07-01_13_Redacted

PCS
Phosphate VAURORA
PCS PHOSPHATE COMPANY, INC.
RO. BOX 48, AURORA, NC U.S.A. 27886 DIRECT: [phone] FAX: [phone]
B. A. Peacock
Manager December 27, 1999
Environmental Affairs
Mr. David Franklin
Regulatory Branch
Wilmington District Corps of Engineers
P. O. Box 1890
Wilmington, North Carolina 28402-1890
Re: PCS Phosphate Company, Inc,
Department of the Army Permit No. 198800449
Cadmium Study Program
Dear Mr. Franklin:
Special Condition No. 2 of the captioned Permit required that PCS Phosphate implement a
cadmium contamination study to look at cadmium levels resulting from land reclamation
activities. PCS Phosphate contracted with the consulting firm of CZR Incorporated (CZR) to
coordinate the study. To assist CZR in this study, PCS Phosphate and CZR selected two of the
nation's foremost metals researchers, Dr. John Trefry of the Florida Institute of Technology in
Melbourne, Florida, and Dr. Terry Logan of Ohio State University in Columbus, Ohio.
Enclosed please find the report resulting from this study entitled "Final Report for the Cadmium
and Other'Metals Study. on and Adjacent to PCS Phosphate Reclamation Areas (R-1, R-2, R-3,
and the Charles Tract)". As per a North Carolina Division of Land Resources condition in our
Mine Permit No. 7-1, this report is required to be submitted by January 1, 2000, with an
earthworm study addendum to be submitted by April 1, 2000.
If you have any questions regarding this report, please call Jeff Furness at [phone] or e-
mail at 'farness cs hos hate.com .
Sincerely,
B. A. Peacock, Manager
Environmental Affairs
BAPIJCF:pwo
Enclosures

PC: (all w/encl.)
Charles Gardner - NCDLR
Tom Augspurger - USFWS
John Dorney - NCD WQ
Lee Pelej - USEPA, Region IV
Frank McBride - NCWRC
William Wescott - NCWRC
John Trefry - FIT
Terry Logan - OSU
T. J. Regan
W. A. Schimming
W. T. Cooper
M. T. Harris / I. K. Gilmore
D. J. Millman / R. Jenner
T. L. Baker / 00-17-000
J. C. Furness / 00-14-000
J. M. Hudgens
K. S. Karriker
15-04-006-08

d•�
t,

PCs AN 13 -00
Phosphate AURORA
PCS PHOSPHATE COMPANY, INC. OWLAND REFP.O. BOX 48, AURORA, NC U.S.A. 27806
Mr. Charles Gardner, Director
Division of Land Resources
North Carolina Dept. of ENR
P. O. Box 27687
Raleigh, North Carolina 27611-7687
Dear Mr. Gardner:
January 4, 2000
,,y�1, sAN 20 U
E
Please find listed below a Cadmium Study update for December-1999.
• The third (Day 90) renewal of soils for the earthworm study was conducted by Aqua
Survey, Inc. (ASI) on 9 December 1999.
• The fifth (Day 100) samples of earthworms for cadmium concentration analyses were
taken by ASI on 19 December 1999.
• By -;letter dated 27-December 1999, PCS Phosphate submitted a report entitled "Final
Report -'for the 'Cadmiiim`a6d`Other Metals Study on and Adjacent to PCS Phosphate
Rcclamatiori Areas (R-1, '•R-2, R-3 and the Charles Tract)" to the reviewing agencies.
This report covers all aspects of the study except for the earthworm study. An earthworm
study addendum is required to be submitted by 1 April 2000.
• The fifth and final round of soil sampling for the earthworm study was conducted on 28
December 1999.
If you have any questions, please do not hesitate to call me at [phone].
ii cerely,
47
QQ . C.7im,,0,.,
J ey Furness
Senior Environmental Scientist
PC: Tom Augspurger — USFWS
William Wescott — NCWRC
Floyd' Williams — DLR,' WaRO� -'
John Dorriey - DWQ `
W. A. Schimming
15-04-066-08
TLB / 00-14-000

Cadmium Study Report
Subject: Cadmium Study Report
Date: Mon, 03 Jan 2000 11:29:09 -0500
From: Charles Gardner <[e-mail]>
Organization: Division of Land Resources
To: [e-mail]
CC: Rick Wooten <Rick,[e-mail]>, Mell Nevils <[e-mail]>,
Tracy Davis <[e-mail]>
Jeff, I received my copy of CZR et al's cadmium report today. After
review, we'll keep that copy with the Land Quality Section's mining
permit file. I would appreciate having an extra copy for the Geological
survey Section of my division, for their review and library, as the
report contains some valuable geochemical information. Could you ask
CZR to send me another copy? If that's not convenient, just let me
know and we'll photocopy the one I now have. Thanks.
Best personal regards, and Happy New Year!
Charles
Charles Gardner, P.G. P.E. <charles. [e-mail]>
State Geologist and Director
N.C. Division of Land Resources
Department of Environment and Natural Resources
i of] 1/3/2000 1:01 PM

•
FINAL REPORT FOR THE CADMIUM AND OTHER METALS STUDY
ON AND ADJACENT TO PCS PHOSPHATE RECLAMATION AREAS
(R-1, R-2, R-3, AND THE CHARLES TRACT)
Prepared by:
CZR Incorporated, Wilmington, North Carolina
Dr. John Trefry, Melbourne, Florida
Dr. Terry Logan, Columbus, Ohio
Prepared for:
PCS Phosphate Company, Inc.
Aurora, North Carolina
Prepared for review by:
U.S. Army Corps of Engineers
U.S. Environmental Protection Agency
U.S. Fish and Wildlife Service
North Carolina Division of Water Quality
North Carolina Wildlife Resources Commission
North Carolina Division of Land Resources
0 December 1999

•
•
•
TABLE OF CONTENTS
COVER SHEET
Paqe
TABLE OF CONTENTS ................................................... ii
LIST OF FIGURES.......................................................iii
LIST OF TABLES.......................................................iii
LIST OF ATTACHMENTS..................................................iii
I. INTRODUCTION AND STUDY HISTORY ................................. 1-1
Il. REVIEW OF EXISTING DATA AND SPECIFIC STUDY OBJECTIVES ............... II-1
A. Review of Existing Data ....................................... II-1
1. Source Material, Soils, and Plants ........................... I1-1
2. Surface Waters and Sediments ............................ II-2
3. Fauna .............................................. 11-3
B. Specific Study Objectives .................................. II-3
Ill. SAMPLING AREAS AND STRATEGY .................................. III-1
IV. REFERENCES .................................................. IV-1

LIST OF FIGURES
Figure Page
1 PCS Phosphate Company, Inc. Reclamation Areas R-1 Through R-5 ............. III-2
2 Charles Tract Clay Ponds and NPDES-permitted Outfall Locations ............... III-3
3 Archbell/Kugler Tract Control Site .................................... III-4
LIST OF TABLES
Table Page
1 Sample location number and abbreviation cross-references III-5
LIST OF ATTACHMENTS
Attachment
A Metals in Source Material from the PCS Phosphate Facility at Aurora, North Carolina
B Trace Metals and Major Elements in Water, Suspended Solids, Sediment, Groundwater, and
Aquatic Organisms from the PCS Phosphate Facility in Aurora, North Carolina and the Pamlico
River Estuary
C Cadmium Concentrations in Soils, Plants, and Terrestrial Animals from the PCS Phosphate
Facility in Aurora, North Carolina
0

•
FINAL REPORT FOR THE CADMIUM AND OTHER METALS STUDY
ON AND ADJACENT TO PCS PHOSPHATE RECLAMATION AREAS
(R-1, R-2, R-3, AND THE CHARLES TRACT)
by
CZR Incorporated, Wilmington, North Carolina
Dr. John Trefry, Melbourne, Florida
Dr. Terry Logan, Columbus, Ohio
I. INTRODUCTION AND STUDY HISTORY
During the Environmental Impact Statement (EIS) process for the continued PCS Phosphate
Company, Inc. (PCS Phosphate} mine expansion, various federal and state agencies expressed
comments, questions, or concerns regarding potential metal contaminants, particularly cadmium, from
mining and reclamation activities. In late 1996, PCS Phosphate took the initiative to begin addressing
the agencies' comments. PCS Phosphate instructed the environmental consulting firm of CZR
Incorporated (CZR) to 1) summarize and evaluate all of the relative agency comments, 2) assemble a
study team, and 3) develop a cadmium and other heavy metals study to collect baseline information
to address the agencies' comments.
CZR previously collected extensive data for the EIS and is quite familiar with the PCS
Phosphate project area, receiving waters, plants, and animals. To assist CZR in the development and
implementation of the study, PCS Phosphate and CZR selected two of the nation's foremost metals
researchers, Dr. John Trefry of the Florida Institute of Technology in Melbourne, Florida, and Dr. Terry
Logan of Ohio State University in Columbus, Ohio. In addition to their own personal knowledge,
experience, and expertise, these university professors offered excellent laboratory facilities and
analytical personnel from their associated university laboratories.
CZR reviewed and summarized agency comments on metals, particularly cadmium, from the
EIS comments. These comments were reviewed by PCS Phosphate and Drs. Trefry and Logan. CZR
also assembled information on relevant project area -specific data, and distributed this information for
review by PCS Phosphate and Drs. Trefry and Logan. This information included reports, articles, or
theses such as:
• "PCS Phosphate Effluent Dispersal in the Pamlico River Estuary: 1996" by Donald W.
Stanley, Institute for Coastal and Marine Resources, East Carolina University,
Greenville, NC, February 1997.
• "Heavy Metal Pollutants in Organic -rich Muds of the Pamlico River Estuarine System:
Their Concentration, Distribution, and Effects Upon Benthic Environments and Water
Quality" by Riggs et al., 20 December 1989.
• "Albemarle - Pamlico Estuarine Study, Fish Tissue Baseline Study, 1989" by the N.C.
Department of Environment, Health and Natural Resources, Division of Environmental
Management, Water Quality Section, 31 May 1991.
• "Report on Water Quality and Sediment Surveys in Support of the Environmental
1-1

Impact Statement for the Texasgulf Inc. Mine Continuation" (Stanley 1990).
• "Draft Preliminary Risk Evaluation of Cadmium in PCS Phosphate Reclamation Lands
and Adjacent Areas" (U.S. Fish and Wildlife Service, Raleigh Field Office, August 1996
Draft).
• "Distribution of Cadmium and Selected Heavy Metals in Phosphate Fertilizer
Processing" (Wakefield 1980).
• "Summary of Cadmium Analyses Done by Dr. Steve Broome from 1990 to 1994 on
Plants from Charles Tract, R-1, R-2 and Natural Soil," April 1996.
• "1994 Annual Report: Radium - 226 Activity and Metal Uptake of Cover Crops Grown
on Phosphogypsum and Phosphatic Clay from a Phosphate Mine in North Carolina"
(Craft at al. 1995, Duke Wetland Center).
• "Phosphate Mining: Past Problems and PCS Phosphate's Progressive Solution Using
the Phosphogypsum and Clay Tailings Blend" (Thesis by Keith Richard Markland,
1996).
• "Phosphogypsum/Clay Blend for Mined Land Reclamation" (Thesis by William G.
Wescott, 1994).
An initial exhaustive literature review on metals toxicology was not conducted. Drs. Trefry and
Logan are at the forefront of the current state of knowledge on the subject; therefore, such a literature
review was deemed unnecessary. The point of the information assembly was to gather metals data
Anspecific to the project area so that issues that the study needed to address could be identified.
Following the review of existing data, PCS Phosphate, Dr. Trefry, Dr. Logan, and CZR met on -
site in Aurora on 21 March 1997, toured potential reclamation sample sites, discussed the available
data and data gaps, and began development of a scope -of -work (SOW) for the baseline study.
The general goal of the proposed baseline study was to gather up-to-date baseline information
on levels of cadmium in various components from the source materials through potential receiving
organisms. This included 1) source materials (clays, gypsum, sand tailings, bucket wheel spoil [BWS1,
clay/gypsum blend), 2) reclamation substrates, 3) water (surface water and groundwater), 4)
sediments, 5) plants, and 6) aquatic and terrestrial organisms. The more specific objective was to
gather data to determine if cadmium has bioaccumulated to potentially harmful levels in animals.
The SOW was developed in March and April 1997, and was reviewed and approved by PCS
Phosphate in May 1997. CZR initiated the study in May 1997 with the collection of samples of
potential sources of cadmium and other heavy metals. The source materials sampled were clays,
gypsum, sand tailings, BWS, and clay/gypsum blend from the PCS Phosphate mining and reclamation
program. Soil samples from the reclamation sites and a control site were collected in July 1997.
Water and sediment samples were collected in August 1997, followed by plant sampling in early
September. Aquatic organism sampling began in August, and terrestrial animal sampling began in
September.
On 27 August 1997, the U.S. Army Corps of Engineers (USACE) issued a Section 404 permit
for Alternative E to PCS Phosphate. The permit contained a special condition relative to cadmium.
0 1-2

Condition #2 reads as follows:
2. Within six months, the Permittee shall develop and implement
cadmium contamination studies and monitoring, subject to approval by
the USACE, in consultation with the North Carolina Division of Water
Quality, and USEPA with regard to water quality issues, and in
consultation with the North Carolina Wildlife Resources Commission,
and USFWS with regard to issues related to uptake by plant species,
and ultimate consumption by foraging wildlife. In the event the USACE
determines that the results of those studies indicate that remedial
action is necessary, the permittee shall implement any such remedial
action directed by the USACE.
This permit condition went into effect approximately nine months after PCS Phosphate had decided
to pursue such a study and assemble a project team, and about three months after the study sampling
had been initiated. In September 1997, PCS Phosphate provided the SOW to the USACE and this SOW
was submitted to the agencies listed in Condition #2. The SOW did not include such information as
goals, analytical methods, detection limits, and other such information, because these items had been
discussed and agreed upon in project meetings. However, such information was needed and requested
by the agencies. A meeting was held at PCS Phosphate's Land Office in Aurora on 3 December 1997.
The U.S. Fish and Wildlife Service (USFWS), N.C. Wildlife Resources Commission (WRC), and USACE
provided input and comments to PCS Phosphate and CZR. Also, the USACE provided written
comments on the SOW by the N.C. Division of Water Quality (DWQ) and the U.S. Environmental
Protection Agency (USEPA).
PCS Phosphate, CZR, and Drs. Trefry and Logan prepared a revised SOW to include information
isrequested by the agencies. A main point of the 3 December 1997 meeting was the need to mesh the
on -going study initiated by PCS Phosphate with the requirements and agency coordination specified
in the Section 404 permit condition #2. A revised SOW was submitted in February 1998 as the next
step in the coordination process (CZR et al. 1998). In April 1998, the USFWS provided PCS Phosphate
with written and verbal comments on the revised SOW. The following additions and changes to the
study were requested:
•
1) The various species of terrestrial invertebrates should be analyzed separately, and an
additional sample should be taken from each site.
2) Laboratory -based bioaccumulation studies using earthworms and site soils (supplemented
with organic matter) should be conducted to determine a site -specific bioaccumulation factor and a
steady-state earthworm tissue cadmium concentration that can be used in USFWS risk assessments
for shrews and vermivorous birds.
3) The livers and kidneys of shrews and cotton rats should be analyzed, rather than the whole
organism.
To address item 2), PCS Phosphate and CZR contracted Aqua Survey, Inc. of Flemington, New
Jersey to conduct a laboratory -based cadmium bioaccumulation study using earthworms. The
earthworm study is being conducted separately from the rest of the cadmium study, and a final report
on the earthworm study is due 1 April 2000.
1-3

II. REVIEW OF EXISTING DATA AND SPECIFIC STUDY OBJECTIVES
A. Review of Existing Data
1. Source Material Soils and Plants
Several researchers have investigated the potential impacts of cadmium and other
metals in the vicinity of PCS Phosphate. Because cadmium is concentrated in the ore, it is also
concentrated in the three by-products of the processing of the ore (sand tailings, clay, and
phosphogypsum). A study by the Tennessee Valley Authority (TVA) of the distribution of cadmium
and other heavy metals in phosphate fertilizer processing included data from PCS Phosphate (Wakefield
1980). The study confirmed that cadmium is present in all three ore processing by-products in levels
that exceed natural background concentrations at the ground surface. Cadmium levels were highest
in the clay (21 ppm) and lowest in the sand tailings (6 ppm). Because these processing by-products
are used to reclaim previously mined land, researchers have been interested in the potential for
bioaccumulation of cadmium on and near the reclaimed land.
Research led by Dr. Stephen W. Broome of North Carolina State University INCSU) has
investigated levels of cadmium in soils and plants on R-1, R-2, and the Charles Tract (Broome at al.
1991, Broome unpublished data, Wescott 1994, Markland 1996). The soils aspect of the research
found that DTPA-extractable cadmium (approximately equal to plant available cadmium) levels in the
clay -gypsum blend soil of R-1 ranged from 1.2 to 6.0 ppm (Wescott 1994). Natural background levels
of cadmium in soil are typically less than 1.0 ppm (Wescott 1994). DTPA-extractable cadmium levels
declined with depth in the soil profile and distance from the sand tailings dike. Wescott (1994)
attributed this finding to anaerobic soil conditions, which cause cadmium to precipitate as insoluble
cadmium sulfide. This suggests that wet soils in the reclamation areas should have lower levels of
bioavailable cadmium.
The NCSU plant research investigated cadmium levels in agricultural crops, cover crops,
native vegetation, and planted trees on R-1, R-2, and the Charles Tract (Broome at al. 1991, Broome
unpublished data). Plant cadmium levels were also studied in greenhouse experiments that varied the
composition of the blend on which the plants were grown (Wescott 1994, Markland 1996). Cadmium
concentrations varied widely among sites, years, and plant species, but it was apparent that cadmium
had bioaccumulated in some species. Experimental additions of sand tailings to the blend reduced
cadmium uptake by rye while reducing growth slightly (Wescott 1994). However, additions of sand
beyond 20 percent by weight significantly reduced growth of sorgo-sudan without decreasing cadmium
uptake (Wescott 1994). Experimental additions of compost to the blend decreased growth of sorgo-
sudan without decreasing cadmium uptake. However, compost additions decreased cadmium uptake
by Swiss chard and crimson clover without affecting growth (Wescott 1994). This suggests that as
organic matter builds up in the reclamation area soils over time, bioavailability of cadmium should
decrease. Experiments with varying the gypsum to clay ratio produced conflicting results: cadmium
concentrations in winter rye increased as the gypsum content of the blend increased, but cadmium
concentrations in Swiss chard and sorgo-sudan decreased as the gypsum content of the blend
increased (Markland 1996).
Craft at al. (1995) conducted a greenhouse study of radium-226 and metals in German
millet and common bermudagrass grown on various gypsum -clay mixtures. Increasing the gypsum
content of the blend decreased cadmium uptake by bermudagrass and increased biomass production
by both species. Radium-226 activity and the concentrations of the other metals studied (nickel, lead,
and zinc) were not high enough to be of concern.
•

2. Surface Waters and Sediments
As part of the supporting information for the EIS, Stanley (1990) studied metal
concentrations in the waters and sediments in the PCS Phosphate vicinity. Metals levels in the Pamlico
River and South Creek waters were generally below state standards. High detection limits precluded
detailed study of patterns or comparisons with other regions. For the sediment data, Stanley (1990)
found that most of the water bodies studied were enriched with cadmium and several other metals,
relative to crustal composition. He noted that this enrichment was consistent with enrichment found
in other southeastern estuaries. Sediment samples taken within the Charles Tract clay ponds showed
significantly higher levels of cadmium, chromium, and nickel than did samples from area creeks and
the Pamlico River. To put the data into perspective, Stanley (1990) compared average sediment metals
concentrations (silt -clay normalized) for all Pamlico -South Creek stations in the PCS Phosphate vicinity
to data collected by the National Oceanic and Atmospheric Administration (NOAA) from 175 estuarine
sites around the continental United States. The metals compared were arsenic, cadmium, chromium,
copper, lead, mercury, nickel, and zinc. For all metals except cadmium, the Pamlico -South Creek data
set ranked 170 or lower. For cadmium, the Pamlico -South Creek data ranked 25. Stanley concluded
that the data probably indicated an anthropogenic enrichment of cadmium.
Riggs et al. (1989) studied heavy metals in the sediments of the Pamlico River and its
tributaries, including areas near PCS Phosphate. They found that the sediments in the middle Pamlico
River near PCS Phosphate and in South Creek were enriched, relative to the rest of the estuary, with
cadmium and several other metals. The area of enrichment in the middle Pamlico roughly corresponds
to PCS Phosphate's main process water outfall. The area of enrichment in South Creek corresponds
to the site where a PCS Phosphate clay pipeline ruptured in 1985. Riggs et al, (1989) compared the
samples from the Pamlico with the highest concentrations of metals to average sediment
concentrations of metals in three Northeastern estuaries that have elevated levels of metals. Jones
Bay (near the mouth of the Pamlico River) was included in the comparisons as a reference. Several
samples from the middle Pamlico River and one sample from South Creek were found to contain
cadmium concentrations that were comparable to the average cadmium concentrations in the
Northeastern estuaries. These comparisons are somewhat misleading because they single out the
Pamlico and South Creek stations with the highest concentrations and compare them to the average
concentrations in the Northeastern estuaries. This tends to overstate the relative level of cadmium in
the Pamlico/South Creek samples. If the average concentrations are compared, the middle Pamlico and
South Creek samples appear to fall somewhere between the reference estuary and the estuaries of the
Northeast.
An important consideration to remember when reviewing existing sediment data is its
usefulness in evaluating the potential for future metal enrichment of the sediments due to current and
future land reclamation activities. Riggs at al. identified two areas of enrichment in the PCS Phosphate
vicinity. One area, near the middle of South Creek, is due to the 1985 rupture of the pipeline that used
to carry mill clays to the Charles Tract clay settling ponds.' Because PCS Phosphate now uses mill
clays in the reclamation process, the pipeline has not been used in nearly 15 years and in fact is
unusable. Therefore, the metals enrichment in South Creek is not useful for evaluating the potential
for future metals enrichment due to land reclamation. The other area of enrichment, in the Pamlico
River near the PCS Phosphate plant site, appears to be associated with PCS Phosphate's main process
water discharge point. Prior to 1992, over the more than 30 years of PCS Phosphate's operation, this
discharge point has received process water from the mineral processing facilities, stormwater drainage
from the entire plant site and materials storage areas, as well as stormwater drainage from the
reclamation areas. Thus it is impossible to determine the extent to which drainage from reclaimed land
contributed to this area of enrichment. In 1992, a water recycle system was completed for the plant
site that recycles and recirculates all process water without discharging it.
II-2

3. Fauna
Very little information on metal concentrations in animal tissues exists for the PCS
Phosphate area. The North Carolina Department of Environment, Health, and Natural Resources
(DEHNR) collected baseline fish tissue data from many sites in the Albemarle-Pamlico'estuarine system
(DEHNR 1991). One sample site for this study was located in the Pamlico River near Garrison Point,
which places it on the western edge of Riggs et al.'s (1989) "area of enrichment" for the middle
Pamlico River. Composite samples of whole gizzard shad, filleted spot, filleted southern flounder, and
blue crab were taken at this site. Cadmium concentrations for all samples were below the 0.10 ppm
detection limit, and concentrations of other metals were either very low or below the detection limits.
The USFWS conducted a preliminary risk evaluation for terrestrial wildlife exposure to
cadmium on PCS Phosphate reclamation lands (USFWS 1996). This evaluation was based on many
assumptions and has never progressed beyond the preliminary draft stage, but at present it is the only
document that has addressed potential cadmium accumulation in animals at PCS Phosphate. Four
species were evaluated: short -tailed shrew, eastern cottontail, American woodcock, and northern
bobwhite. Probable dietary exposure concentrations were estimated based on the TVA source material
data (Wakefield 1980), previously published bioaccumulation factors for terrestrial invertebrates, and
the NCSU plant data (Broome unpublished data). Hazard quotients then were used to assess the
potential risk to the evaluation species. A hazard quotient is calculated by dividing the estimated
dietary exposure concentrations by the lowest observed adverse effect level (LOAEL). LOAELs were
estimated based on published LOAELs for similar species. A hazard quotient of one or greater was
interpreted as indicating a possible risk of adverse effects to the organism. All species except eastern
cottontail had hazard quotients greater than one.
The USFWS (1996) acknowledged that there were sources of uncertainty in the risk
evaluation. Whenever assumptions had to be made, worst -case assumptions were generally used so
that the evaluation would be as conservative as possible. No robust data set for soil cadmium
concentrations was available, and there were no site -specific bioaccumulation factors available for
terrestrial invertebrates. The soil data and the bioaccumulation factors were the most important
components of the dietary exposure calculations for the three species that were identified as potentially
being at risk.
B. Specific Study Obiectives
Based on the preceding review of existing data, the following specific objectives were
formulated for this study:
1) Determine the concentrations of cadmium and other metals in the source materials used in
land reclamation (phosphogypsum, clay, the current gypsum -clay blend, sand tailings and
bucketwheel excavator spoil). The TVA data are now 20 years old, do not provide information
on the blended gypsum and clay, and do not indicate the level of variability of metals
concentrations within each source material. There is a need to know the metals concentrations
in the currently used source materials and to have some idea of the variation within each
source material.
2) Determine the concentrations of cadmium and other metals in surface water and
groundwater near the reclamation areas. Because of high detection limits, the previous data
from the PCS Phosphate area are inadequate for assessing the potential for impacts to surface
or groundwater due to land reclamation. It was especially important to collect data from the
receiving waters around the Charles Tract in addition to receiving waters near the plant site
reclamation areas. This provided data from waters that receive runoff from reclaimed land, but
40 are not affected by stormwater and aquifer depressurization water discharged from the main
plant outfall. Observed concentrations were compared to concentrations from control sites and
II-3

data from other studies to determine the level of metals compared to background levels.
31 Determine the concentrations of cadmium and other metals in the sediments of water bodies
receiving runoff from the reclamation areas. The previous sediment data make no distinction
between metals enrichment due to land reclamation and metals enrichment due to other
sources. For this reason, it was important to collect data from receiving waters around the
Charles Tract in addition to receiving waters near the plant site reclamation areas. This
provided sediment data from waters that receive runoff from reclaimed land, but have not been
affected by process water discharged from the main plant outfall over many years. Observed
concentrations were referenced to aluminum and were compared to concentrations from
control sites and data from other studies to determine the level of metals compared to
background levels.
4) Determine the concentrations of cadmium and other metals in the rooting zone of
reclamation area soils. No previous soil metals data exist for R-2 and the Charles Tract, and
it is possible that leaching and other factors could have caused cadmium concentrations to
change since the NCSU data were collected on R-1. Observed concentrations were compared
to concentrations from control sites to determine the level of metals compared to background
levels.
5) Determine the concentrations of cadmium and other metals in wild plants growing on the
reclamation areas. Earlier studies concentrated mainly on test plots of agricultural crops and
non-native cover crops. However, long-term exposure of herbivorous and omnivorous wildlife
to metals is most likely to occur through the ingestion of native plants that colonize the
reclamation areas. Observed concentrations were compared to concentrations from the control
site for plant species common to the reclamation areas and the control site.
6) Determine the concentrations of cadmium and other metals in aquatic and terrestrial animals
commonly found on the reclamation areas and in nearby receiving waters. Whenever possible
for the terrestrial animals, observed concentrations were compared to previously published
tissue concentrations known to cause adverse effects in similar organisms. For the aquatic
animals that are important food sources for higher trophic level organisms or humans,
concentrations were compared to previously published data and to Food and Drug
Administration Levels of Concern. Tissue concentrations from reclamation areas were also
compared to tissue concentrations from control sites for species common to both sites.
11-4

