20080868 Ver 2_Section III D Metals 2020 PCS Creeks Report_20210701

D. METALS
Additional comparisons of summary metals data were conducted and are included here
for information. Tables or figures showing only 2020 values are included in Appendix F (only on
CD).
For this report, pairwise comparisons (i.e., Student's t-tests) were run for individual
sediment metals and water column metals to compare average concentrations of pre- versus
post -Mod Alt L years as well as pre- and post -Mod Alt L creeks to control creeks. Pairwise
comparisons also were made within individual creeks to compare average sediment and water
column metals of pre- versus post -Mod Alt L years. However, due to the lack of replicates per
creek, creeks were treated as pseudoreplicates, which decrease the specificity of the statistical
analysis. The need for pseudoreplicates is a problem most commonly associated with
environmental data where true experimental replicates are impossible. In this case, "control"
samples are collected from multiple reference sites and "impact" samples are collected from
multiple impacted sites. In this analysis, data from Jacks Creek, Jacobs Creek, Drinkwater
Creek, Tooley Creek, Huddles Cut, Porter Creek, and DCUT11 were essentially treated as
"impacted" samples and data from all control creeks were treated as control samples. Individual
differences among creeks could skew the data in such a way as to increase the risk of false
positive or false negative statistical findings. For this reason, it is also not possible to
statistically evaluate how metal concentrations change over time within a single creek as only
one sample is collected per creek per year. It is possible to visualize trends, but no additional
statistical analyses are possible on a per -creek basis other than to compare pre -Mod Alt L years
to post -Mod Alt L years and treat each year within a creek as a replicate.
In tabular depictions of the data across multiple years (Table III-D1), the current year is
shown but not included in the calculation of the average for the previous years so that it is
readily apparent how the current year concentration relates to the value of the ongoing average
of the previous years and how it, and the average of all previous years, compare to the previous
Pamlico River Estuary study, average continental and marine sediment crust, and the ERL/ERM
(the ERL/ERM guidelines are explained in more detail in Section II-E Q5). Note that when a
metal was not detected, the LOQ/CURL (reporting limit/detection limit shown with < in the
tables) was used as a data point for graphs and statistics. It is anticipated, however, that as
more data are collected by year, trends in metal concentrations over time can be visualized to
better understand the potential relationship between metal concentration and time.
1.0 Sediment Metals
The creek sediment samples were also analyzed for bulk density since 2011 and
Total Organic Carbon (TOC) since 2013. Figure III-D1 shows TOC in the sediments for each
creek each year since 2013. With the exception of Tooley Creek, TOC in the South Creek
tributary creeks in the study increased each year from 2013 to a high in 2016; with the exception
of Little Creek and PA2, TOC declined since 2016. The sandy sediment in Huddles Cut was
apparent with nearly zero TOC values, and with the exception of 2013, DCUT11 had the highest
TOC values every year followed closely by DCUT19 (Figure III-D1). Bulk density and TOC
values are also shown for each creek by year on Table III-D1. In every creek, the highest bulk
density values occurred in 2011 and that year was the final sediment sample analysis
performed by the Florida Institute of Technology (FIT) lab. The FIT lab dry sediment density
result was volume -based, while the dry sediment density result from the current lab is based on
dry weight of original sample. Each lab used a different ASTM bulk density method and both
labs had to slightly modify the method procedure as the samples were not "undisturbed" (i.e., a
III-D-1

