickel were all below normal reporting limits. Iron levels were
all below state standards. Zinc levels increased at Station P-4 but fell
off quickly.
Chlorides, Conductivity, Sulfates and color all increased substantially
at Station P-4. At Station P-13 they were all still considerably higher
than background values, the chlorides as high as 35 times background. The
highest sulfate value of 165 mg/1 at stations P-4 and P-11A was lower than
the state standard for A-2 waters of 250 mg/l. There are no state standards
for Chlorides, Conductivity and Color.
D.O. Temperature, pH, Solids, Fecal Coliform and P&N Series Data is
tabulated in Tables 5, 7, 9, 11 and 13. A D.O. profile shows that the sag
occurs at Station P-5. There is also a small sag which occurs at Station P-11
which is a result of the Waynesville WWTP. The reason for the sag occurring
at Station P-11 instead of Station P-10 is due to the incomplete mixing of the
Waynesville effluent at Station P-10. Downriver of Station P-11 the D.O.
continued to increase and by Station P-13 there was complete D.O. recovery.
30

Only D.O. readings taken on the Dissolved Oxygen meters were accepted,
because the Champion wastewater interferred with the Winkler Method's
operation.
Temperatures increased from 23 to 320C from Stations P-1 to P-4,
but by Station P-13 had returned to upstream levels. Total Residue in-
creased substantially at Station P-4 from 92 to 2440 mg/l and only de-
clined to 688 mg/1 by Station P-13. Total Suspended Residue was
insignificant ranging from 2 to 28 mg/l.
The BOD5 and BOD 30 results are presented in Tables 15 through 17.
A BOD5 plot is shown in Figure 24 and the 30 day P&N values in Tables 18
through 22. The highest in-river BOD5 was 6.0 mg/1 and a BOD30 of 29 mg/l.
An earlier set of BODlt of the Champion effluent were taken on May 14, 1980.
This set of samples was run for 91 days and the data is shown in Figure 25
and Table 23. The 91 day BOD was 75 mg/l.
31

TABLE 4
Intensive Survey
Sampling Schedule
Slug ill Slug Ill Slug #3 Slug #4
P-1 0745 1145 1545 1945 800826
P-2 0800 1200 1600 2000
P-4 0832 1232 1632 2032
P-5 1230 1630 2030 0030
P-6 1705 2105 0105 0505
800827
P-7 2035 0035 0435 0835
P-8 0245 0645 1045 1445
P-10 0715 1115 1515 1915
P-11 0930 1330 1730 2130
P-11A 1440 1840 2240 0240
800828
P-12 1750 2150 0150 0550
P-13 0415 0815 1215 1615
32

TABLE 5
Fecal RESIDUE SERIES (mg/1) N SERIES '(mg/1) P SERIES (mg/1)
R.P. D.O. Temp. Coliform Tot. Tot. Vol. NTO3-N*
Station Date Time (ft.) PH (mg/1) (oC) (/i/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO-N Tot. P Ortho� P
P-0 80082 1130 7.9 8.4 19.8 27 2 < .�1 . �.05
P-1 800826 0740 6.8 6,4 20.0 <.05 .1
P-1 800826 1130 7.5 8.3 23.0 160 60 1 <.05 ,1 .16 < .05
P-1 800826 1540 8.7 8.6 26.0 79 4 < .05 .2 .15 .06
P-1 800826 1940 7.0 7.7 23.0 137 2 .05 .2 .14 .06
-1 MEAN 7.5 7.75 23;0 92 2 .05 .15 .16 .06
P-2 800826 0800 7.1 14 34.0 1.5 FOO.
81
P-2 900826 1200 7.2 q3.434.0
9 34.0 330 (TUBE 2610 18 1.2 .80
P-2 800826 1600 7.26,0 2920 21 1.2 -< .05
P-2 800826 2000 6.8 3.0 3000 '23 1.7 .82
-2 MEAN 7.1 2843 21 1.4 .81
P-4 800826 0832 7.2 2.3 29.5 1.2 .65
P-4 800826 1232 7.45 `1.5 33.0 50 2150 12 1.0 .65
P-4 800826 1632 7.5 4.52M4S� 33.0 2360 11 .88 .64
P-4 800826 2032 7.2• 4.3 33.0 2810 19 1.4 Z.2 .05 .73
-4 MEAN 7.3 32.0 2440 14 1.12 .0 .06 .67
P-5 800826 1230 7.05 1.5W ' 30.8 1.1 8 0.33 .62
P-5 800826 1630 7.25 3.7 33.4 280 2140 15 0.84 .7 0.39 .60
P-5 800826 2030 7.4 3.55M 30.5 2240 15 0.71 L.5 0.39 .59
P-5 800827 0030 7.55 3.65 28.7 2610 18 1.1 .9 0.37 .65
P-5 MEAN 7.3 3.675 30.9 2330 16 .94 .0 0.37 .62
w
w r I

TABLE 6
ROD COD HETALS (ug/1)
Station Date Time ( /1) (m /1) Tot. Cr Cd Cu Fe Pb Mn Ni Zn SO4 Cl Corid
P-0 800828 1130 1.5 <50 <40 < 10 <100 <50 < 5 1.0 26 1
P-1 800826 0740 .8 13 8.0
P-1 800826 1130 1.5 74
P-1 800826 1540 1.4 15 4.0 1 80
P-1 800826 1940 <50 < 40 500 4100 <100 50 1 1 135
P-1 MEAN 1.2 14 1 6.0 91 18
P-2 800826 0800 13.0 2
P-2 800826 1200 7.2 <50 <40 400 <100 <100 140 4390
P-2 800826 1600 6.8 180 200 51 On
P-2 800826 2000 <5p 440 400 <100 <100 609400
P-2 MEAN 9.0 <50 140 400 <100 <100 100 190 100
P-4 800826 0832 6.8 160 � 760 0
P-4 800826 1232 6.2 3680
i
P-4 800826 1632 6.5 170 980 4150 7 6 0
P-4 800826 2032 <50 <40 400 <100 4100 80 i 4800
P-4 MEAN 6.5 6
4
P-5 800826 1230 5.4 180 0 ign 700 700j
P-5 800826 1630 5.1 120 900 F177oo 7nn 7noj
P-5 800826 2030 5-2 150
i
P-5 800827 0030 <50 <40 500 4/ 100 50
P-5 MEAN 5-2 150 863 3553 700 700

TABLE 7 •
Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1)
R.P. D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+
Station Date Time (ft.) PH (mg/1) (0C) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN 11 NO2-N Tot. P Ortho, P
P-6 800826 1705 7.3 1.74JY 31.4- 77 1.4 0.56 �.56
P-6 800826 2105 7.2 1 3.65 28.9 220 1950 11 .60 1.4 0.62 .56
P-6 800827 0105 7.5 3.85 1 27.6 2140 14 .60 1.2 0.57 .54
P-6 800827 0505 7.4 3.60 26.0 2370 21 .68 1.7 0.61 .56
P-6 ME 7.4 3.7 28.5 2154 15 .66 1.4 0.59 .56
P-7 800826 2035 7.35 4.OM 28:5 .68 1.3 0.68 .54
P-7 800827. 00357.45 4.1 27.5 3600 1930 18 .53 1.4 0.72 .54
P-7 800827 0435 7.50 4.0 26.0 2100 9 .40 1.4 0.65 5
P-7 800827 0835 4.3 25.2 .52 1.2 0.73 .56
P-7 MEAN 7.4 4.1 26.8 2015 14 .53 1.3 0.70 .55
P-7A 800826 2100 7.1 5.6 23.0 7.1 1.0 < .05 7.5
P-7A 800827 0100 6.9 5.9 21.0 < 1.8 (TUB ) 285 77 3.7 1.0 c .05 7.1
P-7A 800827 0500 7.0 7.4 20.5 248 58 5.7 8.1 .07 6.0
P-7A 800827 0855 7.0 5.7 20.4 6.6 2.0 .05 6.6
-7A MEAN 7.0 6.15 21.2 267 68 5.8 0.5 6.8
P-8 800827 0250 7.6 5.1 25.0 .52 1.3 .76 .49
P-8 800827 0645 7.7 4.9 25.0 1860 11 .42 1.0 .76 .52
P-8 800827 1045 2.63 7.5 5.65 24.5 2040 11 .29 1.4 .75 .51
'i P-8 800827 1445 7.5 5.1 28.0 2120 12 .40 1.3 .83 .52
P-8 800828 1245 2.62
P-8 MEAN 7.6 5.19 25.6 2007 11 .41 1.3 .78 .51

TABLE 8
BOD COD METALS (ug/1) rotOR
Station Date Time ( /1) (m /1) Tot. Cr Cd Cu Fe Pb Mn Ni Zn SO4 Cl Coiid
P-6 800826 1705 4.3 150 810 700
P-6 800826 2105 4.7 31.00
P-6 800827 0105 4.0 110 880 3250 ' 700 '700
P-6 800827 0505 3550
P-6 MEAN 4.3 130 845 3250 �I
P-7 800826 2035 4.3 120 690 � 282+r, -rr,r,
P-7 800827 0035 4.0
P-7 800827 0435 3.9 3200 600 700 ,
P-7 800827 0835 3410
P-7 MEAN 4.1 135 820 3120 600 700
P-7A 800826 2100 16 1150 34 310 60 70
P-7A 800827 0100 8 I 290
P-7A 800827 0500 6 1 26 38 i 2681 35 60f '
P-7A 800827 0855 1 290
P-7A MEAN 10 88 36 290 ; 481 65I
t
P-8 800827 0250 3.4 130 710 2700 600 600
P-8 800827 0645 3.8 2730
P-8 800827 1045 3.6 180 810 2930 600 700
P-8 800827 1445 < 50 <50 40 600 <100 50 3400
P-8 MEAN 3.6 155 760 2940 600 650 j
I

TABLE 9
Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1)
R.P. D.O. Temp. Coliform Tot. Tot. Vol. NO -N+
Station Date Time (ft. ) g (mg/1) (oC) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO2 Tot. P Ortho' P
P-9A 80082 0500 7.3 6.1 21.0 3.5 5.5 .79 6.4
P-9A 80082 0915 7.3 6.8 21.6 <1.8 (TUBE 628 1 19 2.2 3.6 1.2 4.6
P-9A 80082 1300 7.0 7.0 24.5 630 23 .98 1.9 1.8 4.4
P-9A 80027 1700 6.8 1.5* 26.0 493 14 .23
P-9A ME N 7.1. 6.6 23.3 584 19 1.73 3.0 1.42 4.9
P-10 80082 0715 7.5 6.0 22.6 .49 1.1 .69 .59
P-10 80082 1115 3.15 7.6 6.3 24.5 770 1370 13 EE
.9 .72 .55
P-10 80082 1515 7.7 6.0 27.0 1420 13 .9 .72 .59
P-10 800827 1915 1 3.15 7.5 6.3 24.5 1450 14 .19 .8 .69 .57
P-10 800828 1300 3.17
P-10 ME 7.6 6.2 24.7 1413 13U1 .22
.71 .58
P-11 800827 0930 7.6 5.7 22.5 .73 .63
P-11 800827 1330 7.7 6.3 26.3 4000 * 1300 20 .76 .60
P-11 800827 1730 7.6 6.0 27.7 1320 16 .74 .62
P-11 800827 2130 7.8 5.8 25.0 1490 17 .16 .8 .73 .58
P-11 MEM 7.7 6.0 25.4 1370 18 .28 l .74 .61
P-11A 800827 1450 7.3 6.25 26.1 .30 .4 .78 .65
P-11A 800827 1840 7.6 6.20 26.9 480 1280 12 .23 .9 .81 .59
P-11A 800827 2240 7.8 6.40 24.0 1340 15 .17 . .7 .79 .59
P-11A• 800828 0240 7.7 6.30 23.0 1370 14 .14 .7 1 .75 .57
P-11A 14E N 7.6 6.29 25.0 1330 14 .21 93 .78 .60
V b

TABLE 10
BOD COD METALS (ug/1) COLOR
Station Date Time ( /1) (m /1) Tot. Cr Cd Cu Fe Pb Mn Ni Zn SO4 Cl Cond
P-9A 800827 0500 3.5 81 220 930 18
P-9A 800827 0915 2.5
920
P-9A 800827 1300 2.5 80 230 910 150 '150
P-9A 800827 1700 50 40 100 100 100 110 680
' P-9A MEAN 2.8 81 225 860 165 1 A 9 !
P-10 800827 0715 4.8 - 110 550 11910 400 600
P-10 800827 1115 3.5 I 2000 I
P-10 800827 1515 4.0 110 610 12200 400 450 !!
P-10 800827 1915 2000 I'
P-10 MEAN 4.1 110 580 2028
I I
I I
P-11 800827 0930 4.3 120 390 11820 50 1
0
!
P-11 800827 1330 4.1 12 1 �
P-11 800827 1730 5.2 20 540 2200 0 350
P-11 80082 2130 2400
P-11 MEAN 4.5 120 465 2130 350 350
i
P-11A 800827 1440 4.0 140 420 1900 350 400
P-11A 800827 1840 3.5
2000 j
P-11A 800827 2240 3.2 190 520 2100 400 300
P-11A 800828 0240 2100
P-11A MEAN 3,.6 I165 470 2025 375 350 .I
- :j

TABLE 11
Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1)
R.P. D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+
Station Date Time (ft. ) pH (mg/1) (oC) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO2-N-:=:T�:__ -
Tot. P Ortho' P
P-12 800825 1730 1.97
P-12 800827 1750 7.7 6.60 26.5 .23 .8 .81 .62
P-12 800827 2150 7.9 6.30 23.0 600 1190
P-12 800828 0150 1.89 7.7 6.50 23.0 1310 18 .14 .8 .78 58
P-12 800828 0550 1.87 7.75 6.65 22.6 490 1360 21 .12 .7 .76 .57
P-12 800828 1313 1.89
P-12 ME 7.76 6.51 23.8 545 1287 20 .17 .78 .79 .59
i
P-13 800828 0415 7.6 7.7 21.5 .06 .5 .56 .39
P-13 800828 0815 7.65 8.0 20.4 .20 .8 .62 .49
P-13 800828 1215 7.7 8.0 22.0 .20 .0 .58 .60
P-13 800828 1615 7.35 24.9 1100 6�8 28 .05 .6 .53 .41
P-13 IfEA 7.65 7.76 22.1 .13 .7 .57 47
,P-4A 800826 1510 7.85 8.6 24.7 20 78 22 <.OS .2 1 .19 .05
P-4A 800827 1310 7.1 8.7 22.8 2 6 .05 .2 .19 < .05
P-4A MEA1 7.48 8.7 23.8 �5 14
P-5A 800826 1555 6.95 7.7 22.5 320 94 8 <.05 .3 .34 .05
P-9 800826 1715 7.6 7.4 22.4 140 114 8 .07 .4 .14 L.05
P-9 800827 1400 7.5 7.9 24.8 115 9 .08 .3 .14 .05
P-9 MEAN 7.7 123.6 115 9 .08 .4 .14 ,.05
i1{
y w I

TABLE 12
HOD COD METALS (ug/1)
Station Date Time ( /1) (m /1) Tot. Cr Cd Cu , Fe Pb Mn Ni Zn SO4 Cl Cond
P-12 800827 1750 3.5 150 420 1790 35'0 350
P-12 800827 2150 3.3 1900
P-12 800828 0150 3.3 120 550 2000 50
P-12 800828 0550 4.2 1 2000
P-12 MEAN 3.6 11 135 1 485 1923 350 325
i
P-13 800828 0415 1 2.5 60 1210 ! 930 150 150
P-13 800828 0815 4.2 1 910
P-13 800828 1215 5.4 910
P-13 800828 1615 Iiinn
P-13 MEAN 4.0 963
i
I I
P-4A 800826 1510 2.1 < 50 <40 600 --100 <50 < 5 7
P-4A 800827 1310 0.8 I 1
P-4A MEAN 1.45 66
P-5A 800826 1555 0.8 50. �,40 500 4100 450 8 3 91 15 35
i
P-9 800826 1715 2.2 < 50 40 700 <100 e50 32 3 131 20 45
P-9 800827 1400 2.2 115 I
P-9 TIEAN 2.2 123 j
' I

i
TALE 13
y
Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1)
R.P. D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+
Station Date Time (ft.) H (mg/1) (0C) 0/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO, Tot. P Ortho' P
P-11B 800826 1800 7.65 7.8 23.0 2300 90 11 .05 .3 .26 .17
P-11B 800827 1455 7.6 8.1 22.7 1 84 6 .25 .6 .34 .26
P-11BMEAN 7.65 8.0 22.9 87 9 .5 .30 .22
P-12Z 800826 1845 7.3 7.9 23.2 230 52 13 �.OS .2 .26 .05
P-12A 800827 1545 7.1 8.4 23.0 48 12 OS .2 .27 .05
P-12A M N 7.2 8.2 23.1 50 13 .2 .27 .05
P-12B 800826 2000 7.1 7.1 23.3 1200 82 13 .10 .•5 .14 .24
P-12B 800827 1635 7.0 6.5 25.0 95 16 .25 .0 .17 .64
P-12B ME 7.1 6.8 24.2 89 15 .18 .8 .16 .44
I
�I
i
F I

i
TABLE 14
BOD COD METALS (ug/1) roloR
Station Date Time ( /1) (m /1) Tot. Cr Cd Cu Fe Pb Mn Ni Zn SO4 Cl Cond
P-11B 800826 1800 1.2 50 <40 500 <100 50 �5 2 73 25
P-11B 800827 1455 1.8
fP-11B MEAN 1.5 74
P-12A 800826 1845 1.1 -, 50 <40 500 <100 <50 45 2 40 20 025
P-12A 800827 1545 2.2 29
P-12A MEAN 1.7 35
P-12B 800826 2000 2.6 50 440 700 <100 <50 <5 2 1 69 40 40
P-12B 800827 1635 5.6 61
P-12B MEAN 4.1 65
I
I
I
i
S
I
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T LE 15
BOD5 BOD BODult. BOD It.
\ -
'-0 800828 1130 100 1.70 2.32 2.2 0.25
'=1 800826 1130 100 1.97 4.34 3.8 0.12 3.0 0.23 13.5 .01
'-1 800826 1940 100 1.53 2.83 2.4 0.13
'-2 800826 1200 100 7.57 28.73 35.3 0.05
'-2 800826 2000 100 7.14 29.50 48.2 0.03
'-4 800826 1232 100 6.20 23.47 28.4 0.05 9.3 0.22 72.2 .01
'-4 300826 2032 100 5.95 21.90 127.0 0.05
'-4A 300826 1510 100 1.33 2.80 2.5 0.11 1.5 0.34 7.4 .01
'-4A 800827 1310 100 1.00 2.52 2.1 0.09 1.4 0.25 8.2 ,01
?-5 900826 1630 100 5.13 25.69 95.9 0.01
3-5 300827 0030 100 5.43 27.01 : 101.9 0.01
P-5A 800826 1555 100 0.83 3.37 4.4 0.04 1.9 0.13 6.5 .02,
P-6 800826 2105 100 4.50 25.24 99.8 0.01
P-6 800827 0505 100 3.23 21.79 81.2 0.01
P-7 00827 0040 100 3.93 21.60 48.2 0.02
P-7' 00827 0835 100 3.40 21.73 83.7 0.01
P-7 00827 0835 100 3.43 21.36 82.6 0.01
P-7A 300827 0100 100 6.67 74.16 229.4 0.01
P-7A 800827 0855 100 6.33 71.07 100.1FO-04
P-7A 800827 0855 100 9.83 68.48 122.0 0.03
47