III. SAMPLING AREAS AND STRATEGY
Before the baseline sampling program for metals, particularly cadmium, was initiated, existing
project area information was reviewed and answers to questions such as the following were
formulated:
• Which metals to sample?
• Which source materials to sample?
• Which plants or animals to sample?
• From which locations to sample?
• Location of a control site?
• Which analytical methods and QA/QC procedures to use?
• Lower detection limits?
The rationale was to conduct an up-to-date baseline sampling study in various environmental
components from the source materials to potential receiving aquatic and terrestrial animals. This
included source materials, soils, sediments, waters, plants, and aquatic and terrestrial animals. In
effect, this was a screening study to enable the team to identify potential problems and to focus on
areas where more study or monitoring might be warranted.
The three primary areas selected for sampling included:
1) PCS Phosphate reclamation areas, the adiacent Plant site, outfall canals, and
directly adjacent receiving waters (Figure 1). Sampling was conducted on R-1, R-2,
and the Porter Creek North Wetlands Reclamation Area, which are older and have
established vegetation and some wildlife use. Sediments, water, and aquatic
organisms were sampled from canals and outfalls on the perimeter of the reclamation
areas and from directly adjacent receiving waters of Porter Creek, Durham Creek, and
the Pamlico River.
2) Charles Tract clay ponds and directly adjacent receiving waters (Figure 2). The
Charles Tract clay ponds were started in the mid 1960s and clay ponds 1, 2, 3, 4A,
and 413 have been filled and reclaimed. These areas have the most well -established
vegetation and wildlife populations of any PCS Phosphate reclamation lands. Directly
adjacent receiving waters include Long Creek, Short Creek, South Creek, and Bond
Creek (including Flannigan Gut).
3) Archbell Kugler Tract control site (Figure 31. As a control site for comparison with
the reclamation areas, PCS Phosphate chose the 1,550-acre Archbell/Kugler Tract on
the north side of the Pamlico River. This property, owned by PCS Phosphate, is over
4 miles from the closest reclamation area (R-1) and is upstream from the plant site and
on the opposite (north) side of the Pamlico River. It occupies a similar topographic
position as the plant site and Charles Tract reclamation areas. It is on the shore of the
Pamlico River, is bounded by and drains into adjacent creeks (Duck Creek and Bath
Creek), and has soil types similar to those originally on the reclamation areas. It also
has typical silvicultural and agricultural uses as did the mine/plant site and Charles
Tract before development.
Table 1 provides descriptions of all locations sampled and the parameters sampled on the three
primary sampling areas. Table 1 also cross-references location descriptions to sample location numbers
and abbreviations used in the final reports submitted by Drs. Trefry and Logan.
Specific sampling methodologies and discussions of the results are contained in the final reports
submitted by Drs. Trefry and Logan. These reports are attached in their entirety. Attachment A is

•
•
�i
t
0 3000 6000
scALC i" reer FIGURE 1. PCS PHOSPHATE COMPANY, INC.
RECLAMATION AREAS R-1 THRU R--5

CA)
S.L. PASCHALL
PCs
Phosphatee AURORA DIVISION
DRAWNG TITLE
CHARLES TRACT CLAY PONDS AND NPDES-PERMITTED I
OUTFALL LOCATIONS
FIGURE 2
Mrs
7PCNNG
;INEERING DATE:
JOB No. 1013195
SCALE:
1'=z5ff
DRAWNG No.
AOG- 000- 070

11
•
•
JV
;.`'`; �e •
' f I w r
1 rr N'—I;ea/�
To
Banners
Pt
Han
A. tc
4.
CQ
17 co.
Ir
,. ..,Cool P! .y U�LER'TRA
Nino,
"r+.
`.toFad Beasley _
Ar
n \� \•..� Pie. �p�a
-c � `• ' Mina �..
�_ 1.�.. •1 l CrM1
xa Plum Pt _S
P.M —'-"
• Linty T�
. Hawkins tsndiaa'/"'jr
r•, `\ .� tee_ 6rih0 r`1�s�. •i, ,L, .
,tad +'=may �• ..
.."
1
P R
0 3000
SCALE IN FEET O
FIGURE 3. ARCH BELL/KUGLER'TRACT CONTROL SITE
II!-4

0 Table 1. Sample location number and abbreviation cross-references.
•
•
Number or Number or
abbreviation used abbreviation used Parameters
Location in Trefry report in Logan report sampled'
Reclamation Plant Site and Adiacent areas
Canal draining from R-1 to Outfall 007
Outfall 007
Durham Creek near EIS station 42
Porter Creek near EIS station 47
Porter Creek North Wetlands
Reclamation Area
Outfall 101 canal below R-2
Reclamation Area R-1
Reclamation Area R-2
Reclamation Area R-3 (north)
Reclamation Area R-3 (south)
Pamlico River near PCS barge slip
Groundwater well near R-1
Groundwater well near R-3
Plant site lawn near calciners
Plant site runway
Charles Tract and ad'acent areas
Short Creek
South Creek near Short Creek
South Creek near the mouth
Long Creek
Flannigan Gut
Clay Pond 1
Clay Pond 2
Clay Pond 4A
1
W,D
2
Outfall 007
W,D,A,T
3
W,D,A
4
Porter Creek
W,D,A,T
5
PCN
W,D,L,P,A,
T
6
Outfall101
W,D,A,T
R-1
L,P,T
R-2
L,P,T
R-3 North End
R-3
W,D,T
R-3 South End
W,D
22, 22A
W,D,A
GWM 28
G
GWM 48
G
Plant site lawn
T
Runway
T
7
W,D,A
7A
A
12, 12A
W,D,A
S
W,D,A
9
Flannigan Gut
W,D,A,T
CP1
L,P,T
CP2
T
CP4A
T
Ill-5

Table 1. (concluded)
Number or
Number or
abbreviation used
abbreviation used
Parameters
Location
in Trefry report
in Logan report
sampled'
Charles Tract and adjacent areas (continued)
Clay Pond 4B
CP413
L,P,T
Clay Pond 5A outfall
11
D
Clay Pond 5A
11 (5A)
CPSA
W,D,A,T
Groundwater well outside Clay Pond 3
Charles Tract #1
G
Groundwater well outside Clay Pond 48
Charles Tract #2
G
Charles Tract dikes
CP dike
T
Archbell Ku ler control site and ad 'acent areas
Brickyard Pond on Archbell/Kugler site
15
W,D,A
Archbell/Kugler site -general
Archbell Point
A/K
G,L,P,T
Bath Creek
16
W,D,A,
Pamlico River adjacent to
ArchbelllKugler site
17
W,D,A
Duck Creek
18
W,D,A
Other control/comparison areas
Upper Bond Creek near EIS station 21
13
W,D,A
Pamlico River downstream from Indian
14
W,D,A
Island
Pamlico River near mouth of South
19
W,D,A
Creek
Mouth of North Creek
20
W,D,A
Pamlico River mid -river between plant
21
W,D
site and North Creek
Pamlico River mid -river between Bath
23
W,D
Creek and Durham Creek
11 W= surface water, G= groundwater, D= sediment, L = soil, P= plants, A= aquatic animals, T=
terrestrial animals
0 lil-6

•
•
"Metals in Source Material from the PCS Phosphate Facility at Aurora, North Carolina" by John H.
Trefry and Simone Metz. Attachment B is "Trace Metals and Major Elements in Water, Suspended
Solids, Sediment, Groundwater and Aquatic Organisms from the PCS Phosphate Facility in Aurora,
North Carolina and the Pamlico River Estuary" by Robert P. Trocine and John H, Trefry. Attachment
C is "Cadmium Concentrations in Soils, Plants, and Terrestrial Animals from the PCS Phosphate Facility
in Aurora, North Carolina" by Terry J. Logan.
III-7

•
IV. REFERENCES
Broome, S. W., Seneca, E. D., Campbell, C. L. Jr., and Hobbs, L. L. 1991. Establishment of
vegetation on gypsum/clay blend for mined land reclamation, 1989/90 Annual Report to
Texasgulf Inc.
Craft, C., Richardson, C. J., and Pilgrim, K. 1995. Radium 226 activity and uptake of cover crops
grown on phosphogypsum and phosphatic clay from a phosphate mine in North Carolina.
Report to Texasgulf Inc.
CZR Incorporated, Logan, T., and Trefry, J. 1998. Scope -of -work for the cadmium and other metals
study on and adjacent to PCS Phosphate reclamation areas (R-1, R-2, R-3, and the Charles
Tract). Prepared for PCS Phosphate Company, Inc., Aurora, NC.
Markland, K. R. 1996. Phosphate mining; past problems and PCS Phosphate's progressive solution
using the phosphogypsum and clay tailings blend. M. S. Thesis, North Carolina State
University.
North Carolina Department of Environment Health and Natural Resources. 1991. Albemarle - Pamlico
estuarine study fish tissue baseline study. Report No. 91-05.
Riggs, S. R., Powers, E. R., Bray, J. T., Stout, P. M., Hamilton, C., Ames, D., Moore, R., Watson, J.,
Lucas, S., and Williamson, M. 1989. Heavy metal pollutants in organic rich muds of the
Pamlico River estuarine system: Their concentrations, distribution, and effects upon benthic
environments and water quality. Report on Project No. 89-06 to the Albemarle - Pamlico
Estuarine Study, N. C. Department of Natural Resources and Community Development, Raleigh.
Stanley, D. W. 1990. Water Quality and sediment surveys. Final Report to CZR Inc.
Stanley, D. W. 1997. PCS Phosphate effluent dispersal in the Pamlico River Estuary: 1996. Institute
for Coastal and Marine Resources, East Carolina University, Greenville, NC.
U.S. Fish and Wildlife Service. 1996. Draft preliminary risk evaluation of cadmium in PCS Phosphate
reclamation lands and adjacent lands,
Wakefield, Z. T. 1980. Distribution of cadmium and selected metals in phosphate fertilizer processing.
TVA Publication Y-159.
Wescott, W. G. 1994. Phosphogypsum/clay blend for mined land reclamation. M. S. Thesis, North
Carolina State University.
IV-1

r�
ATTACHMENT A
METALS IN SOURCE MATERIAL FROM THE
PCS PHOSPHATE FACILITY AT AURORA, NORTH CAROLINA
•
by
John H. Trefry
and
Simone Metz
Florida Institute of Technology
0

•
METALS IN SOURCE MATERIAL FROM THE PCS PHOSPHATE
FACILITY AT AURORA, NORTH CAROLINA
John H. Trefry and Simone Metz, Florida Institute of Technology
ABSTRACT
Three different samples of five source materials (clay, sand tailings, bucket wheel spoil, gypsum and
clay/gypsum blend) from the PCS Phosphate facility at Aurora, NC, were analyzed for 66 elements.
The following four trace metals were enriched by 10-fold or more in at least one of the source
materials relative to average continental rocks (average enrichment factor noted in parentheses):
Silver in clay (26) and blend (11); Arsenic in clay (10); Cadmium in clay (45), sand (36), gypsum
(156) and blend (167) and Molybdenum in blend (14). To complement the trace metal data and
better understand the composition of each source substance, the major components of each material
(e.g., S'02, A1z03, CaSO4.2HZ0) also were determined. The collective information on the source
materials will be used to identify key elements for detailed study in the field portion of the program.
INTRODUCTION
PCS Phosphate Company, Inc. mines extensive deposits of phosphate on the south side of the
Pamlico River at Aurora, North Carolina. As the carbonate -apatite deposits are mined and processed
for phosphorus, several by-products are generated including sand tailings, residual clay and gypsum
(phosphogypsum). After a section of land is mined, the land is reclaimed using clay tailings and
gypsum. Phosphate rock and the resultant gypsum are naturally enriched in Cd. Wakefield (1980)
traced the movement of Cd during ore processing from rock to phosphoric acid and fertilizer,
showing that Cd was fairly evenly distributed between the useful fraction and waste material during
the overall beneficiation procedure. After the acidulation process (addition of sulfuric acid), one-
third or more of the Cd was contained in the gypsum with the remainder in filter -grade acid
(Wakefield,1980). Concern has been expressed by government regulators and environmental groups
about possible leaching of Cd from reclaimed soils with subsequent accumulation in terrestrial plants
and animals or transport to the Pamlico Estuary.
During 1997, a study was designed by CZR Incorporated, of Wilmington, NC, in conjunction with
scientists from Florida Institute of Technology and Ohio State University, to investigate the
distribution of Cd and selected trace metals in soils, terrestrial plants and animals, surface water and
groundwater from the PCS Phosphate property and for water, sediment and organisms from the
Pamlico River estuary. As the first part of that study, a detailed investigation of five source
materials was carried out. This chapter describes the results of the source study.
•

The source samples can be described as follows with abbreviated terms in parentheses:
1. Bucket wheel spoil material (BWE Spoil)
2. Sand tailings (Sand)
3. Clay (Clay)
4. Gypsum (Gyp)
5. A blend of clay and gypsum (Blend)
The focus of this source study was on material that forms soils in the reclamation areas. The bucket
wheel spoil is overburden removed from above the main phosphate rock deposit. Clay and sand
tailings are produced during the initial processing of the phosphate rock. Gypsum (phosphogypsum)
is a byproduct of the reaction of sulfuric acid with phosphate rock. Clay and gypsum are the main
components of surface soils in the blend reclamation areas with a typical distribution of 2-4 parts
gypsum to 1 part clay. A common practice is to build a dike with sand tailings and place a slurry of
gypsum and clay in the diked area and allow it to de -water. The de -watered blend is then used for
land reclamation. Samples of each type of source material were collected from three different,
representative sites.
METHODS
Samples of the various source materials were shipped in plastic bags to the Marine & Environmental
Chemistry Laboratories at Florida Institute of Technology and logged upon receipt. Initially, each
is source sample was carefully homogenized with a Teflon mixing rod. Once homogenized, each sample
was split into two separate aliquots. One bulk portion was archived for future reference and the other
portion was freeze-dried and set aside for analysis. The freeze-dried sand tailings were further
homogenized using a SPEX mixer mill.
For metal analysis, about 0.5 g of freeze-dried sample was completely dissolved in a Teflon beaker
using a mixture of high purity HNO3-HC104 HF acids in a multi -step process (Trefry and Metz,
1984). Total digestion of the sediments was preferred because then no doubt remained about the
absolute amount of metal associated with a sample. Because the gypsum and blend samples contained
a significant calcium component, these samples were initially leached with 2 mL concentrated HCl
and about 10 mL of distilled, deionized water (DDW) prior to completely digesting the samples. The
leachate was pipetted off and temporarily stored in 18-mL plastic vials to avoid formation of large
amounts of CaFZ precipitate during digestion. In the digestion process, 1 mL HCI04, 1 mL HNO3
and 3 mL BF were added to the sediment in a Teflon beaker and heated at 500C with a watch cover
in place until a moist paste was formed. The mixture was heated for another 3 hours at 800C with
an additional 2 mL HNO3 and 3 mL BF before being heated to dryness. The leachate for the gypsum
and blend samples was added to the Teflon beakers and the samples were dried. Finally, I mL HNO3
and about 30 mL DDW were added to the sample and heated strongly to dissolve perchlorate salts
and reduce the volume. The completely dissolved and clear samples were then diluted to 20 mL with

DDW. This method has been used successfully in our laboratory for many years. All samples except
the gypsum and blend material were completely dissolved by this technique. The small residue
remaining in the gypsum and blend (-2-3 mg or <1% of the total amount of material digested) was
most likely CaF2.
Initially, a scan for more than 50 elements was carried out using a Perkin-Elmer Model ELAN 5000
inductively coupled plasma -mass spectrometer (ICP-MS) operated in the TOTAL QUANT mode.
From our experience, this approach provides a broad spectrum of semi -quantitative data. Based on
the results of the scan and previously available data (e.g., Wakefield, 1980), concentrations of 21
elements were redetermined by a variety of methods to provide a high quality, quantitative data set.
These focal elements included the major components of the source materials along with trace
elements that were present at elevated levels in one or more samples or that were of particular
environmental interest.
Samples, reference standards and procedural and reagent blanks were analyzed by a variety of
techniques. Table 1 summarizes the instrumental methods used for each metal_ Matrix interferences
were carefully monitored for all elements using the method of standard additions. All our methods
are similar to EPA protocols with modifications needed to obtain lower method detection limits
(MDLs). Sample solutions, as well as reference standards and procedural and reagent blanks were
analyzed for Al, Ca, Cr, Cu, Fe, K, Mg, Na, Si and Zn by flame atomic absorption spectrometry
(AAS) using a Perkin-Elmer 4000 instrument. Silver and As concentrations were determined by
graphite furnace AAS using a Perkin-Elmer 5100 instrument equipped with Zeeman background
correction. Concentrations of Cd, Mo, Ni, Pb, Th and U were determined by ICP-MS using a Perkin-
Elmer model ELAN 5000 instrument in the quantitative mode with rigorous standardization.
Rhodium was used as the internal standard for ICP-MS analysis of Cd, Mo and Ni, whereas Au was
used as the internal standard for Pb, Th and U analysis.
Concentrations of Hg in source samples and reference standards were determined by heating separate
portions of undried material in acid -washed, polyallomer centrifuge tubes with 4 mL HNO3 and 2 mL
H2SO4. Sample tubes were heated for 1 hour in a 90°C .water bath and allowed to cool. Each tube
was centrifuged at 2000 rpm and the supernatant was decanted into a 25-mL graduated cylinder. The
sediment pellet was rinsed twice with 5 mL of DDW, each, centrifuged and decanted into the
graduated cylinder before diluting to a final volume of 20 mL with DDW. Mercury analyses were
carried out by cold -vapor AAS using a Laboratory Data Control Mercury Monitor.
Labware used in the digestion process was acid washed and rinsed three times with DDW. One
procedural blank and one duplicate sample were prepared with each set of source samples for trace
metals and Hg. In addition, one sample each of the Standard Reference Materials (SR.M) BCSS-1
and MESS-2, two marine sediment samples provided by the National Research Council (NRC) of
Canada, were also prepared with each batch of samples by the methods described above for trace
metals and Hg, respectively.
0

Table 1. Analytical instrumentation used for analysis of elements in source material.
Metal Method Detection Limit
Lowest Level in PC Phosphate
W/O
source material (µg/g)
Ag ZGFAAS 0.01
0.02
Al FAAS 200
2,000
As ZGFAAS 0.05
0.1
C NCS 500
1,400
Ca FAAS 5
13,400
Cd ICP-MS 0.01
0.1
Cr FAAS 1
11
Cu FAAS 2
2.3
Fe FAAS 5
1200
Hg CVAAS 0.001
0.005
K FAAS 5
200
Mg FAAS 0.5
20
MO ICP-MS 0.02
0.7
Na FAAS 2
300
Ni ICP-MS 0.02
2.1
Pb ICP-MS 0.01
0.4
Si FAAS 150
30,000
Th ICP-MS 0.001
0.3
U ICP-MS 0.001
1.1
Zn FAAS 1
8
CVAAS = Cold Vapor Atomic Absorption Spectrometry
FAAS = Flame Atomic Absorption Spectrometry
ICP-MS = Inductively Coupled Plasma -Mass Spectrometry
NCS = Nitrogen -Carbon -Sulfur Analyzer
ZGFAAS = Zeeman Graphite Furnace Atomic Absorption Spectrometry
' Determined by method outlined in U.S. Federal Register (1984)
Vol. 49, No. 209: 43430-43431.
4

For total organic carbon (TOC), a separate aliquot of source sediment was treated with concentrated
HCl and dried to remove any inorganic carbon (CaCO3) present. Once dry, the samples were re -
weighed to determine the increase in weight due to the addition of acid and resultant formation of
CaCIZ 2H2O. Then, approximately 10-20 mg of pre-treated sediment were weighed into tin cups and
combusted at 1020°C. The TOC content of the source samples was determined using a Carlo-Erba
NA1500 nitrogen -carbon -sulfur analyzer following the manufacturer's instructions. The TOC
concentrations were corrected to account for the increase in sediment weight. Precision was
determined by analyzing one source sample in triplicate. The accuracy of the TOC analyses was
obtained by analyzing SRM BCSS-1, certified by the NRC. Results obtained for SRM BCSS-1
agreed within the mean f standard deviation of the values reported by the NRC.
The CaCO3 content of the source materials was determined by the CO2 gasometric technique of
Schink et al. (1977) with standardization using pure calcium carbonate. Total P concentrations were
determined by UV -visible spectrometry following digestion with HC104 and HNO3 (Standard
Methods, 1989).
QUALITY ASSURANCE AND QUALITY CONTROL
Sample Tracking Procedure. Each sample received by the Marine & Environmental Chemistry
Laboratories at Florida Institute of Technology was carefully inspected to ensure that the sample bags
were intact and properly labeled.
Quality Control Measurements for Analyses For this program, quality control measures included
balance calibration, instrument calibration, standard checks, duplicate sample analysis, analysis of
standard reference material, procedural blank analysis and matrix spike analysis. With the analysis
of the source sediments, one procedural blank, one standard reference material (BCSS-1 for trace
metals and MESS-2 for Hg), one duplicate sample (triplicate for TOC), and one matrix spike for each
metal were analyzed.
Instrument calibration. Before instrumental analysis of source material digests by FAAS, ZGFAAS,
CVAAS, NCS or ICP-MS, a three- to five -point calibration curve was established and the linearity
of the individual analyte response factors checked. Every 5 to 10 samples, a calibration solution was
re -analyzed. If the relative standard deviations (RSD) for the initial calibration and subsequent
calibration were >15%, a new calibration curve was obtained and the affected samples were
reanalyzed.
Duplicate sample analysis To estimate precision of the analyses, a duplicate field sample was
analyzed with each batch of samples for trace metals and a triplicate sample was analyzed for TOC.
Standard reference material analysis. A common method used to evaluate the accuracy of
environmental data is to analyze standard reference materials, samples for which consensus or
"accepted" analyte concentrations exist. The marine sediment SRM BCSS-1 from the NRC was

analyzed for certified trace metal analytes (except Hg) with the source sediment samples. For Hg,
SRM MESS-2 was analyzed.
Procedural blank analysis. A procedural blank was processed and analyzed with each batch of
source samples in order to monitor potential contamination resulting from laboratory reagents,
glassware and processing procedures.
Matrix spike analysis A matrix spike sample (method of additions analysis) was run with each batch
of samples for every element. The results of the method of additions analysis provides information
on the extent of any signal suppression or enhancement due to the matrix. When necessary (spike
results outside 80-120% limit), samples were analyzed by methods of additions.
REsut,Ts AND DiscussioN
Overvieip
Concentrations of 56 different elements were determined in three different samples of the five source
materials. The results presented here are divided into two groups of elements as follows:
Group 1. 45 elements for which an ICP-MS scan suggested that further, more detailed
analysis was not necessary at this time.
Group 2. 21. elements for which more rigorous quantitative analysis was carried out.
The Group 2 elements include major components of the source material (Al,
Ca, Fe, K, Mg, Na, Si, P and C) that are often present at percent Ievels and
a variety of trace elements (Ag, As, Cd, Cr, Cu, Hg, Mo, Ni, Pb, Th, U and
Zn) that are either present at levels that are higher than in' average continental
crust or are metals that are commonly of environmental concern.
The overall results of this source study enhance the database for various source materials and served
to help guide subsequent field work for this project.
Multi -element Scan
Results from semi -quantitative analysis by ICP-MS for 45 elements are presented in Table 2. As a
screening tool, this approach allowed a general assessment of the magnitude of metal levels in the
various source materials. Concentrations of each element in the source material are compared with
average continental crust in Table 2 to help identify anomalously high values relative to common
rocks on Earth. Concentrations of the following 27 elements in all source samples were at or below
detection limits of 0.1 to 0.2 µglg and in most cases below levels for average crustal rock:
Ga, Ge, Ru, Rh, Pd, In, Te, I, Cs, Pr, Nd, Sm, Eu, Gd,
Er, Tm, Yb, Lu, Hf, Ta, W, Re, Qs, Ir, Pt, Au and Bi

Concentrations of 11 of these 27 elements (Ru, Rh, Pd, In, Te, Re, Os, Ir, Pt, Au and Bi) are at
levels as low as <0.001 µg/g in average continental crust and thus our detection limits using ICP-MS
scans are well above crustal abundances. A greatly enhanced analytical effort would be necessary to
determine actual concentrations of these 11 ultra -trace (<1 ppb) elements. However, based on the
limited potential for these elements to cause adverse biological effects, they were not given further
consideration at this time. In addition to the 27 elements discussed above, actual values from the
ICP-MS scan for 9 other elements (Sc, Ti, Mn, Co, Rb, Zr, Nb, Sn, and Ba) were below levels
reported for average crustal rock on earth (Table 2).
Based on the ICP-MS scans, concentrations of the following 9 elements were higher in some source
samples than in average continental crust (Table 2):
V (clay) Sr (all samples except sand) Y, Ce, La (gypsum, blend)
Sb (clay, blend) Tb, Dy, Ho (clay, gypsum, blend)
However, unlike the Group 2 elements that were considered for more detailed study, these 9 elements
were not at sufficiently elevated concentrations in the source material relative to crustal rocks to
warrant concern from an environmental perspective as elaborated below.
Vanadium levels in the PCS Phosphate clays (125 t 5 µg/g) were only about 30% higher than the
values reported by Wedepohl (1995) for average continental crust (Table 2) and are within the range
of typical values of 105-145 µg/g for marine sediments (Salomons and Forstner, 1984). A similar
trend is observed for Sb (Table 2, along with a value of 1.2 µg Sb/g for average marine sediment
from Salomons and Forstner, 1984).
Concentrations of Sr were enriched in all source samples, except the sand tailings (Table 2), with
levels of 946-1330 µg/g in the gypsum and blend relative to average crustal levels of 333 µg/g
(Wedepohl, 1995). This observation for the PCS Phosphate source materials is consistent with data
for Ca -rich sedimentary deposits because Sr can substitute easily for Ca in minerals due to its similar
size and ionic charge. For example, concentrations of Sr in marine phosphates range from 90-5000
µg/g (Altschuler, 1980). Strontium is abundant in seawater (8 mg/L) and is not considered to be an
element of environmental concern in the study area.
Concentrations of Y in the samples of gypsum (58 f 5 µg/g) and blend (51 t 5 µg/g) were about two
times higher than in average continental crust. This observation is again consistent with observed
enrichment of Y in Ca- and P-bearing minerals (20-1100 µg Y/g, Altschuler, 1980) and the ability for
Y to substitute for Ca in minerals due to similarities in ionic size and charge. Once again, Y is not
considered to be of environmental concern at these levels.