grab sample not a core sample) and the quantities provided to the labs were also different.
Therefore, the 2011 bulk density values were not used in calculation of averages shown in any
table.
One factor that can influence metal availability in aquatic environments is total or
dissolved organic carbon. Metals dissolved in water can readily bind to organic carbon, which
can then limit bioavailability to living organisms through both aqueous and dietary
bioaccumulation pathways (Chen et al., 2016). Therefore, for many benthic environments
enriched in organic carbon, while stronger binding of metals may occur in the sediment, these
metals are generally less available for living organisms to accumulate (Chen et al., 2016). Total
organic carbon (TOC) data were available for sediments beginning in 2013 and statistical
evaluation of creeks began in 2017 with additional creek collections added in subsequent years.
All the TOC and metal concentration data (LOQs used for non -detections) were transformed to
the logo and data from control creeks and creeks with post -Mod Alt L data were evaluated with
a simple linear regression to determine whether metals increased or decreased in a linear
fashion with TOC (significance = p < 0.05). Broomfield Swamp Creek and DCUT11 were
excluded from the analysis as not enough years of data have been collected for a regression
analysis.
Concentrations of all 10 sediment metals significantly increased statistically with
TOC in the control creeks and in Drinkwater Creek. Concentrations for other impact creeks also
significantly increased statistically with TOC but only for some metals: Jacks Creek (As, Cr, Cu,
Zn, Al, and Fe), Jacobs Creek (As, Cr, Cu, and Mo), Tooley Creek (As, Cd, Cr, Cu, Mo, Se, and
Zn), Huddles Cut (As), and Porter Creek (Cr and Cu). With the data currently available for TOC
and water column metals, it does not appear as if creeks with lower TOC in the sediment have
higher water column metal concentration. Huddles Cut, for example, which has very low TOC,
does not have higher water column metal concentration when compared to Drinkwater Creek,
which has high TOC.
Figures III-D2 — D8 illustrate average pre- and post -Mod Alt L sediment metal
data for Jacks Creek, Jacobs Creek, Drinkwater Creek, Tooley Creek, Huddles Cut, Porter
Creek, and DCUT11, respectively, by year. A detailed discussion of pre- and post -Mod Alt L for
individual impact creeks significant differences are presented in Section II-E.
Table III-D1 shows the sediment metals values by year for each monitored creek
and the means and standard deviations of all years previous to the current year. For
comparison, values for the metals sampled in a 1998 study of the Pamlico River estuary, a 1984
study on average marine sediment crust, and a 1995 study on continental crust are also shown.
These previous studies show Al, Ag, Cd, Cr, Se, and Zn higher in the Pamlico River estuary
than in marine sediment crust; for Ag, As, Cd, Cu, Mo, and Se in some creeks in the PCS study,
including control creeks, this relationship seems to be also true as these metal means were
higher than the Pamlico River estuary values shown. Creeks with pre- and post -Mod Alt L
mean values above the 1998 Pamlico River estuary values for Cd, Mo, and Se include Jacks
Creek, Jacobs Creek, Drinkwater, and Tooley Creek. Control creek means for all years for Little
Creek, Long Creek, Muddy Creek, DCUT19, and Duck Creek were also above the Pamlico
Estuary values. The Cd, Mo, and Se means for the corresponding Jacks Creek, Jacobs Creek,
and Tooley Creek pre- and post -Mod Alt L years in the control creeks also were above the 1998
Pamlico Estuary values. Control creek PA2 had a Se value above the 1998 Pamlico River
estuary value and Cd and Mo values below the 1998 Pamlico River estuary values. Post -mod
Al L DCUT11 and pre -Mod Alt L Drinkwater Creek and Tooley Creek were the only creeks to
exceed the 1998 Pamlico Estuary value for As. Huddles Cut showed Cd values above the
III-D-2