TA 3LE 16
STA I % BODSBOD BODult K BODuIt.
P-8 800827 0645 100 3.77 20.91 46.50 0.02
P-8 800827 1445 100 3.37 21.0 45.30 0.02
P-9 800826 1700 100 1.60 6.34 8.60 0.04
P-9 800827 1400 100 1.53 5.42 7.30 0.04 3.6 0.11 18.0
P-9A 800827 0900 100 8.30 19.64 19.10 0.14 17.9 0.16 28.5 .I
P-9A 800827 1700 100 1.87 57.13 57.20 0.15
P-10 800827 1115 100 2.80 -16.00 35.50 0.02
P-10 800827 1915 100 3.80 15.96 23.00 0.04
P-11 800827 1330 100 3.00 15.12 33.60 0.02
P-11 800827 2130 100 3.17 14.77 21.10 0.04
P-11A 800827 1840 100 3.57 14.91 19.40 0.05
P-11A 800826 0240 100 3.07 12.97 19.00 0.04
P-11B 800827 1800 100 2.13 4.97 4.80 0.11
P-11B 800827 1450 100 1.25 5.98 9.70 0.03
P-12 800827 2150 100 3.10 13.04 16.60 0.05
P-12 800828 0550 100 3.30 13.17 16.90 0.05
P-12A 800826 1845 100 1.03 2.49 2.30 0.09
P-12A 800827 1545 100 •73 2.60 2.80 0.05 1.3 0.18 7.8
P-12B 800826 2000 100 3.03 1 7.83 8.40 0.09
P-12B 00827 1635 100 5.47 16.33 17.40 0.08
4

TABLE 17
\ 1 % BODMELJESBOD BODult. K BOD lt. KN
-13 800828 0815 100 3.86 12.56 14.10 0.07 4.5 0.37 12.8 0.12 .
-13 800828 1215 100 6.47 17.73 18.8 0.09
-13 800828 1615 100 3.90 110.90 11.0 0.09
49

TABLE 18
PIGEON RIVER 30 DAY P & N SERIES 26 - 28 AUGUST 1980
Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1)
D.O. Temp. Coliform Tot. Tot. Vol. NO -N
Station Date Time Day (mg/1) , (oC) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO2-N Tot. P Ortho, P
P-0 800828 1130 0
< .05 .1 .19 .05
30 .05 .2 .27 < .05
P-1 800826 1130 0 < .05 .1 .16 < .05
30 .05 .1 .26 .05
P-1 800826 1940 0 .05 .2 .14 .06
30 < .05 .2 .21 < .05
P-2 800826 1200 1.2 2.1 < .05 .80
30 1.3 1.9 < .05 .65
P-2 800826 2000
00 1.7 3.1 < .05 .82
J30 1.8 2.3 .08 .73
P-4 800826 1232 0 1.0 .7 OS 6
30 .99 .2 .20 .59
P-4 800826 2032 0 1.4 .2 <.05 .73
30 1.3 .0 .07 .63
P-5 800826 1630 0 .84 .7 .39 .60
30 .12 .9 1.2 .56
P-5 800827 0030 0 1.1 .9 0.37 .65
30 .07 .7 1.6 .55

TABLE 19
Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/l)
Tot. Tot. Vol. NO -N
D.O. Temp. Col iform 3 +
Station Date Time Day (mg/1) ' (oC) (#/100 ml) Tot. Vol. 'Sus. Sus. NH3-N TKN NO2-N Tot. P Ortho• P
P-6 800826 2105 0 .60 1.4 0.62 .56
30
< .05 .5 1.30
P-6 800827 0505 0 .68 1.7 0.61 .56
30 0 .54
P-7 800827k30
.53 1.4 0.72 .54
.05 1.0 1.30 .47
P-7 800827 .52 1.2.05 0.6 1 .35 .48
P-7A 800827 3.7 11.0 < .05 7.1
0100 0
.06 3.9 7.5 7.2
30
P-7A 800827 0855 0 6.6 2.0 .05 6.6
30 .05 .6 9.3 6.4
P-8 800827 0645 0 .42 .0 .76 .52 _.
30 .4.05 .6 1.3 .45
P-8 800827 1445 0 .40 .3 .83 .52
30 .05 .6 1.3 .45
F-9 00827 0900 0 2.2 .6 1.2 4.6.
30 .06 .6 3.6 5.4
300827 1700 0 .23 .0 1.9 4.0
30 �.OS .9 2.1 4.0

TABLE 20
Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1)
D.O. Temp. Coliform Tot. Tot. Vol. hO3-N+
Station Date Time Day (mg/1) ' ( C) (#/100 ml) Tot. Vol. Sus. Sus. NH3-NTKN NO -N Tot. P Ortho P
P-10 800827 1115 0 .34 .9 .72 .55
30 .05 .6 1.2 .49
P-10 800827 1915 0 .19 .8 .69 5
30
P-11 800827 1330 0 .30 1.4 .76 .60
30 .OS .7 1.2 .54
P-11 800827 2130 0 .16 .8 .73 .58
30 .06 .8 1.0 .53
P-11A 800827 1840 0 .23 .9 .81 .59
30 .09 .5 1.1 .53
P-11A 800828 0240 0 .14 .7 .75 .57
30 .09 .6 .97 .54
P-12 800827 2150 0 .18 .8 .80 .57
30 .11 .9 1.1 .52
P-12 800828 0505 0 .12 .7 .76 .57
30 .10 .8 .97 .52
P=13 800828 0815 0 - .20 .8 .62 .49
30 .05 .3 1.1 .39
P-13 800828 215 0 - .20 .0 .58 60
30 G.05 5 1.3 .50
P-13 800828 IL615 1 0 1 ns F sI 4i

TABLE 21
Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1)
Tot. Tot. Vol. NO -N
D.O. Temp. Coliform 3 +
Station Date Time Day (mg/1) (oC) (Il/100 ml) Tot. Vol. Sus. Sus. NR3-N TKN NO2-N Tot. P Orth'o P
P-4A 800826 1510 0 L.05 .2 .19 .05
30 4.05 .1 27
<-
P-4A 800827 1310 0 z-.05 2 1
30
P-5A 800826 1555 0 .05 .3 .34 < 0
• 30
<.05 .1 .60 c 0
P-9 800826 1700 0
30
P-9 800827 1400 0
30
P-11B 800826 1800 0 4.05 .3 ' .26 .17
j <.OS 2 43
30 .14
P-11B 800827 1450 0 .25 .6 -34 .26
30 11 7 .63 23
P-12A 00826 845 0 .05 2 .26 .05
30 - t 05 1 .38 -e.05
P=12A 00827 545 0 OS 2 .27 OS
30 < 05 1 8 0
P-12B 300826 2000 0 .10 5 .14 .24
30 ' 05 2 .60 17
W
i

TABLE 22
Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1)
D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+
Station Date Time Day (mg/1) (oC) (6/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO2-N Tot. P Ortho P
P-12B 80082f 1635 0 .25 1.0 .17 .64
30 .05 .3 1.0 .52

TABLE 23
PIGEON RIVER 91 DAY BOD P&N'S ,
RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/l) •
Tot. Tot. Vol. NO3-N+
Station Date Time Tot. Vol. Sus. Sus. NH -N TKN NO2-N Tot. P Ortho P
P-1 800514 1100 0 Day 31 8 1 0 �<.05 <.l .25 < .05
P-1 800514 kfter 91 Days 100% No 02 < .05 61 .61 < .05
P-1 800514 4.fter 91 Days 100% 02 <.05
P-2 800514 1030 0 Day 2080 419 23 13 3.6 4.8 < .05 .77 .47
P-2 800514 After 91 Days 1001% <.05 1.0 5.1 74
P-2 800514 After 91 Days 75% Uncorrected Val e <.OS 1 .6 3.611
.48
P-2 1 800514 After 91 bays 501" Unco recte Valu

Model Development
A. Introduction
In August of 1980, a fluorescent dye time-of-travel study and an intensive
water quality survey were performed in the Pigeon River in western N.C. between
the Towns of Canton and Hepco. Data collected during these studies were used to
calibrate a water quality model to determine a wasteload allocation for the
Champion Paper Mill in Canton. The resulting allocation curve for a waste D.O.
of 6 mg/l is shown in Figure3l of this report. Any combination of BOD5 and
NH3-N on or below the curve represents an acceptable allocation for Champion.
A reasonable combination would be a BOD5.of 4 mg/l and a NH3-N concentration
of 1 mg/l. At these concentrations, the D.O. of the modeled 20 mile reach of
the Pigeon River will not fall below 5 mg/l if the River conditions are less
restructive or the same as design conditions used in the model.
B. Model Development
The EPA stream quality model (QUALL II) uses a combination of the hydraulic
characteristics of a stream and the system's chemical and biological reaction
rates to predict in-stream trends in water quality parameters. The hydraulic
portion of the model requires functions describing the relationships between
flow, velocity, depth and reaeration (K2) . Developed to predict measured
conditions in the stream, these functions theoretically adjust velocity, depth
and K2 to changes in stream flow. Calibration of the model's chemical parameter
predictions involves adjusting oxidation rates for organic nitrogen, ammonia
nitrogen and CBOD to best predict the observed in-stream decay of these substances.
These rates are assumed to be independent of stream flow but vary with changing
temperatures. The calibrated Quall II model is adjusted to 7/10 low flows and
design temperatures for the final allocation calculations.
The Pigeon River hydraulic model was primarily based on data collected
56

by the N.C. Dept. of Natural Resources and Community Development (NRCD) in
August of 1980. This information was supplemented by data from a 1965 report
by the Department of the Interior on a biological investigation of the Pigeon
and a 1980 N.C. Wildlife Department report by Wingate and Davies. Pigeon River
calibration flows were calculated from measured tributary discharges, self-monitoring
data from Champion Papers and the Towns of Clyde and Waynesville and conservative
substance mass balances. Table24 shows the measured tributary and waste flows
used to calibrate the model. Additional stream flow contributed by small
tributaries and land runoff was estimated from mass balances of measured
concentrations of total dissolved solids and chloride at the various stream
stations.
The Pigeon River's velocity at the time of the survey was calculated from
data collected during a fluorescent dye time-of-travel study on the 25 and 26 of
August. The River's velocity changes only slightly over the twenty miles modeled
reflecting the relatively constant slope of 15 ft/mi. The average measured
velocity was 0.65 fps. Time-of-travel data from a 1965 Dept. of the Interior
study of the Pigeon River was' combined with the•1980 data to develop a power
function relationship between velocity and flow. Between 1965 and 1980, the
introduction of secondary waste treatment at the Champion Plant has changed the
water quality of the Pigeon River considerably. Despite these improvements in
water quality, the flow-velocity relationships measured in the two studies were
reasonably consistent. The constant velocity of 0.76 fps measured in 1965
reflected flows somewhat greater than those measured in 1980. The two sets
of data were combined to calculate the velocity power equation :
V = 0.143 Q(0.310)
The reaeration constant (K2) for the Pigeon model was calculated using
Owen's relationship between K2, velocity and depth:
K2 = 2.31 (9.41 (Velocity)0.67/(depth)1.85)
Cross sectional areas between stations were estimated from velocity and flow data.
These were combined with widths measured for a 1980 N.C. Wildlife Study of the
River's fisheries to calculate average depths along the modeled reach. The resulting
57

K2 of 2.01 day 1 was assumed to be constant for the entire model.
A relationship between depth and river flow was calculated with the
following relationships:
V A Wxd
d = 1/VW (Q)
d = 0.026 Q
Where: V = average river velocity
Q = average river flow
A = average cross-sectional area
W = average width
d = average depth
Temperatures measured in the Pigeon during the intensive survey ranged
from 330C at the outfall to about 250C at the downstream stations. Therefore,
three design temperatures were employed: 310C for miles 21.0 to 17.9, 280C
for miles 17.9 to 15.9 and 250C for miles 15.9 to 0.
Decay rates for organic nitrogen, ammonia nitrogen and CBOD (Kl) were
developed using average chemical concentrations measured at each station
(Table 25) . Dissolved oxygen concentrations were corrected to the design
temperatures using an analysis based on percent saturation. The decay of all
modeled constituents was assumed to follow first order kinetics. Rate constants
were determined by applying the X2 goodness of fit test. Chemical concentrations
measured at the river stations were compared to concentrations predicted by the
Quall II model with various reaction rates. The rate of organic nitrogen decay
was determined first, since its decay produces ammonia and thus directly affects
the ammonia decay rate. The best fit organic nitrogen rate was then incorporated
into the model and a best fit rate for ammonia decay was determined. Finally, a
decay rate for CBOD was found by fitting the rate to the dissolved oxygen data.
58

CBOD concentrations in the stream are affected by numerous reactions. The
Kl rate theoretically reflects CBOD oxidation rates. However, settling and
resuspension of bottom sediments also remove and replace CBOD in the overlying
water and influence the oxygen demand of CBOD. A rate fitted to dissolved
oxygen data incorporates these complex interactions and models the stream
system as a whole.
Calibration of the Pigeon River model produced the following rate
constants:
Kl = 0.17 day 1
K2 = 2.01 day 1
Korg-N = 0.0 day-1
KNH3 = 0.8 day 1
The results of the calibrated model are illustrated in Figures 26-30. The
solid line shows the constituent concentrations predicted by the model. The
three crosses correspond to the measured maximum, average and minimum
concentration at each station. The scatter in the organic nitrogen data
(Figure 26) made accurate fitting difficult. The pictured calibration shows
the decrease in organic nitrogen concentration caused solely by dilution.
Ammonia nitrogen (Figure 27) decayed smoothy with travel down the Pigeon River.
A decay rate of 0.8 day 1 fit the data well. Although high for most systems,
this rate seems reasonable for the Pigeon River. The warm, turbulent, riffled
reaches of the river provide an excellent environment for nitrifying bacteria.
The metabolisn of these organisms is primarily responsible for. the decay
ammonia in aquatic systems. Oxidized nitrogen (NO2 + NO3) is produced from
the oxidation of ammonia. The calibrated model (Figure 28) underestimated
the measured concentrations of nitrite and nitrate for most of the river. This
is probably due to additional runoff input to the river not accounted for in
the model. Although the CBOD oxidation was fitted to dissolved oxygen data,
the resulting predictions (Figures 29 & 30) fit the measured data well.
C. Allocation
The calibrated model was adjusted to 7/10 flows for the allocation
determinations. USGS data was used to calculate 7/10 flows on the Pigeon and
all the major tributaries. Design waste flows were used for the Champion,
59

Clyde and Waynesville Wastewater Treatment Plants. Allocation flows are
included in Table 24.
Wasteload allocation calculations are routinely made at a calculated
design temperature. The design temperature calculated for Champion Papers
was 220C (71.60F) . However, the elevated temperature measured in the Pigeon
below the Champion outfall are produced by the plant's heated discharge. It
seemed unreasonable to adjust the model to a calculated temperature never
seen in the river. The calibration model temperatures were therefore used
for the allocation determinations.
Other boundary conditions were established as follows:
Upstream temp. = 71.60F
Upstream D.O. = 7.9 mg/l (90% saturation)
Upstream CBOD = 3.0 mg/l
Upstream NH3 = 0.05
Champion waste D.O. = 6 mg/l
A standard allocation procedure is employed for all Level C models.
With all boundary conditions set, the NH3-N in the waste is set equal to
zero and the CBOD concentration is varied until the resulting D.O. in the
simulated stream reach does not drop below 5 mg/l. The CBOD is then set
to zero and the NH3-N is varied until a D.O. = 5 mg/1 minimum is maintained.
The CBOD is then converted to BOD5 using the CBOD/BOD5 ratio determined for
the waste (3.65) . These two points then define the allocation graph shown in
Figure3l. Any combination of NH3-N and BOD5 on or below this line respresents
an acceptable allocation for Champion Paper.
60

Table 24. Measured Point-Source Flows for Calibration & Allocation Models
Calibration Allocation
Source Flow (cfs) Flow (cfs)
Pigeon River upstreaa of Champion Paper 81.66 76.1
Champion Influent 71.66 76.0
Champion Effluent 67.17 75.17
Beaverdam Creek 2.73 1.39
Thichety Creek 0.70 0.36
Clyde WWTP 0.21 .198
Richland Creek 36.60 20.8
Waynesville WWTP 4.43 9.3
Crabtree Creek 6.38 3.0
Jonatharfs Creek 36.01 29.6
Fines Creek 6.34 5.20
l'1
r
I
61