0 0 0
Table 2. Trace metal concentrations in PCS Phosphate source material as determined by ICP-MS scan.
Sample ID
Sc
Ti
v
Mn
Co
Ga
Ge
Rb
Sr
Y
(v9/9)
(N9/9)
(N9/9)
(N9/9)
(li9/9)
(N9/9)
(N9/9)
(p9/9)
(p9/9)
(N9/9)
Clay #1
4,0
2640
123
81
2.9
<0.1
<0.1
43
579
20
Clay #2
4.1
2800
130
83
3.1
<0.1
<0.1
45
611
21
Clay #3
3.8
2600
121
79
3.0
<0.1
<0.1
43
568
18
Sand #1
0.6
395
12
23
0.4
<0.1
<0.1
3
777
19
Sand #2
<0.1
408
8
20
0.3
<0.1
<0.1
3
478
13
Sand #3
<0.1
183
7
18
0.3
<0.1
<0.1
4
431
11
BWE Spoil #1
0.7
2080
17
101
1.8
<0.1
<0.1
13
153
4
BWE Spoil #2
0.9
2760
20
138
2.7
<0.1
<0.1
16
114
5
BWE Spoil #3
1.4
3020
24
139
2.7
<0.1
<0.1
18
144
6
Gyp3/4 #1
<0.1
613
3
15
0.2
<0.1
<0.1
1
1200
59
Gyp3/4 #2
<0.1
539
3
13
0.3
<0.1
<0.1
1
1120
53
Gyp3/4 #3 (117)
<0.1
1160
3
19
0.2
<0,1
<0.1
1
996
62
Gyp3/4 #3 (110)
<0,1
1190
3
19
0.2
<0,1
<0,1
<1
1040
65
Blend #1
0.6
1080
28
24
0.8
<0.2
<0.2
10
946
48
Blend #2
1.0
1090
34
28
0.8
<0.2
<0.2
12
1330
57
Blend #3
0.4
1250
22
28
0.6
<0.2
<0.2
7
1050
47
Ave. Cont. Crust*
16
4010
98
716
24
15
1.4
78
333
24
'Wedepohl (1995)

0 W 0
Table 2. (Continued) Trace metal concentrations in PCS Phosphate source material as determined by ICP-MS scan.
Sample ID
Zr
Nb
Ru
Rh
Rd
In
Sn
Sb
To
I
(lag/9)
(li9/9)
W/O
(N9/9)
(Ng/9)
(Fig/9)
(N9/9)
(N9/9)
(N9/9)
(N9/9)
Clay #1
89
7.4
<0.1
<0.1
<0.1
<0.1
0.6
1.6
<0.1
<0.1
Clay #2
109
7.4
<0.1
<0.1
<0.1
<0.1
1.0
2.4
<0.1
<0.1
Clay #3
56
7.3
<0.1
<0.1
<0.1
<0.1
0.5
2.1
<0.1
<0.1
Sand #1
44
0.8
<0.1
<0.1
<0.1
<0.1
<0.1
0.5
<0.1
<0.1
Sand #2
1
0.6
<0.1
<0.1
<0.1
<0.1
<0.1
0.1
<0.1
<0.1
Sand 03
1
0.3
<0.1
<0.1
<0.1
<0.1
<0.1
0.1
<0.1
<0.1
SWE Spoil #1
32
0.9
<0.1
<0.1
<0.1
<0.1
<0.1
0.1
<0.1
<0.1
BWE Spoil #2
80
6.4
<0.1
<0.1
<0.1
<0.1
<0.1
0.2
<0.1
<0.1
BWE Spoil #3
47
6.9
<0.1
<0.1
<0.1
<0.1
<0.1
0.2
<0.1
<0.1
Gyp3/4 #1
49
1.1
<0.1
<0.1
<0.1
<0.1
<0.1
0.3
<0.1
<0.1
Gyp3/4 #2
30
0.9
<0.1
<0.1
<0.1
<0.1
<0.1
0.4
<0.1
<0.1
Gyp3/4 #3 (117)
20
2.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
Gyp3/4 #3 (110)
5
2.4
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
Blend #1
20
2.3
<0.2
<0.2
<0.2
<0.2
<0.2
0.5
<0.2
<0.2
Blend #2
16
2.2
<0.2
<0.2
<0.2
<0.2
<0.2
0.8
<0.2
<0.2
Blend #3
18
2.3
<0.2
<0.2
<0.2
<0.2
<0.2
0.4
<0.2
<0.2
Ave. Cant. Crust'
203
19
0.0001
0.00006
0.0004
0.05
2.3
0.3
0.005
0.8
`Wedepohl (1995)
z

Table 2. (Continued) Trace metal concentrations in PCS Phosphate source material as determined by ICP-MS scan.
Sample ID
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
(pg/9)
(N9/9)
(Y9/9)
(N9/9)
(Nsf9)
(N9/9)
(N9/9)
(N9/9)
(pl'9)
(N9/9)
Clay #1
<0.1
133
20
41
<0.1
<0.1
<0.1
<0.1
<0,1
1.0
Clay #2
<0.1
147
22
42
<0.1
<0.1
<0,1
<0.1
<0.1
0.9
Clay #3
<0.1
135
20
39
<0.1
<0.1
<0.1
<0.1
<0,1
0.8
Sand #1
<0.1
33
13
24
<0.1
<0.1
<0.1
<0.1
<0.1
0.7
Sand #2
<0.1
32
9
16
<0.1
<0.1
<0.1
<0.1
<0.1
0.5
Sand #3
<0,1
34
8
15
<0.1
<0.1
<0.1
<0.1
<0.1
0.5
BWE Spoil #1
<0.1
134
10
22
<0.1
<0.1
<0.1
<0.1
<0.1
0.4
BWE Spoil #2
<0.1
162
13
33
<0.1
<0.1
<0.1
<0.i
<0.1
0.4
BWE Spoil #3
<0.1
171
11
29
<0.1
<0.1
<0.1
<0.1
<0.1
0.4
Gyp3/4 #1
<0.1
31
40
70
<0.1
<0.1
<0.1
<0.1
<0,1
2.2
Gyp3/4 #2
<0.1
32
36
58
<0,1
<0.1
<0,1
<0.1
<0.1
1.9
Gyp3/4 #3 (117)
<0.1
30
45
78
<0.1
<0.1
<0.1
<0.1
<0.1
2.7
Gyp3/4 #3 (110)
<0.1
29
46
80
<0.1
<0.1
<0.1
<0.1
<0.1
2.8
Blend #1
<0.2
58
29
48
<0.2
<0.2
<0.2
<0.2
<0.2
1.8
Blend #2
<0.2
68
41
70
<0.2
<0.2
<0.2
<0.2
<0.2
2.4
Blend #3
<0.2
51
34
58
<0.2
<0.2
<0.2
<0.2
<0.2
1.6
Ave. Cont. Crust'
3.4
584
30
60
6.7
27
5.3
1.3
4.0
0.6
*Wedepohl(1995)
10

0 9 9
Table 2. (Continued) Trace metal concentrations in PCS Phosphate source material as determined by ICP-MS scan.
Sample ID
Dy
Ho
Er
Tm
Yb
Lu
Hf
Te
W
Re
(N9/9)
(Y9/9)
(N9/9)
(N9/9)
(N9/9)
(N9/9)
(N9/9)
(P9/9)
(N9/9)
(N9/9)
Clay #1
6.0
1.1
<0.1
<0.1
<0.1
<0.1
<0,1
<0.1
<0.1
<0.1
Clay #2
5.4
1.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
Clay #3
5.0
1.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
Sand #1
4.4
1.0
<0. i
<0.1
<0.1
<0.1
<0.1
<0,1
<0.1
<0,1
Sand #2
2.8
0.7
<0. i
<0.1
<0.1
<0.1
<0.1
<0,1
<0. i
<0.1
Sand #3
2.3
0.6
<0.1
<0.1
<0.1
<0.1
<0,1
<0.1
<0.1
<0.1
BWE Spoil #1
1.9
0.3
<0.1
<0.1
<0.1
<01
<0.1
<0.1
<0.1
<0,1
BWE Spoil #2
2.2
0.4
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
BWE Spoil #3
2.4
0.4
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
Gyp3/4 #1
14
2.9
<0.1
<0.1
<0.1
<0.1
<0.1
<0,1
<0.1
<0.1
Gyp3/4 #2
13
2.9
<0.1
<0.1
<0.1
<0.1
<0.1
<0,1
<0.1
<0.1
Gyp3/4 #3 (117)
14
3.0
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0,1
Gyp3/4 #3 (110)
16
3.2
<0.1
<0. i
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
Blend #1
11
2.4
<0.2
<0.2
<0.2
<0,2
<0.2
<0.2
<0.2
<0.2
Blend #2
14
3A
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
Blend #3
11
2.9
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
Ave. Cont Crust*
3.8
0.8
2.1
0.3
2.0
0.35
4,9
1.1
1.0
0.0004
"Wedepohl (1995)
11

0 0 0
Table 2. (Continued) Trace metal concentrations in PCS Phosphate source material as determined by ICP-MS scan
Sample ID
Os
Ir
Pt
Au
Bi
(t'sf9)
(p9/9)
(I19/9)
(Y9/)
(N9/5)
Clay #1
<0.1
<0.1
<0.1
<0.1
<0.2
Clay #2
<0.1
<0.1
<0.1
<0.1
<0.i
Clay #3
<0.1
<0.1
<0. i
<0.1
<0.1
Sand #1
<0.1
<0.1
<0.1
<0.1
<0.1
Sand #2
<0.1
<0.1
<0.1
<0. i
<0.1
Sand #3
<0.1
<0.1
<0.1
<0.1
<0.1
BWE Spoil #1
<0.1
<0.1
<0.1
<0.1
<0.1
BWE Spoil #2
<0.1
<0.i
<0.1
<0.1
<0.1
BWE Spoil #3
Q.1
<0.1
<0.1
<0.1
<0.1
Gyp3/4 #1
<0.1
<0.1
<0.1
<0.1
<0.1
Gyp3/4 #2
<0.1
<0.1
<0.1
<0.1
<0.1
Gyp3/4 #3 (117)
<0.1
<0.1
<0.1
<0.1
<0.1
Gyp3t4 #3 (110)
<0.1
<0.1
<0.1
<0.1
<0.1
Blend #1
<0.2
<0.2
<0.2
<0.2
<0.2
Blend #2
<0.2
<0.2
<0.2
<0.2
<0.2
Blend #3
<0.2
<0.2
<0.2
<02
<0.2
Ave. Cont. Crust`
0.00005
0.00005
0.0004
0.0025
0.085
'Wedepohl (1995)
12

The two lanthanide elements La and Ce were present in samples of gypsum and blend at 30-50%
above values for average crustal rock (Table 2). However, each element was at levels that were well
below concentrations averaging about 100 µg/g for each in sedimentary marine apatite (Altschuler,
1980). Concentrations of three other lanthanides (Tb, Dy and Ho) were 4-5 times higher in the clay,
gypsum and blend relative to continental crust (Table 2). However, the maximum values observed
among the PCS Phosphate source samples were all less than the mean values in marine phosphorites
for Tb (3.2 µg/g), Dy (19.2 µg/g) and Ho (4.2 µg/g) as reported by Altschuler (1980). The
solubilities of these three rare earth elements are low and they are not considered to be metals of
environmental concern.
Major Element Composition
Although the main goal of this study was to investigate the distribution of Cd and other trace metals
in the source material, data for major elements in these substances help describe the overall matrix
with which these trace elements are associated. Concentrations of the following major elements were
determined for the 5 source materials: Al, C (inorganic and organic), Ca, Fe,1C, Mg, Na, P and Si
(average values in Tables 3 and complete data set in Table 4). Silicon is the most abundant element
(excluding oxygen) in the clay, sand and BWE spoil and Ca is the most abundant element in the
gypsum and blend (Table 3).
The elemental values from Table 3 were converted to the appropriate oxide, sulfate or other forms
to establish a mass balance (summation of total mass) for each source material (Table 3).
Concentrations of Al, Fe, K, Mg, Na, Si and P are expressed as oxides (Table 3) because oxygen is
40 most likely the dominant binding element in each case. Carbon content is presented as CaCO3 (from
direct measurement) and as organic matter. The organic matter value in Table 3 is. from loss on
ignition (LOI) at 550 °C (corrected for 200°C water) to account for the entire mass of organic matter.
Total organic C data also are available in Table 4. Values for percent water in Table 3 represent
water released at 105°C plus 200°C. The Ca content is presented as CaSO4, CaCO3 and/or CaO
due to the diverse source components containing Ca. The combined oxide, carbonate and sulfate
forms presented in Table 3 represent components of the particular source material, not the actual
mineral phase. However, this component -by -component accounting allows a generalized view of
the overall matrix with which Cd and other trace metals are associated.
Component summations for each of the five materials ranged from 92 to 109% , averaging 99 f 8%.
We did not try to create a strict I00°/o summation and we did not measure several elements, including
Cl, F, and N, that may comprise a significant fraction of the total material. These omissions may have
led to calculated total values of <100% for clay, sand and BWE spoil in Table 3. In contrast, for
gypsum and blend, the presence of Ca in a phase other than gypsum may reduce the observed
percentage to a value closer to 100%. Sulfur concentrations were not measured in these samples.
Thus, if we assume that the H2O content of the gypsum and blend is stoichiometrically in a 2:1 ratio
with the CaSO4, then the revised amount of CaSO4 is 70.8 and 55.2%, respectively (Table 3) . If the
Ca that remains after decreasing the amount of CaSO4 is calculated as CaO, then the revised totals
are 105 and 100%, respectively, for gypsum and blend (Table 3, values in parentheses). The data
0 13

Table 3. Average major element concentrations and summary of source components.
Source AI Ca Fe K Mg Na H2O Si P
Material (�} (°�) (°�} (°�) (�} (°�) (°�} f�) N
Clay
3.92
8.78
2.12
1.20
1.94
1.29
5.44
19.14
1.31
Sand
0.2
9.42
0.24
0.11
0.1
0.18
0.64
33.01
2.21
BWE Spoil
1.49
1.75
0.93
0.48
0.09
0.19
0.38
39.25
0.03
Gypsum
0.11
22.91
0.13
0.03
0.01
0.22
18.73
4.15
0.47
Blend
0.85
18.8
0.54
0.27
0.36
0.56
14.63
8.27
0.98
Source A1203 LOI' CaCO3 CaO Ca50+ Fe203 K20 MgO Na2O H2O Si02 P205 Total
Material M (°,6) M (%) M M (°i6) M M M (%) (%) M
Clay
7.41
5.27
14.31 4.27
-
3.03
1.45
3.22
1.74
5.44
40.94
3.01
90.1
Sand
0.38
0.74
8.79 8.26
--
0.34
0.13
0.17
0.24
0.64
70.62
5.06
95.4
BWE Spoil
2.82
0.67
4.37 --
-
1.33
0.58
0.15
0.26
0.38
83.79
0.08
94.6
Gypsum
0.21
1.65
-- -
77.82
0.18
0.04
0.02
0.30
18.73
8.88
1.08
109
(2.9)
(70.8)
(105)
Blend
1.62
2.41
- -
63.86
0.76
0.33
0.60
0.75
14.63
17.69
2.24
105
(3.6)
(55.2)
(100)
°LOI = Loss on Ignition at 5500 C.
14

presented in Table 3 provide a good overview of the components present in the different source
materials.
The diversity of major components in the source material is shown in pie diagrams for gypsum
(Figure 1), clay (Figure 2) and blend (Figure 3). These results show that the gypsum (Figure 1) is
at least 90% pure CaSO4.2H2O, with most of the residual accounted for by Si02. In contrast, the
clay shows a wide variety of components (Figure 2). The dominant constituents of the clay are Si02
and A1203 as would be expected. However, the sample also contains significant amounts of CaCO3,
organic matter (LOI) and P205 (Figure 2). The blend prepared from gypsum and clay is
predominantly CaSO4-2H2O (>75%) with the Si02 making up much of the balance (Figure 3). The
overall mixture of gypsum and clay in the average blend is about 3.5.1 (calculation based on 90%
gypsum in "gypsum", 70% gypsum in blend, and no gypsum in the clay). This calculated mixing ratio
of gypsum at 3.5 is compatible with ranges of 2-4 parts gypsum to l part clay reported by PCS
Phosphate.
The sand tailings are predominantly Si02 and Ca components (Table 3). The sand also had the
highest P20, content of the five source materials. The BWE spoil is even more S'02 rich than the
sand (Table 3) with the residual having a composition consistent with the clay fraction.
Cadmium and Trace Metals
Concentrations of Cd and 11 other trace metals (Ag, As, Cr, Cu, Hg, Mo, Ni, Pb, Th, U and Zn)
were determined by more rigorous quantitative analysis. These elements were chosen because
preliminary scans or previous work (e.g., Wakefield, 1980) showed them to be present in one or more
of the source materials at elevated levels or because they were of particular environmental concern.
Despite variable metal concentrations in the different source materials (Table 4), none of the source
materials were enriched with Cu (Figure 4), Hg, Ni, Pb (Figure 4) or Th relative to average
continental crust. Thus, these elements are unlikely to be introduced to the environment from the
PCS Phosphate facility at levels that would create adverse effects.
Cadnuum, a focal element of concern in phosphate minerals and in this study, was present at levels
as high as 21.8 µg/g in gypsum #1 and 20.9 µg/g in gypsum #2 (Table 4), more than 200 times
enriched relative to concentrations of 0.1 µg/g in average continental crust and the BWE spoil (Figure
5). In contrast, gypsum #3 contained about 4 µg Cd/g. These concentrations show the same degree
of Cd enrichment reported in previous data (Table 5) and are generally consistent with the distribution
of Cd between useful and waste products of the original ore. The clay, sand and blend also contained
elevated Cd levels (Table 4).
0 15

•
•
•
CaSO4
Gypsum
OI
Si02
Other
z0
P205
Figure 1. Pie diagram showing the major components of gypsum from the PCS
Phosphate facility at Aurora, N.C.
16

E
Si02
0 Fe203
Clay
A1203
LOI
'205
CaO K-Mg-Na Oxides
Figure 2. Pie diagram showing major components of clay from the PCS
Phosphate facility at Aurora, N.C.
17

•
•
•
CaSO4
Blend
Fe203
32
A1203
LOI
P205
K-Mg-Na Oxides
Figure 3. Pie diagram showing the major components of blend from the PCS
Phosphate facility at Aurora, N.C.
18

Table 4. Major element, trace metal, phosphorus, total organic carbon and calcium carbonate concentrations in source material from PCS Phosphate
source
A9
Al
As
Ce
Cd
Cr
Cu
Fe
Hp
K
M9
Mn
Na
Ni
Pb
Sf
Th
U
Zn
P
Total
CaCO3
Matarid
W9l91
N
Wv
M
O4ft)
(14M
(WO)
M
(tr9i9)
M
OWO)
(p9f9)
(%)
w9)
(PW
(NG191
lx)
Organic
(11)
Carbon
N
y
1A3
3.04
1 .1
9,87
4.0
329
22.6
2.17
0.08
1.22
201
9.9
1.43
10.2
1'5
19.4s
1.0
30
1 2
1.31
2,9
18.5
Clay 02
1.00.
4,00
10.0
8.95
4.6
352
227
2AS
0.08
1.23
1.97
9.9
1.33
10.2
IS
19.75
1.0
2,9
177
1.32
3.09
15.0
Clay03
1,i10
3.02
21.5
7.72
4.4
267
220
2.03
000
1.16
1.77
9.5
1.11
10.2
1.5
18.22
0.9
28
165
1.3t
3.24
11.4
Sand #I
Q14
0.21
5.8
13.E
3.0
3.9.2
O.o
0.31
0.01
0.11
0.14
1.8
0.25
4.8
0.5
35.20
0A
9.3
58.5
2.77
0.28
13.1
Sand 02
0.11
0.19
3.4
7.70
3,6
27.0
3.3
0.20
0.01
0.10
0.00
0.8
0.15
2.5
0.7
27.45
0,4
5.4
53.3
2.19
0.18
0.4
Sand 03
1111
0.20
26
0.72
3.5
21.9
3A
0.20
0.01
0.13
0.08
0.0
0.14
2.1
0.4
38.39
0.3
4.3
46.5
1.67
0,14
0.8
OWE Spoil01
0,03
1.27
0.1
1.78
0.1
14.1
2.3
0.65
0.01
0.42
0.06
1.2
0.15
3.0
44
38.93
26
t.4
8.4
0.03
0,15
4,3
OWE Spoil 02
0.02
1."
0.2
1.34
0A
18.7
2.3
0.92
0.01
0.40
0.09
0.7
0.18
3.8
5.1
39.08
3.0
1.1
11.3
0.03
0.10
2.8
BWE Spoil 03
0.03
1.77
0.3
2.13
0.1
20.7
3.3
1.03
0.01
0.53
0.11
0.9
0.24
4.7
5.8
39.14
3.3
1.4
17.4
0.04
0-20
49
GypY4IM
0.20
0.09
0.3
23.71
21.8
23.0
10.1
0.14
0.03
0.02
0.02
5.0
0.32
11.5
1.9
3.42
2.9
17.7
101
0.56
0.53
N.D.
Gyp3f402
0.85
0.10
9.2
21.93
20.9
18.0
9.8
0.13
0.03
0.03
0.02
5.1
0.32
11.2
1.9
3.03
2-6
17.0
104
0.05
0.53
N.D.
Gyp314 "a)
0.35
0.13
1.7
24.02
4.3
11.9
5.4
0.13
0.01
0.02
0.003
2.8
0.03
5.5
1.8
6.00
3.1
8.1
21.7
0.21
0.22
N.D.
Gyp314#*)
0.32
0.12
1.7
22.10
3.7
13.2
6.3
OA2
0.03
0.002
2.5
0.03
4.5
1.7
-
3.2
8.0
21.4
-
-
at" R1
0.78
0.86
13.0
MAO
17.0
70,8
13.6
0.53
0.04
0.29
0.30
14.0
0.39
1&5
3.6
7.20
3.8
17.1
101
0.01
1.07
N.D.
Bland 02
0.90
1.05
15.8
19.10
MAI
90.6
14.4
0-07
0.05
0.31
0.45
17.8
0.52
22.2
4.2
7.25
4.1
18.4
1t0
0.90
1.33
N.D.
Blend lea (a)
0.62
Q04
10.0
17.90
14.8
57.8
11.7
0.42
0,03
0.20
0,27
10.1
0.77
14.2
3.0
10.42
3.3
15.0
78.8
1,05
0.75
N.D.
Bled p3 (b)
-
-
--
-
-
-
-
-
-
-
-
-
-
-
-
10.30
-
--
-
-
-
h, QoL Coar
0.07
7.96
1.7
3.85
0.1
120
25.0
4.32
0.04
2.14
2.20
1.1
2.36
56.0
14.8
30.80
8.5
1.7
85,0
0.08
0.20
-
Results for Sedlrnent (Sod.) Standard Reference Meterta! (SR". Meant Standard Deviation.
(NRC + National Reaeerch Council of Cerrada). Values in porerd Ovals not certified.
Sad. SRM 0.08 8.27 13.8 0.57 0.28 112 1&1 3.37 0.09V 1.78 1.42 2.3 2.00 50.0 22,0 29.4 8.2 25 112 Z12 -
BCSS1
This Study
Sod. SRM 0.11 0.20 11.1 0.54 0.25 123 18.5 3.29 0.092" 1.80 1.47 (1.9) 2.02 553 22.7 30.9 (9) (3) 119 - 2.19 -
OCSS.1 30.03 20.22 11.4 30.05 30.04 314 12.7 30.10 to.009 30.03 to.14 30.10 13.0 13.4 t0.5 312 t0.09
NRC Certified
9Nedepohf (1995)
-SRM MESS-2 issued by the NRC was used for Hp.
19

•
•
30
q 20
1
V 10
0
16
12
=. g
4
0
Gyp l&2 Gyp 3 Clay Blend BWESpoil Send
Source Material
Gyp l&2 Gyp 3 Clay Blend BWESpoil Sand
Source Material
Figure 4. Graphs showing concentrations of Cu and Pb for source
material from PCS Phosphate at Aurora, N.C. Dashed lines show
values for average continental crust (Wedepohl, 1995).
20

•
30
q 20
-v
U 10
a
30
p 20
v
y
d 10
0
Gyp l&2 Gyp 3 Clay Blend BWESpoil Sand
Source Material
Gyp l&2 Gyp 3 Clay Max] BWESpoil Sand
Source Material
Figure 5. Graph showing concentrations of Cd and As for material from
PCS Phosphate at Aurora, N.C. Dashed lines show values for average
continental crust (Wedepohl, 1995).
0 21

0
Table 5. Summary of metal concentrations in original ore material and various by-products and related reclamation materials
Cd Cr
Cu
Ni Pb
U Zn
Al
Ca
Fe
PZOS
1
1
1 1
1 1
%
%
%
(0/0)
Rock feed
38 150
25
18 11
62 303
0.23
29.6
0.47
28.1
(Wakefield, ISM
Rock Concentrate
39 142
22
16 <1
93 287
0.21
27.3
0.43
26.2
(Waken. 19M
Sand Tailings
This study (Mean) 4 29 4 3 0.5 6 54 0.20 9.4 0.24 1.5
Waketlsld.IM 6 15 12 <1 <1 9 42 0.08 2.1 0.17 2.1
Gypsum
This study (High) 22 23 10 12 2 18 104 0.13 24 0.14 1.5
0-4 4 12 5 4 2 8 21 0,09 22 0.12 0.5
Wakefield.19W 14 26 11 8 17 22 45 0.03 22 0.05 1.3
Clay
This study (mean) 5 320 22 10 1.5 3 170 3.9 8.8 2.1 3.0
Bucket wheel spoil
This sway (mean) 0.1 18 3 4 5 1 12 1.5 1.8 0.9 0.08
Blend
This study (mean) 17 73 13 18 4 17 97 0.8 19 0.5 2.2
22