Pamlico River estuary only in pre -Mod Alt L years and Mo values in post -Mod Alt L in Huddles
Cut were also above the 1998 estuary value. However, changes in laboratory methods and
laboratory equipment may contribute to some of the differences when results are compared to
the earlier studies.
2.0 Water Column Metals
Figures III-D9 a — d illustrate average water column metals for all creeks in
different combinations: a) pre- and post -Mod Alt L water column metal data for Jacks Creek,
Jacobs Creek, Drinkwater Creek, Tooley Creek, Huddles Cut, Porter Creek, and DCUT11
combined across years, b) average pre -Mod Alt L creek concentrations combined and
compared to controls, c) average post -Mod Alt L creek concentrations combined and compared
to controls, and d) average post -Mod Alt L creek 2020 concentrations only combined and
compared to controls. No increases in metal water column concentrations in post -Mod Alt L
years were significant statistically relative to pre -Mod Alt L years.
Table III-D2 displays the water column metals results on a per creek basis with
years divided into pre- and post -Mod Alt L categories and for comparison shows values for total
and dissolved metals sampled in 1998 in three of the same creeks in the current study, a 1983
study on trace elements in the world's oceans, a 1995 report on trace elements in natural
waters, and current US EPA national recommended water quality criteria for aquatic life
(freshwater and marine, acute and chronic for four of the 10 metals measured in this study and
partial criteria for another four in this study). In every creek, at least two of six metals with
means higher than earlier studies (As, Cr, Cu, Mo, Se, and Zn) have occurred (averages for Fe
were lower than earlier studies in all creeks); higher averages for all six metals have occurred in
post -Mod Alt L Drinkwater Creek while three control creeks have also had higher means for
these six metals (Little, PA2, and Duck). For a number of the six metals, averages in many of
the creeks also were higher than the world's oceans or rivers, and higher than the values
collected from the three local creeks in the 1998 study. All creek averages were above chronic
marine aquatic life criteria for Cu, with the exception of pre -Mod L DCUT11, pre -Mod Alt L Cu
averages in Broomfield Swamp, Drinkwater, and Jacobs creeks and post -Mod L Huddles Cut
exceeded acute marine aquatic life criteria, as did the averages in five control creeks (SCUT1,
Little, PA2, Long, and Muddy).
As noted in the sediment discussion above, changes in laboratory methods and
laboratory equipment may contribute to some of the noted differences when results are
compared to the earlier studies.
III-D-3

350
300
250
200
an
150
100
50
0
Total Organic Carbon in sediments by creek and year
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Asterisks indicate control creeks
2013 ■ 2014 2015 2016 ■ 2017 2018 2019 2020
Figure III-D1. Total organic carbon values in each study creek each year since 2013.
III-D-4

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III-D-5

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III-D-6

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III-D-7

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III-D-8

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III-D-9

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III-D-10

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III-D-11

AVERAGE WATER METALSACROSSALL SITES
1200.0
1000.0
800.0
600.0
400.0
200.0
0 Pre -Mod Alt L 0 Post -Mod Alt L
0
0
0.0 0 0 9 0 0 a (54
Ag As Cd Cr Cu Fe Mo Se Zn
METALS (ALL YEARS COMBINED)
0
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Ag As Cd Cr METALS (ALL YEAMo YEARS COMBINED)
Se Zn
0
Figure III-D9 a - d.
pre -Mod Alt L years
Average water colum
Mod Alt
WATER COLUMN
Average water column metals (µg/L) for all control creeks combined across years
relative to post -Mod Alt L years. 9b) Average water column metals for pre -Mod Alt
n metals for post -Mod Alt L creeks relative to control creeks, 2020 concentrations
L creeks. LOQ/CL/RL used if
1200.0
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METALS (2020 DATA ONLY)
0
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0
Ln
d
and creeks with both pre- and post -Mod Alt L data combined across creeks and years. 9a) Average water column metals for
L creeks relative to control creeks. 9c) Average water column metals for post -Mod Alt L creeks relative to control creeks. 9d)
only. No statistical elevations in average water column metals were present in post -Mod Alt L creeks relative to control or pre -
metal was not detected or detected below LOQ/CL/RL.
III-D-12