Pigeon River
Water Quality Data
August 26 and 27, 1980
Table 25.
Avg. D.O. @
Design Design
River Temp Temp CBOD Org-N NH3-N NO2+NO3
Station Mile °C mg/1 mg/l mg/l mg/l mg/l
P-1 63.31 31 6.75 2.20 0.1 0.05 0.16
P-2 63.21 31 4.5 35.40 1.1 1.40 .05
P-4 62.91 31 4.55 23.73 0.88 1.12 0.06
P-5 61.41 31 3.63 21.37 1.06 0.94 0.37
P-6 59.51 28 3.67 22.40 0.74 0.66 0.59
P-7 57.91 25 4.23 21.48 0.77 0.53 0.70
P-8 55.91 25 5.24 18.79 0.89 0.41 0.78
P-10 54.11 25 6.11 17.30 0.57 0.33 0.71
P-11 52.81 25 5.99 19.39 0.82 0.28 0.74
P-11A 50.55 25 6.28 13.82 0.72 0.21 0.78
P-12 49.11 25 6.37 13.39 0.61 0.17 0.79
P-13 43.71 25 7.36 7.20 0.57 0.13 0.57
f _
62

Figure 26. Organic Nitrogen Calibration, K = 0.0 day-1
r
� m +
tq +
to
r- to +
J + + +
ur m +
M tdL Li + +
Z +
M + +
a m + r $ +
I—
Z td
v +
Z m
CG
0 �
m
n
m
to
in
+
1 1 1 r 1 1 1
t _=.1.W 1 7.Q1 I S.0 13.E 1 1 .m 9.® '7.rA S.® 3.@1
MIL E S R B O V E H E P C O
rn
w '
i
I

Figure 27. Ammonia-Nitrogen Calibration, K = 0.8 day-1
r�
_I — +
\ m
L'7 r!
I-_ —
u m
N
Z —
_pm
F-
EE ID
IE tR
Z ea
lJ
z
Q
LT_ m +
zt +
Q +
M in
cc B
m +
t +
+
m
r1
+ +
m
R! +
ID +
+ F +
m
•► +
�1 n.QI �1 7.Ld 5:34 1 .0 1 1 An 110 ky.1a .tytl .QI
MILES FIFSOVE HEPC0
F
I ih -

Figure 28. Oxidized Nitrogen Calibration
4.
KI + t
r, + +
J + + + .
+ $ $
M + +
u +
Ll + +
Z m +
w +
11
m
+
0
w
N
n
om
+
+
$
19.1a 17.0 15.0 I3.® 1 1 .9 5.0 7.0 '.C.0 3.0
L�11LE5 FIBS E HEPC0
rn
i

Figure 29.. CBOD Calibration
m + +�+
14
r, + +
4.
� +
u
Q +
CO to
V m
+
+
W
w
+
+
+
I J.m 1 7.0 1 S.0 1 J.Q! I 1 .14 0.va 7.9a - ^a.fa J.m
P'lILES FiB0VE HEPC0
rn
rn

\'-,qm -low _ ..
Figure 30. Dissolved Oxygen Calibration
N
RI
D
M +
Y- t +
u r +
z +
* +HE
— —
x +
o + +
a
ba
o � +
* +
1 +
c�
W
1 W.U3 17.m 15.0 1 3.14 1 1 .0 M.m '7.m 5.cd 3.0
MILES RF3OVE HEPCO
rn

Figure 31. Champion Allocation, D.O. = 6 mg/1
t
l�
� � f
� r '
LO
3 I
u i
Z
1E E
`L
Z _
1 .0 2.0 ;i.ra -1.0 S.0 G.0 7.0 0.0 '>-.0
LJL>—s:1 Ernr;L_:]
00

LIST OF TABLES
TABLE PAGE
D2.1 Checklist of fish species collected in the Pigeon River,
1980. 79
D2.2 Distribution of fish species in the Pigeon River. 80
D2.3 Standing Crop (kg/ha) and number of fish/ha in the
Pigeon River. 81
D2.4 Water quality data of fish sample stations on the Pigeon
River. 82
D3.1 Fish analyzed for complex organics and heavy metals. Pigeon
River, August 1980. 83
D4.1 Pigeon River Discharge (CFS) at Canton, North Carolina. 84
D4.2 Temperature Data (oC) , Pigeon River stations. 84
D4.3 Dissolved Oxygen (mg/1) , Pigeon River stations. 84
D4.4 Taxa Richness Values, by group, for Pigeon River collections. 85
D4.5 Comparison of Station 4 with the Mountain River Control
(MRC) Data Set. 86
D4.6 Taxa Richness Values, by group, for the Pigeon River 87
tributaries.
D4.7 Level I Data 88
�nn 69
�7

LIST OF FIGURES
FIGURE PAGE
D2.1• Station location, fish survey
Pigeon River, Haywood County, North Carolina, August, 1980 77
D4.1 Effect of Champion's effluent under varying flow and
temperature patterns. 78
70 �,

D. Biological Surveys
1. INTRODUCTION
The North Carolina Division of Environmental Management agreed to
J
cooperate with the Tennessee Valley Authority in the development of work
plans for implementing water quality studies. A work plan to determine the
current impact of Champion Paper Company's discharge into the Pigeon River
at Canton, North Carolina was submitted to TVA for review in July of 1980.
The biological integrity of the Pigeon River, as outlined in the work plan,
was evaluated using several accepted biological methods. The first was
an evaluation of the composition of the indigenous fish populations of the
Pigeon River above and below the discharge point. The survey was conducted
by the North Carolina Wildlife Resources Commission. As part of this in—
vestigation several representative fish species were sent to the EPA
laboratory in Athens, Georgia for analysis of heavy metals and complex
organic compounds within the fish flesh. A supplemental survey of benthic
macroinvertebrates was also conducted. Biologists with the North Carolina
Division of Environmental Management were responsible for the results of
this survey. Additionally, a series of static bioassays were conducted on
Champion Paper Company's effluent. Also, in—situ acute bioassays were
conducted using live boxes and indigeous fish species to determine acute in
stream toxic effects. Bioassays were conducted by biologists with the North
Carolina Division of Environmental Management. Each of these surveys are
reported upon separately in the following sections of this report. Because
several groups and individuals were responsible for this report, there may
be some overlap of information.
71

2. FISHERIES INVESTIGATION
a. Introduction
The Pigeon River is a tributary of the French Broad River in Tennessee.
The river flows for 63 km in North Carolina before entering Tennessee and
has a mean width of 24.4 m and an estimated surface area of 293 he (Fish 1968) .
This surface area includes the 138 ha Waterville Reservoir located 16 km up—
stream from the Tennessee state line. The ecological classification of the
Pigeon River ranges from brown trout upstream from the Canton water supply
intake to smallmouth bass in the rest of the river in North Carolina (Fish
1968) . Many of the river's tributaries downstream from Canton have a trout
ecological classification (Fish 1968) . The Pigeon River, downstream from
the Champion Paper Company's effluent discharge, is severely degraded and
the smallmouth bass ecological classification is not being attained.
The Division of Environmental Management (DEM) and The Tennessee Valley
Authority (TVA) assisted the North Carolina Wildlife Resources Commission in
collecting qualitative and quantitative fish samples on the Pigeon River, This
work was part of a major study DEM was conducting on the Pigeon River to
determine the parameters to be included in a new discharge permit for Champion
Paper Comapny.
b. Methods and Materials
Four sample sites were selected on the Pigeon River (Figure D2.1) .
Sample station 1 was located approximately 300 m below the confluence of the
East and West Forks Pigeon River. An island splits the river in approximately
equal halves with the east side channel being sampled. This corresponds to
river mile (RM) 69.2 for TVA. The sample area was 100 m in length and
averaged 17.2 m in width. This station served as the control since it was
located above the Champion Paper Company's effluent discharge.
72

Sample station 2 was located approximately 1.6 km downstream from the
paper company's effluent discharge in Canton. This site was at a bend in
the river approximately 500 m beyond the end of Haywood County SR 1552.
This corresponds to RM 62.2 for TVA. The sample area was 75 m in length
and averaged 15.6 m in width.
Sample station 3 was located approximately 8.9 km downstream from the
paper company's effluent discharge. The site was adjacent to Haywood County
SR 1513 northeast of Clyde. The Champion Paper Company landfill was adjacent
to and on the opposite side of the river. This corresponds to RM 59.1 for
TVA. The sample area was 100 m in length and averaged 20.0 m in width.
Sample station 4 was located approximately 22 km downstream from the
paper company's effluent discharge. It was located adjacent to Haywood County
SR 1355 approximately 1 km downstream from the Haywood County SR 1363 bridge
crossing. The nearer side channel of the river was sampled. This corresponds
to RM 47.7 for TVA. The sample site was 100 m in length and averaged 16.6 m
in width.
Rotenone fish toxicant was used to collect all fish samples. All stream
measurements (width, depth, flow, etc.) were taken four days prior to the
actual sample. The depth was measured with a meter stick at 7-15 equidistant
points on transacts across the river and the data averaged. Depth transects
were taken every 25 m in each sample area. At each depth transact, the stream
width was measured and mean stream width for the sample calculated.
Stream velocity was calculated in meters per second (m/s) by determining
the average time for a partially submerged object to traverse 10 m. A
minimum of three drifts were timed and the results averaged to determine
stream velocity.
73

Volume of,stream flow was calculated from the following formula: V =
wdfc; wherein V = volume in cubic meters per second (m3/s) ; w = average
width in m; d = average depth in m; f = velocity in m/s; and c = coefficient
of roughness (0.8 for a rough bottom) (Bayless and Smith 1962) . The amount
of rotenone required to yield a 1 ppm concentration in the stream for 5 min
was then calculated.
Immediately upon entering the sample site, a downstream block net
(0.64 cm stretch mesh) was placed across the channel and securely anchored.
An upstream block net was unnecessary because of the high stream velocity.
Five percent emulsifiable rotenone was applied at the upper end of the
sample site area to provide for a 1 ppm concentration of the toxicant over
a period of 5 min. Potassium permanganate was applied immediately above
the block net to neutralize (oxidize) the rotenone.
Fish were collected, identified, measured and weighed at each sample
site. Fish not identifiable at the site were preserved and later identified
by TVA personnel (Joe Freeman) . All fish identified in the laboratory are
located in either the TVA or University of North Carolina - Charlotte
ichthyology collections.
Water samples were collected and analyzed by DEM at each sample station.
These parameters included: dissolved oxygen, turbidity, temperature, total
hardness, methyl orange alkalinity, pH, suspended residue, total residue,
fecal coliforms and BOD.
c. Results and Discussion
An evident change in the ecosystem of the Pigeon River occurred between
stations 1 and 2. Compared to station 1, fish species diversity (Tables D2.1
and D2.2) , fish relative abundance and standing crop (Table D2.3) and water
quality (Table D2.4) were greatly reduced at station 2. Centrachid species
74

collected at both stations exhibited a significant reduction in relative
abundance, standing crop, condition and a mean size at station 2 as
compared to station 1. An exception was the redbreast sunfish, Lepomis
auritus, which exhibited a slight increase in abundance and standing crop
at station 2. The elevated water temperature at station 2 probably afforded
the redbreast sunfish a competitive edge. Both stenothermal and eurythermal
fish species were collected at station 1, while only eurythermal species
were found at stations 2, 3 and 4. Black bullhead, Ictalurus melas, and
carp, Cyprinus carpio, which are typical warmwater species, first appeared
station 2.
The lowest fish standing crop, relative abundance and species diversity
occurred at station 3 (Tables D2.2 and D2.3) . No game fish species were
collected at this station. The dissolved oxygen sag recorded near station 3
(see DEM chemical study report) and possible seepage from an adjacent Champion
Paper Company landfill are suspected causes of this degradation.
The Pigeon River appears to begin recovering from its pollutional load
near station 4, as species diversity, relative abundance and standing crop _
of game and nongame fish increases (Tables D2.2 and D2.3) . Part of this
recovery might be attributed to the inflow of higher quality water from
tributary streams of this section which carry a trout ecological classification
(Fish 1968) . In addition, the natural regenerative processes within the stream
begin having a positive effect on water quality.
i
This study indicates that the Pigeon River is severely impacted at
stations 2, 3, and 4. While the theory of longitudinal succession predicts
natural changes in the fish population along a stream's course, such an abrupt
demarcation, as exists in this section of the Pigeon River can only be the
result of unnatural influences on the aquatic system. Since the Champion
75

Paper Company discharge is the only significant pollutant entering the river
between stations 1 and 2, this would strongly indicate that this discharge
is a major limiting factor to a healthy fish population in this stretch of
the Pigeon River.
The Pigeon River downstream from the Champion Paper Company outfall
presently has a carp-catfish ecological classification. This section would
have an ecological classification of smallmouth bass (Fish 1968) if it were
not for the elevated water temperatures associated with the discharge from
Champion Paper Company. This elevated water temperature has resulted in a
change in fish species composition. r
The Pigeon River has the regenerative capacity to become an excellent
smallmouth bass stream if the chemical, thermal and solid effluents that
are presently being discharged into the river were reduced or eliminated.
3. FISH TISSUE ANALYSES
a. Introduction
Another part of the overall biological assessment of the Pigeon River
was to determine if complex organic material (including pesticides) and
heavy metals were being concentrated in fish flesh. During the fish survey
conducted by the NCWRC, several representative whole fish were preserved
and shipped to the EPA laboratory in Athens, Georgia for analysis. Station
location and water quality were similar to that reported in section D2 of
this report (figure D2.1 and table D2.4) . An additional station was added
by the Tennessee Division of Water Quality Control.
b. Methods and Materials
Ideally, it would have been best for the project if we could have
collected similar size class fish from different feeding groups from each
station. At the upstream station, it was decided to preserve several I
hogsuckers (Hypentelium nigricans) and several redbreast sunfish (Lepomis
76 I

auritus) from two size classes. We had assumed that of all the fish we
would collect these would be most representative. Table D3.1 lists the
fish sent to EPA for analysis. Fish taxa used in the organics analysis
were double wrapped in aluminum foil and iced for delivery, specimen used
in the heavy metal analysis were double wrapped in plastic bags and iced for
delivery. EPA preparation procedure and extraction are included in
Appendix I.
c. Results and Discussion
The results from both scans can be seen in Appendix I. Very little
bioconcentration of most parameters are detected. This is particularly
true for pesticides and other chlorinated hydrocarbons, purgeable organic
compounds and extractable organics. High concentrations were recorded for
several metal compounds (Sodium, Aluminum, Calcium, Magnesium and Zinc) .
Because whole fish were used in the analysis, we would expect these higher
concentrations. However a previous survey (Tedder et al, 1980) reported
detectable concentrations of three of these compounds (Sodium, 420 mg/l;
Aluminum, 1.40 mg/l and Zinc 0.11 mg/1) in the water. Certain ionic forms
of these metals may be toxic to juvenile fish. At this point it isn't clear,
or statiscially valid, to evaluate or to corrolate these observations. The
only conclusion we can make at this point, is that we found higher concentrations
of several metals in flesh of redbreast sunfish at station 2 immediately below
the discharge. Chronic bioassays using indigeneous fish species should be
performed.
4. BENTHIC SURVEYS
a. Introduction
One specific purpose of the TVA—EPA Subagreement was to develop the
water pollution control needs required to improve the quality of the Pigeon
River in North Carolina and Tennessee. The North Carolina Division of
Environmental Management agreed to develop and carry out biological water
77

j
quality studies of the Pigeon River. NCDEtf assisted the NCWRC in the fisheries
investigation and conducted both the benthos and bioassay surveys.
The Division has utilized and supported the use of aquatic community
structure, especially for benthic macroinvertebrates, in environmental
assessment. It is the intent of this report to review the results from
previous benthic surveys on the Pigeon River and to comment on current benthic
integrity as part of the overall Pigeon River investigation.
b. Methods and Materials
Several benthic surveys have been conducted to determine the biological
integrity of the Pigeon River. We will concentrate only on the most recent
surveys in this report. This first two collections were made by the
Operations Section of the Division of Environmental ?Management (October 1978
and June 1979) . The results of their investigations were reported in Tedder
et al. (1980) . A third collection was conducted only at five sites in May of
1980. These sites were the same sites as reported in Tedder et al. (1980)
and are numbered accordingly. The most recent survey, complying specifically
with the sub—agreement between NCDEM and TVA, was conducted in August of 1980.
Four stations were sampled. These four stations were located at the fish
collection points, but do not compare precisely with prior benthic surveys.
The station numbers were assigned to each station on the basis of its proximity
to previous benthic stations. For example, during the August 1980 survey a
control station was located above Champion's effluent and near station 4
from a previous survey. The only exception to this is station 4A where there
is no prior benthic data. Station 4A is located approximately 1.6 km down—
stream from Champion Paper Company's discharge. Precise station locations are
described for previous benthic surveys in Tedder et al. (1980) and for the most
recent survey in the Methods and Materials section of the fisheries in—
vestigation of this report.
78

Benthic collections were made either with a Surber sampler (Tedder
et al. 1980) or by a "kick" technique (Penrose et al, 1980) . Both
techniques involve physically disrupting a known area of stream substrate
and allowing the organisms to drift into a collection net. The samples
are then preserved and brought back to the lab for processing and identification.
Sample processing and data analysis generally follow the techniques described
in Penrose et al, (1980) .
Data summary tables include both Level I (single number summaries,
table D4.7) and Level II (data summarized for major groups, tables D4.4, D4.5
and D4.6) . More complete data for May and August, 1980, is included in
Appendices II and III.
Fish collection techniques did not facilitate effective fish stomach
content analysis. This part of the survey was not completed.
c. Results and Discussion
Survey I October 1978 (Station locations as of Tedder at al. 1980)
Identification procedures improved after this collection period, therefore
comparisons with other collections must be made with caution. However, the
general pattern is still quite obvious. Ephemeroptera disappear completely
at stations 6 through 8A (Table D4.4) indicating severe stress at all areas
above Waterville Lake. The most degraded conditions were found at Station 6,
an area dominated by the snail Physa and tubificid worms. These organisms
are typically associated with very low dissolved oxygen conditions. A
limited recovery was observed at stations 8 and 8A, where tolerant caddis—
flies (Hydropsyche spp) became dominant. Station 9 was located in an area
of the river that receives little Champion effluent. The tunnel from
Waterville Lake bypasses this area, therefore this area is largely fed by
groundwater and several streams. This area was diagnosed as unstressed.
79