Zinc, an element usually associated with Cd, was present in the source materials at concentrations of
49.5-177 µg/g. Relative to continental crust, no enrichment of Zn was observed for sand -tailings,
BWE spoil and gypsum sample #3. In contrast, gypsum samples #1 and 2, blend and clay were 20-
170% enriched with Zn when compared with continental crust. Cadmium is usually associated with
Zn in common rocks and sulfide minerals (e.g., sphalerite, ZnS) at a ratio of several hundred to one,
whereas phosphate rocks have Zn/Cd ratios that are typically about 10/1 (Altschuler, 1980; Nathan
et al., 1997). Such enrichment of Cd, relative to Zn, in phosphate rocks is ascribed to analogous
behavior between Cd and P in seawater and organic matter (Bruland et aL, 1978; Altschuler, 1980).
By-products generated during processing of phosphate rocks such as sand, gypsum and blend all had
Zn/Cd ratios in the range of 5-15 relative to 40 to >100 in the clay and BWE spoil. The Zn/Cd ratio
may thus serve as a useful tracer of phosphate -derived material in local sediments.
Arsenic, as arsenate, shows analogous behavior to phosphate in aquatic systems and the observed As
enrichment in source material from the PCS Phosphate deposit is consistent with this process. Arsenic
was enriched by factors of about 10 in the clay and 5 in gypsum (#i and 92) relative to average
continental crust (Table 4 and Figure 5). As observed for Cd, gypsum #3 contained about five times
less metal than gypsum #1 and #2.
Concentrations of Cr were high only in the clay samples at 319 t 48 µg/g (Table 4 and Figure 6).
Relative to a crustal abundance of 126 µg Cr/g, the clay samples are about 150% enriched. All the
other source samples had Cr values <100 µg/g.
Silver was the second most enriched trace metal in the source material from this study with a maximum
enrichment factor of 27 in the clay relative to continental crust (Table 4 and Figure 7). The gypsum
and blend samples also were enriched with Ag (Figure 7). Marine phosphates show a similar degree
of enrichment with an average of 2 µg Ag/g (Altschuler, 1980). Silver is believed to be incorporated
into the original phosphate mineral via transport with organic matter or by adsorption from seawater.
Concentrations of Mo are enriched by factors of about 5 to 13 in the clay, gypsum and blend relative
to average continental crust (Table 4 and Figure 7). Finally, U, at concentrations as high as 18 µg/g,
is enriched in the gypsum, and thus the blend, by as much as about 11 fold relative to average
continental crust. However, these U values are considerably lower than average phosphate rock
values of 120 µg/g (Tooms et al., 1969).
0 23

•
•
400
300
all
200
V
100
0
200
a�
=L 100
N
0
Gyp 1&2 Gyp 3 Clay Blend BWESpoil Sand
Source Material
Gyp 1&2 Gyp Clay Blend BWESpoil Sand
Source Material
Figure 6. Graphs showing concentrations of Cr and Zn for source
material from PCS Phosphate at Aurora, N.C. Dashed lines show values
for average continental crust (Wedepohl, 1995)
24

•
•
•
tj
C
20
15
�- 10
0
5
0
Gyp 1&2 Gyp Clay Blond BWESpoil Sand
Source Material
Gyp I &2 Gyp 3 Clay Blend BWESpoil Sand
Source Material
Figure 7. Graphs showing concentrations of Ag and Mo for source
material from PCS Phosphate at Aurora, N.C. Dashed lines show
values for average continental crust (Wedepohl, 1995).
25

Conclusions
A database for 66 elements in three different samples of five source material from the PCS Phosphate
facility at Aurora, N.C., showed that the following elements were >I0-fold enriched in one or more
of the source material relative to average continental rocks:
Metal Material Average Enrichment Factor
Ag Clay 26
Blend 11
As Clay 10
Cd Clay 45
Sand 36
Gypsum 156
Blend 167
Mo Blend ' 14
In addition, concentrations of Ag in gypsum, As in blend, Cr in clay, Mo in clay, and U in gypsum and
blend were >5 times enriched relative to average continental crust. This information provides an
updated and enhanced data set that will be used to help identify the key metals for detailed study in
the field portion of this program.
0 26

References
Altschuler Z.S. 1980 . The eochemist r elements in marine phosphorites:
( ) g ry of trace e p osp orates. Part 1.
Characteristics, abundances and enrichment. In: Marine Phosphorites -Geochemistry,
Occurrence, Genesis. Society of Economic Paleontologists and Mineralogists, v. 29, pp. 19-
30.
Bruland K.W., Knauer G.A. and Martin J.H. (1978). Cadmium in northeast Pacific waters. LimnoL
Oceanogr. 23. 618-62 5 .
Nathan Y., Soudry D., Levy Y., Shitrit D. and Dorfman E. (1997). Geochemistry of cadmium in the
Negev phosphorites. Chem. GeoL 142: 87-107.
Salomons W. and F6rstner U. (1984). Metals in the Hydrocycle. Springer-Verlag, Berlin, pp.349.
Schink J.C., Stockwell J.H, and Ellis RA. (1978). An improved device for gasometric determination
of carbonate in sediment. J. Sed Pet. 48: 651-653.
Standard Methods for the Examination of Water and Wastewater (1989). American Public Health
Association, Washington, D.C., pp. 4-177.
Tooms J.S., Summerhayes, C.R. and Cronan D.S. (1969). Geochemistry of marine phosphate and
manganese deposits. 'Oceanogr. Mar. Biol. Ann. Rev. 7: 49-100.
Trefiy J.H. and Metz S. (1984), Selective leaching of trace metals from sediments as a function of
pH. Anal. Chem. 56: 745-749.
Wakefield Z.T. (1980). Distribution of cadmium and selected heavy metals in phosphate fertilizer
processing. Tennessee Valley Authority Publication.
Wedpohl K.H. (1995). The composition of the continental crust. Geochim. Cosmochim. Acta 59:
1217-1232.
is 27

0
ATTACHMENT B
TRACE METALS AND MAJOR ELEMENTS IN WATER, SUSPENDED SOLIDS,
SEDIMENT, GROUNDWATER AND AQUATIC ORGANISMS FROM THE
PCS PHOSPHATE FACILITY IN AURORA, NORTH CAROLINA AND THE
PAMLICO RIVER ESTUARY
•
by
Robert P. Trocine
and
John H. Trefry
Florida Institute of Technology
0

TRACE METALS AND MAJOR ELEMENTS IN WATER, SUSPENDED SOLIDS,
SEDIMENT, GROUNDWATER AND AQUATIC ORGANISMS FROM THE
PCS PHOSPHATE FACILITY IN AURORA, NORTH CAROLINA AND
THE PAMLICO RIVER ESTUARY
Robert P. Trocine and John H. Trefry
Florida Institute of Technology
ABSTRACT
Trace metal concentrations in water, suspended matter, sediment, groundwater and aquatic
organisms collected from the PCS Phosphate property in Aurora, N.C. and adjacent Pamlico River
estuary were measured to determine whether any enrichment related to ore processing and waste
remediation could be identified. Analysis of source materials used in reclamation of mined areas
indicated that Ag, As, Cd, and Mo were enriched in one or more of these materials, and thus
potentially available for geochemical and biological transfer. When appropriate, these elements as
well as Al, Cr, Cu, Fe, Se and Zn were analyzed in all sample types. Compared to control stations,
high concentrations of Ag, Cd, Cr, Mo, Se and Zn were limited to aquatic sediments on the PCS
Phosphate property. Concentrations of dissolved As, Cd, Cr, and Mo and particulate As, Cr, Mo,
and Zn in surface water samples collected on PCS Phosphate property were also found to be greater
than respective values from the control stations. Metal concentrations in groundwater varied from
site -to -site, but individual enrichments of Cd, Cr, Cu, Mo and Zn were observed. Anomalously high
metal levels in organisms were limited primarily to ponds on the PCS Phosphate property or adjacent
outfalls. Trace metal concentrations within the Pamlico River estuary were within the range of
values common to such environments.
INTRODUCTION
One concern in mining operations is disposal of residual material that remains after the commercial
product has been obtained. Reclamation of the overburden and residual solids are designed to
minimize and mitigate any possible environmental impacts. During 1997, PCS Phosphate Company,
Inc., initiated a study designed by CZR Incorporated, in association with Florida Institute of
Technology and Ohio State University to investigate the distribution of Cd and other selected
elements on the PCS Phosphate property in Aurora, North Carolina and in the adjacent Pamlico
River estuary. One aspect of this study was to determine whether Cd and other trace metals found
in source materials used in mined land reclamation were being transported to the estuary and
accumulating in sediment, water and organisms.
To address the aquatic portion of the study, the following samples were collected and analyzed for
trace metals by scientists from Florida Institute of Technology (FIT):
0

•
1. Sediment from water bodies on the PCS Phosphate property and from the
Pamlico River estuary.
2. Groundwater from the PCS Phosphate property.
3. Water and suspended sediment from water bodies on the PCS Phosphate
property and the Pamlico River estuary.
4. Aquatic organisms from the PCS Phosphate property and the Pamlico River
estuary.
Data from these samples are presented here by category in the order listed above. In each case, metal
concentrations are traced from the PCS Phosphate property to the estuary and more distant control
sites. The choice of elements for study were based on metal concentrations in five source materials
(clay, sand tailings, bucket -wheel spoil, gypsum and blend) from the PCS Phosphate Aurora facility.
Field sampling was conducted during August 1997 by personnel from FIT, with assistance from staff
from CZR Incorporated, and PCS Phosphate. Figure 1 shows the geographic setting of the study
area. For the purposes of discussion, the study area has been divided into the following areas: (1)
� .�l��
:*
t r
Bath
Creek
Creek
�,y�ItLWLMrr�S•vE�'i^Ya y; }�«�`f! ��_
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fy
�.Y rJ f 1�� �JJ����'<1}
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} F� i -�ri(, fw,f
�ih
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i� � 1 � liF2 ly•�N,�w.i E�:-N} ` .1 r �+�
i } YT Yf '' 1F�ilt'.1pMt41 4fG
i"R
^➢'Qii'ff�-
W tbid"'x
�ysC � �', w i ^'�. ✓ y!r u
rs.
t� 'w tK�
3
r• a
i n! s. k
w'
Muddy
#,
F
n'� r
�rr
Bond
Clay Pond
Figure 1. Study area with major geographic features indicated.

. the PCS Phosphate property (land and reclamation ponds between Porter Creek and the Clay Ponds),
(2) the southern creeks along the PCS Phosphate property which empty into the Pamlico River
(including Durham, Porter, South, Long, Short and Bond Creeks), (3) the main body of the Pamlico
River, and (4) a northern control area in the estuary (Duck and Bath Creeks).
METHODS
Metals in Sediments.
Sediment samples were collected using a stainless steel grab -sampler (Wildco Instruments). After
the grab sample was collected, the overlying water was siphoned off using a small plastic tube.
Surficial sediment (0-2 cm) was placed in a plastic snap -cap vial with a polypropylene spatula. The
samples were sealed with a layer of Parafilm® between the vial and the cap, labeled and stored at
4°C until return to FIT.
In preparation for metal analysis, each sediment sample was freeze-dried in a Labconco® Model 5
freeze -dryer and then homogenized with a Teflon® mixing rod to provide dry, powdered sediment
for acid digestion. Approximately 0.45 g portions of freeze-dried sediment and a sediment Standard
Reference Material (SRM) were totally dissolved in Teflon® beakers containing concentrated, trace
metal grade HF, HNO3 and HC104. Once the sediment samples were completely dissolved, the
clear/colorless solutions were transferred to graduated cylinders, diluted to 20 mL with distilled,
deionized water (DDW) rinses ofthe beakers and stored in acid -washed 30-mL polyethylene bottles.
Concentrations of Ag, Al, As, Cd, Cr, Cu, Fe, Mo, Se and Zn in the digested sediment samples, SRM
and procedural blanks were determined by flame atomic absorption spectrometry (FAAS) and/or
graphite -furnace atomic absorption spectrometry (GFAAS). Concentrations of Al, Cd, Cr, Cu, Fe
and Zn were determined by FAAS using a Perkin-Elmer® Model 4000 instrument. Sediment
concentrations of Ag, As and Se were determined by GFAAS using a Perkin-Elmer® Model
5100PC instrument with HGA-600 heated graphite furnace and AS-60 autosampler. Cadmium and
Mo concentrations in the sediment samples were measured by GFAAS using a Perkin-Elmer®
Model 4000 spectrometer equipped with an HGA-400 heated graphite furnace and AS-40
autosampler. In all cases, the instrument manufacturer's specifications were followed and adherence
to QA/QC requirements was maintained. The relevant Quality Assurance/Quality Control (QAIQC)
data are presented in Appendix 1.
Metals in Water.
Water samples from the study area were collected in acid -washed, low -density polyethylene bottles
prepared at FIT. These bottles were sealed in plastic bags and placed in cleaned coolers for transport
to the field. On -site, surface water samples were collected using a clean -hands technique where one
technician wearing powder -free gloves would carefully take the sample bottle from the plastic bag
held by another technician, hold it beneath the surface of the water, remove the bottle cap to partially
fill the bottle, shake and discard this water as a rinse, refill and seal the bottle under water, and return
the filled bottle to its labeled plastic bag. Water samples collected in the field by FIT personnel were
-

all kept cold until filtered through 0.4 µm pore -size, 47 mm diameter, polycarbonate filters
(Poretics®) within hours of collection. All filtration, subsampling and sample acidification took
place within a ,Class-100 laminar -flow hood using acid -washed vacuum filtration glassware,
polycarbonate filters, polyethylene bottles and Teflon® materials. Samples collected subsequently
by PCS Phosphate (September 1997) and CZR (March 1998) used FIT prepared materials and were
shipped cold to FIT where they were processed. Samples received at FIT were processed in a
laminar -flow hood in a cleanroom facility. All surface water samples analyzed for dissolved metal
concentrations were acidified immediately after filtration to pH <2 using Ultrex II® HNO3 Q.T.
Baker). The groundwater samples were not filtered and were acidified immediately after
subsampling.
Water parameters measured in the field included salinity, pH and concentrations of dissolved
orthophosphate. Salinity was determined using a Reichert -Jung® Model 10419 optical refractometer
and pH was measured using an Orion® Model 230A pH meter. Dissolved orthophosphate
concentrations were determined on freshly filtered, unacidified subsamples using the ascorbic acid
method (Clesceri et al.; 1989) with a Perkin-Elmer® Lambda 3B UVNIS spectrometer. Phosphate
was not determined on the groundwater samples shipped to FIT in September 1997 or March 1998,
because of the delay between sampling and processing.
Dissolved concentrations of As, Cd, Cr, Cu and Zn were determined at FIT following pre -
concentrations using the reductive precipitation procedure modified from Nakashima et al. (1988).
The method involves using ultra -high purity Pd, Fe and NaBH4 to precipitate the metals, filtering
the precipitate and redissolving the precipitate in Ultrex II® HNO3 and HCl. This procedure was
performed in a cleanroom facility using 400-mL aliquots of water and a seawater SRM, provided
by the National Research Council of Canada (NRC). The final extract volume of —4 mL was
equivalent to a 100-fold concentration of the dissolved metals prior to analysis.
Metal concentrations in the water samples, extracts, SRM and blanks were determined by FAAS,
GFAAS and/or inductively coupled plasma -mass spectrometry (ICP-MS). Concentrations of
dissolved As were measured by GFAAS using a Perkin Elmer® Model 5100PC instrument
equipped with an HGA-600 heated graphite furnace and AS-60 autosampler. Concentrations of
dissolved Cd were determined by ICP-MS using a Perkin-Elmer® ELAN 5000 spectrometer or
GFAAS using a Perkin-Elmer® Model 4000 instrument equipped with an HGA-400 heated graphite
furnace and AS-40 autosampler. Chromium and Cu concentrations were determined using both the
Perkin-Elmer® Model 4000 and 5100PC instruments in GFAAS configuration. Concentrations of
dissolved Zn were determined by FAAS using the Perkin-Elmer® Model 4000 AAS or by ICP-MS
using the Perkin-Elmer® ELAN 5000 spectrometer. Dissolved Mo levels in unextracted water were
measured by GFAAS using the Perkin-Elmer® Model 4000 system. In all cases, the instrument
manufacturer's specifications were followed and adherence to QA/QC requirements was maintained.
The relevant QA/QC data are presented in Appendix 2.
Total Suspended Solids.
Polycarbonate filters (Poretics®, 47 mm diameter, 0.4 µm pore -size) were acid -washed in 5N HNO3,
rinsed 3 times with DDW, dried and weighed to the nearest µg using a Sartorius® Model M3P, 6-
place electronic balance. The filters were weighed under cleanroom conditions, with controlled

temperature and relative humidity. Each filter was weighed twice in random order; a minimum of
5% of the filters were weighed in triplicate. Static effects on filter weight were controlled by the
placement of two 21DPo anti -static devices near the weighing -pan within the balance. The standard.
deviation in weights for each filter was required to be <2 µg for the value to be accepted. Weighed
filters were placed in tightly -sealed, acid -washed plastic petri dishes labeled with a unique
identification number, divided into lots of 20 filters and double bagged in plastic. Before leaving
the cleanroom, the filter lots were placed in a third plastic bag for handling during shipment. After
being used to filter water samples collected in the field, each filter was rinsed with three 10-mL
aliquots ofpH 8 DDW (Ultrex II® NH4OH) to remove residual salts before being vacuum -dried and
sealed in a plastic dish. Upon return to FIT, the filters were placed in the cleanroom, removed from
their plastic packaging, dried and reweighed as described above.
Metals in Suspended Solids.
Samples of suspended solids and milligram quantities of a sediment SRM, provided by National
Institute of Standards and Technology (MIST), were analyzed for Al, As, Cd, Cr, Cu, Fe, Mo and
Zn. Prior to analysis, complete digestion was carried out in stoppered, 15-mL Teflon® test tubes
to which Ultrex II® HNO3, HF and HCl were added. The sealed test tubes were placed in a heated
water bath where refluxing of the acids completely dissolved the particulates from the filters. After
digestion, the resultant solutions were transferred to acid -washed, 15-mL polyethylene bottles,
diluted to —6 mL with DDW rinses of the Teflon® test tubes, sealed, labeled and then stored in a
plastic bag until analyzed.
Metal concentrations in the suspended solids, SRM and blanks were determined by FAAS or
GFAAS. Aluminum, Fe and Zn concentrations were determined by FAAS using a Perkin-Elmer®
Model 4000 spectrometer. Arsenic values were determined by GFAAS using a Perkin-Elmer®
Model 5100PC instrument equipped with an HGA-600 heated graphite furnace and AS-60
autosampler. Concentrations of Cd, Cr and Cu were obtained by GFAAS using both the Perkin-
Elmer® Model 5100PC instrument and Perkin-Elmer® Model 4000 instruments. Molybdenum
levels were determined by GFAAS using the Perkin-Elmer Model 4000 system. In all cases, the
instrument manufacturer's specifications were followed and adherence to strict QA/QC requirements
was maintained. The relavent QA/QC data are shown in Appendix 3.
Metals in Organisms.
During the August 1997 field sampling operations, male and female blue crabs (Callinectes sapidus)
were collected at nine locations along the Pamlico River from commercial fishermen. These crabs
were placed in plastic bags, and frozen for transport to FIT. In addition, small clams (<25 mm) were
found at Station 17. These clams were depurated for 24 hours in estuarine water collected on -site
to remove residual sediment in the gut, frozen and transported to FIT. Additional samples of clams,
crabs, as well as other macrobenthos and fish were collected by CZR personnel during October and
November 1997. They were placed in plastic bags or containers, frozen and shipped to FIT.
Soft tissue from thawed crab claws and clams (Rangia cuneata) was carefully excised with stainless
steel and polypropylene instruments and homogenized as necessary with a Teflon® policeman or
Tekmar Tissumizer® (stainless -steel homogenizer). The crab samples included tissue from both

claws when available. The clams were randomly grouped into two subsamples prior to
homogenization. All other composite samples (macrobenthos and fish) included all the individuals
in a single homogenate. Large whole fish were dissected with stainless -steel instruments and then
homogenized with the Telmar Tissumizer® or in a Waring& Laboratory Blender (depending on
size). For acid digestion, —5 g of wet, homogenized tissue was placed in weighed, 100-mL glass
digestion flasks, freeze-dried and then re -weighed to provide the percent water content of the tissue.
These freeze-dried samples, and portions of the tissue SRM from the NRC, were digested on
hotplates by the sequential addition and refluxing of trace metal grade HN031 UItrex® H202 and
trace metal grade HCl. After the tissues were completely dissolved, the solutions were transferred
to graduated cylinders, brought to a final volume of 20 mL with DDW rinses of the digestion flasks,
and stored in acid -washed, 30-mL polyethylene bottles for analysis.
Concentrations of Ag, As, Cd, Cr, Cu, Fe, Se and Zn in the digested tissue samples, SRM and blanks
were determined by FAAS or GFAAS. A Perkin-Elmer® Model 4000 instrument was used to
determine Cu, Fe and Zn concentrations by FAAS. Silver, As and Se concentrations were
determined by GFAAS using a Perkin-Elmer® Model 5100PC spectrometer equipped with an HGA-
600 heated graphite furnace and an AS-60 autosampler. Cadmium and Cr values were quantified
by GFAAS using a Perkin-Elmer® Model 4000 AAS equipped with an HGA-400 heated graphite
furnace and an AS-40 autosampler. In all cases, the instrument manufacturer's specifications were
followed and adherence to QA/QC requirements was maintained. The relevant QA/QC data are
presented in Appendix 4.
0 QUALITY ASSURANCE/QUALITY CONTROL
Sample Tracking Procedure. Upon receipt at the Marine & Environmental Chemistry Laboratories,
each sample was carefully inspected to insure that the containers or bags were not broken and that
the identification on the sample container matched those on the custody sheets or shipping
documents. All samples were then refrigerated (sediment and water samples) or frozen (organisms)
until processed for analysis.
Analytical QA/QCMeasurenrents. To ensure data quality, QA/QC requirements included balance
and pipet calibrations, FAAS, GFAAS and ICP-MS instrument calibrations and standard checks,
matrix spike analyses for each metal, duplicate sample analyses, SRM analyses, and procedural
blank analyses.
Instrument Calibrations. Electronic balances used for weighing samples and reagents were
calibrated prior to each use with their internal electronic calibration and then verified with NIST-
traceable standard weights. All pipets (electronic or manual) were calibrated prior to use. Each
spectrometer used for metal analysis was initially standardized with a three- to five -point calibration
curve with a linear correlation coefficient of r;_>0.999 required before experimental samples could
be analyzed. Analysis of complete three to five -point calibrations and single standard checks
alternated every eight samples until all analyses were complete. The relative standard deviation
(RSD) between complete calibration and standard check was required to be <10% or recalibration
and reanalysis of the samples would be performed.
6

Matrix Spike Analysis. Matrix spikes were prepared for a minimum of 5% of the total number of
samples for each metal. The results of these matrix effect checks are shown in Appendices 1-4. The
results were all within acceptable limits for the analytical procedures used.
Duplicate Sample Analysis. To estimate analytical precision, a minimum of 5% of the experimental
samples were processed and analyzed using duplicate subsamples created in the Iaboratory. These
duplicates are identified in data tables with a "*" attached to the sample station identification. The
precision data (as Relative Standard Deviation or RSD) are shown in Appendices 1-4.
Standard Reference Material Analysis. Extractions of water samples for trace metals included
aliquots of the coastal seawater SRM CASS-3 with metal concentrations certified by the NRC. The
suspended matter and sediment digestions included samples of the SRMs Buffalo River Sediment
(#2704) and marine sediment BCSS-I, certified by the NIST and NRC, respectively. Tissue
digestions were accompanied by samples of the dogfish muscle SRM DORM-2 provided by the
NRC. The metal concentrations of the SRMs determined experimentally were all within the range
of certified values as shown in Appendices 1-4.
Procedural BlankAnalvsis. Procedural blanks were prepared with each set of 20 samples to monitor
any potential metal contamination during samples processing, digestion and analysis. These blanks
utilized the same reagents, handling techniques and analytical scheme as the experimental samples.
No contamination was observed during processing and analysis. Metal concentrations due to
impurities in reagents were within accepted limits (<1 % of the analyte concentrations).
•
11

0
RESULTS AND DISCUSSION
Sediment Metals.
Sediment samples were collected from 23 locations in the study area during August 1997 (Figure
2). A key to sample abbreviations is contained in Table I of the SAMPLING AREAS AND
STRATEGY section, page III-1.
Figure 2. Sediment sampling stations in the study area.
Two additional sediment samples, both from reclamation area R-3, were subsequently collected
during March 1998. Results from the sediment analyses are compared with data for average
continental crust (Wedepohl,1995) in Table 1. For each metal, the sediment data are first presented
as a bar graph showing concentration versus station identification to compare individual sites as well
as the four geographic groups. Then, metal concentrations are plotted versus Al, an environmentally
stable reference element. These scatter plots can be used to link sediment metal values to "clean"
sediment quality criteria. The "clean" sediment quality criteria used in this study are from Schropp
4D et al. (1990) and are based on natural estuarine sediment from Florida. Our experience has shown
that these criteria are applicable in most sedimentary environments.

