NC0003255_Monitoring proposal_20161128

PotashCorp
Helping Nature Provide
November 28, 2016
CERTIFIED MAIL
NCDENR - Division of Water Resources
1617 Mail Service Center
Raleigh, North Carolina 27699-1617
PotashCorp -Aurora
RECEIVE INCQUE /W
DEC 0 7 2015
Water Qoaiity
Perrpitting Section
PCS Phosphate is required, under Part III.G.3 of our NPDES Permit No. NC0003255, to
submit on or before December 1 a monitoring proposal which outlines the company's
plans for the next year's monitoring.
We will again support the Pamlico River grid sampling program performed by East
Carolina University.
The 2016 monitoring report will be forwarded to you after the first of the year. If you
have any questions on this matter, please me at [phone].
Sincerely,
ID, 4:;L��
D. Daniel Winstead III
Senior Environmental Engineer
PCS Phosphate
Attachments
PC:
Will Hart WaRO (w/attachment)
12-01-003-06 (w/attachment)
J. C. Furness (w/attachment)
1530 NC Hwy 306 South, Aurora, NC USA 27806 T [phone]
PotashCorp. I www.potashcorp.com

A PROPOSAL
for
Continued Support of Research on
PCS PHOSPHATE EFFLUENT AND WATER QUALITY MONITORING IN
THE PAMLICO RIVER ESTUARY, N.C.: 2017 Support
Submitted to: PCS Phosphate
Amount requested: $75,012
Contract period: 1 January 2017 - 31 December 2017
Date: 15 November 2016
Principal Investigator:
Enrique Reyes, Professor
Department of Biology/Institute for
Coastal Science and Policy
University Representative:
Cheryl Walters, Grant and Contract Officer
Office of Sponsored Programs

INTRODUCTION
With funds provided by PCS Phosphate, the Institute for Interdisciplinary Science and
Policy (ICSP), at East Carolina University (ECU) has maintained a Pamlico River water
quality monitoring program since July 1975. This program is one of the longest -running
intensive monitoring efforts for an estuarine ecosystem in the United States. The
principal objectives of the program are:
• To monitor the Pamlico River for the purpose of detecting any perturbations in water
quality that may occur in the vicinity of the PCS Phosphate facility near Aurora,
North Carolina.
• To assess the environmental significance of any water quality perturbations that may
be detected.
• To develop the ecological database that is required for environmental assessments in
the Pamlico watershed.
Water quality monitoring of the Pamlico River estuary will be continued during 2017,
using methodologies similar to those used in 2016. In addition, monitoring of the
dispersal of phosphorus and fluoride along four transects originating at the PCS
Phosphate outfall will be continued, with no changes from the 2016 protocol.
METHODOLOGY
HISTORY OFPAMLICO WATER -QUALITY MONITORING: A program of routine
measurements of Pamlico nutrients and related hydrographic parameters was begun in
1967 by Dr. John Hobbie at N.C. State University. That study, which continued through
1973, was supported by funds from two sources: 1) the Office of Water Research, U.S.
Department of the Interior, through the University of North Carolina Water Resources
Research Institute, and 2) Texas Gulf Sulfur Company. The initial objective was to study
the effects of phosphorus from the phosphate mining operation (Copeland and Hobbie
1972). Later, when it became obvious that phosphorus was not the only factor
controlling algal growth in the estuary, the scope of the project was broadened to include
nitrogen.
After the N.C. State University sampling ended, there was an 18 -month lapse until East
Carolina University began a new program in 1975. This program has run continuously
since then. In addition to these two long-term monitoring programs, there were two
research projects in the mid-1970s which produced significant amounts of nutrient and
hydrographic date (Kuenzler et al. 1979; Davis et al. 1978).
In terms of parameters measured, stations sampled, and analytical techniques employed,
there have been few changes in the program in recent years. In the early years, however,
more substantial changes took place. In 1967 only surface water temperature, salinity and
phosphorus concentrations were monitored. Bottom water temperature and salinity were
added in mid -1968, and surface and bottom water dissolved oxygen in late 1968. Then, in
mid -1969, Hobbie expanded the program again to include surface water pH, and two
surface water nitrogen fractions, ammonium and nitrate. Finally, in 1970, surface water
total nitrogen, total dissolved nitrogen, and chlorophyll a were added to the suite of
parameters analyzed. All these parameters except two have continued to be measured up
until the present. In 1985 surface water particulate nitrogen and particulate phosphorus