Station 10 was located below the bypass tunnel, and the community was
similar to that recorded at Stations 8 and 8A.
Survey II: June 1979 (Station locations as of Tedder et al. 1980)
Conditions are still assessed as excellent at control Station 4 (Table
D4.4) . This area was characterized by a diverse assemblage of Ephemeroptera
and Trichoptera (11 taxa each). Both groups are sharply reduced at
Station 6 and Tubificidae become abundant. As in October 1978, there was
an increase in tolerant Hydropsychidae at Station 8. There was a gradual
recovery through Station 9, although recovery was not complete. Station 10,
at the North Carolina state line, was very severely stressed. All taxa
occur in very low density at this station. Further field investigations
should be planned to determine the causes of such deterioration.
Survey III: May 1980 (Station location as of Tedder et al. 1980)
May 1980 was a period of high flow and low temperature. Under these conditions,
Champion's effluent had less effect on river biota than observed during other
surveys. A diverse mayfly fauna was found at all stations above Waterville
Lake (Table D4.4) , although a decline was evident at stations 6 and 8A. Also
note the absence of stoneflies at Station 8A. Recovery was complete at
Station 9, but Station 10 was found to be severely stressed. During this
survey there was a 76% reduction in average density of organism at Station 10
compared to Station 8A and a 59% reduction in total taxa richness, indicating
severe stress according to criteria developed by DEN biologists (Penrose et al.
1980) . Note that the dominant oligochaetes are not "sludgeworms", but
Iumb riculidae.
80

Survey IV; August 1980 (Station locations as of Section 2 of this report)
This survey was conducted in conjunction with the fisheries survey. It in—
cludes only the areas above Waterville Lake. Physical conditions appeared
very similar to the first survey conducted in October 1978. The benthic
fauna was also very similar and most differences between these two surveys
can be attributed to differing levels of taxonomic identification. This
data indicates that there has been no significant changes in the effects of
Champion's effluent since 1978.
It is interesting to note the similarity between benthic data and
fisheries data (Table D4.4) .
Champion Papers (1981) conducted their own study of the river during
this period. Their results generally agreed with the DE11 studies.
Level I data for these four station and three tributary streams can be
seen in Table D4.7.
General spatial trends
Station 4, above Champion's effluent was typical of a clean mountain
river.. A comparison of data from station 4 (using only the last 3 dates)
with the Mountain River Control (MRC) data set (Table D4.5) showed very good
agreement.
Station 6, just below Champion's effluent, was generally in very poor
condition. Sensitive mayfly — stonefly taxa are found only during high
flow — low temperature conditions. Dominant taxa are usually organic
pollution "indicator" species, i.e. , those taxa tolerant of low dissolved
oxygen conditions. These include Limnodrilus hoffineisteri, Nais, and Physa.
The leech Mooreobdella melanostoma was often very conspicuous in benthic
collection. Prior records of Helobdella elongata, Glossiphonia sp, etc. are
81

probably referable to the above species.
Stations 8-8A These stations were located approximately 15-18 miles
below Champion's effluent. They vary from fair to poor depending on flow
and temperature. Some recovery was indicated by the increase in moderately
tolerant filterfeeders, esp. Hydropsyche - Symphitopsyche. These organisms
build cases on the upper surface of cobble - rubble substrates. Therefore,
they are less affected by the clogging of the interstitial habitat with
organic particulates. In fact, organic matter in the effluent may be an
abundant food source for these few tolerant organisms. Taxa richness in
this region was usually depressed by 40-55%, relative to the control station.
This suggests severe stress. The population structure at this station does
not suggest simple dissolved oxygen problems. Long-term. (chronic toxicity)
may also be a problem. The benthic community at this area was similar to
that described by Winner et al (1980) for areas recovering from a toxic
(heavy metal) stress. This may, in part, reflect the impact of Richland
Creek water.
Station 9 This station was located below Waterville dam and receives
no effluent during low flow. During these periods flow from Waterville Lake
completely bypasses this section of the river in a 1 mile tunnel used in
the generation of hydroelectric power. This area was usually very similar
to the control station.
Station 10 Station 10 was located below the tunnel discharge from
Waterville Lake. This area was usually in very poor condition. All taxa
are very 1ow,with Lumbriculidae dominant. An investigation conducted by the
Tennessee Department of Public Health (1978) also indicated that the problem
continues well into the state of Tennessee to a point at least 13.8 miles
from the state line. The severity of the problem suggests that the states
cooperate in assessing the effectiveness of management practices. A
82

possible source of the problem is Waterville Lake. Flow from Waterville
Lake comes from the hypolimnion, an area of the Lake often anaerobic,
potentially high in HZS and other toxic materials. This type of system
may modify and reconcentrate Champion's effluent so as to increase potential
toxicity.
Temporal Patterns
1. Seasonal Natural seasonal changes in temperature and/or flow may
tend to mitigate the effects of Champion's effluent. The four collections
can be roughly separated into three flow—temperature classifications:
A. Low flow/high temperature This is the normal late spring and
summer conditions. It includes collections from October 1978 and
August 1980.
B. High flow/high temperature This situation includes one potential
mitigating factor, i.e., the dilution effect of high flows. This
conbination of flow and temperature was observed during June 1979
collections.
C. High flow/low temperature This normal winter condition 'includes
two potential mitigating factors. This combination of flow and
temperature was observed during the May 1980 collections.
Figure D4.1 illustrates the effect of Champion's effluent for these
three flow and temperature categories. The benthic community has been
classified into five categories:
A. Good Community similar to control station and/or control data
set. Many taxa present, including a high proportion of intolerant
species.
83

B. Good-Fair Many intolerant taxa present, but total taxa richness
below that expected from comparisons with controls.
C. Fair Community dominated by moderately tolerant species although
intolerant species still recorded.
D. Poor Taxa richness very low, especially within the mayfly - stone-
fly groups. Highly tolerant species present in substantial numbers.
E. Very Poor Highly tolerant taxa dominant, sensitive species absent.
The low flow - high temperature combination results in poor, or very
poor, conditions for most of the Pigeon River within North Carolina. Only
the bypassed segment below Waterville dam is unaffected.
High flow - high temperature conditions improve conditions at most
Pigeon River stations, but note that Station 9 (below Waterville dam) has
been downgraded from good to good-fair. Under high flow, water is released
over Waterville dam and the normally by-passed river segment can be affected.
High flow-low temperatures results in further water quality improvement.
Only station 10 remains in poor condition.
The above flow-temperature combinations should not be thought of as
single point measurements, but rather as flow and temperature regimes
averaged over 1-2 months prior to sampling. Even during high flow/low
temperature periods the benthic populations undoubtedly reflect stresses
from earlier periods.
2. Comparison with 1965 data Champion upgraded its waste treatment
facilities in 1973 adding a clarifier, improved their sludge dewatering process
and improved biological treatment of suspended solids. An additional clarifier
was also added in 1977. The effects of these changes can be assessed by
comparing DEM data with the data of Kemp & Stewart (1966) . They sampled in
34

July - August with high temperatures and low flow conditions. They found -
the entire North Carolina section of the Pigeon River to be grossly
polluted (Figure D4.1) . Mayflies, stoneflies and caddiflies were absent
all the way to the N.C. - Tennessee border; five river miles were barren
of life with the remainder dominated by tubificidae (sludgeworms) .
Under similar flow and temperature conditions during 1978 - 1980,
considerable improvement can be observed; although the river is still in
"poor" condition the barren zone of life has improved and the zone dominated
by sludgeworms is reduced to a region of 2-5 miles below the effluent.
Tributary streams (Table D4.6) Four Pigeon River tributaries have
been sampled. Palmer Creek, an unimpacted stream in the Pigeon River water-
shed, was sampled once in May 1980 as part of a survey of mountain "control"
areas. Three other streams (Richland Creek, Crabtree Creek and Fines Creek)
were sampled during the August 1980 survey.
Richland Creek was found to be in poor condition with the sensitive
mayfly - stonefly group being extremely rare. A tolerant community of
grazers (Hydroptilidae, Orthocladiinae) and filter-feeders (Hydropsychidae,
Rheotanytarsus) was dominant. No organic "indicater" groups were present
in high numbers, suggesting that toxicity from industrial effluents is of
greater importance than sewage BOD. This stream enters the Pigeon River
between Stations 6 and 8, adding to the pollution load at Stations 8 and
8A. Kemp and Stewart (1966) also indicated poor conditions in this stream.
The other two streams -were assessed as "clean" by Kemp & Stewart, but
current data suggests some water quality problems. In addition to the data
in this survey, these streams were sampled by Champion Paper Company (1981)
and by the Division of Environmental Management as part of a recent (Un-
published) qualitative survey. These areas were dominated by highly tolerant
diptera and oligochaeta suggesting "fair" conditions.
85
* Station 8A is located on the Pigeon River at Fines Creek exit off of I
1-40 where the riu,r' �r,] �� - r_..___. _._

5. BIOASSAY
a. Introduction
A series of on-site toxicological tests were performed on the
Pigeon River in relation to Champion Paper Company's industrial discharge
at Canton, North Carolina. The objectives of these tests were to evaluate
the extent of acute toxicity which may occur as a result of the discharge.
There are many forms of environmental impact for which anindnsrr,, - ---
c. Results and Discussion
Daphia pulex Effluent Bioassay. Test results revealed 100% survival
at all concentrations. This would indicate minimal acute toxicity can be
associated with the effluent if this effluent sample is typical.
Effluents of the type dealt with in this study are difficult to
quantify with respect to toxicological impact. Typically, an industry will
discharge an acutely toxic waste which is diluted by the receiving waters.
Through several toxicological methods, the toxic effects may be measured.
When these effects are examined with respect to dilution ratios, a judgement
may be made as to the chronic toxicity within the receiving waters. This
method works well for an industry discharging acutely toxic waste at high
dilution rations. The series of tests performed by the Division of Environ-
mental Management indicates a different situation exists in the case of
Champion Paper Company. The effluent is not significantly toxic (acutely) ,
but is discharged at such high volumes as to make chronic toxicity (exposure
for entire life cycles) a possible factor in the decrease in benthic
community health found downstream from the waste discharge (Tedder et al 1980) .
Other factors such as habitat distruction (through sedimentation) , or physical
stress such as low dissolved oxygen and high temperature may be primarily
responsible.
In-stream bioassay. Three of the nine stations had partial mortality
Iafter 68 hours exposure using rainbow trout. These were stations BE

fish were more tolerant of the high temperature, low dissolved oxygen
than the rainbow trout. No mortalities were recorded at any sites.
The worst temperature/oxygen conditions were recorded at Station BE with
a temperature of 290C and a dissolved oxygen value of 4.2 ppm. Upstream
control values were 8.4 ppm oxygen and 190 water temperature.
89

exsesGu Figure D2°1 Location of Pigeon
Pj� r v f✓ XF80�MM.MP9.S.99S�
] ]�^� ,,�• £ � River biological
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HIGH TOP f \�\too ij 9 /�

Figure D4.1 Effect of Champion's Effluent Under Varying Flow & Temperature Patterns.
1978-1980
A. Low Flow, High Temperature (Oct.'78,Aug,'BO)
GOOD VERY POOR POOR GOOD VERY POOR
B. High Flow, High Temperature(Jun:79)
GOOD POOR FAIR GOOD-FAIR POOR
C. High Flow, low Temperature(Moy'BO)
GOOD FAIR GOOD VERY POOR
1965
A. Low Flow, High Temperature(Jul.65-Aug.'65)(Keup and Stewart, 1966.)
GOOD VERY POOR ? VERY POOR
Tunnel
STATION: 4 4A 6 7 B BA v 1
muuuuuuumr1(1 u�uumuuuw unniuwinuii III umn111111 HIM
nuuunuui1fiuuuuunuuuuunuuuuuuuu
RIVER MILES: 5� 10 1 0 1 q
CHAMPION RICHLAND CR. WATERVILLE NCC//TN
LAKE
N
I ,

Table D2.1. Checklist of fish species collected in the Pigeon River,
1980.
Common Name Scientific Name*
Brown trout Salmo trutta
Stoneroller Campostoma anomalum
Goldfish Carassius auratus
Carp Cyprinus carpio
River chub Nocomis micropogon
Golden shiner Notemigonus crysoleucas
Warpaint shiner Notropis coccogenis
Whitetail shiner Notropis galacturus
Saffron shiner Notropis rubricroceus
Mirror shiner Notropis spectrunculus
White sucker Catostomus commersoni
Northern hogsucker Hypentelium nigricans
Black redhorse Moxostoma duquesnei
Shorthead redhorse __ toxostoma macrolepidotum _
Black bullhead Ictalurus melas
Channel catfish Ictalurus punctatus
Rock bass Ambloplites rupestris
Redbreast sunfish Lepomis auritus
Bluegill Lepomis macrochirus
Smallmouth bass Micropterus dolomieui
Tuckasegee darter Etheostoma blennioides gutselli t
Greenfin darter Etheostoma chlorobranchium
Tangerine darter Percina aurantiaca t
Mottled sculpin Cottus bairdi
* After American Fisheries Society, Special Publication Number 6, 1970. '
92

Table D2.2. Distribution of fish species in the Pigeon River
Station*
Species 1 2** 3** 4**
Brown trout X
Stoneroller X X
Goldfish X
Carp X X
River Chub % X
Golden shiner X X
Warpaing shiner X
Whitetail shiner X X X X
Saffron shiner %
Mirror shiner X
White sucker X X
Northern hogsucker X X X X
Black redhorse X
Shorthead redhorse X Y
Black bullhead X
Channel catfish X
Rock bass X X X
Redbreast sunfish X X X
Bluegill X
Smallmouth bass X X
Tuckasegee darter X
Greenfin darter X
Tangerine darter R
Mottled sculpin X
See Figures 1 and 2 for station locations.
** Located below Champion Paper Company outfall.
93

Table D2.3. Standing crop (kg/ha)a and numbers of fish/ha in the Pigeon River.
Stationc
1 2d 3d 4d
Fish collected during sampling
kg (number)
Game fish 3.4 (57) 0.6 (24) 0 0.3 (54)
Nongame fish 37.4 (1,910) 2.4 (34) 3.0 (91) 3.7 (34)
Total 40.8 (1,967), 3.0 (58) 3.0 (91) 4.0 (88)
Calculated standing crop
kg/ha (Number/ha)
Game fish 19.8 (331) 4.7 (205) 0 1.6 (325)
Nongame fish 217.6 (11,105) 20.9 (291) 14.9 (455) 22.2 (205)
Totalb 237.4 (11,436) 25.6 (496) 14.9 (455) 23.8 (530)
aPounds/acre = kg/ha x 0.8924.
bCalculated on the basis of kg of fish collected and the area of the sample.
cSee Figure 1.
dLocated below Champion Paper Company outfall.
94

Table D2.4
Water quality data of fish sample stations on the Pigeon River.*
�1
Station
1 2 3 4
BODS (mg/1) 0.7 2.9 2.9 3.6
Fecal coliform (per 100 ml) 140 190** 1,700** 1,600**
Total residue (mg/1) 40 1,120 972 924
Suspended residue (mg/1) 5 19 24 74
nH 7.0 7.5 7 4 7.7
Methyl orange alkalinity (mg/l) 8.0 90 77 77
Total hardnesg (mg/1) 4.0 310 250 220
Temperature ( C) 21.0 29.0 27.5 27.0
Dissolved oxygen (mg/1) 8.0 3.9 3.8 —
Turbidity (FTU) 2.1 11.0 15.0 44.0
*Collected and analyzed by Division of Environmental Management.
**Many non—fecals present.
95

Table D3.1. Fish Analyzed for Complex Organics and Heavey Metals.
Pigeon River. August 1980
Size
Class (cm) Taxa Analysis
Pigeon River 1
201-225 3 Hogsucker Metals
201-225 3 Hogsucker Organics
2 @ 100-225 and
1 @ 125 3 Redbreast Metals .
1 @ 75 3 Redbrease Organics
Pigeon River 2
100-125 1 Redbreast Metals
125-150 1 Redbreast Organics
Pigeon River 3
226-250 3 Hogsucker Metals
226-250 2 Hogsucker Organics
Pigeon River 4
125-150 1 Redbreast Metals
125-150 1 Redbreast Organics
Pigeon River (Tenn)
102 1 Hogsucker Metals - Organics
135-218 7 Redbreast Metals - Organics
96

Table D4.1 Pigeon River Discharge (CFS) at Canton, NC.
From USGS Data.
Discharge (CFS) Comment
12 Oct. 78 83 Base Flow
6 June 79 240 High
14 May 80 237 High
15 Aug. 80 76 Base Flow
Table D4.2 Temperature Data (0C) ; Pigeon River Stations.
4 4A 6 8 8A 9 10
12 Oct. 781 22 - 30 16 14 12 16
6 June 791 20 - 22 24 26 25 21
14 May 80 16 - 22 - 18 16 15
15 Aug 802 21 29 28 27 - - -
Table D4.3 Dissolved Oxygen (mg/1) , Pigeon River Stations.
12 Oct 781 8.3 - 3.3 7.7 8.3 9.5 9.6
6 June 791 9.3 - 7.0 7.2 5.4 5.6 5.4
14 May 80 7.0 - 6.0 - 9.8 9.2 9.1
15 Aug 802 8.0 3.9 3.8 - - - -
1from Tedder et. al (1980)
2from Wingate and Davies (1981)
97