Table 1. Concentrations of metals in sediment (on a dry weight basis) from the PCS Phosphate property and the Pamlico River estuary
with
average continental
crust data
for comparison.
Underlined numbers Identify sites where an anthropogenic
Input was
determined from metal/Al plots. Underlined
numbers that also have been shaded show sites with an anthropogenic
input outside
the PCS Phosphate property.
Sample
Sample Location
AI
Ag
As
Cd
Cr
Cu
Fe
Mo
Se
Zn
ID
M
(Ng/g)
(N9/g)
(Ng/g)
W/O
(N9/g)
M
(P9/9)
(Wg/g)
(ug/g)
R-3 North
End
PCS Phosphate
2.03
1.07
12.8
24.7
229
24.3
1.45
L 1
6100
176
R-3 South
End
PCS Phosphate
4.11
2.21
19A
45.7
434
40.1
2.54
25.5
11.5
318
1
Outfall 007 Canal
3.49
0.40
11.0
15.3
127
12.6
2.71
Z.66
1.03
162
2
Outfall D07
3.01
0.08
10.8
1.88
12.5
5.91
4.29
102
2.62
212
3
Durham Creek
7.17
0.22
5.5
0.69
74.3
21.8
3.14
2.33
0.85
101
4
Porter Creek
8.13
0.18
5.1
0.72
86.7
21.2
3.69
2.14
1.05
98.7
5
Porter Creek North
1.35
0.09
1.8
2.61
17.1
1.79
0.69
0.72
0.09
32.7
6
Outfail101
1.29
0.08
2.2
0.49
50.7
4.20
0.70
0.82
0.36
24.6
7•
Short Creek
6.50
0.11
5.9
0.53
73.2
13.0
2.83
2.41
0.79
81.4
8
Long Creek
7.98
0.14
8.7
0.65
88.2
15.5
3.17
2.44
0.89
98.7
9
Flannigan Gut
4.48
0.18
3.9
_ 1'.31 y#
54.7
7.45
1.33
1.56
0.41
48Z
11
Claypond 5A
3.91
1.91
12.7
16.7
238
20.3
2,02
48_0
4.30
140
Outfall
11(5A)
Claypond 5A
3.23
1.61
9.9
18.2
215
15.4
1.64
30.4
3.60
128
12
South Creek
9.17
0.13
11.3
0.47
103
16.8
3.73
3.09
0.90
117
13
Upper Bond Creek
9.34
0.17
9.0
1.14
106
23.8
3.45
3.66
1.04
118
14
Indian Island
5.19
0.10
4.2
0.35
45.7
10.3
1.93
1.34
0.41
62.1
15
Brickyard Pond
6.90
0.15
5.6
0.32
87.1
18.8
2.43
1.91
0.85
113
16
Bath Creek
9.36
0.24
10.0
0.45
99.8
32.4
4.27
2.45
1.01
148
17`
Pamlico River
1.52
0.06
0.9
0.06
21.0
2.73
0.52
0.30
0.11
21.8
18
Duck Creek
5.90
0.19
4.7
0.37
62.3
19.2
3.09
1.69
0.69
90.6
19 (0-2 cm)
Pamlico River
8.14
0.19
7.0
0.99
87.1
19.4
3.32
1.76
0.85
129
19 (2-4 cm)
Pamlico River
8.15
0.18
8.0
1.06
88.5.
19.6,..
3.45
1.77
0.72
125
20
Pamlico River
1.10
0.05
1.3
0.02
14,0
1.61
0.35
0.19
0.10
8.40
21
Pamlico River
9.54
0.22
0.7
0.78
107
26.6
4.01
1.88
0.88
159
22
Pamlico Riva
1.5
18.7
3.04
0.62
0.31
0.10
26.5D
23
Pamlico River
6.45
0.23
6.8
0.54
53.3
19.9
3.36
1.47
0.60
108
Continental
7.96
0.07
1.7
0.10
125
25
4.32
1.1
0.12
65
Crust -
Values are the average of duplicate subsamples. Analytical precision is shown in Appendix 1.
•` Wedepohl (1995)
9

is
•
The focal element in this study was Cd, which is naturally enriched in phosphate minerals. As
previously discussed, the source materials contain 30 to —200 times more Cd than concentrations of
—0.1 µg/g found in average continental rock. Cadmium concentrations >2 µg/g were found in seven
sediment samples from the PCS Phosphate property (Table 1; Figure 3). The highest concentrations
(z25 µg/g) were observed in two sediment samples collected below surface water from the northern
Figure 3. Spatial distribution of Cd concentrations (µg/g) in surficial sediment.
and southern ends of the R-3 reclamation area (Figure 4a). One of these two values, Station R-3 South
End, is about double the highest value obtained for any of the source materials. This same sample was
comparatively enriched with each trace metal listed in Table 1. With the exceptions of Station 9
(Flannigan Gut, 1.31 µg Cd/g) and Station 22 (in the Pamlico River, 0.98 µg Cd/g), the remaining
sampling sites have Cd levels at or within the limits for unimpacted sediment (Figure 4b). The solid
lines on the scatter plot show the mean value of Cd as a function of Al concentration for estuarine
sediments from Florida. The dashed lines show the 95 % prediction intervals for the Cd/Al ratio in these
natural systems. Samples with metal values that plot above the upper prediction interval have most
10

•
•
•
(a)
CD
CD
a
U
c
m
E
m
(b)
30
25
20
15
10
5
0
c ¢ .Stations }
102
101
tM
CD
3 100
E
M
1.0-2
-3
PCs Property
•
South Creeks
Q Pamlico River
A North Control
0
O
10
102 103 104 106
Aluminum (N9Ig)
Figure 4. Sediment Cd concentrations (a) from the PCS Phosphate property and the Pamlico River
estuary and (b) plotted versus natural sediment quality criteria from Schropp et al. (1990) where the
solid line shows the average Cd value as a function of Al, and the dashed lines represent the upper and
lower limits for unimpacted sediment.
11

•
likely been enriched with Cd by anthropogenic input or some atypical natural mechanism. The
general trend apparent in the off -property data for Cd is a decrease in the mean concentration from
the southern creeks along the Pamlico River (0.8 ± 0.3 µg/g) to the river as a whole (0.6 f 0.4 Ag/g)
followed by the northern control area (0.4 t 0.1 µg/g). However, all of these Cd levels are within
the limits outlined in Figure 4b for unimpacted sediments.
The highest concentrations of Mo in the sediment also were observed for samples from the PCS
Phosphate property (Figure 5a). Compared to the source materials, the maximum sedimentary Mo
concentration of 102 µg/g at Station 2 exceeded the maximum source material concentration of 18
µg/g in the Blend by a factor >5. Sampling stations from the southern creeks, Pamlico River and
northern control area all had Mo/Al ratios only slightly above the ratio for continental crust (Figure
5b). MoIybdenum is one of the metals in this study for which natural estuarine sediment quality
criteria have not been established. For such metals, data from average continental crust have been
used to indicate natural trends and thereby identify potential impacts (Goldberg et al., 1979;
Klinkhammer and Bender, 1981; Trefry et al., 1985). In Figure 5b, the solid line represents the mean
Mo/Al ratio from continental rock and the dotted lines show a 5-fold enrichment or depletion of Mo
relative to Al to approximate the range of values which might be expected due to natural variation.
Data points greater than 5-fold above the continental crust ratio may reasonably be considered to
indicate sites of potential concern as found at 6 sites on the PCS Phosphate property (Figure 5).
Sediment As values ranged from 0.7 to 19.4 µg/g among the spatial station groups (Figure 6a);
however, a general decrease in mean concentrations was observed from the PCS Phosphate property
(10 f 6 µg/g), to the southern creeks (7 f 3 µg/g), and finally the Pamlico River (5 f 3 µg/g).
Arsenic concentrations in the unmined northern control area (7 f 3 µg/g) were the same as those of
the southern creeks. The observed maximum level of 19.4 µg As/g at Station R-3 South End is
within the range of concentrations found for the source material. When evaluated with Florida
sediment guidelines, no surficial sediment sample, on or off the PCS Phosphate property, was
outside the natural range of As values (Figure 6b).
Elevated concentrations of Ag in sediment were found at 5 sites on the PCS Phosphate property
(Figure 7a). Sediment from the southern end of the R-3 reclamation area had the highest value with
2.2 µg Ag/g (at 4.1 % Al) and an Ag/Al ratio >60 times the ratio for continental crust. The closest
match among the source material components was the clay fraction, which averaged 1.8 µg/g Ag (at
3.9% Al). This similarity in Ag and Al concentrations implies that like As, and unlike Cd and Mo,
the observed maximum for Ag in surficial sediment may be explained by the presence of reclaimed
clay, without any additional enrichment process. Only one site in the estuary, Station 22 in the
Pamlico River, had an Ag/Al ratio >5 times the crustal ratio (Figure 7b); however, the absolute Ag
concentration of 0.09 µg/g at this site was too low to be considered a potential environmental
concern. Silver concentrations in sediment from the southern creeks adjacent to the PCS Phosphate
property (0.16 t 0.04 µg Ag/g) were comparable to those from the northern control area (0.19 f 0.04
µg Ag/g).
Chromium concentrations were highly variable on the PCS Phosphate property, ranging
from12.5µg/g at Station 2 to 434 µg/g at Station R-3 South End, with four additional sites having
12

•
•
•
(a)
(b)
50
40
0 30
c
E 20
m
rn 10
0
Stations
102
CO 102
tb
Z
E
10-1 '--
103
• PCs Property
South Crooke
Q Pamlico River •
Q North Control ••
•
•
O
104
Aluminum (pg/g)
10s
Figure 5. Sediment Mo concentrations (a) from the PCS Phosphate property and the Pamlico River
estuary and (b) plotted versus the Mo crustal abundance ratio 'to Al (solid line) from Wedepohl
(1995) with 5-fold enrichment and depletion shown as dashed lines.
13

•
•
(a) 15
(b)
10
a
V
m
In
5
H
tM
0
x
Stations ; a m a
103
102
10.1
PCS Property
South Creeks
Q Pamlico River
Q North Control lie
r �O
10.2 L--
102
103 104 105
Aluminum (Ng/g)
Figure 6. Sediment As concentrations (a) from the PCS Phosphate property and the Pamlico River
estuary and (b) plotted versus natural sediment quality criteria from Schropp et al. (1990) where the
solid line shows the average As value as a function of Al and the dashed lines represent the upper
and lower limits for unimpacted sediment.
14

�11
•
•
(a) 2.5
(b)
CM 2.0
tM
z
CD 1.5
a
E 1.0
m
0.5
0.0
Stations
10,
100
tM
`tz
10-1
ID
CO
10.2
F PCs Property
[ ♦ South Crooke
0 Pamlico River
0 North Control
��- O
10-g "
104
104
Aluminum (jigJg)
105
Figure 7. Sediment Ag concentrations (a) from the PCS Phosphate property and the Pamlico River
estuary and (b) plotted versus the Ag crustal abundance ratio to Al (solid line) from Wedepohl
(1995) with 5-fold enrichment and depletion shown as dashed lines.
15

Cr concentrations >100 µg/g (Table 1). Except for the maximum value, the remaining stations with
Cr-enriched sediment on the PCS Phosphate property have concentrations that compare well with
source material clay samples (319 f 48 µg/g Cr). Most Cr in the clay fraction of natural sediments
is bound within the silicate lattice, and not readily bioavailable (Loring, 1979; Mayer, 1988). The
Cr content of samples collected from the southern creeks, Pamlico River and northern control area
was relatively uniform with a grand average of 71 t 30 µg/g (Figure 8a). Sediment from all stations
excluding the 5 sites on the PCS Phosphate property have Cr levels that plot within the range of
natural estuarine values (Figure 8b).
In addition to the elements found in elevated concentrations in one or more of the phosphate source
materials, several other elements were studied due to their geochemical significance (Fe and Zn) or
potential toxicity (Cu and Se). The concentrations of Fe and Al correlated well in the sediment
samples collected (r = 0.94) with the exception of sediment from Station 2 which is enriched in Fe
(Figure 9a). The calculated Fe/Al ratios were generally equivalent to that for average continental
crust. Zinc, Cu and Se are all micronutrients that may limit biological growth at low concentrations
but become toxic at high concentrations (Howarth and Sprague, 1978; Bates et al., 1982; Dobbs et
al., 1996). Zinc is a sensitive indicator of anthropogenic inputs to the sediment because of the wide
variety of potential pollution sources. Applying the sediment quality criteria, six stations on the PCS
Phosphate property had elevated Zn concentrations (Figure 9b). With the exception of Station R-3
South End, Zn levels in sediments from the PCS Phosphate property were relatively close to the
mean value of 170 µg Zn/g for the source clay material. All Cu concentrations were within the range
of values for natural estuarine sediments (Table 1; Figure I Oa). No Cu enrichment was found in any
of the source materials. Concentrations of Se and the Se/Al ratios were markedly higher in
sediments from seven sites on the PCS Phosphate property than in adjacent creek and estuarine
locations (Table 1; Figure 10b). The highest Se values at these sites were within the range of the
source material clays (9 f 3 µg Se/g). When plotted versus Al concentrations, sediment Se values
from the southern creeks, Pamlico River and northern control area were all similar (0.8 f 0.2 µg Se/g
excluding sandy samples) and showed a linear Se/Al relationship at five times the crustal ratio
(Figure 10b). This probably represents the natural relationship for sediment from this region.
One limitation in accessing the potential for sediment metals to cause harmful biological effects is
that concentration data alone maybe insufficient. Sediment toxicity and/or bioaccumulation studies
may be required in addition to chemical analysis. In lieu of such testing, effects -based guidelines
have been developed for marine and estuarine sediments by Long et al. (1995). Two guideline
values for each metal are provided. An effects -range -low value (ERL) is defined as the
concentration below which adverse effects would occur only rarely. An effects -range -median value
(ERM) is defined as the concentration above which harmful effects would occur frequently. The
range of concentrations between the ERL and ERM represent values which may occasionally cause
deleterious effects. These criteria have been applied to the sediments from this study for the six
metals with ERL and ERM values. The ERM value was exceeded for Cd at five sites on the PCS
Phosphate property and for Cr at Station R-3 South End (Table 2). The ERL values for the other
four metals were exceeded as follows: Cr at 13 stations, As at 11 stations Ag at 4 stations, Cu at 1
station, and Zn at 4 stations. All values for Ag, Cu and Zn that exceeded the ERL were from
sediments collected from the PCS Phosphate property. The ERL values given by the literature for
As and Cr are not representative of impacted sediments and need revision.
16

•
•
•
(a) 400
(b)
300
y 100
0
K � n n� w o w a a«� a n• n n w e� N$ a
Stations
103
CM
102
U 10°
10•t
102
• PCs Property •
South Creeks • M _
0 Pamlico River _
A North Control •
103 104 10e
Aluminum (ug/g)
Figure 8. Sediment Cr concentrations (a) from the PCS Phosphate property and the Pamlico River
estuary and (b) plotted versus natural sediment quality criteria from Schropp et al. (1990) where the
solid line shows the average Cr value as a function of Al and the dashed lines represent the upper
and lower limits for unimpacted sediment.
17

•
•
•
(a)
(b)
5
4
3
c
D 2
1
0
20
0 PCS Property •
0,-" ♦ South Creeks
Pamlico River
North Control
O Q
0 2 4 6 8
Aluminum (%)
103
102
tM
D)
3 10,
U
N
100
10-'
102
• PCS Property
♦ South Creeks —
Q Pamlico River
jNor,Ih Control — — —
" O -
10
103 104 105
Aluminum (Vg/g)
Figure 9. Sediment concentrations of Al versus (a) Fe and (b) Zn concentrations from the PCS
Phosphate property and the Pamlico River estuary. The solid line in Figure 9a is from a linear "
regression (r = 0.94 excluding Station 2) and the dashed line is the crustal abundance ratio from
Wedepohl (1995). Zinc concentrations in Figure 9b are plotted versus natural sediment quality
criteria from Schropp et al. (1990) where the solid line shows the average Zn value as a function of
Al and the dashed lines represent the upper and lower limits for unimpacted sediment.
18

(a)
(b )
103
102
tM
s 101
W
Q 100
c
U
10.1
10.2
102
102
101
4M
CM
3 100
E
m 10-1
m
rn
10-2
10 -2
• PCS Property
South Creeks
Q Pamlico River
Q North Control �• ~
• A
103 104 105
Aluminum (Nglg)
• PCS Property
South Creeks •
O Pamlico River
Q North Control
•
•
102 103 104 Jos
Aluminum (pig/g)
Figure 10. Sediment concentrations of Al versus (a) Cu and (b) Se concentrations from the PCS
Phosphate property and the Pamlico River estuary. Copper concentrations in Figure 1 Oa are plotted
versus natural sediment quality criteria from Schropp et al. (1990) where the solid line shows the
average Cu value as a function of Al and the dashed lines represent the upper and lower limits for
unimpacted sediment. The solid line in Figure 10b is the Se crustal abundance ratio to Al from
WedepohI (1995) and the dashed lines represent 5-fold enrichment and depletion.
19

Table 2. Sediment metal concentrations exceeding the effects-range4ow (ERL) or effects -range -median (ERM) values (Long et at. 1995) with metal concentrations from typical marine sediments for comparison.
Only those stations which exceed one or both effects -range
values are shown.
Sample Sample
Ag
As
Cd
Cr Cu
Zn
Station Location
ERL ERM
ERL ERM
ERL
ERM
ERL ERM ERL ERM
ERL ERM
(1.0 p9r9) (3.7 p919)
(6-21rg19) (70 pgl9)
(1-2 p919)
(9-6 p919)
(81 p919) (370 v9r9) (34 p919) (270 p91g)
(150 p919) (410 pg19)
R3 North PCs Phosphate
1.07 -
12.8
-
24.7
229 -
178
End
R3 South PCS Phosphate
2.21
19.4
45.7
- 434 40.1
318
End
1 Cutfall007
-
11.0
-
15.3
127 - -
162
Canal
2 Outfall007
10.8
1.88
-
- -
212
4 Porter Creek
-
-
-
86.7 -
-
5 Porter Creek
-
-
2.61
- -
-
North
8 Long Creek
-
8.7
-
88.2
N . 9 Flannigan Gut
-
- -
1.31
-
-
O
11 Clay pond 5A
Outfall
1.91
12.7 -
-
16.7
238
11(5A) Clay pond 5A
1.61
9.9 -
18.2
215 - - -
-
12 South Creek
- -
11.3 -
-
-
103 -
13 Upper Bond
9,0 -
106 -
Creek
15 Brickyard Pond
-
87A - -
-
16 Bath Creek
10.0
-
-
99.8
19 (0-2 cm) Pamlico River
-
-
-
87.1
-
19 (2-4 cm) Pamlico River
-
- -
88.5 -
21 Pamlico River
-
8.7
107 -
159
Typical Marine Sediments"
0.06
7.7
0.17
72 33
95
Salomons and FOrstner (1984)

•
Sediments from the control sites as well as various other sites in the study area exceed the ERL
values for As and Cr and yet are similar to typical marine sediments (Table 2). Based on effects -
range values, the most significant potential for sediment -related adverse biological effects is
confined to the PCS Phosphate property, with minimal risk to estuarine surficial sediments.
Metals in Groundwater
Groundwater was collected from five wells in the study area (Figure 11). The GWM and Charles
Figure 11. Groundwater stations sampled in the study area.
Tract wells are located in areas which have been developed by PCS Phosphate, The Archbell Point
well is on PCS Phosphate property that has not been mined and was used as a background control.
Results from the groundwater analyses are shown in Table 3. Salinity at groundwater sites GWM
2B and GWM 4B ranged from 2 to 4 %o (parts per thousand). The remaining samples had a salinity
of about 0.2 ,6o. A Cd concentration of 1.58 µg/L was determined for groundwater from site GWM
2B. This well also had the highest concentrations of As, Cu and Zn. Cadmium concentrations in
the other groundwater samples were much lower at s 0.020 µg/L. In general, metal concentrations
in water from GWM 4B and the two Charles Tract wells compare well with the sample taken from
. Archbell Point. One exception was a high Mo concentration found in water from GWM 4B. This
21

Mo value and the high Cd value from GWM 2B may need to be confirmed by repeated sampling.
The higher salinity at stations GWM 2B and GWM 4B could be a result of dissolved salts from the
blend. All metal concentrations observed in groundwater samples from the PCS Phosphate property
were significantly below the national primary and secondary drinking water standards (Table 3).
Table 3. Metal concentrations and related data from groundwater samples collected in the study area.
Sample
pH
Salinity
As
Cd
Cr
Cu
Mo
Zn
Phosphate
(960)
(pg/L)
(Ng/L)
(Ng/L)
(u9/L)
(Ng/l-)
(Ng/L)
(pg/L)
GWM 26
6.6
2
0.84
1.58
0.033
0.318
3.9
6.71
182
GMW 413
7.1
4
0.27
0.020
0.136
0.068
28.4
0.33
10.7
Charles Tract #1
7.0
0.2
0.15
0.002
0.057
0.083
1.6
2.09
-
Charles Tract #2
6.9
0.2
0.14
0.002
0.316
0.098
0.2
0.81
-
Archbell Point
7.1
0.2
0.22
0.001
0.108
0.037
0.2
0.32
-
Drinking Water Standards"
50
10
50
1000
-
5000
Mackenthun and Bregman (1992)
0 Metals in Surface Waters.
Surface water samples from the study area were analyzed for both dissolved and particulate metals.
The operational definition of dissolved metals for this study was based on passage through a 0.4 µm
pore size filter. Concentrations of dissolved metals are presented as µg/L in Table 4 with average
world ocean and river water values provided for comparison. Data for particulate metals are
presented as µg metal/g suspended matter in Table 5 with comparison to average suspended matter
values from world rivers. Water quality criteria (WQC) for inland and coastal waters have
traditionally been expressed as total recoverable metal levels (dissolved + particulate); however, a
gradual transition to the use of dissolved concentrations is presently occurring. This shift results
from recognition that the dissolved form of metals is more bioavailable and a primary source of
toxicity in the aquatic food chain (Sunda and Guillard, 1976; Fisher et al., 1984; Eisler and
Hennekey,1977; Howarth and Sprague,1978; Str6mgren,1982). Because both dissolved and total
metal concentrations are currently in regulatory use, Table 6 presents total metals concentrations (as
µg metaVL) based on the calculations shown in Equations I and 2.
where
•
[Metal in µg/L]T.,j = [Metal in µg/L]Di,,.IY,d + [Metal in µg/L]Part;cuia« Eq. 1
[Metal in µg/L]Pan;,u,a« = [Metal in µg/g]Part;cu1a« x [Total Suspended Solids in g/L] Eq. 2
22

Table 4. Dissolved metal Concentrations and associated water quality parameters in surface water from the PCS Phosphate property
and the Pamlico
River estuary with
world ocean and river values provided
for comparison,
Sample
pH
Salinity
As
Cd
Cr
Cu
Mo
Zn
Phosphorus
S n
Location n
{960)
(Ng/�)
(ug/�)
(p9«)
(Ng/�)
(ttg/�)
(Ng/L)
(Ng/�)
R-3 North
End
PCS Phosphate
7.7
2
13.7
0.730
0.893
1.65
103
1.71
'
R-3 South
End
PCS Phosphate
8.5
2
11.1
0.877
0.195
1.03
49.2
1.04
-
1
Outfall 007 Canal
8.2
4
6,92
0.014
0.141
0.040
52.2
0.21
173
2
Outfall007
7.4
2
11.3
0.015
0.107
0.052
37.4
3.16
473
3
Durham Creek
8.0
6
0.39
0.023
0.109
0.310
1.5
1.23
11.4
4 Surface
Porter Creek
8.3
6
0.32
0.015
0.226
0.219
1.9
0,76
6.2
4 Bottom
Porter Creek
7.8
6
0.24
0,016
0.150
0.268
1.0
1.20
9.0
5
Porter Creek
7.9
4
0.93
0.007
0.084
0.061
56.4
0.06
0.2
North
6
Outfall101
7.9
0.5
0.06
0.001
0.040
0.053
N.D.
0.11
1.3
7
Short Creek
7.0
8
0.39
0.036
0.075
0.241
1.9
2.96
3.9
8
Long Creek
6.7
8
0.54
0.032
0.078
0.260
1.4
2.81
13.7
9
Flannigan Gut
7.6
8.5
0.38
0.013
0.085
0.216
1.4
0.34
18.0
11(5A)
Clay pond 5A
7.4
4
4.75
0.157
1.37
0.885
253
0.59
5.1
12
South Creek
7.0
8.5
0.55
0.023
0.146
0.789
2.1
1.91
4.5
13
upper Bond
7.5
8
0.66
0.008
0.104
0.196
1.6
0.19
133
Creek
14
Indian Island
8.1
10
0.43
0.008
0.123
0.310
1.8
0.28
12.1
15
Brickyard Pond
8.5
1.5
0.14
0.004
0.042
0.017
N.D.
0.12
5.7
16
Bath Creek
7.4
6.5
0.27
0.007
0.061
0.285
1.1
0.65
14.8
17
Pamlico River
7.1
6
0.33
0.017
0.084
0.298
1.5
0.81
23.0
18
Duck Creek
7.6
5
0.53
0.007
0.075
0.424
1.0
0.41
9.9
19
Pamlico River
8.0
8.5
0.59
0.015
0.054
0.487
1.8
0.26
14.8
20
Pamlico River
8.5
8.5
0.42
0.008
0.038
0.249
1.6
0.52
12.1
21
Pamlico River
8.2
8.5
0.38
0.007
0.044
0.252
1.1
0.18
17.1
22 Surface'
Pamlico River
8.3
7
0.32
0.008
0.113
0.232
1.0
0.18
36.5
22 Bottom
Pamlico River
8.0
7
0.45
0.012
0.053
0.267
0.9
1.08
49.6
23 Surface'
Pamlico River
8.3
6
0.32
0.010
0.081
0.297
1.0
0.66
19.9
23 Bottom
Pamlico River
7.4
6
0.39
0.042
0.123
0.297
0.8
3.45
35.9
World Ocean"
8
35
2
0.068
0.320
0.116
11
0.38
62
World Rivers"'
7
0.2
1.7
0.01
1.0
1.5
0.5
0.6
40
' These metal values are the average of laboratory duplicate subsamples. Analytical precision Is shown In Appendix 2.
" Quinby-Hunt and
Turekian (1983)
Broecker and Peng (198); Donat and Bruland (1995)
23