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SEDIMENT METALS, DRY BULK DENSITY, AND TOTAL ORGANIC CARBON (TOO
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N Vm V V m V V V V
0 V 0.- d' N 0 N 0 0
(O N 0 O (0 N N N N
0 0 0 0 0 0 00 0
.4 6 N 0 0 (h N (h (0
00 00 0N000000
VcoO (0(0r N(0(0(0
0 CO N V 0 V 0) I. N
0 O 0 O O O)
0 0 0,— 0 V V V
o vNi 0
m v 0 00
(0 N 0 V N (0 (0 N N
10 m 0 N
O m 0 CO 0 0) N
0 0 0 0 0 V 0 V V V
V V V V
0
0) 0 0 N. 0) 0 O N O (0
N N O N CO m IN (O V m
N. CO o 0 V (0 N N N N
N(0 V N (O N. 00 0) 0
0 0 0 0 0 0 0 0 0 0
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O
U
Little Creek
N (NO
O
IN O
O 0
(O O)
O) IN
r (0
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N
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0 0 0
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m
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Jacobs Creek
0000000 O
O r O N
M 00 IN0 0 IN
O N IN CO IN O O IN 0
(h (h (M N V (h N (h
O O O O O O O
0 v 0000000
0 O) O) V (0 N N O
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0 (h N O N O) 0 O if)
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Q Q 0 (0 V 0
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V V V v
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N IN IN N IN O (O
N O N N N N N N N
O m CD 0 o0 0 0 0 0
0 O W O N N LO N
r r 0000000
0) (O N r m IN V V O
O Co (0 O) N N V r
V N N N (h (0 (h
N r.�.�..(0 O N CO O N CO
(O O N r
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V V
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N N N N N N N
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IN 0
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m
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7. CO
m
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s
a
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III-D-13
N r O O O N V
(O W N W m 0 IN (O
N V
0) N r N N 0 0 N V
(O (O (O (O r V V (M W
N 0 0 0 0 0 0 0 0
0 00) 0 0 0 00 0 0 0 0
Co O O O) N N N N N m
N N N N N (O (O O N
O (r) V O N 0 0 0 0 0
m (O V O V r (O
0 v 0 0 0 N (0 m
0 0 N 0) •N O) N
N N r O V m
V v V— V v V V V
N
.-00 0) 0) (0 0 MOO
0 N 0 0 0 0 N 0) V
0 0 0 N N N 0 0
N r co O r r ON
m N N N W 0 7 V
N0o000(C00
N N O(0 M(0 O
O ON N N N 0) 0 0
N V 0 N V (0 O•
O O O O O- O V V V
0 10 m y v 0 0 0 0
(O 0 O N (M 0 (O N (6
N V N 0 N m N
N 0)O N N M N o o o N
0 0 0 0 0- o V V
V V V V
N COLO 0 M 7r N CO Ire
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N(6 V N (O r 00 0) 0
0 0 0 0 0 0 0 0 0 0
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U
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c
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000
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..:: CO N COCOW N V CO .... N N r
N 0 0) CO 0) 0
r (h (h m V N m
0 0 0 0 0 0 0
r
0 0 0 0 0
CO 0 0 O N
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0) N r 0 0 0 0 0
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coV r co 0) 0)
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N
(0 .:: 0 0 N 0 CC) LO 0 r O
N 0::::: 0 N V N N N N N
O
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(O
V 0)
N O)
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N 0 (M V O V
r O N N r (O (O N
(0 (0 (0 N (0 (0 (0
N V I. 0) 0 O O
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O 0::::: O o,— —0 v v v
vim) �::::oONO m o 0 0 0
r N 00
v 0 0 0 0 r 0
0 (0
N
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0 0) (0 (0 0 0) (O r
N N N N N N
(h v 10 m N. 00 CD
E'O O O O O O O O
' N N N N N N N N
J
a a N
Drinkwater Creek
CC/
CN
N O
CC)
0
(O N
O N
N
N
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N
O m
LOm
NCi
O N
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s
a
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V O N
6(0 V co V N N
N N
O CO 0 N. V O) N V V
N N N V V N N r (M C)
N 0— 0 0— 0 0 0 0
0 0 O 0 0 0 0 0 0 0
m m O O N (O (O (O N O
CD N O co co co co r (O
N O 0 O CC/O 0) 0 0 0 0
0 0 0 0 N V V
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N N N (O V 0) r
N V V V V V V V V V
N (O O N V (O 0 (O
r 0 (6 N (0 r 0 N
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co O L.0 CD O O r (O 0 088
r N (O W V W V 71-
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r co co co CD N
N N V M
0 0 V V 0 0) O O
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0 0 0 0 0 0 0 0 0 0
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U
0
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c
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m
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0
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CO
N.
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m(0 N CD 0) 7 O(0