Table D4.4
Taxa Richness Values, by group, for Pigeon River
benthic collections.
October '78
Group Station: 4 6 8 8A 9 10
Ephemeroptera 4 0 0 0 6 2
Plecoptera 1 1 1 0 1 2
Trichoptera 2 1 3 3 5 2
Coleoptera 4 0 0 1 3 1
Diptera 2 3 3 1 5 3
Other 6 11 4 3 6 9
TOTAL 19 16 11 8 26 19
June '79
Ephemeroptera 11 4 2 7 8 2
Plecoptera 4 2 0 2 3 1
Trichoptera 11 6 3 4 6 2
Coleoptera 4 2 1 0 1 1
Diptera 16 11 15 14 14 5
Other 5 5 3 3 4 3
TOTAL 51 30 24 30 36 14
1Oct. '78 and June '79 data from Tedder et al, 1980
May '80
Group Station: 4 6 8A 9 10
Ephemeroptera 17 11 11 14 2
Plecoptera 5 5 0 4 0
Trichoptera 11 5 4 10 3
Coleoptera 2 0 1 2 1
Diptera 20 20 20 23 5
Oligochaeta 4 4 3 3 3
Other 2 0 0 2 2
Total 61 43 39 58 16
August '80 4 4A 6 8
Ephemeroptera 14 0 0 1
Plecoptera 3 0 1 2
Trichoptera 11 4 4 8
Coleoptera 3 2 4 1
Diptera 12 3 7 12
Oligochaeta 0 5 1 3
Other 6 4 4 5
Total 49 19 22 33
#Fish species2 18 8 5 10
2from Wingate and Davies (1980) 98

Table D4.5
Comparison of Station 4 with the Mountain River
Control (MRC) Data Set.
Group 4 MRC
Ephemeroptera 14.0 14.8
Plecoptera 4.0 6.7
Trichoptera 11.0 . 9.1
Coleoptera 3.0 3.4
Diptera 16.0 19.2
Other 5.6 1.9
Total 53.6 55.1
99

Table D4.6
Taxa richness values, by group, for Pigeon River Trib.
Palmer Richland Crabtree Fines
Creek Creek Creek Creek
MSC* May 80 Aug 80 Aug 80 Aug. 80
Ephemeroptera 9.7 14 3 12 9
Plecoptera 6.5 11 0 4 1
Trichoptera 7.8 10 6 5 5
Coleoptera 2.5 1 0 1 2
Diptera 14.5 27 13 11 18
Other 2.6 1 6 4 4
Total 44.5 65 29 37 39
Yeup & Stewart (1966) - 8 20 21
Champion Paper Company 26 37 35
(1981)
"< 14SC = Mountain Stream Control
100

Table D4.7. Level I Data (Single Number Summaries)
May 80
Stations
4 4A 6 8A 9 10
Avg. Density (N) 1294 - 272 248 379 59*
Taxa Richness (S) 61 - 43* 39* 58 16*
Biotic Index (BI) 2.3 - 3.0* 2.3 2.5 2.8
Diversity (H) 2.8 - 3.6 3.4 3.6 1.6*
August 80
Richland Crabtree Fines
4 4A 6 8 Creek Creek Creek
Avg. Density (N) 182 683 112 324 587 68 294
Taxa Richness (S) 49 19* 22* 33* 29* 37 39
Biotic Index (BI) 2.7 4.2* 3.9* 2.3 3.0* 2.5 2.6
Diversity (H) 3.0 1.5* 2.3* 3.0 1.9* 3.2 3.3
*Comparison with control indicates stress
101

REFERENCES
American Fisheries Society. 1970. A list of common and scientific names
of fishes from the United States and Canada. Am. Fish. Soc. , Spec.
Publ. No. 6. 150 pp.
Bayless, J. D. , and W. B. Smith. 1962. Survey and classification of the
Neuse River and tributaries, North Carolina. Div. Inland Fish. , N.C.
Wildl. Res. Comm. , Raleigh, 94 pp.
Champion Paper, 1981. Pigeon River benthic study, unpublished data.
Fish, F. F. 1968. A catalog of inland fishing waters in North Carolina.
Div. Inland Fish. , N.C. Wildl. Res. Comm., Raleigh. 94 pp.
Keup, L. E. and R. K. Stewart, 1966. Effects of pollution on biota of
the Pigeon River, North Carolina and Tennessee. Federal Water
Pollution Control Adm., 35 pp.
Penrose, D. L., D. R. Lenat and K. 11. Eagleson. 1980. Biological
evaluation of water quality in North Carolina streams and rivers,
N. C. Division of Environmental Management, Technical Services,
Biological Series #103. 181 pp.
Tedder, S. W. , J. Sauber and L. Ausley. 1980. Pigeon River Investigation,
N. C. Division of Environmental Management. Operations Section, 83 pp.
Tennessee Department of Public Health, 1978 Biological Assessment and
Inventory, Chemical and Bacteriological Sampling Pigeon River, Newport
Cooke County.
Wingate, P. J. and J. H. Davies. 1981. An evaluation of stream degradation
in the Pigeon River. N. C. Wildlife Resources Commission, 10 pp.
Winner, R. W. , M. W. Boesel and M. P. Farrell. 1980. Insect Community
.structure as an index of heavy metal pollution in lotic ecosystems.
102

.;A:A
PESTICIDESMB'S, AND OTHER C:10RINATED CQ:U?OU.40S Athens, CA 4/80
P90.i ECT NcrLh Carolina Da n nf CHEMIST E. W. Loy, Jr. YZC'D. 10/16/80 CO1U?L'D. 3/23/81
Natural Resources @ 1430
.7
ric
SAD NO. BIC0075= 0076=81C 810077 BI00078
Pigeon River Pigeon River Pigeon River Pigeon River
SOURCE & STATION 02 3
Hogsucker Redbreast Redbreast Hogsucker
DATE/TIRE
COZIPOUND lConcentra- Concentra- Concentra-
tion mg/kg Lion
89. aldrin Z/ 34680 0.02U Olu 0.03U
dieldrin ZI 39404 2 IU .009U O.Olu 0.02U
90. 0:20215
'I. chlordane (tech. mixture_&
metabolites) V- - 34682 0.2U 0.07U 0.2U O. mooww_",;,�.
93-o 4:4:t_'-DDT (RP�-5F)27 39302 0.01 U.01-1 . U.U)U I 0.05U.
93. 4.4'-DDE (p,p'-DDEL-_ �39322 0.01927 U.U4U I O.O.0
94. 412 _uou 'PIP -1 j_,)&f 39312
0,Ol&:V 0.0085�' 1 0.03U
95. dosulfan-Alpha A 34365 0_01U 0.01U I 0.02U
96. b-endosullan-beta ell 34360 Oj2U O.Olu U.UZU
Y/. endoSultan sulfate Ll 34355 0,01U, O.Olu U.UZU 0.02U
,a. endrin V 3.685 0,0211 O.Olu 0.03U
99. end:in aldehyde 37_3L370 0.02U 0.03U
NA
j4b87
2 T.03U
I NA NA NA
111� heptachl
or------lor2Dox,ae 41 J4bdb O.Olu 0.02U
.at_
at encachl,r
102. a-BF.C-AIpba &1 Oyu,.,
0.008U O.Olu 0.02U 0.05U
103 b-BC-Beta 2/ 34258 0.008U U.UIU
--
�2U 0.03U
104, Y-BHC-(lindane)-Gamma Z 7S5 0.008U 0.(luNU105. A-BHC-Delta Y O.VZU
3U 0.01U
106. PCB-1242 (Aroclor -1242)9/3�,689 O.lu O.OBU 60�jou
107. L 4 (klrocoE 2124 0.3U
IN j�r 11 1)J' 36690 0.2U 0.2U 0.4U 0.6U
108. B-1�2 0 1 5 i" 14664 O.lu O.OBU 0.3U 0.3U
109. PCB-1232 (A oclor 1232) 34667 0.1U 0.08U 0.3U 0.3U
110. PCB-1248 (A oclor 1248) 34669 u 0
5 O.3U 0.3U
U:2 .......
0 U DU 0.4U
660 A oclor 1260) 34670- 2LU
PCM_ 01 oclor 1016)- iLAw. n.lU O.O8U 0.3U 0.3U
113. Toxavhene 34691 0.2U 0.2U 0.4U 0.6U P.
Lropaclor (Ramrod) NA NA NA
Pro=eton NA
NA NA NA TA_
2.4-D �39734 NA NA NA NA
Silvex NA NA NA NA
2 4,5-T NA NA NA NA
129. 2,3-7.8-Ttrachlorodibenzo-
-dioxin (TCDD)- 34679 NA NA NA
NA - Not Analdyzed
J - Estimate value.
K - Actual value is known to be less than value given.
L - Actual value is known to 6e greater than value given.
U -.Material vas analyzed for but not detected. The number is the Itinimum Detection Limit.
Tentative Identification.
On N1UDC List of Priority Pollucant7s.
103

�.- PESTICID'£S/!C3'S, !\D OTHER C!ILDRL'7AIC0 cc,OUNDS Athens, GA ~^ "�- t
4/80 'ss .a• .. ..M:%2-s.._^>< .z.
pca4`d✓i�w ..n♦ .,.
PRO.:ECT No\th Caro llna Dept. of CIIE.`ilBT E. W. Lov. Jr. DEC'D. 10/16/80 CU.YPL'D. 3/23/81
Natural Resources 3 - n.
Ra ei h N
SAD NO. 8100079 8100080
"u Pigeon River Pigeon River
SOURCE S STATION 94 @ Tennessee
Redbreast Redbreast 6
Hogsuckers
DATE/TINE
i Concentra- Concentra- .COMPOUND Concentra- Concentra-
tion mg/kg tion mg/kg tion mg/kg cion m /k
g g
39. aldrin Z 3-';Sn 0.02U _
"a 70_ dieldrin _ .3V.J_ 0.02U - ^
'91. chlordane (tech. mixture 6 -- '
metabolites) 3/ 3468' 40•2U O.lU
92. 4,4'-DDT ( ,o'-DDT)_/ 3933 0.03U
` 93. 4,4'-DDE (. o'-DDE)_ 39322 0.03U 0.03U -
94. 4,4'-DOD ( -TDE)_ 3i 312 0.02U 0_03U
75. a-endosul fan-A1 ha _ 34365 0.02U 0.0?I1
'S. b-endosulfan-Beta 34360 0.03U 0.0411 '-
il, endosulfan sulfate _ZF 34355 0.03U -_ -
3. endrin _ 34685 0.04U 0.04U
0.02U I
9. endrin aldehede 3 3437J I NA yq
10. hentachlor _ +o3i 0.02U 0.008U
•)1. heptachlor a .side - 34686 0.02U 0.008U
1R .)2. a-BHC-Alpha _ »u,.
o.Dsu 0.01M
b-BHC-Beta 2 34258 0'02U 0.008U _
:04. •-BHC-(lindane)-Caeca _ 91 5 0.02U 0.008U _
A-BHC-Delta 2 j4zo 0.02U O.OlU ---
:06_ PCB-1242 (Aroclor 1242)_ 34689 0.2U O.lu
5 L07. PCB-1254 (Aroclor 1254)- 4 .,3 1 0,3U
108. PCB-1221 (Aroclor 1221)_1 4 _ 0.2U O.lU
109. PCB-1232 (Aroclor 1232)_ 34667 0.2U O.I.0
:10: PCB-1248 (Aroclor 1248)_ 34669 0.2U 0.1U
PCB-126O Aroclor 1260)_ 34fi i0- 0.4U 0.3U
'_'_ PCB-1016 (Aroclor 1016)_ 34674 0.2U O.IU
13_ Toxa hene _ 34691 0.4U 0.3U =�•,�Y•:= ---�:=�Y�b= cry.-._:�.
Pro aclor Ramrod NA NA. _
Prometon NA NA
2 4-D 39734 NA HP
Silvex NA NA
2 4 5-T .A NA _
29. 2 3 7 8-Tetrachlorodibenzo-
F dioxin TCDD _ 34,679 NA NA NA
q
G
\ - Not Analyzed.
S - Estimated value.
K - Actual value is known to be less than value given. _ -
L - Actual value Ss known to be greater than value given.
U -.Material was analyzed for but not detected. The number is the Minimum Detection Limit.
2�. Tentative identification.
- On NRDC List of Priority Pollutants. '
104

FISH
DAM AC^i):3, .;A
PURGEABLE ORGANIC ANALYSIS 4/30 1
PROJECT pig, v+,., CHEXIST E. W. Loy Jr. REC'D. 10-16-90 CCI.PLCT'D. 1-77-81
North Carolina
SAD NO. 81 007 81CO076 B C0077
Pigeon River Pigeon River Pigeon River
SOURCE 4 STATION p1 UL 02
(Hogsucker) (Redbreast) (Redbreast)
DST=/T L9E
- - Cot:oound
.. - . .. .... ...- mg/kg mg/kg mg/kg
dLchlorodifluoromethane2/ 34335 ---6-02-,U I 0.025U
nechvl chloride2 34422 v- 0.025U
-- methyl-bromide_7 34417 0.025U 0.025U
vinyl ch 34693 0.025U 0.025U
chloroe[haneV 34315 0.025C 0.025C
.ene chloride? 344C7 I 0,025U 0.025L'
[richlorofluo ronechane< 34492 0.025U 0.0256'
_ 1.1-d4chloroethe1ene_ 3 5U5 0.025U 0.025C
1.1-dichloroethane2 34500 0.025L' 0.025L'
1 2-trans-dichlo meth lens= 3 55U 0.025U Noc Analyzed 0.025L'
chloroform 3431 0.025U Insuif icienc 0.220
1,2-dichloroethane=1 34535 0.025❑ Sample 0.025U
1,1,1-trichloroethane 345iu 0.025L' O.OZ'C
carbon tetrachloride_ o V 0.025U 0.0251:
_ dichlorob romane Dane= 34JJI 0.023L' 1 0.025C
1 2-dichlorcorooane_ o4a 0.025U 0.025U
..... . . 1 3-d.chloroo roo lens 0.025U 0.0251:
trichloroethvlene 0.02 0.025U
benzene_ �+ 0 0 O.G25[
chlorodibror..omethane_ 0.02 U 0.025C
1 1 2-trichloroethane_ 34515 0.025U 0.025L'
'''�""'s�'" "� '�•'yOj" " ''a 2-chloraethvl vinvl ether (mixed)_ N NA
bromoform_ 34291 0.025U 0.025L'
1,1 2 2-tetrachloroethane_ 34520 0.025U 0.025L'
tecrachloroethvlcn� 34479 0.025U 0.025U
toluene_ 3448G 0.025U 0.025U
chlorobenzene_ 34305 0.025U 0.025U
e thvlbehaene_� 14375 0.025U 0.025C
acrolein_ 34214 O MOOD I 0.5000
acrvlonitrilp4l 34219 0.5000 O.SOOL'
propana 1.9001 O.S10J
• utana 1/ 1.000J 0.100J
" - pentane 1/ 0.300J O.IOOJ _
pentanar 1/ 0.400J 0.3001
exana 1 2.200J 2.600J
total unknown alkyl hydrocarbons 0.200J 0.025K
J - Estimated value. '
K - Actual value is known to be less than value given.
L - Actual value is known to be greater than value given.
U - Material was analyzed for but not detected. The number is the Minimum Detection Limit.
NA - Not analyzed.
Tentative identification.
�/- On NRDC List of Priority Pollutants.
". ..a 105

DATA Y.LYUri;lSC .,d GEI df-c:li,,UA
PURGEABLE ORC•Ni[C ANALYSIL 4/8U
- - - PROJECT Pigeon River CUE`IIST E. U. Loy, Jr. COM?LET'D -3030
To aro ina
3-
sx
d SAD NO. 81C 0078 81C 0079 81C 00,
Pigeon River 93 Pigeon River B4 Pigeon Rive
SOURCE 4 STATION (Hog Suckers) (Red Breast). Tennessee U
Breast S Ho!
Suckers)
DATE/TINE
Compound mg/k& mg/kg mg/kg
dich loradifluoromechane2/ 34735 .025U 025C
methyl chloride 34421 .0zbu .025L'
' methyl-bromides 34417 1 .025U .025C
° vinvl chloride;V _ 34693 nl ' .0 5U I .025L'
chloroethane2 34715 .U25C 25L' .025Umeth-.-lane chloride-' 3442 .073, -r .025�
trichlorofluorore[hane- J4492 I 02 r .025C
11
1-1
1
ch to roe[h•�Lene_ 345U5 �0 - .025C
1 1-dichlor°e[haae_ 3450U U _ •025U
1 2-trans-dfchloroeth lene_/ 34550 .025L• n .025L'
chloroform _ 34J1 .080 + .025C
1 2-dichloroethane_ 345 5 .025C .025 '
1 1.1-tric1
1
o:2
ethane _ 431 .025C 0 .025U
K carbon [e trachloride_ .025C •025 + .025E
dichlo rebromome thane-1 34311 .025 L• 02 ' •025L
1 2-dichloroo rooanes/ .025C .025C I .025C
1 3-dichloroo roovlene .025C .025E .025U
tzichloroethvlene- ° .025 L' .025L' .025L'
benzene_/ IR .025E .025U I .025E
chlorodibromomethane_ .025U .0251' .0151
1 1 2-crichloroethane_ 34515 .025C .025L' .025L'
yg_ xlea! 2-chloroethvl vinvl ether (mixed)_ NA NA NA
bromoform_ 34291 .025U .025U .025C
tI 1 1 2 2-tetrachlor°ethane_ 34520 .025E .025L' .025U
--- - tetrachl°roeth lane_ 34479 .02 1 .025U .025C
toluene_ 34484 .025U .025E I .025L'
chlorobenzene_ 34305 .025U .025ti .0251
h ethvlbenzene_ 34375 .0251' .025U .025C
w acrolein_Tr 34214 500V .S000 -.5000
ac lonitrile_ 34219 .500U .S000 I .500L'
ro anal 1 .9001 .100J .SOOJ
" butanal 1 .100J .200J .100J
pentane .200L+ .IUUJ .LODJ
entanal _ .3001 .2001 0 ]
hexanal _ 2.7001 1.8001 1.400J
total unidentified alkyl h drocarbons .100] SKI .025K
t
J - Estimated value. '
K - Actual value is known to be less than value given.
L - Actual value is known to be greater than value given.
U - Material as analyzed for but not detected. The number is the Minimum Detection Lim!
NA - Not analyzed.
t/- Tentative identification.
2/- On NRDC List of Priority Pollutants.
: -_ 1C