Table 5. Particulate metal and total suspended solids (TSS) concentrations in surface water from the PCS Phosphate property and
the Pamlico River estuary with world river values provided for comparison.
Sample
Sample
TSS
Al
As
Cd
Cr
Cu
Fe
Mo
Zn
Station
Location
(mg/L)
M
(Nglg)
(Pg�g)
(N9/g)
(u9/9)
M)
(Itg/g)
(N9/9)
R-3 North
End
PCS Phosphate
62.9
2.55
38.6
41.7
296
48.2
1.70
14.7
218
R-3 South
End
PCS Phosphate
6.13
1.69
107
208
265
49.2
2.71
12.0
420
1
Outfall 007 Canal
13.2
0.39
62.2
3.33
21.4
60A
1.30
4,9
71.3
2
WWI007
14.2
0.02
109
6.36
18.5
77.3
1.34
132
6560
3
Durham Creek
8.69
2.88
15.7
4 26
374
330
339
3 1
92 3
4 Surface
PorterCreek
15.2
3.06
13.2
3.77
38.7
17.6
2.92
1.3
95.3
4 Bottom
Porter Creek
55.9
6.27
9.4
2,00
81.9
24.4
3.93
2.9
103
5
Porter Creek
38.1
1.92
30.0
4.46
27.6
11.3
9.45
7.0
47,7
North
6
Outfall101
6.56
8.83
10.3
1.10
125
29.8
3.70
2.2
130
7
Short Creek
11.5
6.91
9.7
1.22
83.3
15.6
3.16
2.3
119
8
Long Creek
16.5
6.56
11.4
1.96
82.4
16.5
3.23
2.9
95.8
9
Flannigan Gut
22.4
6.72
13.4
4.01
103
14.5
3.34
1.5
110
11(5A)
Clay pond 5A
27.1
3.33
41.5
35.6
319
60.0
1.94
18.7
148
12
South Creek
9.32
5.56
15.3
1.72
78.4
23.5
3.67
2.6
139
13
Upper Bond
17.1
3.25
16.5
2.52
43.7
10.0
2.07
1.3
69.9
Creak
14
Indian Island
7.46
1.61
9.8
2.71
52.4
15.3
2.03
0.7
98.7
i5
Brickyard Pond
13.7
0.16
8.9
1.56
13.0
5.7
6.06
3.3
30.1
16'
Bath Creek
7.85
2.10
20.3
1.62
26.6
18.4
3.45
2.6
129
17
Pamlico River
6.74
2.89
12.8
1.67
33.7
23.2
3.35
1.6
71.2
18
Duck Creek
9.83
2.56
16.0
0.21
26.4
97.3
3.08
2.4
102
19
Pamlico River,
7.89
3,44
7.9
1.18
44.2
133
2.40
1.2
125
20
Pamlico River
7.68
2.73
12.5
0.43
17.3
12.5
2.04
1.8
188
21
Pamlico River
6.29
2.60
7.6
0.53
9.6
37.0
1.78
1,3
145
22 Surface"
Pamlico River
10.4
3.03
8.8
2.82
25.6
26.2
2.78
1,5
135
22 Bottom"
Pamlico River
62.4
5.92
9.5
5.03
90.4
26.1
3.91
4.6
145
23 Surface"
Pamlico River
5.84
0.83
12.0
0.54
10.6
39.4
1.76
5.3
167
23 Bottom
Pamlico River
6.88
2.27
19.4
4,92
10.2
37.2
2.97
2.9
165
World Rivers"
100
9.4
5
1.2
100
100
4.8
3
250
* These metal values are the average of laboratory duplicate subsamples. Analytical precision is shown in Appendix 3.
" Martin and Maybeck (1979)
24

Table 6. Total metal concentrations (as ug/L) in surface water samples from the PCS Phosphate property and the Pamlico River
estuarywith chronic water quality criteria (WOC) for freshwater and marine total recoverable metals provided for comparison.
0. Underlined values exceed WQC concentrations.
Sample
Sample Location
As
Cd
Cr
Cu
Mo
Zn
Station
(NgIL)
(pg/L)
(pg/L)
(pg/L)
(pg/L)
(ug/L)
R-3 North End
PCS Phosphate
16.1
3.35
19.5
4.69
104
15.4
R-3 South End
PCS Phosphate
11,7
2.15
1.82
1.33
49.3
3.61
1
Outfall 007 Canal
7.74
0.058
0.42
0.84
52,3
1.15
2
Outfall007
12.8
0.105
0.37
1.15
39.3
96.3
3
Durham Creek
0.53
0.060
0.43
0.60
1.53
2.03
4 Surface
Porter Creek
0.52
0,072
0.81
0.49
1.92
2.21
4 Bottom
Porter Creek
0.77
0.128
4.73
1.63
1.16
6.96
5
Porter Creek North
1.83
0.177
1.14
0.49
56.7
1.88
6
Outfall101
0.13
0.007
0.89
0.25
0.01
0.96
7
Short Creek
0.50
0.050
1.03
0.42
1.93
4.33
8
Long Creek
0,73
0.064
1.44
0.53
1.45
4.39
9
Flannigan Gut
0.68
0.103
2.40
0.54
1.43
2.81
11(5A)
Clay pond 5A
5.88
1.12
10.0
2.51
254
4.60
12
South Creek
0.69
0,039
0.88
1.01
2.12
3.21
13
Upper Bond Creek
0.94
0.051
0.85
0,37
1.62
1.39
14
Indian Island
0.50
0.028
0.51
0.42
1.81
1.02
15 -
Brickyard Pond
0.26
0.025
0.22
0.10
0.05
0.53
16
Bath Creek
0.43
0.020
0.27
0.43
1.12
1.66
17
Pamlico River
0.42
0.028
0.31
0.45
1.51
1.29
18
Duck Creek
0.69
0.009
0.34
1.38
1.02
1.41
19
Pamlico River
0.65
0.024
0.40
1.54
1.81
1.25
20
Pamlico River
0.52
0.011
0.17
0.35
1.61
1.96
21
Pamlico River
0.43
0.010
0.10
0.49
1A1
1.09
22 Surface
Pamlico River
0.40
0.037
0.38
0.50
1.02
1.58
22 Bottom
Pamlico River
1.05
0,327
5.69
1.90
1.18
10.1
23 Surface
Pamlico River
0.39
0.013
0.14
0.53
1.03
1.64
23 Bottom
Pamlico River
0.52
0.076
0.19
0.55
0.82
4.59
•
Freshwater chronic WQC* 190 1.1 11(210)*' 12 - 110
Marine chronic WQC 36 9.3 50(-)** 2.9 - 86
' Metal concentrations are for a water hardness of 100 mg/L CaCO3.
*" Values for Cr`6 and (Cr*3).
25

The highest concentrations of dissolved and particulate Cd were observed for reclamation site R-3
South End at 0.877 µg/L and 208 µg Cd/g particles, respectively (Figure 12). Total Cd levels at this
location were 2.15 µg/L with 41 % dissolved and 59% particulate. Chronic federal WQC for Cd are
I µg/L (dissolved) and 1.1 µg/L (total recoverable) for freshwater (at 100 mg CaCO3/L) and 9.3 µg/L
for marine waters. Thus, the Cd concentration at this site is below the freshwater criteria based on
dissolved Cd, but greater than the WQC for total recoverable Cd. Overall, none of the sample
stations had dissolved Cd levels above the WQC (Table 4) and only sites R-3, North and South End,
and Station 11 (Clay Pond 5A) had Cd concentrations greater than the freshwater WQC for total
recoverable Cd (Table 6).
A spatial overview of surface water dissolved and particulate Cd concentrations is shown in Figure
13. A large range of dissolved Cd concentrations were observed on the PCS Phosphate property,
from a high of 0.88 µg/L in the R-3 reclamation area to 0.001 µg/L at Station 6. Similarly,
particulate Cd values ranged from >200 µg/g to 1.1 µg/g at these locations. In the Pamlico River
estuary, dissolved Cd concentrations ranged from 0.004 µg/L to 0.042 µg/L (Table 4), while
particulate values were between 0.2 µg/g and 5 µg/g (Table 5). There is overlap in Cd
concentrations between geographic sample groups (Figure 12); however, mean dissolved and
particulate Cd values decreased in the order PCS Phosphate property > southern creeks adjacent to
the PCS Phosphate property > the Pamlico River > northern control sites. Overall, an average of
63% of the total Cd was carried by suspended solids. No significant correlations between Cd and
other elements were observed within the dissolved and particulate phases.
i Toxicity data suggest that dissolved Cd concentrations in excess of 0.4 µg/L to >100 µg/L may be
! required for the onset of negative effects to phytoplankton species (Hollibaugh et al., 1980; Kayser
and Sperling, 1980; Rebhun and Ben-Amotz, 1984). Such toxicity levels are greater than observed
in estuarine water samples collected during this study (Table 4). In general, higher trophic levels
might be expected to be more tolerant to Cd, but sensitivity varies greatly and length of exposure
is also important (Spargue, 1987; McLeese et al., 1987; and references therein). Overall, a
comparison of reported toxic Cd concentrations and values observed in this study suggest that Cd
entering the estuary via the PCS Phosphate operation is minimal and of no significant threat to
aquatic organisms.
The average concentration of dissolved As from sample locations on the PCS Phosphate property
was 7 t 5 µg/L (Figure 14a), a value — 16 times greater than the mean in both the southern creeks
and the Pamlico River (0.4 µg/Q). The average dissolved As concentration from the northern
control stations was only slightly less at 0.3 µg/L. Dissolved As levels in the creeks and river are
significantly less than the average world river and oceanic values of 1.7 µg/L and 2 µg/L,
respectively (Table 4), but are comparable to other southeastern estuarine concentrations (Trocine
and Trefiy, 1996). Differences between As concentrations from the PCS Phosphate property and
the estuary also were found for the suspended matter samples (Figure 14b). Particulate As values
from the northern control stations, the Pamlico River and southern creeks averaged 15 ± 6, 11 f 4
and 13 f 3 µg/g, respectively; however, the mean concentration from sites on the PCS Phosphate
property was 57 f 38 µg/g with a range of 10 to 109 µg/g. Total As values (Table 6) are all well
below the federal chronic WQC levels forboth freshwater (190 µg/L) and marine samples (36 µg/L).
An average of 72% of the total As was in dissolved form.
26

•
(a) 0.80
0.60
U
0.40
0
0 0.20
0.00
0 (b)
so
40
U 30
2
20
'C
a 10
0
11 - a a 1 g O A b a j N :! :E V �g �:� p a03
N
• ' Stations q a a
W8 ' Stations a a
Figure 12. Concentrations of (a) dissolved and (b) particulate Cd from the PCS Phosphate property
and the Pamlico River estuary.
27

•
(a)
Figure 13. Spatial distribution of (a) dissolved Cd in µg/L and (b) particulate Cd concentrations in
µg/g. Average values are shown for those stations where surficial and bottom water concentrations
were determined.
28

•
•
(a) 15
U
(b) 120
100
ea
80
N
a
m 60
..
m
40
0
a ~ ' Stations R R R
I - M a 11 a a n a a g a n 1 e 2 t V t a j I
= a
• ' Stations R R R
Figure 14. Concentrations of (a) dissolved and (b) particulate As from the PCS Phosphate property
and the Pamlico River estuary.
29

•
Molybdenum is a trace nutrient required for many phytoplankton species (Manheim and Landergren,
1978) and not generally considered to be toxic to aquatic biota. As shown in Figures 15a and 15b
respectively, the highest concentrations of Mo were found on the PCS Phosphate property, at Station
11(Clay Pond 5A) for dissolved Mo (253 µg/L) and Station 2 for particulate Mo (132 µg/g). The
range of values was again large, as dissolved Mo concentrations from stations on the PCS Phosphate
property averaged 92 f 82 µg/L with the corresponding particulate samples averaged 27 f 47 µg/g.
Off the PCS Phosphate property, dissolved Mo concentrations in the different spatial groupings were
quite similar, averaging 1.6 f 0.4 µg/L in the southern creeks along the estuary, 1.3 f 0.4 µg/L in
the Pamlico River, and 1.1 f 0.1 µg/L in the northern control stations. Particulate Mo values for
these groups were also similar with a grand average of 2.4 ± 1.2 µg/g. Total Mo values in the
estuary (Table 6) are well below the average seawater dissolved value of 11 µg/L (Quinby-Hunt and
Turekian, 1983). Of the elements analyzed for both dissolved and particulate metals in this study,
Mo had the highest percentage of its total concentration in dissolved form at —97%.
The maximum dissolved Cr concentration found during this study (1.37 µg/L) was from the clay
pond station 11(5A), which also had the highest particulate Cr value at 319 µg/g (Tables 4 and 5,
respectively). A comparatively straight forward gradient in dissolved Cr concentrations was
observed between the different station groupings with mean values decreasing from 0.409 f 0.512
µg/L on the PCS Phosphate property to 0.122 f 0.051 µg/L, 0.079 f 0.034 µg/L and 0.059 f 0.017
µg/L respectively in the southern creeks, Pamlico River and northern control stations (Figure 16a).
Particulate Cr values show a similar trend, decreasing from 153 f 137 µg/g for the PCS Phosphate
property stations to 69 ± 25 µg/g in the southern creeks, 33 f 27 µg/g for the Pamlico River, and 22
f 7 µg/g from the northern control stations (Figure 16b). The particulate Cr concentrations
(excluding values >200 µg/g on the PCS Phosphate property) show the best correlation to suspended
matter Al of the metals examined, r = 0.92, which suggests there is no significant perturbation of
their natural relationship in the estuary. An average of 80% of the total Cr in the surface water
samples was bound to suspended matter. With the exception of the PCS Phosphate property stations
11(5A), R-3 North End and R-3 South End, the dissolved Cr concentrations compare favorably to
average seawater (0.320 µg/L) and world rivers (1.0 µg/L) and are similar to other southeastern
estuarine values (Trocine and Trefry, 1996). Relative to freshwater and marine WQC values, total
Cr concentrations from this study were generally far below chronic levels for Cr+6, which is a more
toxic form than C1*3 (Holdway, 1988; Nieboer and ]usys, 1988). The one exception was the
reclamation area station R-3 North End which had a total Cr concentration of 19.5 µg/L (Table 6).
However, the Cr+3 freshwater WQC of 210 µg/L is more applicable to this low salinity sample.
Enriched concentrations of Cu in coastal estuaries have generally been linked to industrial inputs
(Han et al.,1994) and the use of Cu-based antifouling paints on marine vessels (Claisse and Alzieu,
1993). Copper is an essential micronutrient that also is toxic at varying concentrations. The mining
waste components examined in the source material study were not enriched in Cu and measurements
were made in the surface water samples because they might show impacts to the estuary from a
source(s) other than the PCS Phosphate facility. Stations 1,2, 5 and 6 had low dissolved Cu
concentrations of 0.051 f 0.009 µg/L that were similar to most groundwater samples (Table 3).
However, at the clay pond station 11(5A) and the R-3 reclamation area stations, concentrations of
dissolved Cu were >0.8 µg/L (Figure 17a). In the estuary, dissolved Cu concentrations overlap
30

0
7
(a) 100
80
eA
z
60
m 40
0s
Vl
0 20
L
40
tM
z
g 30
m
a° 20
10
0
W Wg9s
Stations A A
• ' Stations A A
Figure 15. Concentrations of (a) dissolved and (b) particulate Mo from the PCS Phosphate property
and the Pamlico River estuary.
31

•
•
(a) 1.0
(b)
0.8
v 0.6
V
m
0.4
0
0
to
� 1 R
0.0 _
II -aaI 0VN0a!Va:V2t_tis9 !
2 0.?-• Stations a 0 a a
300
250
3 200
U
w 150
100
IL 50
0 p pp py • W a. p 4 O M1 O O�' ' Y b e � �� 111 Of
Stations a p a a
Figure 16. Concentrations of (a) dissolved and (b) particulate Cr from the PCS Phosphate property
and the Pamlico River estuary.
32

C
E
•
(a) 1.5
V 0.9
0 0.3
[duo
(b) 150
v 90
a 30
0
K � q A•� 10 p N 9 p ^� � � .'. �� � p p� q�� a
Stations p a a a
• Stations a a a
Figure 17. Concentrations of (a) dissolved and (b) particulate Cu from the PCS Phosphate property
and the Pamlico River estuary.
33

greatly, averaging 0.312 f 0.196 µg/L, 0.299 ± 0.076 µg/L and 0.242 f 0.207 respectively in the
southern creek, Pamlico River and northern control station groupings and are similar to other
southeastern estuaries (Windom et al. 1983, Trocine and Trefry, 1996). The highest particulate Cu
concentrations were found off the PCS Phosphate property at Station 18, the Duck Creek control
station, and Station 19 in the Pamlico River at the mouth of South Creek (Figure 17b). These data
suggest that point -sources of Cu occur at widely separated locations. The PCS Phosphate property
stations had the highest average particulate Cu concentration, 48 t 22 µg/g. The southern creek
stations had the most uniform Cu concentrations and the lowest average, 19 :� 7 µg/g. As a
percentage, particulate phases contained 57 t 22% of the total surface water Cu. None of the PCS
Phosphate property sample sites exceed the chronic total recoverable freshwater WQC concentration
of 12 µg Cu/L (at 100 mg/L CaCO3) and the estuarine samples were all below the corresponding
marine WQC value of 2.9 µg Cu/L (Table 6).
Zinc is an essential micronutrient with a very low concentration in surficial seawater that has been
suggested to limit phytoplankton growth (Anderson et al., 1978; Brand et al. 1983). Dissolved Zn
concentrations observed in surface waters from the estuary and PCS Phosphate property ranged from
0.06 µg/L to 3.45 µg/L, and were quite variable within each spatial group of stations (Figure 18a).
Values >2 µg/L (five times the seawater average; Table 4) were not limited to any one area. Average
values of dissolved Zn from the PCS Phosphate property, the southern creeks and the Pamlico River
were similar; 0.98 f 1.13 µg/L, 1.43 ± 1.05 µg/L and 0.82 t 1.03 µg/L, respectively. A lower mean
value was calculated for the northern control group at 0.39 f 0.27 µg Zn/L. Particulate Zn
concentrations within the station groups were much more uniform than the dissolved values, with
the exception of data from the PCS Phosphate property (Figure 18b). On the PCS Phosphate
property, particulate Zn concentrations ranged from 48 µg/g at Station 5 to 6560 µg/g at Station 2
(Table 5). The extremely high Zn concentration at Station 2 may be due to its close proximity to the
ore processing property and be industrial rather than geochemical in nature. Average particulate Zn
concentrations in the southern creeks and Pamlico River were 103 ± 20 µg/g and 138 f 26 µg/g,
respectively. A lower mean Zn value of 85 f 51 µg/g was observed in suspended matter from the
northern control stations. On average, 70% of the total Zn in the surface water samples was in
particulate form. Neither the freshwater nor marine WQC values for total Zn concentrations were
exceeded in the water samples collected. The highest total Zn concentration observed was —93 µg/L
at Station 2 on the PCS Phosphate property (25w salinity), which compares favorably with the
freshwater WQC value of 110 µg Zn/L (Table 6).
Metals in Organisers.
Sampling for aquatic organisms was designed to spatially cover the study area and to obtain animals
from different trophic levels. Organisms were taken from the ponds and outfalls from the PCS
Phosphate property and from the Pamlico River and tributary creeks (Figure 19). The entire food
chain could not be sampled at any one site; however, different trophic levels of invertebrates and fish
were collected across the study area in an attempt to identify any enhanced bioaccumulation and/or
biomagnifcation of metals. The organism metal data are arranged by type as follows: Table 7
contains the invertebrate results, Table 8 presents the whole fish data, and Table 9 lists the
concentrations observed in crab claw flesh (a species harvested for human consumption in the
34

•
•
(a) 4
d, 3
c
N
m
2
a
0
co
1
G
❑+
S00
400
s
C 300
ca
200
U
r.
a. 100
0
C I r p q ! q P 1 P P 9 V � � P P 1 V �a d m
iCb r
• • Stations p a
a •n
a Stations p a
Figure 18. Concentrations of (a) dissolved and (b) particulate Zn from the PCS Phosphate property
and the Pamlico River estuary.
k1i

•
•
Figure 19. Aquatic organism sampling sites.
estuary). Invertebrates, particularly bivalve molluscs, have routinely been used as monitors of metal
contamination in estuarine systems (Phillips, 1976; Byran and Hummerstone, 1978; Sinex and
Wright, 1988; Riedel et al., 1995). Crabs have been used less often in pollution studies, but also
have the potential to concentrate trace metals (Trefry et al.,1983, Jop et al.,1997). The toxicity and
accumulation of metals in fish have been widely studied (Howarth et al., 1978; Sprague, 1987;
Holdway, 1988; and references therein). Together, these organisms help link potential aquatic
contaminants with the aquatic and terrestrial food chains.
Metal concentrations were calculated on a dry weight basis to factor out variations in water content
and normalize the data for comparative purposes. Size and percent water content data are provided
for assessment calculations that often use metal levels as µg metal per gram wet weight. To obtain
a first approximation of the wet (or fresh) weight metal concentrations, all clam dry weight values
(Table 7) may be divided by nine and whole fish dry weight concentrations (Table 8) may be divided
by four, based on average water content of —90% and —75%, respectively. Metal concentrations in
crab claw flesh (Table 9) may be divided by four (-80% water content) to convert metal values from
36

Table 7. Trace metal concentrations (dry weight) in invertebrate organisms. The sample from Station 17 was collected In August 1997;
0 named stations were sampled in October and November 1997.
Water Ag As Cd Cr Cu Fe Se Zn size....
Sample Station Content (pg/g) (uglg) (ug/g) (ug/g) (ug/g) (ug/9) (Ng/g) (ug/g) (mm)
M
Clams'
17"
90
1.48
1.64
0.904
0.26
8.54
177
2.19
141
<25
Short Creek
86
3.55
5.19
0.316
2.55
12.7
994
3.85
140
33,33,35,37,60
Short Creek
86
2.34
5.17
0.399
2.54
10.8
1070
3.24
135
32,32,33,35.52
Long Creek
86
0.97
3.85
0.324
0.90
8.48
487
2.50
130
33,35,36,37,37
Long Creek
88
1.41
3.55
0.335
0.46
8.47
323
3.02
176
32,34,34,37,37
Flannigan Gut
87
7.67
4.88
0.429
2.94
12.6
560
4.05
86.4
52,52,57,63
Flannigan Gut
88
2.20
4.51
0.564
2.33
11.7
692
3.32
87.5
46,47,58,60
Upper Bond Creek
91
0.82
4.32
0.201
1.26
10.7
536
2.14
88.4
31,47,65
Upper Bond Creek
89
0.34
3.97
0.147
1.25
11.0
650
1.74
94.1
38,49,49,53
Pamlico River
Outfall 007
88
1.91
8.16
0.581
1.14
6.40
307
3.34
112
37,39,39,40,48
Pamlico River
Outfa11007
87
0.53
4.29
0.505
0.83
6.24
269
2.75
109
37,38,40,42.52
Durham Creek-
90
11.3
7.79
0.235
2.78
25.1
499
3.38
84.6
56,67,61
Durham Creek
90
6.62
6.42
0.338
2.30
22.8
444
2.65
94.6
57,57.59
Porter Creek
88
1.59
3.32
0.286
1.10
11.3
791
1.97
116
29,32,32,35,44
Porter Creek
87
1.03
4.18
0.290
1.78
6.82
639
1.95
106
29,29,31,53
Bath Creek
86
1.49
4.83
0.151
1.31
14.3
453
1.67
91.3
34,46,52,54.56
Bath Creek
89
3.29
6.92
0.354
2.17
25.1
417
2.27
103
49,50,56.61
Duck Creek
87
2.09
4.98
0.166
0.99
11.6
504
1.91
91.8
37,45,45,50.54
Duck Creek
87
1.70
5.99
0.205
0.83
11.1
474
1.82
117
46,49,49,50
Macrobenthos'
Porter Creek
79
0.12
1.57
0.093
1.19
13.9
621
0.49
56.0
-
North Pond
Brickyard Pond
77
0.05
1.00
0.330
3.40
12.9
2390
0.33
91.6
-
Crayfish*
Duck Creek
82
0.17
1.76
0.093
7.90
45.0
801
0.90
66.1
-
` Composite samples, small Crustacea and insects for the macrobenthos, 14 individuals for the crayfish.
" Depurated in water
from the
site, the other clam samples were not depurated.
Average of laboratory duplicate subsamples. The
precision of analysis
is shown in Appendix 4.
Left valve length of clams in
composite samples.
37

•
Table 8. Trace metal concentrations (dry weight) in whole fish. Samples were collected during October and November 1997.
Water Ag As Cd Cr Cu Fe Se Zn Length
Sample Station Content (p919) (Nglg) (ug/g) (ug/g) (ug/g) (ug/g) (Ng/g) (Pglg) (mm)
Pumpkinseed
Short Creek
74
0.003
0.37
0.004
0.199
2.49
109
0.72
77.8
165
Short Creek
76
N.D.
0.84
0.006
0.144
2.35
57.6
0.73
77.1
165
Short Creek
76
N.D.
0.78
0.013
0.276
3.21
115
0.61
90.4
150
Long Creek*
73
N.D.
0.99
0.034
0.386
2,62
137
0.46
86.6
180
Long Creek
72
0.004
0.98
0.017
0.409
3.26
164
0.32
85.4
160
Durham Creek
75
N.D.
0.94
0.006
0.319
2.74
164
1.00
87.7
125
Durham Creek
76
N.D.
0.53
0.004
0.479
2.24
73.9
0.75
110
75
Durham Creek
75
0.034
1.04
0.018
0.230
3.29
62.2
1.04
131
60
Porter Creek
74
0.008
0.40
0,009
0.167
3.76
69.0
0.35
75.0
180
Porter Creek
74
0.007
0.40
0.013
0.190
4.76
106
0.34
82.8
175
Porter Creek
75
0.010
0,20
0.007
0.271
5.04
128
0.35
90.9
155
Bath Creek
74
0.003
0.62
0.011
0.349
5.62
U7
0.58
92.6
165
Bath Creek
76
N.D.
0.20
0.015
0.384
5.99
232
0.48
85.8
150
Bath Creek
76
0.007
0.66
0.008
0.184
3.24
110
0.58
102
125
Duck Creek
75
N.D,
0.61
0.005 '
0.155
4.37
94.8
0.35
68.2
180
Clay Pond 5A
74
0.032
0.22
0.228
2.13
2.41
87.6
5.47
113
45-65-
Clay Pond 5A
75
0.082
0.18
0.395
1.34
2.78
101
8.35
117
50-60*"*
Clay Pond 5A
75
0.051
0.13
0.355
0.985
2.38
75.7
7.98
112
45-70***
Common Carp
Duck Creek
71
0.010
0.16
0.014
0.111
4.49
38.1
0.31
89.4
240
Duck Creek
76
0.002
0.22
0.034
0.241
11.0
76.4
0.65
127
220
Porter Creek
78
N.D.
0.37
0.078
1.37
5.71
1790
0.87
136
350
North Pond
Porter Creek
North Pond
75
0.002
0.51
0.187
2.08
4.15
2620
89.4
172
300
N.D. = Not Detected; method detection limit of 0.002 pglg.
*" Average of laboratory duplicate subsamples.
Analytical precision
is shown in Appendix 4,
*** Composite samples of six, six and eight
individuals, respectively.
•
38