V V
(0 0) 0 N. 0) 0) (0 N O
m N W m V V m m
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0 (M N O 0) 0) 0)
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TooleyCreek
N V
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r
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m
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N
m
N
z z
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Pamlico River Estuary
O 0
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Table III-D1 (concluded).
Al (%) Ag (N9/9) As (N9/9)
0
0
J
O O
ci N Q r Iry N d)
O O
CO M CO r CO LO M CC) 71- LO N N
N O O O O O O O O O
88 R 88888888u0ic00OM0O000
- CO 0) 0- LO
0 r- O DO 0) (V O M O O to O
r- 0 0 0 0 O N 0 O M Q co O CO CO co r
O N O N O O O O O (O In 8 O N 8 8 ON
O O O O O C) C) N Q to
0 0 0 0 0 0 0 O 0 0 0 0 N CO CO •O co M CO
O CO O r W CO d) Q LO CO M (rj M CO N r 0
M NM NM N N N N N NV V V M V V V V V
co co O co o 0 co O M 0) 7 Q O CO CO CO0CO W CO V
M M N N M M M M M M M N O
O O O O O O O O O O O O O O O O O O O O
u) co co lf) O O M lf) Q co co r O O N to N 0
O N O O O O Q Q r 0 to Qto(rj 0) to O O O r
co co N co N N N N N N N N N CO N
O O O O O O O O O O O O O O O O O O O O
CO.COCO.O.CO.COCOCO
O O O In O O O O O r Q N O
M N M C) r CO 0 0) CO CO M N r 0) O
O O 0 0 0 O O O- O V v v
0 0 0 0 co 0 0 LO 0 0 0 CO M O) Q Q 0 0 0 0
N Q • co. Q r 0co. co. co. r d) to 00 co. r o
to (0 co co r Q co (0 (0 Q N r- Q lf) to O (0
0)
0) co O co_ N lf) N M Q lf) CO CO O COr O r N CO Q
O
O 0 0 0 0 0 0 0 0 0 0 V 0 0 0 V v V V V
- CO 0) In r CO CO N O Q O M O lf) O O co CO O r-
O N 7 O O 0) 00 0) CO 0) 0) O to r 0) Q N N
✓ CO 0 CO 0 r O co r O r C) O Q C) C) N C) N
CO 80 pp Cp) Qp Mp rrp p Op Op) 0 7 N M Q If) O r O O) 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
- N N N N N N N N N N N N N N N N N N N
O
0
U
Muddy Creek
O CO 00 O O c))
C )) (( • 00 MO N
O 3O O
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r 0 In O O O
7 N N 0 0 0
Q Q In O CO
N O O O
7 N N 0 0 0
0 0 0 0 0 0
00 0 0
CO IN 0
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O O O CO Q N
CO CO N- 0 0 0
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M to O O O O
O pO p� pr pO 00))
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Huddles Cut
N N N N N
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M CO
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17.
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8 M.
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8R88
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0 0 0 0.-0 0 0
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N • N M O O M
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Q M (.0 r CO 0) 0
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co. O O M O co.
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2063AER888
O O O O M N co Q lf)
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M Do 00
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c) O r O O c) 00 c) c)
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co r
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co Q O O Q lf) co Q r 0
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r 0) M In r CO CO O r
r d) O 0 d) N If) CO. CO CO
O N O O— N N O
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0 0 0 0 0 0 0 0 0 O
N N N N N N N N N N
O
0
U
Duck Creek
0) 0
Io M
O N 8 0 0 0
In
�MNOOl,_
O 8 N cy
O O O O
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V N 7 DO. OM
CO
N M Q Q
Q N 0 0 0
N O cO
coN
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T- V W o 0 0
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o. CO 0
N O O O
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w (
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8 8
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III-D-14

c E a)
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a)
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a)
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(Q a) (1)
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co O
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oci
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a) • E :_.
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Table III-D2
a)
U
O
U
WATER COLUMN TOTAL METALS a
As (pg/L) Cd (pg/L) Cr (pg/L) Cu (pg/L) Fe (pg/L) Mo (pg/L) Se (pg/L) Zn (pg/L)
o
✓ V
lC
N l
V V V
v co
O O
v lv
V V
O
O o
LO LO
v
V V
O O
v Lv
V V
O
O o
v lv
V V
O
O O
v lv
V V
O
O 0
O O
Broomfield Swamp Creek Pre
o
V V
lC O
LC)
V V
0
O 0
O O
v lv
V V
O
O o
LO LO
v
V V
O O
v Lv
V V
O
O o
v lv
V V
O
O O
v lv
V V
O
O 0
O O
0
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