FISH
C.\TA PF.POR'I i::O SHEET Ef.\; S,'ul, 'r.0:1, Iv
,j;T:;:y^•.;,, _ � EXTRACTABLE ORGANIC ANALYSIS Athens, CA 4/60
PROJECT v r nopp of Natural Resources CHEMIST E. V. Loy, Jr, REC-D. 10-16-8@OMPL'D. 2-26-&
Ralei¢h, N.C.
SAD NO. 81C 0075
Pigeon River Ol
SOURCE 6 STATION (Hogsucker) ,
DATE/TIRE
Compounds on NRDC Lis[ of Priority Concentration - Concentration Concentration
Pollutants /k mR/k mg/kg
17, bis thlorometh 1 ether lU .
61. N-nitrosodim;thvlamine 34442 lU
25. 1 2-dichlorobenzene 34540 lU
26. 1 3-dichlorobenzene 34570 lU
27. 1 4-dichlorobenzene 34575 1U
Id. bis(2-chloroethvl) ether 34277 lU
12. hexachloroechane 34400 LU
42. bis(2-chloroisooro 1) ether 34287 lU
63. N-nitrosodi-n-oroo lamine 34432 2U
56. nitrobenzene 3445L I lU
52. hexachlorobutadiene 34395 lU
8. 1,2 4-trichlarobenzen. 34555 TO 55. naoh[halene 34446 1K'
43, bis(2-chloroethoxv) methane 34282 LU
54. isoohorone 34412 U
53. hexachloroc cloventadiene 34390 lU
20. 2-chlorona hthalene 34585 lU
77. acenaohth lene 34204 lU
1. acenaohthene 14209 1U
71_ dime
thvl hthalate 34145 lU 1
35. 2 4-dinitro toluene 4 lU
-"' 36, 2 6-dinitrotoluene 366.30 lU
40. 4-chlozo hen 1 henvl ether 4 lU
80. fluorene 34385 lU
70. diethyl phchalate 34 40 lU
37. 1 2-di hen lh drazine _ 34350 lU
62. X-n1trosodinhenylaninell 34437 1 lU '
9, hexachlorobenzene 34688 1 lU
41. 4-bromo hem•1 ohenvl ether 34640 lU
- 81. Mth1 34465
M. anthracene_/ 34224 lU -
68. di-n-but 1 phthalate 34683 lU
_ 39. fluoranthene 34380 lU
o rene 344 3 lU -
•- 67, butyl benz 1 ohthalate 34296 lU -
- 5.' benzidine 34241 2U
_ 66. bia(2-ethvlhexvl) 2hthalace 39099 ' lU
76. chr sene _ 3 324
72. 1 2-benzanthratene _ 34530 LU - --
28. 3 3'-dichlorobenzidine 34635 lU
69. di-n-oct 1 2
hthalate 34bOu lU
74. 3 4-benzoflucranthene _bi 14714 - -
75. 11 12-benzofluoranthene_- 4246 lU '
73. 3 4-benzopyrene 34251 lU '
83_ indeno (1.2,3-cd) orrene 34407 lU
82, 1 2 5 6-dibenzanthracene 34560 lU
12-benzooervlene 34525 lU
24, 2-chloro henol 34590 8U
57. 2-nitro henol 34595 BU
652
. henel (CC/HS) 34468 BU
34. 2 4-dimethvl henol 34610 SO
31. 2 4-dichloro henol 34605 8U
21, 2 4 6-trieoro henol 34625 BU
22. ar.chlohl
rome[a cresol 34456 BU
59. 2 4-dinitro henol 34620 64U
60, G 6-dinitro-o-cresol 34661 BU
64. pent.ichloronhenal 39U60 BU
58. 4-nitro henol 34650 16U
A - Not analyzed. 5/- Chrysene and/or 1,2-benznnthtac.
-- J - Estimated value. - 6/- 3,4-benzofluoranthene and/or
O- Actual value is known to be less than value given. 11,12-benzofluoranchene.
Actual value is known to be greater than value given.
Material was analyzed for but not detected. The number is the Hinimum Detection Limit.
�•::7W
�/- Tentative identification.
..._ . -.... -.. .. -: 21 and/or azobenzene. fOVF.31 107

FISH
1,g0'FCT N.C. Dept. of Natural Resources y, •C'].30-16-BOCO:!P!.'!
CH?:IIST E. W. Loy, Jr. ?r 2
).
Raleigh, N.C.
SAD NO. 81C 0076 ---
Pigeon River U1
._SOURCE b SnTION (Redbreast)
DATE./T1:1E
Compounds on NRDC List of Priority Concentration Concentration Concentrat
Pollutan cs ,.1'r.� n2/k in- 1.,
* g
17. his(ch lornmeth•1 ether 4 lu
61. N-ri trosod ime city la nine 34442 lU.
25. 1,2-dichlorobenzene 34340 lU
26. 1,3-dichlorobenzene 3457U lU
27. 1,4-dichlorobenzene 34573 lU
IS. bis(2-chloroeth•ll ether 34277 lC
12. hexachloroethane 34400 lU
42. bis(2-chlor0isa ropvl) ether 3':287 I 1❑
63. N-nitrosodi-n-propel:mire 3G4'ro U
Sb. nitrocenzcne 34451" lU
52. hexachlorobutndiene 34395 lU
8. 1,2,4-trichlorobencene 34555 lU
55. nnohthalene 34446 lri
43. bas(2--rr-hlorncthoxv) methane 34 i2 lU
54. ' isoni:_:ane 3441^ 3U
53. hexas�a:loroc•;clooencadiene 34190 I lU
20. 2-ch!oronaohthalene 345A5 lU
.. I/. acenaphthvlena 4 4 lU
1. aconaohehene i4209 lU
71. dine thvl oh the Late 34345 1L'
35. 2 4-dinitrotoluene trts lU
36. 2 6-dinitrotoluene 346.30 lU
'�`•"• 1 ="F '^"'""'�"„�'KA 40. 4-chlora hen 1 Phenvi ether 11LA4q lU
80. fluorene '34185 lU
70. diethyl phChalate 34340 lU
- _ 37. 1 2-di hen lhvdrazine _ 3G350 - lU
62. N-nitrosodinhenvlanine_ 34437 lU
xachlorobenzene 34688 lU
41. •4-bromo henvl phenvl ether' 34640 lU
.. 81. 34465
id. anthraceneJ 34224 'lu - - -
68. di-n-6ut 1 hthalate 34683 lU
_ - 39, fluoran thane 34380 lU
84. - nyr,:ne 3 4473 1U . . . . .
67. butyl benz 1 Dhthalate 347.90 lU
. •.. `-. : Si., benzidine . . . 34241
_ ..
66. bis(2-ethvlhe:<vl) phthalate' "39099 'lU
. .- .' . .. - . . 76. chr ne _ .. '34324 . .. . . . . . .
. •72. 1 2-benzanthracene _ 34530 lU -
•' - - 28. 3 3'-di-hlorobenzidine 31635 lU . • . . . ..
69. di-n-octyl phthalate 340LIO lU' _
74. 3.4-benzofluoranthene _ - -.
75. 11 12-benzofluoranthene._ 4246 lU - -
73. 7 4-benzo rani " 34251 lUY'
r'P1 '•MOf '" ' 83.indeno (1 2 3-cd) Tone '- 34407 ' lU
82. 1.2,5,6-dibenzanthracene 34560 lU
_.- -�✓ ... ... .... ..:_-...: 79. 1.12-ben oncry z lane 34525 lU
24_ 2-ehloro henol 34590 BU
57. 7-nitroohannl 34595 8U
65a. '?,_nol (CC/I15) 34468 AU
_.._
. . 34. 2,4-dimer' 1phcnnl 34b10 DU
31. 224-dfr;_..nro henol. 3460; gp
zz- 2,4,6-[r3ahloronhanol _ ' 34G2S 8U -�
22. nnrachlommgta cresol 3443E _ SU
S9_7 Lzcinftronhnnnl 94620
_� 64U
617. 4,6-dinttro-o-_resol 3466J. 8U
64, pentachlnrn In lanai 39060 8U
58. 4-nitronh:-aol 3GGSU1 16U
A - Not analyzed. Ch r}'sena and/or 1,2-henzan[ht
J - Estimated value. 6/ 3,4-ben.-.oflunranthene and/or
- • - - _ - - - C - Actual value is known to be less than value liven. 11.12-benzof luoranthone. I
L - Actual value is known to be greater than value given.
Y - Material was analyzed for but not detected. The number is the Minimum Detection Linic.
wi
Tentative identification.
]/= n
and/-r azobenzee. - - ._ (OVER) 108 I
+l5's+i<.7iciA: i:.a+•i..•.s.+,:.u...aa..ac�w

FISH _
_ ;g1y EC;N.C. Dept. Of Natural Resources Cili MSi E. W. Loy, 7r. Ri.C'D. 10-1640;APL'D 2-26-81
Raleieh, N.C.
$AD NU. 71C 0077
Pigeon River 92
SOURCE 4 STATIO:! (Redbreast)
OATS/TINE
Compounds on NRDC List of Priority. Concentration Concentration Concentration
Pollutants ke ma/kg mg/kg
•_-+ci=%r.�i ;F--Fr: 17. bis(chlornmeth l) ether 14771 lU
61. N-6itrosodinethv.lamina 34442 lU .
25_1 2-diehlorobenzone 34540 lU
26. 1,3-diehlorobenzene 34570 lU
27. 1 4-diehlorobenzene 34575 lU
18. bis(2-chlornetb 1) ether 34277 lU
12. hexachloroethnna 34400 lU
42. bis(2-chlornisooronvl) ether 34287 lU
63. N-nitrosodi-n-nroo lamine 34431 2U
5'6 nitrobenzene 34451" I lu
52. hexachlorobucndieae 34395 lU
8. 1,2,4-trichlarobenzene 34555 lU
55. naohri±lene 34446 1R
43. bis(2-chloroethorv) methane 3428? LU
54. ' isoohorone 34412 2U
53. hexachloracvcloaentadieae 4390 i lU
20. 2-chlorona hthalene 34585 1 lU '
. - 77. acena hthvlene 14704 lU
1. acenaohtheue - 34209 lU
71. dimethvl phthalate '34345 lU
35. 2 4-dinitrotoluene 16615 'lU
_ 36. 2 6-dinitrotoluene - 34630 lU
r ... 40. 4-chloro hen 1 Phenvl ether 34645 lU
80. fluorene "34385 IU
_ 70. diethyl phthalate 34340 lU
"'- 37. 1,2-di hen lhvdrazine Al34350 . lU '-
62. N-nitrosodiuhenylamine_ 34437 lU '
"- 9. 'bexachlorohr.-mene 34688 lU
41. .4-bromo hen-1 henvl ether 34640 A -
.. 81, a e1 34465 '
16. anthracanaa4i 34224 'LR
_ 68. di-n-but 1 phthalate 34683 lU
39, fluoranthene ' " 34380 1L'
84:. nvrcne 3 473 lU
67. but lbenz 1 hthalate 34296 1U
5. benzidine . . .. . .. .34241 2U . . . . .
66, bis(2-e[h lhex 1) hthalate" "39099 � „'lU
760 chtvsene _ ' ' '3 324 • -
72. 1 2-benzanthracene 21 34530 lu - - '-
28. 3,3'-dichlorobenzidine " 34G35 lU
69.. di-n-oc[ 1 phthalite !qb 00 -lu - -
74. 3,4-benzofluoranthene
75. 11 12-benzofluoranthene. 4246 lU
73. 3 4-benzo wren: ' 34251 ' lU '
83. indeno (1,2,3-ed) pyrene " 34407 " lu
82. 1,2,S,G-dihenzanthricene 34560 lu
'
79. 1,12-benzonerVlene 34525 lU
24. 2-chloronhenol 36590 6U
57. 2-nitrnnhcnol 34.391 6U _ -
65a. nhonol (CC/NS) 344 6 6U --
34. 2,4-dimethy10b.'aol 34610 U . -
31.. 2 4-dichloro henol 34605 6U
21, 2,4,6-trichloronhenol. ' 34625 6U _
22, Parnchlorometa cresol. 34456 6U
. . 59. 2 4-dinitronhenol 74620 48U ---
60. 4 6-;linitro-o-cresol 34G61. bu
64.. nen[_nchlo ronhcnnl 3'IUGO _U
58. 4-n-.tronhanoL 34650 .12U
_
A - Not analyzed. 5/- Chrysene and/or 1,2-benzanthrac
3 - Estimated value. 3,4-benzofluoranthene and/or
F - Actual value is known to be less Loan value given. 11,12-benzofluoranthene.
L - Actual value is known to be greater than value given.
Y - Material was analy.-.ed for but not detectvd. The number is the Minimum Detection L>m Lc.
� _ -.,:`.?•3 �- Tentative �.
109
idenCificatic.
.. ...-.- ,...��. -_._... 3 ii-'and/or azobeazene. .. ._ (OVER)

FISH
PROJECT N.C. Dept. of Natureal Resources CHEMIST E. W. Loy. Jr. RrC'D.
Raleigh, N.C.
SAO W. 81C 0078
Pigeon River
SOURCE & STATION (Hogsuckers)
DATF/TRI".
Compaunds-on NRD--- List of Prio,icy Concentration n uncetra
PollutAnts /k- ./k� P
17. bis(chloro"r y.1) ether 141-7, lu
61. ';-oitrosodi.orhvtamine 34442 111:,
N EN lob .12L"le lu
26! 1 345/0
27. 1,4-dichlorobenzene 34575 lu
18. bis(2-chlorcedwi) ether 34277 U,
12. hcxachloroechane 344CO
42. bis(2-chloroisonropvl) ether 34287 1 U�U'
4
63. N-nitrosodi-n-pronylanine 34431=I zu
T6. -nitrobentena 34451- lu
52. hexachicrobutodiene 343'15 lu,
5� JL,
8. 1.2,4-trichlarobenzene 3�5��. lU
55. rnDhthalene 3444,� lK
43. 01$(2-Chloroethoxy) methane 34M lu
34. isophorone
34411. U
53. hexachlorocyclovenzadiane IL39,1
20. Z-chloronaphthalene 34585 lu
77. ncenaphthylene 34906 lu
1. acenaohthnne 34"19
ri. dinethvl Phthalate 34345 ii
35 2.4-dinitrocol_ueri I4615 IU
36 2,6-dinitrozolte-, 34630 1 lu
40 4-chlarophenyl ph_n vl'ether 34645 lu I
80. f1torene 3418i I lu
To. diethyl phtb.late 34340
37. 1 2-diohenylhyd ajzine �E/ I iui
ylaminel/ 34437 1
2 sodi.hen lu
9. h-machlo roSor%e ne 34686
41. 4- omophe.,L Phenyl etl:cr 34640 UP
br
65 4=�mI rnnq,
W 344
78. anthracene_41 34212±4j lu
68. u I hchal7to 34683 1 lu
5 111ZN�,�tE.P. 3438n
39 lu
4... avrene _34417 lU •
67. butyl bent phtbalate 34296 lu
5. benzidine 34241 zu
66. bis(2-ethylhexvl) nhthalace_3909 IU
3+324
12* 3: i 2 g2,thr2cene 2/ 34530 lu
r.b;nzidine 34635 lu
69. di-n-octyl phthalate 34t,00 it)
_74._34-beonzo fluorant)
-.2- 6 lu
73. J 4-hcnzonyrcne 3425i lu
83 inde..�(1,2,3_cd lu
r22e 0
82. 1,2,5,b-CibenzincdrH--e 3!5511 1U
iV. 1.12-benzoperylell., 345*15 1 R'
!S11. 2-chloroehenol 34590 6U
34595 6L,
57* 2-!,itroplenol
65a. lhcnol (Gr.!Z:S) 31.46- 6 L;
T4. 2�4 ,1.,.rj
�.Y_jph,nol 34610 6U
31. 2,4--d I ch I c;­o-.hm,o I 34fi0', 6U
11_�
34625 6u
22-__Zjr.,,-h1ornmpra cresol 341,56 bu
-7 59. 2 7 Z- -L I initroijh(nol 94620 48LI
60. 4.U-dinicro, cr(!t%,,] 3466,1
6u
U4. .01 mu.,) 6U
4-n4rronhvn,,1 . 12U
A - Not analyzed. 5/
Ch,yscne and/or 1,2-henin
J - Estimated value. 3.'-henzufIu,-ranthzn. and/
K - Actual value is known to be less than value gi. on.
I1.I2-bcnzofluor.,nth_-!,L.
v`iL - Actual value is known to be greacer than value given.
- I- �LItLrial was analyd for but not detected. The wimber is the Mini.nu.n Detection LjLlit.
Y Tentative id�ntifcication.
and/or azob,ve.e.
110