Table 8. Trace metal concentrations (dry weight) in whole fish.
(Continued).
Samples were collected during October and November 1997
Sample Station
Water
Content
Ag
As
Cd
Cr
Cu
Fe
Se
Zn
Length
(Ng/g)
(Ng/g)
(Ng/g)
(N9/g)
(Ng/g)
(u9/g)
(ug/9)
(pg/g)
(mm)
Blueaill
Brickyard Pond
73
0.031
0.05
0.157
2.16
10.9
1160
0.32
229
210
Brickyard Pond
76
N.D.
0.22
0.047
0.163
2.45
145
0.47
70.5
210
Green Sunfish
Outfall001/101
74
N.D.
0.08
0.142
0.264
4.61
126
0.47
76.2
170
Outfall001/101
80
N.D.
0.45
0.284
2.55
2.99
178
1.06
108
125
Lonynose Gar
Pamlico River"
62
0.008
1.06
0.034
0.034
2.59
67.9
0.97
50.7
-
Pamlico River
73
0.013
1.08
0.107
0.088
3.86
284
1.38
39.2
-
Bullhead
Upper Bond
68
0.010
0.95
0.019
0.374
6.16
138
0.86
37.7
435
Creek
Upper Bond
75
0.014
0.77
0.123
4.26
7.92
935
0.84
187
500
Creek
spot
Short Creek
79
0.003
1.05
0.012
7.04
2.46
253
1.41
66.6
115
Short Creek
77
0.009
1.21
0.012
1.49
1.64
187
1.17
66.4
100
Long Creek
70
0.006
1.03
0.005
0.430
3.21
240
0.85
54.4
190
Long Creek
77
0.011
1.37
0.016
0.749
3.99
303
1.22
44.7
170
Flannigan Gut
74
N.D.
0.95
0.014
0.838
2.95
201
0.81
52.3
160
Flannigan Gut
79
N.D.
1.28
0.015
5.38
2.64
257
1.40
72.6
120
Upper Bond
79
0.005
0.49
0.020
8.63
2.78
575
1.41
46.5
115
Creek
Upper Bond
77
0.006
0.86
0.018
2.10
2.64
515
0.96
74.2
110
Creek
Porter Creek
76
0.005
0.69
0.017
0.533
4.36
494
0.70
64.5
150
' Average of laboratory duplicate subsamples. Analytical precision is shown in Appendix 4.
•
39

Table 9. Trace metal concentrations (dry weight) in crab claw flesh. Samples from numbered stations were collected in August 1997,
named stations were sampled
in October
and November 1997.
Sample Station
Sex
Water
Content
Ag
As
Cd
Cr
Cu
Fe
Se
Zn
Size"
M
(N9/g)
(N9/g)
(Nglg)
(pglg)
(pglg)
(uglg)
(Nglg)
(pglg)
(mm)
7A
M
82
0.57
1.65
0.021
0.177
7.41
9.57
1.10
172
142
7A
F
77
0.50
1.89
0.083
0.186
17.2
4.86
1.06
127
127
12"
M
88
0.64
2.66
0.026
0.349
20.4
8.93
1.42
206
137
12
F
84
0.26
1.22
0.118
0.268
12.6
8.87
0.85
300
154
12A
M
83
0.27
1.24
0,040
0.323
15.7
8.37
0.83
241
141
12A
F
84
0.41
1.87
0.078
0.326
21.6
10.4
1.56
261
149
16
M
84
0.49
1.44
0.034
0.316
10.2
9.73
0.90
294
117
16
M
87
0.90
1.76
0.105
0.317
24.1
16.1
1.54
261
119
16
F
87
0.61
1.53
0.037
0.388
26.5
12.8
1.17
305
152
19
M
85
0.55
1.58
0.009
0.268
22.5
8.26
1.37
296
158
19
F
83
0.60
1.59
0.014
0,228
10.9
8.01
1.39
294
159
20
M
83
0.67
2.54
0.009
0.208
9.68
5.72
1.45
216
127
20
F
88
0.70
2.58
0.008
0.434
27.7
8.47
1.47
264
156
22
M
84
0.64
1.54
0,045
0.254
11.7
7.43
1.63
300
140
22,
F
86
0.66
0.81
0.017
0.499
19.1
7.99
1.58
281
148
22A
M
82
0.74
1.59
0,021
0.298
10.3
7.40
1.00
262
131
22A
F
80
0.62
1.81
0.052
0.189
14.4
7.17
1.58
324
125
22A
F
89
0.83
1.49
0.017
0.335
13.9
9.05
1.46
291
158
Indian Island
M
79
0.56
1.87
0.018
0.200
8.90
5.05
1.46
232
125
Indian Island
F
84
0.60
2.10
0,069
0.315
11.9
11.1
1.62
272
152
Long Creek
M
87
1.19
2.44
0.005
0.050
14.4
13.8
1.61
182
160
Long Creek
M
87
1.36
2.36
0.023
0.276
20.7
24.0
1.43
210
155
Upper Bond Creek
M
86
0.38
1.84
0.011
0.037
18.0
10.8
1.37
235
150
Upper Bond Creek
M
84
0.29
1.42
0.003
0,055
15.2
12.0
1.46
204
115
Durham Creek"
M
87
0.94
1.81
0.040
0.108
14.7
19.7
1.32
335
180
Durham Creek
F
78
0.60
0.54
0.038
0.056
9.68
11.5
1.05
333
145
Porter Creek
M
86
1.40
1.31
0.005
0.040
17.1
13.5
0.99
230
180
Porter Creek
M
85
0.75
1 A4
0,017
0.032
19.1
17.4
1.99
223
105
Duck Creek
M
84
0.72
0,99
0.032
0.041
15.2
9.05
1.38
323
155
• Size refers to point-to-point width of the carapace.
•• Average of laboratory
duplicate
subsamples. Analytical precision is shown in Appendix 4.
40

0 dry weight to wet weight.
Concentrations of Cd in aquatic invertebrates ranged from 0.093 µg/g to 0.904 µg/g on a dry weight
basis (Table 7). Clam samples (Rangia cuneata) were the most widely collected invertebrates within
the study area. The trend observed for Cd concentrations showed an increase from the control
stations in Bath and Duck Creeks (0.219 f 0.093 µg/g) to the southern creek stations (0.357 t 0.188
µg/g). However, the highest Cd value in the clam samples came from Station 17, which is located
upstream of the PCS Phosphate facility and therefore unlikely to have been exposed to mining -
derived Cd. If these shellfish were to be consumed by humans, the Cd concentrations are well below
the Federal Food and Drug Administration's Level of Concern (FDA-LOC) value 3.7 µg/g (US
FDA,1993a). Cadmium concentrations in clams from the Pamlico River estuary compare favorably
to Rangia samples collected from Chesapeake Bay, which ranged from 0.14 µg/g to 1.99 µg/g with
a mean of 0.54 f 0.04 µg/g (Di Giulio and Scanlon, 1985). In general, the whole fish Cd values are
much lower than observed in the invertebrates (Table 8). The range in Cd values for the pumkinseed
fish was 0.004 µg/g to 0.395 µg/g, with Cd concentrations >0.040 µg/g only in Clay Pond 5A on the
PCS Phosphate property. Data from this study suggest that the greatest risk of Cd to higher
(terrestrial) trophic levels would be to those individuals that feed from ponds on the PCS Phosphate
property and outfalls leading from it, as typified by Clay Pond 5A and the 001/101 Outfall.
Arsenic concentrations in the invertebrate samples ranged from 1.00 µg/g to 8.16 µg/g (Table 7).
Clam values from the Bath Creek and Duck Creek control stations averaged 5.68 f 0.97 µg/g As and
are comparable to the mean from all other clam stations, 4.94 f 1.79 µg/g. These values are quite
low compared to the FDA-LOC for As in shellfish of 86 µg/g (US FDA, 1993b). Arsenic
concentrations in the macrobenthos and crayfish composite samples were all <2 µg/g. The whole
fish levels were again lower than observed in the invertebrates, but in this case no comparative
enrichment of As concentrations was found in the pond and outfall water samples. The
concentration of As in all fish species at all stations averaged 0.66 f 0.38 µg/g.
The Ag concentrations observed in the invertebrate organisms were quite variable, ranging from 0.05
µg/g in the Brickyard Pond macrobenthos sample to 11.3 µg/g in clams from Durham Creek. Most
of the clam values are comparable to the mean Ag concentration from the control stations (2.14 f
0.80 µg/g), but all the values from Durham Creek and one composite from Flannigan Gut seem high
(Table 7). The uptake of Ag by oysters is primarily through the accumulation of dissolved metal
rather than feeding (Abbe and Sanders, 1990; Connell et al., 1991). The whole fish Ag data range
from below detection (0.002 µg/g) to 0.082 µg/g, and are similar to Cd in that the highest Ag
concentrations were observed in samples taken from Clay Pond 5A (Table 8).
The lowest concentration of Cr found in the invertebrate data came from clams collected at
"upstream" Station 17 (0.26 µg/g). The concentration of Cr in the clam samples averaged 1.33 ±
0.60 µg/g in the control creeks (Duck and Bath) and 1.80 t 0.92 µg/g at the remaining stations.
Chromium concentrations in whole fish show the comparative enrichment in the ponds seen for Cd
and Ag, but there also appears to be a difference between species; excluding the Clay Pond 5A
samples, pumpkinseed from the estuary averaged 0.283 t 0.106 µg/g Cr while spot averaged 3.02
± 3.15 µg/g (Table 8).
41

Selenium concentrations among the invertebrate samples were substantially higher in the clams (2.66
f 0.74 µg/g) than the macrobenthos and crayfish (<1 µg/g). This metal serves as an essential
micronutrient for many organisms, but may become toxic at elevated concentrations (Shamberger,
1983; Lemly and Smith, 1987). In contrast to Ag, the accumulation of Se from particulate sources
(as well as dissolved) has been demonstrated to be important in bivalves (Luoma et al., 1992). Data
from the whole fish analyses yield an average of 0.76 t 0.34 µg Se/g for all samples excluding Clay
Pond 5A. The mean Se value from the three pumpkinseed composite samples collected from this
pond was 7.27 f1.57 µg/g, approximately a 10-fold increase. The mean Se level for pumpkinseed
from the clay pond is not greatly enriched relative to the upper limit of the food organism values in
natural waters (0.1 to 4.7 µg Se/g) reported by Hodson and Hilton (1983), but trophic transfer of Se
from algae up through shrimp and fish has been observed in laboratory experiments (Besser et.al.,
1993; Dobbs et al., 1996).
Copper, Fe and Zn are elements that are essential to the metabolic processes of most organisms and
many aquatic species have the ability, at least in part, to regulate their concentrations of these metals
(White and Rainbow, 1982; Devineau and Amiard-Triquet, 1985). Within the invertebrate group
of samples, higher concentrations of Cu and Fe were detected in the crayfish from 001/101 Outfall
(45 µg/g Cu) and macrobenthos from the Brickyard Pond (2390 µg/g Fe). The remaining samples
(Table 7) had average concentrations of 13.1 f 6.0 µg/g Cu and 555 f 220 µg/g Fe. A comparison
of the depurated clams from Station 17 versus the undepurated samples suggests that sediment in
the gut may contribute a large percentage of the total Fe in some of the creek samples. Zinc
concentrations in the invertebrate samples are relatively uniform at 104 f 27 µg/g. Copper
concentrations in Rangia clams from this study are comparable to samples taken from Chesapeake
Bay (14.4 f 1.4 µg/g), whereas Zn values are lower than the 170 f 10 µg/g reported for this more
northern estuary (Di Giulio and Scanlon, 1985). In the whole fish samples, Cu and Zn
concentrations were comparable between both species and location, averaging 3.93 f 2.08 µg/g and
89.8 f 39.5 µg/g, respectively (Table 8). Iron concentrations were much more varied, ranging from
38 to 2620 µg/g. There also may be some species differences for Fe, as pumpkinseed averaged 114
f 43 µg Fe/g relative to the mean value observed for spot at 336 f 149 µg/g.
The harvesting of blue crabs (Callinectes) from the Pamlico River estuary forms a large part of the
local commercial fishery. Silver concentrations in crab claw flesh (Table 9) ranged from 0.26 µg/g
to 1.40 µg/g. The concentration of As in crab flesh averaged 1.73 f 0.52 µg/g. Cadmium
concentrations in the crabs were quite similar to the whole fish with a mean flesh value of 0.034 t
0.029 µg/g. The average concentration of Cr in the crab flesh (0.227 f 0.130 µg/g) compares well
with the lower range of Cr values found in the fish and is much less than observed in the clam
samples. The crab Fe values, 10.8 f 4.5 µg/g, are significantly lower than either the other
invertebrates or the whole fish. Selenium values found in crab flesh, like As, had an average which
fell between the clams and fish (1.36 f 027 µg/g), while Zn concentrations in the crabs (261 f 47
µg/g) were greater than either of these other organisms.
No clear spatial pattern was found for metal concentration in the crabs, nor were any sex -based or
size related trends observed in metal concentrations. Compared to Callinectes sampled from
Connecticut estuaries (Jop et al., 1997), concentrations of Ag, As, Se and Zn in crab flesh from the
Pamlico River estuary are greater and Cu values are similar. Copper concentrations available from
42

•
•
southern and Gulf coast crab samples are generally greater than seen in this study with --46 µg/g
from the Indian River Lagoon and 33-36 µg/g from San Antonio Bay (Trefry et al.,1983 and Trefry
et al., 1976, respectively). Concentrations of Cd reported for blue crab flesh from other estuaries
are reported to be equivalent, <0.1 µg/g (Trefry et al., 1976; Jop et al., 1997) or greater (0.40 f 0.79
µg/g; Jop et al., 1997) than found during this study. Zinc concentrations obtained from the Pamlico
River, however, are much greater than observed in Connecticut (-32 µg/g) and equal to values of
—250 µg/g from San Antonio Bay (Jop et al., 1997 and Trefry et al., 1976, respectively).
43

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46

•
•
APPENDIX 1.
Quality assurance and quality control (QA/QC) data for the sediment metal analyses.
47

•
Results for the Marine Sediment Standard Reference Material (SRM) BCSS-1. Mean and (Standard
Deviation). NRC is the National Research Council of Canada.
SRM Al
Ag
As
Cd
Cr
Cu
Fe
Mo
Se
Zn
N
W/g)
W/g)
W/g)
W/g)
Gig/g)
(°/n)
(lag/g)
(lrg/g)
O g/P)
BCSS-1 6.18
0.13
11.2
0.24
124
19.5
3.24
1.91
0.49
116
This Study 6.26
0.12
10.7
0.23
120
19.5
3.32
1.94
0.49
119
6.17
0.09
12.2
0.24
111
18.5
3.22
2.05
0.47
114
-
-
-
0.23
-
-
-
-
-
-
-
-
-
0.26
-
-
-
-
-
-
Certified 6.26 0.11 11.1 0.25 123 18.5 3.29 1.9* 0.43 119
Mean
Standard (0.22) (0.03) (1.4) (0.04) (4) (2.7) (0.10) - (0.06) (12)
Deviation
* Reference Value, not Certified.
Percent Spike Recovery.
Al Ag As Cd Cr Cu Fe Mo Se Zn
Mean (n = 3) 94.2 93.7 94.0 92.4 99.8 100.6 97.7 97.0 96.1 98.1
Standard Deviation (3.1) (1.5) (3.9) (5.9) (2.1) (1.3) (1.6) (4.7) (7.4) (2.3)
Analytical Precision as RSD**
Sample Al Ag As Cd Cr Cu Fe Mo Se Zn
Station
7 2.8 6.7 1.4 0.0 2.8 3.8 2.8 2.8 1.8 2.8
17 2.8 12.9 6.1 23.6 1.0 0.8 0.0 0.0 0.0 6.2
** RSD = (standard deviation / mean) X 100
Method Detection Limits (MDL)
Al Ag As Cd Cr Cu Fe Mo Se Zn
N (pg/g) (pg/g) (Ng/g) (pg/g) (ug/g) N (pg/g) (4g/g) (pg/g)
MDL*** 0.006 0.01 0.1 0.002 6.7 1 0.001 0.03 0.03 1
*** Based on 0.45 grams of sediment.
48

•
•
•
APPENDIX 2.
Quality assurance and quality control (QA/QC) data for the dissolved metal analyses.
49

Results for the Seawater Standard Reference Material (SRM) LASS-3 and Trace Metals in Elements # 1643d.
Mean and (Standard
Deviation). (NRC -National Research Council
of Canada; NIST = National
Institute of Standards and Technology).
' SRM As
(µg/L)
Cd
(µg/L)
Cr
(µg/L)
Cu
(µg/L)
Mo
(µg/L)
Zn
(µglg)
CASS-3 1.12
0.031
0.095
0.482
-
1.02
This Study 1.12
0.032
0.095
0.551
-
1.05
1.14
0.030
0.097
0.533
-
1.03
1.12
0.029
0.095
0.545
-
1.06
1.08
0.032
0.094
0.549
-
1.28
Certified Mean 1.09
0.030
0.092
0.517
8.95
1.24
Standard Deviation (0.07)
(0.005)
(0.006)
(0.062)
(0.26)
(0.25)
#1643d -
-
-
-
113.9
This Study -
-
-
-
112.5
-
Certified Mean 56.02
6.47
18.53
20.5
112.9
72.47
Standard Deviation (0.73)
(0.37)
(0.20)
(3.8)
(1.7)
(0.65)
Percent Spike Recovery.
As
Cd
Cr
Cu
Mo
Zn
Mean (n = 4) 94.1
101.5
100.2
93.5
97.4
98.4
Standard Deviation (1.2)
(5.8)
(5.1)
(4.1)
(2.5)
(8.2)
Analytical Precision as RSD*.
Sample Station As
Cd
Cr
Cu
Mo
Zn
22 Surface 4.7
9.4
9.4
2.1
0.0
1.6
23 Surface 4.2
7.4
7.9
1.7
0.0
0.5
RSD = (standard deviation / mean) X 100
Method Detection Limits (MDL)
(µgh-)
(PA)
(µyw
(A)
00')
(41)
MDL** 0.008
0.001
0.005
0.003
0.13
0.10
•' Based on 400 m1 aliquots for extracted metals (As, Cd, Cu and Zn), and no dilution for Mo.
•
50

•
0 APPENDIX 3.
•
Quality assurance and quality control (QA/QC) for the particulate metal analyses.
51

Results for the Standard Reference Material (SRM) Buffalo River Sediment #2704 and Trace Elements in Water # 1643d. Mcan and
(Standard Deviation). (MIST =
National Institute of Standards and Technology).
SRM Al
NO
As
(µ8/8)
Cd
Cr
Cu
Fe
Mo
Zn
(Ag g)
(µg/8)
W/O
(%)
048)
(µ /g)
#2704 6.01
23.9
3.67
136
99.6
4.09
3.5
434
This Study 6.13
24.2
3.61
139
100.E
4.16
3.5
443
5.95
23.8
3.65
139
99.5
4.08
4.4
446
6.09
24.0
3.60
138
101.9
4.17
3.8
444
6.05
23.7
3.59
132
101.3
4.14
4.6
443
Certified Mean 6.11
23.4
3.45
135
98.6
4.11
-
438
Standard Deviation (0.16)
(0.8)
(0.22)
(5)
(5.0)
(0.11)
-
(12)'
#1643d -
-
-
-
-
111.9
This Study
-
-
111.5
-
-
-
-
-
112.5
-
Certified Mean -
-
-
-
112.9
Standard Deviation
-
-
-
(1.7)
Percent Spike Recovery.
Al
As
Cd
Cr
Cu
Fe
Mo
Zn
Mean (n - 4) 98.4
97.9
107.1
91.9
91.8
94.9
96.0
97.8
Standard Deviation (3.3)
(3.8)
(0.3)
(1.8)
(2.5)
(2.1)
(2.0)
(5.3)
Analytical Precision as RSD*.
Sample Station Al
As
Cd
Cr
Cu
Fe
Mo
Zn
16 2.7
1.0
5.2
7.2
2.7
6.4
10.9
0.6
22 Surface 9.6
1.6
7.3
1.9
0.3
2.8
0.0
6.8
22 Bottom 0.4
1.5
5.9
0.7
2.7
0.5
1.6
2.4
23 Surface 6.0
7.1
6.6
3.4
1.4
2.4
6.7
4.7
• RSD - (standard deviation 1 mean) X 100
Method Detection Limits (NIDL)
Al
As
Cd
Cr
Cu
Fe
Ma
Zn
NO
(gg/g)
W/O
(14g/8)
W/O
M
W/O
(Ng/g)
.
M DL• • 0.02
5.5
0.05
0.5
0.7
0.02
0.7
35
"• Based on 1 mg of suspended matter.
52

•
rI
APPENDIX 4.
Quality assurance and quality control A/ C data for the tissue metal analyses.
Q Y 9 Y iQ Q) Y
53

Results for the Standard Reference Material (SRM) DORM-2 (Dogfish Muscle). Mean and (Standard Deviation). (NRC = National
Research Council of Canada).
SPIM Ag As Cd Cr Cu Fe Se Zn
(Ng/g) W/O W/O (Ng/g) (Ng/g) (Ng/g) W/O (Ng/g)
DORM-2
0.043
18.9
0.045
30.0
2.48
136
1.44
24.1
This Study
0.036
18.5
0.049
32.8
2.30
134
1.40
25.1
0.031
18.8
0.045
29.8
2.27
137
1.36
24.2
0.034
17.4
0.042
29.7
2.31
144
1.34
24.6
0.034
18.4
0.046
31.2
2.37
133
1.48
24.4
0.034
18.2
0.046
31.1
2.18
135
1.45
25.4
Certified Mean
0.041
18
0.043
34.7
2.34
142
1.40
25.6
Standard
Deviation
(0.013)
(1.1)
(0.008)
(5.5)
(0.18)
(10)
(0.09)
(2.3)
Percent Spike Recovery.
Ag As*
Cd*
Cr
Ctt
Fe
Se
Zn
Mean (n = 6) 92.1 81.7
87.7
95.4
98.1
100.5
103.8
96.2
Standard (1,9) (I1.1)
Deviation
(11.0)
(6.7)
(2.2)
(3.3)
(2.8)
(3.2)
The metal concentrations reported are corrected for spike
recovery.
Analytical Precision as RSD**.
Sample Station Organism
Ag
As
Cd
Cr
Cu
Fe
Se
Zn
12 male crab
1.9
3.5
8.3
5.7
3.1
2.7
13.1
0.0
Durham Creek male crab
4.6
3.1
5.4
1.3
4.3
2.9
2.1
1.1
Durham Creek clams
6.9
0.9
7.5
2.8
1.4•
3.4
5.7
0.6
Long Creek Pumpkinseed
N.D.
7.9
6.3
2.8
6.5
6.7
4.7
1.6
Pamlico River Longnose Gar
17.7
4.7
8.3
2.1
3.0
2.2
2.2
3.1
•+ RSD = (standard deviation / mean) X 100
Method Detection Limits (MDL)
Ag As
Cd
Cr
Cu
Fe
Se
Zn
(Ng/g) (Ng/g)
(Ng/g)
W/O
(Ng/g)
(Ng/g)
(Ng/g)
W/O
MDL*** 0.002 0.029
0.0003
0.003
0.7
2.5
0.05
0.4
*•• Based on 0.5 grams of tissue (dry weight)
•
54

•
ATTACHMENT C
CADMIUM CONCENTRATIONS IN SOILS, PLANTS, AND TERRESTRIAL
ANIMALS FROM THE PCS PHOSPHATE FACILITY IN
AURORA, NORTH CAROLINA
by
Terry J. Logan
Ohio State University
•

CADMIUM CONCENTRATIONS IN SOILS, PLANTS, AND TERRESTRIAL
ANIMALS FROM THE PCS PHOSPHATE FACILITY IN
AURORA, NORTH CAROLINA
Terry J. Logan, Ph.D.
Professor Emeritus
School of Natural Resources
The Ohio State University
2021 Coffey Road
Columbus, OH 43210
Introduction
This study was conducted as part of a larger effort to assess the environmental impact of Cd in mine
waste from the PCS phosphate mining operations in Aurora, North Carolina. This component of the
study investigated the transfer of Cd from mine waste at various locations on the mine to native
. vegetation and wildlife species. Samples were collected from the following three major sites: (1)
a control area, the Archbell-Kugler tract, to give comparative data on soils, vegetation and wildlife,
(2) from the Charles Tract clay disposal ponds, the oldest of the reclamation areas, and (3) from the
plant site vicinity, which includes the gypsum/clay blend reclamation areas and the Porter Creek
North Wetlands Reclamation Area.
Methods
Soil, Plant Tissue and Animal Tissue
General
The three types of samples (soil, plant tissue and animal tissue) were all analyzed by similar
procedures. These include: sample drying, sample homogenization, subsampling, sample digestion,
and analyte quantification. All samples were dried in a forced -air oven to constant moisture but at
1

different temperatures for each sample type; homogenization varied with sample type. All digestions
were performed in a CEM microwave digestion system, with different acids and digestion
parameters for each sample type. Analytes (As, Cd, Cr and Zn) were analyzed with either a Perkin-
Elmer Model 303B flame atomic absorption spectrophotometer (AAS) with background correction,
or a Perkin Elmer 4100ZL graphite furnace atomic absorption spectrophotometer with Zeeman
background correction. QA/QC consisted of digestion blanks, digestion duplicates, standard
reference material (SRM), and analytical standards and blanks. Soil and plant samples were digested
in duplicate. The SRM for soil is a soil prepared in our laboratory and used for at least 10 years for
trace element research. The SRM has been used in a round-robin with the University of
California -Riverside and USDA-ARS-Beltsville, MD. The SRM for plant tissue is citrus leaves
(SRM 1572) supplied by NIST. The SRM for the animal tissue is NIST bovine liver (SRM 1577a).
Soils
Soil samples were taken in July 1997 by Ohio State University (OSU) staff. Samples were taken
from the 0-15 cm depth, and each sample was a hand composite of 10 subsamples. Samples were
. placed in polyethylene bags and transported to OSU.
1. The samples were sieved through a 2 mm sieve, air dried at 25°C in the laboratory and mixed
by hand.
2. Approximately 0.5 g was weighed in duplicate for each sample. The CEM microwave digestion
method Soil (OS-14) was used. This method uses 10 ml deionized (DI) water, 5 ml concentrated
HNO3, 4 ml concentrated-HF and 1 ml concentrated HCL A blank and standard soil were
included in each digestion batch.
3. After digestion the samples were brought up to approximately 30 ml total volume by weight. The
exact weights and volumes were recorded.
4. Standards were prepared by weight using high quality standard solutions.
5. Cd, Cr, and Zn were analyzed by flame AAS. If the flame AAS registered no concentration for
Cd, those samples were repeated on the graphite furnace AAS. All measurements were recorded
within the standard range. If a concentration exceeded the standard range, the range was adjusted
to include the concentration of those samples.
2