measurements were substituted for the total N and P analyses, but the totals can still be
computed by summation of the dissolved and particulate fractions. Beginning in January,
1988, total fluoride analyses (surface water) became a part of the program. Bottom water
samples for nutrient, chlorophyll a, and fluoride analyses have been collected since
January 1989. The hydrographic sampling (salinity, temperature, and dissolved oxygen)
was expanded in January 1991 to include measurements throughout the water column at
0.25-m depth intervals. Finally, in January 1988, we began periodic sampling for
phosphorus and fluoride concentrations along four transects radiating outward from the
PCS Phosphate outfall.
Estuarine sample station locations also changed frequently in the early years (1967-
1975), but less in more recent times. Generally, the number of stations was highest in the
1960s and early 1970s, ranging between 30 and 40. At the beginning of the ECU program
in 1975, there were only 12 stations. Except for a station near the mouth of South Creek,
all were at mid -channel in the Pamlico River. In July1976, several new sampling stations
were added. These additional stations were established to provide data on water flowing
into the Pamlico from the river's major sub -tributaries. One other site was added in
January 1977, raising the total number of stations to 20. In January 1988 a Tar River
sampling station was added; it is located about 10 km above Washington at Seine Beach,
near Grimesland, NC. The last changed occurred in January 1993, when the total number
of stations sampled was reduced to 11.
The nominal sampling interval was approximately every two weeks up until 2007, when
it switched to every three weeks. Poor weather and mechanical breakdowns of the
sampling vessels (18-24 ft. outboard powered boats) are typically the causes for
postponed sampling.
Analytical techniques have changed more for the nutrients than for the hydrographic
parameters. The trend has been to use nitrogen and phosphorus chemistries that are
commonly used by estuarine ecologists and oceanographers, rather than those employed
by workers in the field of wastewater treatment. The former are better suited for detecting
the low concentrations sometimes found in the Pamlico. Changes - a few major, but
mostly minor - have been incorporated into the Pamlico work as they have become
generally accepted. More details regarding changes in the Pamlico sampling and
analytical methods can be found in Stanley (1988, 1993) and Stanley and Nixon (1992).
METHODS TO BE USED IN 2 017.-
1. Pamlico River Estuary Water Quality Monitoring:
Ten stations in the estuary and one on the Tar River will be sampled in 2017 (Table 1).
Sampling trips will be made every third week. Temperature, salinity, and dissolved
oxygen will be measured at 0.1 m below the surface ("surface"), at 0.5 m above the
sediment -water interface ("bottom"), and at 0.5-m intervals between the "surface" and
"bottom" measurements. Photosynthetically available radiation will be measured at one-
half meter intervals from the surface to the bottom. Water samples for pH, chlorophyll a,
fluoride, nitrogen, and phosphorus will be collected.
These water samples will be taken in polyethylene bottles and stored inside an ice -filled
cooler for transport to the Environmental Research Laboratory at East Carolina
University in the afternoon. There, subsamples will be taken for the various analyses.

Precombusted glass fiber filters will be used to separate particulate and dissolved
fractions. The filtrate will be stored frozen in a polyethylene bottle for later analyses of
total dissolved phosphorus (TDP), dissolved orthophosphate (PO4-P), ammonia nitrogen
(NH4-N), nitrate nitrogen (NO3-N), and dissolved Kjeldahl nitrogen. The filter pads will
also be stored frozen for particulate nitrogen (PN), particulate phosphorus (PP), and
chlorophyll a determinations. Total fluoride analyses will be carried out using unfiltered
water samples. Techniques to be used for these analyses are summarized in Table 2.
Table 1. Locations of sampling stations in the Pamlico River Estuary.
No. Coordinates Location
1 N35021'00" -W76029'00"
lA N35°21'30" -W76°31'30"
3 N35022'23" -W76038147"
5 N35°24'01" -W76°44'18"
6 N35023'12" -W76046'07"
Between Pamlico Point and Rose Bay
Between Abel Bay and Cedar Island
Lighted marker "3" off Indian Island
Between 5N and 5S
TG Outfall
7
N35025'50" -W76050'30"
Lighted marker "5" off Core Point
7S
N35023'58" -W76049'04"
Day marker "2" at Durham Creek
8
N35°27'10" -W76°55'10"
Lighted marker "7" at Mauls Point
10
N35°28'55" -W76°59'15"
Lighted marker "12" at Camp Hardee
12
N35°31'52" -W77°02'55"
Railroad Bridge
13
N35°33'30" -W77°11'00"
S.R. 1565 Bridge near Grimesland
Table 2. Summary of techniques to be used for chemical and physical measurements.
Parameter Technique Reference
Nutrients:
Total Dissolved
Phosphorus
Particulate Phosphorus
PO4-P
NH4-N
NO3-N
Dissolved Kjeldahl
Nitrogen
Particulate Nitrogen
Chlorophyll a
Fluoride:
Fluoride electrode
Hydrographic Data
Salinity
Temperature
Dissolved Oxygen
pH
PAR
Kjeldahl Digestion
Kjeldahl Digestion
Molybdate
Berthelot
Cadmium Reduction
Kjeldahl Digestion
Kjeldahl Digestion
Colorimetric
YSI Meter
YSI meter
YSI meter
Corning meter
LICOR quantum sensor
EPA (1979)
EPA (1979)
EPA (1979)
Solorzano (1969)
Strickland and Parsons
(1972)
APHA (1975)
APHA (1975)
Strickland and Parsons
(1972)
Orion (1987)
The Tar River station near Grimesland (at Seine Beach) will be sampled on the same
days as the estuarine stations. Surface grab samples will be taken for nitrogen,
phosphorus, fluoride, and chlorophyll a. Data from this station will help us to determine