:.., ...: .:..:-.. FISH . .
CA
' - --"""+b'P"''==' ""�'"•• PROjFC, I N.0 Dept. of Natural Re gmreegCHEMIST E. GI. Lov, dz. RFC'D.10-16-80C43.!PL':12-26-81
Raleigh, N.C.
SAn ;:0. 81C 0079
Pigeon River B4
SOURCE 4 STATION (Redbreast)
DATF./TI9E
Compounds on NRUC List of Priority Concentration Concentration Concentratioa
Pollutants
17. b-tni[rosodime 1U
61. N thvlamih
lU
25. 1 2-d ichlo-oSenzene 34540 lU
26. 1 3-dichlorobenzene J457U 1L'
27. 1,4-dichlarobenzene 34575 lU
18. bis(2-chloroeth 1) echer J4277 lu
12, hexachlorn._thane 3=»UO 1U
42. bis(2-chlaroisooro vl) ocher 34187 lU
. - 63. N-nitrosodi-n-prooylamine 4'1 2U
-56. nitrobenzene 34451- lU
- 52_ hexachlorobutodiene 34395 lU
.. 8_ 1 2 4-trichlorobenzene 34555 lU
55. naphthalene 34446 LK
43. bis(2-chlo roethoxv) nietl:aae 34282 lu
54. ' isw'wrona 34410 2U
53. hexachlorucyclopentadiene 43 n 1U
20. 2-chloronaph[halene 34 85 lU "
77. acena hchvlene 4 III
1_ acpnaohthene 4009 it,
71, dimethvl Dhthalat,� 34345 lU
35. 2 G-diniarotoluene 4 lU
36_ 2,6-dini trotoluene
- J4630 lU
40. 4-ehloronhen 1 henvl et:cr 4G4 lU
80. Fluorene 4385 1U
70. diethyl phthalate 34340 lU _
=di henvIhcdrazine _ 34350 lu
62. N-nitrosodiohenvlamine / 34437 lu
9. hexachlorobenzene 34688 lU
41. A-bromo hen-I henvl ether 34640 lu
81_ nhenan rti 34465
- - 78_ anthracene_ 34224 'lU - - -•
66. di-n-butvl nhthalace 34683 lU
39. fluoranthene 34380 lu
84:_ Py.ene 34413
67. butyl bent 1 phthalate 34296 lU --
5_•' benzidine - 342 1 2U
. . 66. bis(2-ethvlhe 1) hthalate '39099 "lu -
- 76_ chr sene if 4324
72_ 1 2-benzanthracene _ 3453U : ' lu - -
28. 3 3'-dick Lorobenzidine 34635 lu - -
• 69_ di-n-out 1 hthalare 3Ibu ' lU
74. 3.4-benzofluor.n theme _ •
.�
75_ 11 12-benzofluorantbenr- 4v46 IU
73_ 3 _4-benzooyrene ' 34051 lU
83, in
duno (1 2 3-cd) pyrone " 34407 - 1U
82- 1 2 5 6-dihenzanthracene 34560 lU
79. 1.12-benzopervlcne 11,525 lU
24_ 2-chloronhenol _ 31,590 6U
57, 2-nicr^ph••no1 31595 6C
65a. henol (CC 1t5) --- 31.468 6❑ -'
34. 2 G-di:oe[ht•1 henol 346LO 6U
- 31. 2,4-dfrhlorophvnoL 34605 6U
21_ 2 4 6-trichloro hunol 34625 6U
- 22, parch lorn-ecn cresul 34456 6U
59. 2,4-dinitro Leanl J462u 48U I---
60. 4,6--0 ni[r.=oo-tresnl 34661 6U
61. puntachlo r"iM.00L 390u0 6U r-
58. 4-n-to hymn). 3465U
12U
A - l:ot :,na1 zed. 5/
y 61 Chrysene and/or 1,2-h mzanch:a:
3 - tima[ value. - J 4-benza ELuo ranthcn.: and/or
Actual
value
K - Actual value is knnun to be less than value given. 11,12-benzofluoranthone.
- _ • - :', L - Actual value is kno,m to be greater than wLie given.
- Micerial vas analyzed for but not detected. Thu number is the iLLniaum Detection Limit.
�- Sentative identification.
ik,'a u and/or ...ha,,,
111

FISH ..
PROTECT N.C. Dept. of Natural Resources C171E`IST. E. M. Loy, Jr. vcC'D,10-16-80 rn.lPl_•D 2_I
Raleigh, N.C. -
SAD ::0. �B1C 0080
Pigeon River at
-SOURCE S STATION Tenn. (Red breast
6 Hogsuckers)
DATE./TIM: _
Coapauads on NRDC List of Priority Concentration Concentration Coucentral
Pollutants k2 ne/ko /k,
- - .. - - 17. bis(ehlo-nse thvl ether + lU
61. N-nitroso•!imethvlamine 34442 lU .
25. 1 2-dichlarobenaone 31,540 IV
'�-`- 26, 1.3-dichlorobenaene 3457U IV
27, 1.4-dichlorobenzone 34575 lU
18. bis(2-chloroechvl) ether 34277 10
12. hezachlorcethana 344UO lU
42. bis('_-'cbloroisoo ronvl) ether 34287 lU
63. N-nitrosodi-n-nro lamina• }44;� 2U
56, nitrobenzena 3445L lU -
52, nezachlo:abucadiana 34395 lU
8. 1 2 4-M chlorobenzene 34555 lU
• 55. naohthainne 34446 lU
43, bis(2-chloroethosv) nethane 34282 l
_ u
54. ' isnnH-one 34412 2L'
53. hexaehloroe•:c12 2L adiene 34390 iU
20. 2-chloronaDhthalene 34585 10
77. aconaohthvlene 3A•'n.: lU
1. ac..aanthene 342,19 llt
71. dimethvl hthalate 34345 lll I
35. 214-dinitro to luene "" 4 t4 lU
_ - 36. 2 6-dinitrotoluene 34!>30 lU
�"�'•`� �- '�"'^""'""`�"'�-' •-'ir"�?+ 40. 4-chtoroohen 1 henvl ether 4645 lU
80, fluorene '34385 1U '
70. diethyl phthalate 3434U lU
37. 1 2-di henvlh drnzioe _ 34350 lu
62_N-nitrozodiohenylaaice_ 34437 lU
9_ he:<achlorobenzene 34686 1U
41. �4-hre_o henvl phenyl ether 34640 lU
81. - 34465
16. anthracene_ 34224
68, dL-n-butyl 2hthalat, 34683 lU
39. fluoranthen- 34380 lU
S4, 02e 344 3 IV
.• 67. butyl henzvl ohchalate 34296 2'I
5." benzidine " " 34241 2U .
66. bis(2-ethvlhexvl) hthalate' '39099 'IV
. 76. chrynene a . . '3 324 . .
72 1.2-benzan th scene - " ' 34530 1U - _ -
'" 2S. 3 3'-dichlarobenzidine 34635
. ... . ..
69. d1-a-oct 1 phthalace 'Jib 'lU - - -
747 3,4-benzofluoranthene _ - :. . . .. . . ... ..
75_ 11,12-benzofluorantben•• 4246 lU
73. 3,4-benzoovrene 34251 1U -'
°'� �'`�'�"'-'•"-•""" "�'T""`��'- g3_ indeno (1,2 3-cd) rcne -" 34407 ' lU '
Oz. 1 2 5 6-dibenzanchracene 34560 1U
79, 1,12-benz2nervlene 34525 10
24. 2-chloronhenol 34590 5U '-
57. 7-nitronhencl 34595 5U - '-
65a. r1:cool (CCl:IS) 34568 - SU
. 34. 2,4-di:.:ct1n•Inhcnnl 34610 5U "-
31. 2,4-dirhlor. •,henol 34605 5U
21. 2,4,6-tr1.1h!ororhenpl 34625 SU --
22, narachlorometn cc,,sol 34456 5U -
397 2,4-div.'t trophenol 34620 _ 40U
60. 4,6-d iu itro-o-cr,:s_o1 34661 _5U
64. :antachla pImnn rnl_ 390u0 SU
58. 1-:m trrohunol 34650 lUU
A - Not analyzed, S/- Chrysenc and/or 1,2-benzan'
J - Estimated value. 6/- 314-1,enzofluoranthene and/t
R - Actual value is known to be lose Lhan value given. 11,12-henzofluorancl:ene.
L - Actual value is known to be greater than value given.
Nacerial was analyzed for but not detected. The number is Lhe :lininu.-t Detection Lir,ic.
.Tentative identification.
3/ .and/or azobenzene. _ IZ
.. .- (OVER)

DATA REPORTISG SHEET
PISd
ROJvC_ NC Dept. Nat'l Resources CrE 15T B. McDaniel REC'D 10-16-80 CC[-L'D 4-30-81
Raleigh. Ng
'RO3ECr Y.UMHLR 81-13
:AD a0. B1C 0075 81C 0076 81C 0077 81C 0078
:OURCE d STATION Pigeon River tl Pigeon River #1 Pigeon River 42 Pigeon River
(Hogsucker) (Redbreast) (Redbreast) (Hogsucker)
LATE/TIMZ
:LE`'.F::T (mg/kc).
Silver* 34474 1K 1K 1K 1K
lrsenic* 01004 2K 3K 3K 2K
loron 81657
3ariva 81658 4 5 2 2
3erv11i=* 3.252 1K 1K 1K I 1K
Cad=iu:* 71940 1 1K 1K IK
=obalt 81659 1K 1K 1K 1K
Chromium* 71939. .
C000er* 71937 0.8 1K 1 -
Holvbdenua 81662 IKlK 1R
1R
• _ Vickel* 01069 1K ZK 2K 1K
Lead* 71936 1K 2K 3A 1K
Antimony* 01099 IK lK 2K I 1K
Selenium* 01149 1K 2K 3K 1K
Tin 81663 4 6K 6K
Strontium 81950 _ 13 35 11 7 -
Tellurium lK 2K 2K 1K
Titanium 81664
Thallium* 01073 4K 6K 6K 4K
Vanadium 81665 IK lK IK 1K
Yttrium 1K 1K lK 1K
Zinc* 71938 18 23 37 21
Zirconium
Mercury* 71930 0.09 0.09 0.02K 0.04
Calcium 81655 3490 10950 11450 6950
Magnesium 81656 335 450 480 400
- CONTINUED ON BACK -
K - Actual value is known to be less than value given.
L - Actual value is known to be greater than value given.
* - Priority Pollutant.
113

CONTINCATIbN E?A_SdD-LS B-+
DATA R-PORTING HEET
FISH
.L0JUCT NC Dept. Nat'l Resources CHEMIST H. He Dan.'. _ REC-0 10-16-80 COAPL'J 4-3
Raleigh, NC
ROJECI NUIMER 81-13
AD NO. 81C 0015 81C 0076 SIC 007 SIC
OURCE 6 STATION Pigeon River dl Pigeon River fil Pigeon River,:-- Pigeon A
(Hogsucker) (Redbreast) (Redbreast) (Hogsuck
ATE)Tii-
.LENIENT (cc he
.1,minu 816d6 72 :10 34
ran 81660 92 1`0 70 54
Ian anese 81741 7 35E0 3110 7
;odiu 938 1030 1500 1050
anide-(Net Weisht)34326
'ercent Moisture (2)70320 '
lsbestos * 34229 NA NA NA NA
ANALYSES ON WET WEIGHT.
R - Actual value is known to be less than value given.
L - Actual value is known to be greater than value given.
• - Priority Pollutant.
114

DATA REPORTING SHEET FISH EPA-LS=-SAU /b0
R03EC: NC Dept. of Nat'l Resources CHEMIST B. McDaniel FEC,D 10-16-80 CO+iRi •D 4-30-81
R,IPfgh NC
RO3ECI NU?BER 81-13
61D NO. 81C 0079 81C 0080
:OURCE S STATIO% Pigeon River D4 Pigeon River at
(Redbreast) Tennessee;
(Redbreast and
Hogsucker).
)ATE/TINE
:LE4:.VT (m /k )
;ilver* 34474 IK 1K
',rsenic* 01004 1K 3K
ioron 81657
3ari= 81658 1 3
lervlliur..* 34252 IK 1K
;admi=* 71940 1K 1K
Cobalt 81659 lK 1K
.hromium* 71939 .
Zouoer* 71937 0.7 1
it
Io1 bdenum 81662 lK l
9ickel* 01069 1K 2K
Lead* 71936 1K 3K
Antimony* 01099 1K 2K
Selenium* 01149 1K 3K
Tin 81663 2K
Strontium, 81950 3 19
Tellurium lK 2K
Titanium 81664
Thallium* 01073 '2K 6K
Vanadium 81665 1K IK
iK IK
Yttrium
Zinc* 71938 13 27
Zirconium
Herter * - 71930 0.03 0.06
0alcium 81635 5780 26550
Ha,nesium 81656 360 770
CONTINUED 01 BACK -
K - Actual value is know to be less than value given.
L - Actual value is known to be greater than value given.
* - Priority Pollutant.
115

CONTINUATION E?A-SAD-LSS--.�.•
DATA Rc20RTING SHEEI
FISH
R03GCr NC Dept. of Nat'l Resources CHEMIST B. McDaniel REC'D 10-16-80 CW1:1L'D 4-30-81
eigh, NC
RO]ECI NUMBER 81-13
AD NO. SIC 0079 81C 0080
Figeon River 84 Pigeon River at
OURCE G STATION (Redbreast) Tennessee;
(Redbreast and
Hogsucker).
NTE/TI'LE
:LE:IZZIT (r.. /k
.luminu= 81666 70 20
:ton 81660 I 30 30
Ian anese 81741 9 17
;odi= 1210 1730
anide-(Net I:eiQht)3-326
'ercent Moisture (S)70320
lsbestos + 34229 NA NA NA NA
ANALYSIS ON WET WEIGHT.
i
K - Actual value is known to be less than value given.
L - Actual value is known to be greater than value given.
- Priority Pollutant.
116

6/23/81
PREPARATION PROCEDURE FOR THE ANALYSIS OF FISH FOR METALS
Whole fish are ground using a large commercial meat grinder and freezing.
A five-gm subsample is weighed into a 125-ml erlynmeyer flask with a
screw cap and teflon liner. Add 5 mis concentrated high-purity nitric
acid and autoclave for two hours at 15 psi.
Transfer flasks to hood/hot plate and remove caps. Beflux gently on hot
plate until volume is reduced to near dryness or until residue begins to
turn brown (do not char) : Remove flask from hot plate and add two mis of
30% hydrogen peroxide. Return to hot plate to warm mixture until effervescence
subsides. Carefully add 2 mis of concentrated nitric acid and again reflux
until brown. Repeat peroxide nitric acid additions as before until digestion
is complete but no more than. 10 mis of each or five additions.
After 5th addition, carefully bring mixture to dryness (do not bake) and
add 1 ml conc nitric acid and 1 ml cant hydrochloric acid. Return to a
warm hot plate until residue is in solution. Quantitatively transfer to a
100-ml volumetric flask and make up to volume with distilled deionized
water.
The sample is now ready for plasma analyses.
tt,
! 117

Method PPB 10/80
U.S Environmental Protection Agency
S&A Division, Region IV
Laboratory Services Branch
Athens, Georgia
Extraction and Analysis of
Priority Pollutants in Biological Tissue
1. Scope and Application
1.1 This method covers the determination of priority pollutants .
in biological tissue.
1.2 The limit of detection for this.method is usually dependent
upon the level of interferences rather than instrumental
limitations. ,There interferences are not a problem, the
limit of detection for most compounds analyzed by GC/MS
is 2 mg/kg (wet weight basis) .
1.3 This method is recommended for use only by experienced
residue analysts or under the close supervision of such
qualified persons.
2. Summary of Method
Two 10 gm samples of homogenized fish are mixed with 40 gm of sodium
sulfate, dried, and extracted -- one for pesticide:; and the other
for base/neutral and acid compounds. The pestici '. . are extracted
with petroleum ether and base/neutral/acids are ex.Liracted with
methylene chloride using an ultrasonic probe. The samples are _
filtered, concentrated to 10 mis or less, cleaned up with
acatonitrile partitioning, and concentrated to 1 ml. The extract
is analyzed with a gas chromatograph equipped with appropriate
detectors.
3. Interferences
3.1 See the summary for General Interferences. (Appendi:� No. 1)
3.2 Fish oil is eliminated by acetonitrile partitioning.
3.3 The ultrasonic probe must be scrupulously cleaned between
samples. The procedure is:
1) Rinse the probe with solvent into the sample.
2) Remove residue on the probe with a wet kimwipe.
118

3) Rinse the probe with methylene chloride.
4) Sonicate with hexane for 3-4 minutes on 50% pulse.
4. Apparatus and Materials
4.1 Beakers - 400-m1.
4.2 Buchner funnels - 9 cm.
4.3 Filter paper - whatman 41, ashless.
4.4 Vacuum filtration apparatus (Fisher 9-788) or 500 ml suction
filtration flasks.
i
4.5 Filter vacs.
4.6 Kuderna-Danish (K-D) Apparatus. j
4.6.1 Concentrator tube - 10 mil, graduated (Kontes K-570050-
1025 or equivalent) .
(Kontes K-570001-500 or equivalent) .
4.6.2 Evaporative flask
4.6.3 Snyder Column - three-ball macro (Kontes K-503000-
121 or equivalent) .
4.6.4 Boiling chips = Beryl saddles (Fisher, 91915) crushed. i
4,7 Separatory Funnels - 120 ml and 2L.
4.8 dater bath - Heated, with concentric ring cover, capable of
temperature control (+20C) . The bath should be in a hood.
umns - 25'mm x 200 mm packed with 4 cm of glass
4.9 Drying Col I
wool.
4.10 Florisil Columns - Pyrex, 400 mm x 25 mm OD with Teflon
stop cock, but without glass frit.
4.11 Vials - Varian 2 ml.
4.12 Sonicator - cell disruptor - Model 1?-375 with the high gain
3/4 in. probe from Heat. Systems - Ultrasonics, Inc. or equivalent.
4.13 Food Processor - (Hobart food processor - 8181D -or equivalent) .
119