•
b. As and Cd were then analyzed by the graphite furnace AAS. If the concentration was greater
than that of the standard range, those samples were diluted until they fit within the standard
range.
Plant Tissue
Plant tissue samples were taken in September, 1997 by CZR and were shipped to (OSU) in
polyethylene bags for analysis. Samples of several dominant species of emergent vegetation were
taken. The samples were dried in a forced air oven at 70°C. .
1. The samples were ground in a Wiley Mill with a stainless steel blade and screen. The ground
sample was mixed by hand.
2. Approximately 0.5 g was weighed in duplicate for each sample. The CEM microwave digestion
method Pine Needles (AG-10) was used. This method uses 15 ml concentrated HNO3. A blank
and SRM were included in each digestion batch.
3. After digestion the samples were brought up to approximately 30 ml total volume by weight. The
exact weights and volumes were recorded.
4. Standards were prepared by weight using high quality standard solutions.
5. Concentrations of Cd were determined using graphite furnace AAS. All measurements were
recorded within the standard range. If a concentration exceeded the standard range, the range was
adjusted to include the concentration of those samples.
Animal Tissue
Animal samples were taken by CZR and shipped frozen to OSU. Specific tissues or organs were
subsampled for each species and categorized as muscle, liver, kidney, or whole sample. Kidney and
liver are known storage organs for Cd (Logan and Chaney 1983).
1. The samples were placed in a porcelain crucible and the wet weight was recorded. The goal was
to obtain about 25 g of moist tissue. This was not possible in every case because of differences
in the size of the collected tissues.
2. The samples were then dried in a 105 °C oven for about 24 hours and the dry weight was then
3

recorded. Blanks and standards were included for each set of 16 samples.
3. The crucible with sample was then placed in a muffle furnace and the temperature was slowly
increased in 100 ° increments until the temperature reached 800 °C. The samples were held at the
high temperature for at least 12 hours.
4. After slowly cooling the ashed samples, they were then rehydrated on a hot plate using dilute
HNO3, HC 1 and high purity water.
5. After volume reduction on the hot plate, the samples were filtered and brought to a known
volume of about 30 ml. The exact weights and volumes were recorded.
6. Standards were prepared by weight using high quality standards.
7. Concentrations of Cd were determined by graphite furnace AAS. All measurements were
recorded within the standard range. If a concentration exceeded the standard range, the sample
was diluted with high purity deionized water until it fit within the standard range.
Results
0 Soils
Table 1 is a summary of the soil pH by site. Soil pH was relatively uniform (6.9 ± 0.3) across sites
and nearneutral. At this pH, trace metals like Cd have relatively low bioavailability for plant uptake.
Table 2 gives total soil concentrations of As, Cd, Cr and Zn. In most cases, laboratory duplication
of the soil test results was good, with most samples having a relative percentage difference (RPD)
of < 20 % (Table 2). Laboratory duplication represents variation in sample digestion and assay.
There were striking differences in total soil metal concentrations across sites for all four trace
elements. Values of all of the metals were generally in the order:
R2=Charles Tract pond 4B>R-14Charles Tract pondl»Porter Creek North>Archbell/Kugler
The trace elements were highly correlated with each other (Figures 1 to 4). The oxyanions As and
Cr were linearly correlated as were the trace metals Cd and Zn. Cadmium and Zn are known to
coexist in most ore bodies because of their similar chemistry. It should be noted that the ratio of Zn
4

to Cd is only 6 (see slope of Zn-Cd line, Figure 4) and it has been suggested that ratios > 100 to 1
are needed for Zn to inhibit Cd uptake by plants. This. suggests that Cd bioavailability should be
relatively high, but this is countered by the relatively high soil pH.
Plants
Laboratory plant analysis duplicates were good, except where concentrations were near the analytical
limits of detection (Table 3). Variation in Cd content of plant samples by species on a given site was
quite high, with coefficients of variation of 50 % or higher in many cases. This appears to represent
real site variation rather than analytical differences.
Cadmium concentrations varied widely across sites for a specific plant species, and across species
on a given site (Table 4). Species differences were in the range:
Sal ix»Eupatorium»Solidago>Myrica>Phragnrites
0
Salix was the most sensitive species, exhibiting three orders of magnitude differences in Cd
concentrations and generally responding to soil Cd levels (RZ = 0.64; regression not shown).
Concentrations of Cd in Eupatorium also responded to soil Cd levels. Myrica and Solidago showed
small but measurable responses to soil Cd, while Phragnrites was insensitive to soil Cd levels.
Animal Organism Tissue Concentrations
Cadmium concentrations in the tissues of various wildlife species from the control and
phosphate -impacted sites are given in Tables 5-8.One mourning dove (Zenaida macroura) from the
Reclamation area R-1 and a quail (Colinus virginianus) from the Charles Tract had to be discarded
because they had decomposed. One Plant site Canada goose (Branta canadensis) kidney sample and
one R-1 quail kidney sample were lost during digestion. With the exception of one dove, all tissue
Cd concentrations were low (<6.79 mg/kg) at the control site (Table 5). The Cd concentrations in
one of the doves were extraordinarily high (up to 37.1 mg/kg), but the results were not due to
5

•
analytical error because muscle, liver and kidney Cd concentrations were all extremely high.
Interestingly, these concentrations were higher than those of the dove with the highest level on the
reclamation site (see Table 7). The range of birds is such that this specimen could have come from
more impacted areas. As is commonly found in most species, Cd concentrations were generally
highest in kidney, intermediate in liver and lowest in muscle.
In general, specimens collected from the Charles Tract had the highest Cd concentrations (Tables
6 and 8). Highest kidney and liver concentrations were observed in quail, and deer (Odocoileus
virginianus) also had high kidney levels compared to the control.
Specimens taken from the Reclamation/Plant site also had elevated Cd concentrations in liver and
kidney (Table 7 and 8). There was insufficient muscle data to make comparisons among species and
sites. One eastern cottontail (Sylvilagus floridanus) and one goose had particularly elevated levels
among those sampled at the Plant site, but there were no specimens of these species at the control
site for comparison.
Cadmium concentrations in specimens from the Reclamation/Plant site were generally lower than
those from the Charles Tract (Table 7 and 8). As at the control site, one dove had much higher
kidney Cd levels than the other specimen collected.
Turtles were collected from three locations on the Reclamation/Plant site. The yellow -bellied slider
(Chrysemys scripta) captured at the 101 outfall had higher liver and kidney Cd concentrations than
the snapping turtle (Chelydra serpentina) from the Porter Creek wetlands creation site and the
chicken turtle (Deirochelys reticularia) from the Porter Creek shoreline (Table 7). The elevated
concentrations for the slider from the 101 outfall cause the average turtle Cd concentrations from the
Reclamation/Plant site to appear elevated relative to the control (Table 8).
Table 8 gives mean Cd concentrartions by species for each site. Because some species were not
represented at all three sites, complete comparisons are not possible for all species. The species
represented at all three sites were cotton rat (Sigmodon hispidus), deer, least shrew (Cryptotis parva),
6

grasshoppers (Acridiidae), opossum (Didelphis virginiana), raccoGn, (Procyon lotor), and pillbugs
(Oniscoidea). Rankings of Cd concentrations by species and tissue are:
Cotton rat liver: Charles Tract > Reclamation/Plant >> Control
Cotton rat kidney: Charles Tract > Reclamation/Plant >> Control
Deer muscle:
Reclamation/Plant > Charles Tract > Control
Deer liver:
Charles Tract > Control > Reclamation/Plant
Deer kidney:
Charles Tract > Reclamation/Plant >> Control
Least shrew liver:
Reclamation/Plant > Charles Tract >> Control
Least shrew kidney:
Reel amation/Plant > Charles Tract > Control
Grasshoppers:
Charles Tract > Reclamation/Plant ». Control
Opossum liver:
Charles Tract > Reclamation/Plant > Control
Opossum kidney:
Charles Tract > Reclamation/Plant > Control
Raccoon liver:
Charles Tract > Reclamation/Plant > Control
Raccoon kidney:
Charles Tract > Reclamation/Plant > Control
Pillbugs:
Charles Tract > Control = Reclamation/Plant
Quail liver:
Charles Tract >> Reclamation/Plant
Quail kidney:
Charles Tract >> Reclamation/Plant
Turtle liver:
Reclamation/Plant >> Control
Turtle kidney:
Reclamation/Plant >> Control
Among the other species sampled, gray fox (Urocyon cinereoargenteus) showed similar liver Cd
levels at the control and Reclamation/Plant sites, while kidney levels were somewhat higher at the
Reclamation/Plant. In the case of dove sampled at the Control and Reclamation/Plant sites, each site
had one specimen with very high Cd concentrations, particularly in kidney. This may suggest that
this species ranges freely among sites and has a high potential to accumulate Cd, more so than any
other species surveyed. Nutria sampled at the Control and Charles Tract showed little accumulation
of Cd in liver or kidney and did not respond to site differences. Rabbit showed no difference in Cd
accumulation between the Charles Tract and Reclamation/Plant sites, but Cd levels were high,
reflecting the similarity in Cd exposure between these two sites.
C

.7
Discussion
Few studies have been conducted on wildlife species exposed to trace elements like Cd. In a risk
assessment prepared for USEPA to evaluate the effects of trace elements in sewage sludge on
wildlife species, Efroymson et al. (1996) summarized data from a field experiment on a forest site
in Washington state. The authors also reported critical toxicity concentrations for rat and least shrew.
In a separate study, Donker et al. (1992) report Cd concentrations for terrestrial invertebrates on a
smelter site. The levels of Cd in the Washington soils were only slightly above 1 mg/kg and the Zn
to Cd ratio was about 100. In the present study, Cd concentrations were 15 to 30 mg/kg on the
Charles Tract and Reclamation sites, and the Zn to Cd ratio was about 4. Zinc inhibits the uptake
of Cd by plants and animals. In the case of deer, liver and kidney levels were similar between this
study and the sludge site in Washington (Table 8), suggesting that Cd bioavailability may be lower
in the phosphate mine waste or that deer may be grazing species with relatively low Cd uptake. Of
0 the plant species sampled, only Salix and Eupatorium had highly elevated Cd levels.
In the case of dove, Cd concentrations were comparable among those from the present study and the
Washington site, with the exception of the two highly impacted specimens from the Control and
Reclamation/Plant sites.
Least shrew is one of the most studied species in soil contamination investigations. Organ
concentrations were lower from the present study than from the Washington site (Table 8), again
suggesting that Cd bioavailability may be lower in the mine waste than in sludge -amended soils.
This could be attributed in part to the relatively high soil pH (5.93-7.34) on the North Carolina sites
(Table 1), and possible precipitation or co -precipitation of Cd with phosphate. Terrestrial
invertebrates were also lower in Cd from the present study than in Washington (Table 8), but the
single quail taken from the Charles Tract had much higher Cd levels than reported for the
Washington study.
E

•
•
Cadmium toxicity data for wildlife species is limited. Efroymson et al. (1996) report a critical kidney
concentration for laboratory rat of 350 mg/kg. This is about 18 times higher than the 19 mg/kg found
in cotton rat on the Charles Tract. Likewise, Efroymson et al. (1996) report a critical kidney
concentration for least shrew of 696 mg/kg, almost 50 times greater than the concentrations observed
in least shrews on the Charles Tract.
Conclusions
The highest total Cd concentrations in soil of 15 to 30 mg/kg represent increases above background
by 150 to 300 fold. On a risk basis, these concentrations can be compared to the maximum allowable
Cd concentration in soil of20 mg/kg in the USEPA regulations for land application of sewage sludge
(EPA,1993). It should be noted that this value was based on sludge data in which the Cd to Zn ratios
were much smaller than observed in the present study. However, comparison of data from this study
and the Washington sludge experiment suggest that Cd bioavailability may be no greater or even
lower than for sludge.
Plant uptake was highly species specific, with only Salix and Eupatorium showing much Cd
accumulation. Visual observations indicated that Cd levels in these two species were not phytotoxic.
These species may be Cd accumulators, in which case they can take up large amounts of the metal
without adverse effects. The extent to which the various animal species sampled forage on these two
plant species is not known.
All animal species sampled in the Charles Tract and Reclamation/Plant site had elevated Cd
concentrations compared to the Control site, particularly in the liver and kidney, which are known
storage organs for Cd. AIthough toxicity data is limited for wildlife species, reported critical kidney
concentrations for rat and least shrew suggest that the elevated Cd levels measured in this study are
not life threatening, although sub -critical effects cannot be ruled out.
z

9 References
Donker, M.H., H.E. van Capelleveen and N.M. van Straalen. 1993. Metal contamination affects
size -structure and life -history dynamics in isopod field populations. Pg. 383-399. In R. Dallinger
and P.S. Rainbow (eds) Ecotoxicology of Metals in Invertebrates. Lewis Pubs., Boca Raton, FL.
Efroymson, R.A., B.E. Sample, R.J. Luxmoore, L.S. Tharp and L.W. Barnthouse. 1996. Evaluation
of the ecological risks associated with land application of municipal sewage sludge. Final report.
Oak Ridge National Laboratory, Oak Ridge, TN.
Logan, T.J. and R.L. Chaney. 1983. Utilization of municipal wastewater and sludges on land -metals.
Proc. Workshop on Utilization of Munic. Wastewater and Sludge on Land. Univ. California -
Riverside, Riverside, CA.
U.S. EPA. 1993. Standards for use or disposal of sewage sludge. Final rule, 40CFR Part 503. Federal
Is Register.58:9248-9415.
•
10

v
i
•
0
60
50
40
a�
30
20
10
0
y - - 0.14517 + 0.10690x RA2 - 0.842 •
• Arsenic vs Chromium
•
• •
•
•
0 100 200 300 400 .500
Cr (mg/kg)
Figure 1. Relationship between total arsenic and chromium.

•
•
T
is
60
50
.. 40
30
20
10
0
•
y a 1.9007 - 1.1113x + 9.6864e-W2 RA2 = 0,764
•
• Arsenic •
0 ]0 20 30
Cd (mglkg)
r
Figure 2. Relationship between total arsenic and cadmium.
12

i
0
•
i
�i
500
400
300
ao
200
U
100
0
y=15.019 - 8.3740x + 0.81450xA2 RA? = 0.905
•
• Chromium •
•
•
0 10 20 30
Cd (mgAg) .
Figure 3. Relationship between total soil Cr and Cd.
13

:7
I
J
30
25
5
0
= 0. 154x + 0.00 1 0
O O
O
O
O
O
' Ln Cm LM
W" 0-1
Zinc (mg/kg)
Figure 4. Relationship between total soil Cd and Zn.
0
14

0 Table 1. Soil pH.
Site' Sample
number
Rep
pH
Mean
A/K
1
1
_
6.37
6.50
A/K
1
2
6.62
A/K
2
1
6.30
6.65
A/K
2
2
6.99
A/K
3
1
6.70
6.80
A/K
3
2
6.89
CP1
1
1
7.02
7.06
CP1
1
2
7.10
CP1
2
1
7.03
7.09
CP1
2
2
7.15
CP1
3
1
7.23
7.27
CP1
3
2
7.30
CP48
1
1
5.93
6.02
CP413
1
2
6.11
CP413
2
1
6.61
6.53
CP48
2
2
6.55
CP4B
3
1
7.00
7.02
CP48
3
2
7.04
PCN
1
1
6.96
6.95
PCN
1
2
6.94
PCN
2
1
6.75
6.78
PCN
2
2
6.80
PCN
3
1
6.87
6.92
PCN
3
2
6.96
R-1
1
1
7.04
7.04
R-1
1
2
7.03
R-1
2
1
7.02
7.01
R-1
2
2
7.00
R-1
3
1
7.01
7.02
R-1
3
2
7.02
R-2
1
1
7.22
7.16
R-2
1
2
7.10
R-2
2
1
7.21
7.20
R-2
2
2
7.18
R-2
3
1
7.34
7.34
R-2
3
2
7.33
" A key to sample abbreviations is contained in Table 1
of the SAMPLING AREAS AND STRATEGY
section, page 111-1.
15

Table 2.
PCS Soils Total Metals - Laboratory Replicate Means and Relative Percent Difference (RPD)
Sample'
Cd (mg/kg)
Cr (mg/kg)
Zn (mg/kg)
As (mg/kg)
Mean
RPD
Mean
RPD
Mean
RPD
Mean
RPD
A/K 1
0.049
4
4.25
137
6.6
19
0.381
12
A/K 2
0.046
9
2.70
73
6.1
16
0.315
8
A/K 3
0.082
15
6.82
45
8.6
15
0.858
15
CP1 1
15.8
2
149
5
107
0
5.73
39
CP1 2
19.6
3
103
8
131
2
3.12
7
CPI 3
18.0
3
125
1
123
3
5.65
6
CP4B 1
28.0
4
410
0
200
3
37
4
CP46 2
24.7
5
251
11
147
4
-b
-
CP413 3
21.1
0
148
1
136
0
14.9
43
PCN 1
0.37
5
10.8
10
6.4
19
2.06
31
PCN 2
1.13
2
18.7
4
13.6
14
1.85
23
PCN 3
0.86
4
23.1
24
23.3
10
3.22
24
R-1 1
18.3
5
118
8
90
4
17.3
4
R-1 2
21.7
1
158
1
110
4
26.3
30
R-1 3
14.7
1
87
1
68
5
17.6
17
R-21
25.3
0
390
1
185
0
55
5
R-2 2
24.5
1
347
14
158
3
32
16
R-2 3
21.9
0
291
1
143
4
30
6
' A key to
sample abbreviations is
contained in Table 1
of the SAMPLING AREAS
AND STRATEGY
section, page
III-1.
b Sample was lost.
•
16

Table 3. Plant Cd Concentrations - Site Means
Site Plant
Mean (mg/kg)
STD
Control site--Archbell/Kugler
Salix
0.19
0.09
Solidago canadensis
0.04
0.01
Myrica cerifera
BDL
BDL
Eupa torium
0.38
0.36
capillifolium
Charles Tract - Clay pond 1
Phragmites
0.08
0.06
Salix
76.9
19.1
Solidago canadensis
0.63
0.29
Myrica cerifera
0.29
0.11
Eupa torium
1.80
1.27
capillifolium
Charles Tract - Clay pond 4B
Phragmites
0.07
0.13
Myrica cerifera
0.49
0.11
Solidago canadensis
0.58
0.32
Aster subulatus
2.18
0.39
Eupatorium
4.11
2.77
capillifolium
Porter Creek North Wetlands Reclamation
Area
Phragmites
0.34
0.29
Salix
1.86
0.74
Solidago canadensis
0.33
0.16
Aster subulatus
0.22
Eupa torium
0.61
0.29
capillifolium
Myrica cerifera
0.18
0.05
Reclamation site - R-1
Phragmites
0.07
0.00
Salix
94.0
1 1 .7
Solidago canadensis
1.11
0.66
Eupa torium
39.61
3.41
capillifolium
Myrica cerifera
0.35
0.18
Reclamation site - R-2
Phragmites
0.10
0.03
Salix
43.4
38.0
Aster subulatus
1.56
0.14
r-I
L.J
17

•
•
•
Table 4. Plant Cd Concentrations - Site and Species Mean
Site
Aster
Eupatorium
Myrica
Phragmites
Salix
Solidago
Site
Mean
S_T_D
Mean
STD
Mean
STD_
Mean
STD_
Mean
STD
_ Mean
_ STD
Mean _
STD
A/K Control
--- e
-
0.38
0.36
BDE_
---
---
-
0.19
0.09
0.04
0.01
0.20
0.17 _
Clay Pond 1
---
---
1.8
1.27
0.29
0.11
0.08
0.06
76.99
19.14
0.63
0.29
15.96
34.1
Clay Pond 4B
2.18
0.39
4.11
2.77
0.49
0.11
0.07
0.13
---
---
0.58
0.32
1.49
1.67
Porter Creek
0.22
---
0.61
0.29
0.18
0.05
0.34
0.29
1.86
0.74
0.33
0.16
0.59
0.64
North
R-1
---
---
39.6
3.41
0.35
0.18
0.07
0.00
94.0
11.7
1.11
0.66
27.0
41.1
1
R-2
1.56
0.14
---
---
---
---
0.10
0.03
43.4
38.0
---
---
15.0
24.6
Species Mean
1.32
1.00
9.30
17.0
0.33
0.05
0.13
0.12
43.3
42.6
0.54
0.40
No sample.
CD

9 0 0
Table 5. Organism tissue cadmium concentrations (mg/kg) - Archbell/Kugler Control Site.
Organism
Muscle
Liver
Kidney Whole
Cooter spp. Turtle
0.02
0.29
Cotton rat (composite n=4)
0.06
0.25
Deerl
0.02
4.95
1.53
Deer2
0.01
0.19
6.59
Deer3
0.01
0.14
2.18
Mourning dovel
0.00
0.26
3.71
Mourning dove2
0.10
0.54
5.03
Mourning dove3
2.01
37.1
458
Grasshoppers (composite)
0.069
Gray foxl
2.22
1.83
Gray fox2
0.03
0.17
Gray fox3
1.03
0.36
Least shrew (composite n = 8)
0.44
2.09
Nutria
0.12
0.09
Opossuml
1.09
6.79
Opossum2
0.11
1.06
Opossum3
0.87
4.43
Racoonl
0.11
0.23
Racoon2
1.82
1.99
Racoon3
0.08
1.25
Pillbugs (composite)
2.0

Table 6. Organism tissue cadmium concentrations (mglkg) - Charles Tract
Organism
Location'
Muscle
Liver
Kidney Whole
Cottonrat (composite n = 7)
CP413 & CP4A
4.27
18.94
Eastern cottontail)
Unspecified
0.031
4.42
42.80
Eastern cottontail2
Unspecified
0.023
0.97
8.89
Marsh rabbit
CP2
2.290
10.45
42.53
Deerl
CP dike
0.029
6.12
56.68
Deer2
CP dike
0.015
2.65
14.25
Deer3
CP dike
0.079
5.10
73.50
Deer4
CP dike
0.035
5.37
72.08
Grasshoppers (composite)
CP48
4.87
Least shrew (composite n=5)
CP413
4.59
4.59
Nutria
Unspecified
0.20
0.57
Opossuml
CP1
5.53
25.73
Opossum2
CPSA
3.16
10.44
p Opossum3
Unspecified
1.97
37.13
Quail
CP4B
0.100
32.61
109.7
Raccoonl
Flannigan Gut
18.42
4.03
Raccoon2
Unspecified
3.10
17.58
Pillbugs (composite)
CP413 & CP4A
8.11
a A key to sample abbreviations is contained in Table 1 of the SAMPLING AREAS AND STRATEGY section, page III-1.

•
Table 7. Organism tissue cadmium concentrations (mg/kg) - Reclamation areas and Plant site.
Organism
Location'
Muscle
Liver
Kidney Whole
Canada goosel
Plant site lawn
0.180
8.49
60.1
Canada goose2
Plant site lawn
0.067
4.03
28.1
Canada goose3
Plant site lawn
0.180
3.70
Grasshoppers icomposite)
R-2
2.82
Gray fox
Runway
1.07
3.91
Opossum 1
R-1
2.21
11.8
Opossum2
Outfall 007
0.68
1.67
Opossum3
Unspecified
1.09
2.33
Quail
R-1
0.54
3.76
Quail
R-1
0.014
5.08
__o
Eastern cottontail)
Runway
0.026
4.07
21.5
Eastern cottontai12
R-1/R-3
0.058
12.8
115
Eastern cottontail3
Unspecified
0.013
4.63
30.7
~' Racoon 1
Outfall 007
1.45
11.6
Racoon2
Unspecified
1.12
4.28
Pillbugs (composite)
R-1
1.99
Cottonrat (composite n =10)
R-1
2.36
6.75
Morning doves
R-1
0.018
0.29
6.85
Morning dove2
R-1
0.020
1.41
281
Least shrew (composite n =14)
R-1
13.0
15.4
Deer1
Near R-1
0.027
0.10
37.6
Deer2
Near R-1
0.032
0.52
33.0
Deer3
Near R-1
0.040
0.08
40.6
Yellow -bellied slider turtle
Outfall 101
2.71
14.7
Snapping turtle
PCN
0.16
0.21
Chicken turtle
Porter Creek
0.08
0.58
a A key to sample abbreviations is contained in Table 1 of the SAMPLING AREAS AND STRATEGY section, page III-1.
b Sample lost during digestion.

9 0 0
N
N
Table 8. Comparison of organism tissue Cd concentrations (mg/kg) across sites.
Organism
Tissue
Site
Other findings (mg Cdlkg)
Reference
Control
Charles
ReclamationlPlant
Turtle spp.
Liver
0.022
0.98
Kidney
0.289
5.18
Cotton rat
Liver
0.057
4.27
2.36
Critical conc = 350 in kidney
Efroymson et al., 1996
(composite)
Kidney
0.253
18.9
6.75
Deer
Muscle
0.016
0.039
0.084
Liver
1.76
4.81
0.236
Control = 0.5; sludge = 0.5 13,1) black-
Efroymson et al., 1996
taillwhite-tail}
Kidney
3.44
54.1
37.1
Control = 5.4; sludge = 5.3 131) black-
Efroymson et al., 1996
tail(white-tail)
Mourning dove
Muscle
12.66 10.0571
0.020
Liver
1.76 10.401)
0.848
Control = 0.88; sludge = 0.8-5.3 {robin}
Efroymson et al., 1996
Kidney
155.7 14,37)
144
Control=3.2; sludge=2.8-18 (robin)
Efroymson et al., 1996
Grasshoppers
Whole
0.069
4.87
2.82
(composite),.__
,....,..
Gray fox
_ ..
Liver
1.09
1.07
„_
Kidney
0.789
3.91
Least shrew
Liver
0.439
4,59
13.08
Control=2.6-3.9; sludge =22-62
Efroymson et al., 1996
(composite)
Kidney 2.09 4.59
15.45 Control =9-13; sludge=33-126; toxic Efroymson et al., 1996
level = 696
Control liver=0.18, control kidney=0.32 Efroymson et al., 1996
Fed contaminated earthworms: liver = 0.44, kidney = 0.39
Nutria Liver
0.120
0,195
Kidney
0.088
0.570
Opossum Liver
0.688
3.56 1.33
Kidney
4.09
24.4 5.27
Raccoon Liver
Kidney
0.67
1.16
10.8
10.8
1.28
7.94
Pillbugs Whole
2.08
8.11
1.99 Control = 6.7; smelter site = 81 Donker et al., 1992

Table 8. (concluded)
Organism ' Tissue
Site
Other findings Img Cdlkg) Reference
Control Charles
Reclamation/Plant
Liver
5.28
7.17
Kidney
42.8
55.8
Quail Muscle
0.10
0.015
Liver
32.6
2.812
Control= 0.88;- sludge = 0.8-5.3 (robin} Efroymson et al., 1996
Kidney
110
3.76
Control = 3.2; sludge = 2.8-18 (robin) Efroymson et al., 1996
Canada goose Muscle
0.142
Liver
5.41
Kidney
44.1
N
W