more accurately the relative importance of nutrient inputs from the Tar River watershed
in comparison to inputs in the immediate vicinity of the Pamlico River estuary.
2. PCS Phosphate Effluent Dispersal Monitoring:
Effluent dispersal in the estuary will be monitored by measuring concentrations along the
same transects used in 2016 (see Stanley 1995). The 4 transects radiate outward from
PCS Phosphate Outfall 010 with 7 sample locations on each transect, at 50, 100, 200,
400, 800, 1600, and 3200 meters from the outfall (Figure 1). These 28 stations will be
sampled every 6 weeks.
At each location, surface and bottom dissolved oxygen, temperature, salinity, and pH will
be measured. If stratification is present, as evidenced by the presence of one or more of
the three conditions given in Table 3, then these 4 parameters will be measured at 0.5 -
meter depth intervals, from surface to bottom.
D
rr
rr
rr
rr
rr
0 1 600 rrrr
rr
METERS
Figure 1. Map showing locations of four sampling transect

Water samples from the surface and bottom of the water column at each station and a
sample from the outfall canal will be collected during each sampling period and analyzed
for total phosphorus and total fluoride by methods given in Table 2.
Table 3. Water column stratification criteria. For sampling purposes, the water column
is considered stratified if one or more of the following conditions exist.
Parameter Condition
Dissolved Oxygen The bottom measurement differs from the
surface measurement by 40% or more, or if
either measurement is 5.0 mg/l or less.
Salinity The bottom measurement differs from the
surface measurement by more than 50%.
Temperature The surface and bottom water measurements
differ by more than five (5) Celsius degrees
REFERENCES
American Public Health Association. 1975. Standard methods for the examination of
water and wastewater. American. Publ. Health Association., New York.
Copeland, B.J. and J.E. Hobbie. 1972. Phosphorus and eutrophication in the Pamlico
River estuary, NC, 1966-1969 - a summary. University of North Carolina Water
Resources Research Institute, Report No. 65. Raleigh. 86 pp.
Davis, G.J., M.M. Brinson, and W.A. Burke. 1978. Organic carbon and deoxygenation
in a coastal plain estuary: phytoplankton growth in large scale continuous cultures.
University of North Carolina Water Resources Research Institute, Report No. 131.
Raleigh. 123 pp.
Environmental Protection Agency, 1979. Methods for chemical analyses of water and
wastes. EPA -600/4-79-020.
Kuenzler, E.J., D.W. Stanley, and J.P. Koenings. 1979. Nutrient kinetics of
phytoplankton in the Pamlico River, North Carolina. University of North Carolina
Water Resources Research Institute, Report No. 139. Raleigh. 155 pp.
Orion Research Inc. 1987. Model 94-09, 96-09 Fluoride Combination Fluoride
Electrodes Instruction Manual. Orion Research Inc., Boston, MA. 37 pp.
Solorzano, L. 1969. Determination of ammonia in natural waters by the
phenylhypochlorite method. Limnol. Oceanogr. 14:799-801.
Stanley, D.W. 1988. Water quality in the Pamlico River estuary, 1967-1986. Institute for
Coastal and Marine Resources, East Carolina University, Technical Report No. 88-
01. Greenville, NC. 199 pp.

Stanley, D.W. 1990. Report on water quality and sediment analyses, in support of the
Environmental Impact Statement for the Texasgulf, Inc. mine continuation. Report
prepared for CZR, Incorporated. 199 pp.
Stanley, D.W. and S.W. Nixon. 1992. Stratification and hypoxia in the Pamlico River
estuary. Estuaries 15:270-281.
Stanley, D.W. 1993. Long-term trends in Pamlico River estuary nutrients, chlorophyll a,
dissolved oxygen, and watershed nutrient production. Water Resources Research
29:2651-2662.
Stanley, D.W. 1995. Texasgulf effluent dispersal in the Pamlico River estuary: 1994. East
Carolina University, Institute for Coastal and Marine Resources, Technical Report
95-01. Greenville, NC. 33 pp.
Strickland, J.D.H. and T.R. Parsons. 1972. A practical handbook of seawater analyses. J.
Fish. Res. Bd. Canada 167:1-311.