I
/ 5. Gas Chromatograph
5.1 Gas Chromatograph - Analytical system complete with gas
chromatograph suitable for on-column injection and all required
accessories including flame ionization detector and electron
capture detector, column supplies, recorders, gases, and syringes.
5.2 Base/neutral column and analytical conditions - Chromos°rb
W (100/120 mesh) , coated with 3% OV-17 packed in a 6' X 2mm
ID pyrex glass column. Use ultra pure nitrogen at a flow
rate of 30 ml/min. Column temperature is held at 800C for
2 min. , programmed to 290 at 8°/min. , and held at 2900C
for 16 min.
5.3 Acid column and analytical conditions - Supelcoport (100/120
mesh) , coated with 1% SP-1240 DA, packed in a 4' X 2mm ID
' pyrex glass column. Use ultra pure nitrogen carrier gas at
a flow rate of 30 ml/min. Column temperature held at 800C
for 2 min. programmed to 2900C at 8°C%min. , and held 'at
2900C for 16.min.
5.4 Pesticide column and analytical conditions. Supelcoport
(100/120 mesh) coated with 1.5% SP-2250, 1.95% SP-2401, packed _
in a 6-ft. X 4mm ID pyrex glass column. Use Argon 95%/methane
5%, carrier gas at a flow rate of 60 ml/min. Column temperature,
" isothermal at 2000C.
5.5 Gas Chromatograph/Mass Spectrometer, Finnigan 3200 & INCOS
2300 Data System.
5.5.1 Piirge-and-Trap - Chemical Data System - 310 or equivalent.
5.6 VOA column and analytical conditions - Carbopack B (60/80 mesh)
coated with 1% SP-1000 packed in a 10 ft. X 2 mm ID pyrex
glass column. Use ultra pure helium carrier gas at a flow
rate of 30 ml/min, Column temperature is held at 500C per
4 min. programmed to 2100C and held for 11 min.
5.7 Gas Chromatograph/Mass Spectrometer, Finnigan 4000 and INCOS
2300 Data System. Scanned from 33-450 a m u with a scan time
of 3 m sec./a m u. Operated in the electron ionization mode.
5.8 GC columns = Same as listed in 4-17.1 and. 4.17.2.
6. Reagents
6.1 Sodium Sulfate, anhydrous, reagent grade - heated 2 hours
at 500°C, called in a desiccator for 4 hours, and stored in
a glass bottle.
12

6.2 Petroleum ether - Burdick & Jackson pesticide quality, distilled
in glass or equivalent.
6.3 Methylene Chloride - Burdick & Jackson or equivalent. '
6.4 Hexane - Burdick & Jackson or equivalent.
6.5 Ethyl ether --preserved with 2% ethenol, Burdick & Jackson
or equivalent.
6.5.1 Must be free of peroxide as indicated by EM Quant Test
Stripes (test stripes -are available from EM Laboratories,
Inc. , 500 Executive Blvd. , Elmsford, New York 10523) .
. 6.6 Florisil - (See appendix 11) .
i
7. Quality Control ! .
7.1 See Section 8 page 2 of the Laboratory Services Branch
Operations and Quality Control Manual.
8. Sample Extraction
8.1 For volatile organic analysis the fish must be ground in
i area free of volatile organic compounds.
I
8.2 . The preferred procedure is to use a blender and blend equal
amounts of Dry Ice with the fish.
i I.
Ir 8.3 If the sample is very large a food processor or meat grinder
is used.
I
8.4 Immediately after making the fish homogenious, weigh 1 gm
I into a screw cap tube lined with aluminum foil. Store in
a freezer until analyzed on QCIMS for volatile organic
I compounds.
8.5 Weigh 10 gm of homogenious sample into a 400 ml beaker and
mix with 40 gms of sodium sulfate. Dry thoroughly. Label' I
Pesticide.
8.6 Repeat 8.5 and label Base/Neutral/Acid.
i
8.7 ' Extract the pesticide sample with 100 ml of petroleum using
an ultra sonic probe. Souicate at 50% pulse for 3 minutes.
8.8 Decant solvent through a Buchner funnel filtration system.
8.9 Repeat 8.7 - 8.8 twice. The last time pour the entire sample
into the Buchner funnel.
I
I
121 I

8.10 Repeat 8.7 - 8.9 for base/neutral/acid using 100 ml of methylene
chloride. (NOTE: Clean probe between sample) .
8.11 Quantitatively transfer the extract to a K-D flask equipped
with a 10 ml concentrator tube.
8.12 . Add a boiling chip.-to .the flask and attach a three-ball
Snyder column. Place the K-D apparatus on the water
bath and concentrate to 10 mis.
8.13 Acetonitrile Partioning for Pesticides
This procedure is used to isolate fats and oils from the
sample extracts. It should be noted that not all pesticides
are quantitatively recovered by this procedure. The analyst
must be aware of. this and demonstrate the efficiency of the
partitioning for specific pesticides.
8.13.1 Quantitatively transfer the previously concentrated
extract to a 125-ml separatory funnel with enough
hexane to bring'the final volume to 15 ml. Extract f
the sample four times by shaking vigorously for one i
minute with 30 ml portions of hexane-saturate acetonitrile.
8.13.2 Combine and transfer the acetonitrile phases to a
one liter separatory funnel and add 650 ml of distilled
water and 40 ml of saturated sodium chloride solution.
Mix thoroughly for 30-45 seconds. Extract with two
100-m1 portions of hexane by vigorously shaking about
15 seconds. j
8.13. 3 Combine the hexane extracts in a one-liter separatory
funnel and wash with two 100-ml portions of distillud
water. Discard the water layer and pour the hexane
-4 inch glass-wool drying column
layer through a 3
into a 500-ml K-D flask equipped tTith..a".100-n1::ampo1.
Rinse the separatory funnel and column with three
10-ml portions of hexane.
8.13.4 Concentrate the extracts to 6-10 ml in the K-D evaporator
in a hot water bath.
8.13.5 Use nitrogen blow down to concentrate the extract to
1 ml.
8.13.6 Transfer to GC vial. The extracts are ready for analysis.
122

8.14 Acetonitrile Partitioning for Base/Neutral/Acid
8.14.1 Repeat 8.13.1.
8.14.2 Repeat 8.13.2, make the aqueous layer basic (pH 12) .
8.14.3 Repeat 8.13.3 - 8.13.6.
8.13.4 Make the aqueous layer acidic (pH 2) . Repeat 8.14.2 -
8.14.6 substituting methylene chloride for hexane.
9. Analysis by Gas Chromatography_
9.1 Gas Chromato ra h/Flame Ionization Screening of B/N and A
Extracts
9.1.1 The BIN and -A extracts are screened on GC/FID using the
appropriate column to determine if GC/MS analyses are
necessary.
9.1.2 Calculate the FID response of 50 ng of hexachlorobenzene f
(HCB) for BIN compounds and 100 ng of pentachlorophenol
(PCP) for A compounds. (The GC/PIS requires about 50 ng
HCB and 100 ng PCP to give a complete mass spectra.)
9.1.2.1. If any peaks are present that are > the response
calculated in 9.1.2, calculate the concentration 11
of the largest peak. r•
9.1.2.1.1 If concentration is >2mg/kg (wet I
weight basis) , analyze by GC/MS.
9.1.2.1.2 If concentration is <2mg/kg, report
as <2mg/kg. i
9.1.2.2 If all peaks are < the r6sponses required in f
9.1.2, record the minimum detection limit in
the master log.
9.1.3 Analyze all blanks and spikes and record precision-
and-accuracy data in the QC log book.
9.2 Gas Chromatograph/Electron Capture Analysis of Pesticide
Extracts
9.2.1 A 50X dilution of most samples will provide adequate
I
minimum detection limits for most samples such as MDSD,
EGD, and waste-site samples.
9.2.2 Analyze all blanks and spikes and record precision-
and-accuracy data in the QC book. i
123

10. Volatile Organic Analysis
10.1 Add 5-ml of organic-free water already spiked with the surrogate
spike to the VOA tube. Replace the cap and shake the contents
until the solids are dispersed throughout the water.
10.2 Immediately place the tube on the purge-and-trap apparatus and
heat at 550C for 12 minutes while purging.
10.3 The volatiles are trapped on a 24" tenax trap and backflushed
onto the GC column at 1800C for 4 min. while the column is
held at room temperature (500C) . . The GC is then programmed
to 2100C at 80C/min. and held for 11 minutes.
10.4 The volatile compounds are identified and quantified by the
PLS computer system.
124

Appendix II
Level III Data
Pigeon River & Palmer Creek
May 1980
# Collected/Station
Palmer Pigeon River
Creek 4 6 8A 9 10
Oligochaeta
Limnodrilus spp. (immature) 1 128
L. hoffineisteri 20
Lumbriculidae 4 1 7 2 82
Opisthopora 1 1
vais spp. 1 99 1 9 7
Ophidonais serpentine 1 4 1
Hirudinea
Mooreobdella melanostoma I
Ephemeroptera
Baetis spp. 20 65 4 178* 245
Pseudocloeon sp. 30 256 8 51* 42
Paraleptophlebia sp. 12
Isonychia sp. 23 19
Ephemerella lata 10 6 9 25
E. cornutella 69 8 2
E. tuberculata 23 7 2 2
E. wayah 9
E. walkeri 1 15 6
E. simplex 2 3 1
E. temporalis 1 1
E. catawba gr. 16 1150 23 35 317
E. invaria 16 8 4 13 1
E. rossi 15
E. hispida 16
E: berneri 2
E. deficiens 1 1 9
Cinygmula subaequalis 124 36 2 1
Heptagenia spp. 3
Epeorus sp. 1 gr. 97 6 4 2
E sp. 2 4 1
Rhithrogenia sp. 17 13
Stenonema annexum 25 15 1
S. rubromaculatum 6 30 1 18
125

Palmer Pigeon River
Odanata Creek 4 6 8A 9 10
Argia sp: 1
Plecoptera
Allocapnia sp. 1
Leuctra sp. 7 1
Amphinemoura sp. 8 -1
Peltoperla sp. 2
Pteronarcys sp. 8 2
Acroneuria abnormis 6 2 3 3
A. georgiana 4 47 6 46
Paragnetina immarginata 1
Perlesta placida 6 13
Isoperla transmarina 46 3
I. orata 5
Isogenus decicus 3
Alloperla sp. 1
Sweltsa gr. 15
Trichoptera
Micrasema sp. 38 41
Glossosoma nigrior 2 2 1 20
Lepidostoma sp. 1 4
Stactobiella sp. 1
Cheumatopsyche sp. 84 45 1
Diplectrona modesta 2 2
Hydropsyche venularis 80 7 11 5
Symphitopsyche bronta 1
S. morosa 3 3
S. slossonae 16
S. sparna 28 1 1 6 2
Doliphilodes sp 67 25 1 10 1
Lype diversa 1 1
Polycentropus sp. 2 2
Nyctiophylax celta 1
Rhyacophila carolina 7 1
R. fuscala 8
R. melita 1
R. vuphiphes 3 1
Coleoptera
Promoresia elegans 114 1 11
Optioservus ovalis? 2 1
Psephenus herricki 1
126

Palmer Pigeon River
Creek 4 6 8A 9 10
Megaloptera
Corydalus cornutus
Nigronia serricornis 2 1
Misc, Diptera
Palpomyia (complex) 2
Blepharicera sp. 24 2 1
Atherix lantha 6
Protoplasa fitchii 4
Antocha sp. 18 1 1 3
Dicranota sp. 5
Tipula sp. 1
Hexatoma sp. 2
Simulium vittatum gr, 60 75, 13 2 37
S. (Phosterodoros) sp• 3 1516 141 9
Prosimulium mixtum (?) 1
Empididae 11 4 5
Diptera: Chironomidae
Microtendipes sp. 2 1
Polypedilum aviceps 37 1 2 2
P. convictum 92 2
P. fallax 1 1
P. angulum 1 4
Micropsectra sp. 12
Rheotanytarsus sp. 2 8 2 41
Tanytarsus sp. 4 1
Conchapelopia gr. 1 1 6 1 2 1
Diamesa sp. 7
Sympotthastia sp. 10
Brillia sp. 4
Cardiocladius sp. 1 3 10 19
Cricotopus/Orthocladius gr (C/0)
C/O sp. 1: Cricotopus (C.) bicinctus 28 5 16
C/O sp. 5: C. (C.) c.f. infuscatus 44 9
C/O sp. 6: C. (C.) sp 3 1
C/O sp. 46: C. (C.) sp 4 2 10
C/O sp. 7: Orthocladius (0.) nr. dorenus 6 4 15
C/O sp. 10: 0. (0.) c.f. obumbratus 1 2 20 2 2
C/O sp. 54: 0. (0.) nr. clarkei 7 1 12
C/O sp. 35: 0. (0.) sp. 4 1 4
C/O sp. 36: 0. (0.) sp. 5 52 4
C/O sp. 13: 0. (Euorthocladius) sp. 1
(Type III) 10 148 52 14 2
127

Palmer Pigeon River
Creek 4 6 8A 9 10
C/O sp. 61: 0. (E.) nr. rivulorum
(Type II) 2
C/O sp. 2: 0. (E.) sp. 3 2 2
C/O sp. 20: 0. (E.) sp. 4 1 2 89 92
Eukiefferiella bavarica gr. 3 8 4 2
E. devonica gr. 16 32 24
E. discoloripes gr. 3 8 3
E. claripennis gr. 1 2 1
E. potthasti gr. 10
E. brehmi gr. 3 1 4 1
Paraphaenocladius sp. 1 2
Rheocricotopus c.f. robacki 1
R, sp. 3 2
Gastropoda
Goniobasis sp. 2
Hydracarina 2
12E

Appendix III o
Level III Data -
Pigeon River and Tributaries
August 1980
Pigeon River Creeks
1 2 3 4 Richland Crabtree Fines
EPHEMEROPTERA
Stenonema annexum 126 - - - 3 - 10
S. ithaca 4 - - - + 28 8
Heptagenia sp. - - - - - + -
Epeorus sp. 1 2 - - - - 1 1
Caenis sp. 4 - - - - 1 2
Tricorythodes sp. 2 - - - - - -
Ephemera blanda + - - - - - -
Isonychia sp. + - - - - + -
Baetis nr. intercalaris 39 - - - - + 71
B. flavistriga 19 4
B. Pluto (?) + - - - - 1 14
Pseudocloeon sp. 15 - - - 4 4 21
Cloeon sp. + - - - - + -
Ephemerella deficiens + - - + - 1 2
E. serrata + - - - - - -
E. serratoides + - - - - -E. bicolor - - - - - + -
PLECOPTERA
Acroneuria abnormis 7 - 4 + - 2 -
Paragnetina immarginata 1 - - 1 - + 13
Leuctra sp. 2 - - - - + -
Allonarcys sp. - - - - - 1 -
TRICHOPTERA
Cheumatopsyche sp. 71 1 - 1 141 29 29
Hydropsyche bronta 8 - - - - 9 9
H. morosa 22 1 - 20 - 1 87
H. sparna 16 - 11 11 2 14 114
H. venularis 3 1 18 172 3 - -
H, incommoda + 1 5 11 10 -H. phalerata
H. betteni -
Oecetis sp. -
Glossosoma nigrior 2 - - -
Goera sp. - 1 -
Hydroptila sp. 69 - -
Leucotrichia pictipes - - - 1 18 - 5
Brachycentrus sp. + - - -
Micrasema charonis + - + -
Polycentropus sp.
129

Pi. o m i;ivrr Creeks
1 2 3 4 Richland Crabtree Fines
COLEOPTERA
Jptioservus sp. 1 4 1 1
Oulimnius latiusculus - - - -
Promoresia elegans + - 1 -
Stenelmis sp. - 2 + -
Psephenus herricki - - +
Dineutes sp. + - - -
Helichus sp. - - +
ODONATA
Lanthus parvulus - - - +
,Gomphus sp. + - - -
Macromia sp. + - - - + - -
HEMIPTERA
Sigara sp. - - +
MEGALOPTERA
Corydalus cornutus 20 10 1 3 1 7 14
Nigronia fasciatus - - - +
DIPTERA: Misc
Empididae 5 - 3 26 83 3 -
Antocha sp. 18 - - 46 - - 54
Simulium (Phosterodoros)sp. 3 - - 1
S. vittatum gr. 1 5 6
Protoplasa fitchii 1
Atherix lantha 4 - -
Palprmyia (complex) - - - 1
Atrichopogon sp. - - + - i +
DIPTERA: Chironomidae
Chironomus sp. - + - - + - +
Cryptochironomus fulvus - - + - + - -
Microtendipes sp. 2 - - -
Polypedilum convictum - 8 4
P. illi.noense - + + - 1 - 2
P. halterale - 1
Phaenopsectra sp. + - -
Stenochironomus sp. -
Rheotanytarsus sp. 142 - 5 56 1264 48 287
PSicropsectra sp. - 1 -
Conchapelopia gr. - - 33 42 1 - -
Cricotopus/Orthocladius
C/0 sp. 1:Cricotopus biciactus 1 - - 117 28 - 19
C/0 sp. 5: :ricotopus nr. infus- - - - 1 8 - 36
catus
01/0 sp. 6:C. tremulus gr. sp. 2 2 - - 20 8 - 8
C/o sp. 14:C. c.f. cylindraceus - - 4

Piseon River Creeks
1 2 3 4 Richland Crabtree Fines
C/0 sp. 54:Orthocladius (0) nr. - - 4
clarkei
C/O sp. 3:Orthocladius - - - 4 - - 3
(Euorthocladius)sp.
Cardiocladius sp. 2 - - 79 45 1 27
Nanocladius sp. - 4 1 -
RheocricoLopus c.f. robacki 4 - +
Thienemaniella sp. - + 11
Eukiefferiella bavarica gr. - 1
E. discoloripes gr. 4 - - - - 2
E. brehmi gr.
MGLLUSCA
Physa sp. - 593 99 8 1 - -
Ferrissia sp. - 3 34 + - - 3
Gyraulus sp.
Goniobasis sp. + - - - - + -
HIRUDINEA
Mooreobdella melanostoma - 1 10 1
OLIGOCHAETA
Nais spp. - 959 - 4 36 - 5
Dero sp. - 6 - -
Pristina sp. - 31 - -
Limnodrilus spp. (immature) - 310 32 11
L. hoffineisteri - 123 80 1
Lumbriculidae - 1 - - 17 6 -
Enchytraeidae - - - 4
MISC.
Prostoma graecens 1 - - - 14 - 2
Hydracarina 2 - - -
Nematoda - + -
131