20080868 Ver 2_Section II E Q5 Metals 2020 PCS Creeks Report_20210701

E. Question 5- Has mining increased contaminate [sic] levels within creek
sediments to levels that could impact fish or invertebrates?
To be compliant with the 2015 EPA Publication SW-846, in 2016 certified laboratories
replaced Method 6010C with Method 6010D and Method 6020A with Method 6020B. With
the change in methods, the limit of quantification, control limit, or report limit (LOQ/CL/RL)
had to be raised for some metals in order to meet the QA/QC criteria for analysis which
resulted in a higher LOQ/CL/RL for some metals in some creeks than previous limits for the
same metal. (As explained by Greg Dickson, Technical Director of SGS laboratory, the
QA/QC criteria for the lowest level standard run by the SGS lab with each batch were much
tighter than before. These criteria provide better data for results that are at the lower end of
the calibration range). For tabular depictions of the data, the current year is shown but not
included in the calculation of the mean for the previous years so that it is readily apparent
how the current year value compares to the value of the ongoing mean of the previous years
and to the Effects Range Low/Effects Range Medium (ERL/ERM); also, only the detected
concentrations are used in calculations of the means for these tables. However, when the
raw data are entered into the spreadsheets for statistical comparisons and figure depictions
the < sign is removed and the reporting limit value is used as the concentration "detected"
for that metal that year and the current year is combined into the data set for analysis. The
reporting limit for any given metal can vary from year to year and from creek to creek within
a year due to different factors applied to the laboratory analysis of each sample; these
factors may include differences in initial sample volume and dilution factors.
The ERL/ERM concepts represent water quality concentrations for specific elements
or compounds below which adverse toxicological effects rarely occur and above which
adverse toxicological effects frequently occur (NOAA 1999). The ERL is generally the 10th
percentile concentration and the ERM is generally set to the 50th percentile concentration.
Concentrations that occur between the ERL and ERM reflect the "possible effects range"
and concentrations below the ERL reflect the "low end of a continuum roughly relating bulk
chemistry with toxicity" (O'Conner 2004). Therefore, ERL and ERM are not predictive of
toxicity, but do indicate sediment toxicity probability values and are guidelines that relate
sediment contaminant concentration with possible toxicological outcomes in exposed
organisms, either through the sediment directly, or through the aquatic environment. The
National Oceanic and Atmospheric Administration (NOAA) has published additional
guidelines and recommendations that include threshold effects levels (TELs) and probable
effects levels (PELs), which are sometimes lower (i.e., more protective) than ERLs and
ERMs (NOAA 2008).
In estuarine and coastal areas, metal concentrations are influenced by a large variety
of physical and chemical factors, which include the combination of natural and
anthropogenic inputs, erosion, activities of organisms in the environment, and interactions of
metals with particles and sediments (Khan et al., 2014). Therefore, due to these dynamic
physical and chemical factors present in estuarine and coastal areas, collected samples can
exhibit enormous temporal variability even when collected repeatedly from the same
physical site. In addition, retention time of samples in collection containers also can
influence apparent metal concentrations in solution due to sorption of metals to certain types
of plastics (samples are collected in amber glass jars provided by lab to reduce this effect).
These multiple factors affect metal concentrations from year to year, even from the same
creeks, and may cause variability to be quite large. The appearance of variability may also
II-E-1

have been introduced with the change in laboratory methods and procedures in 2011/2012
(Florida Institute of Technology [FIT] laboratory to SGS laboratory) and with the change in
law mentioned above that affected the laboratory methods used in this study, as well as the
laboratory applied sample analysis factors.
Figure II-E1 illustrates metal sediment data only for the seven creeks for which both
pre- and post -Mod Alt L data are available (Jacks Creek, Jacobs Creek, Drinkwater Creek,
Tooley Creek, Huddles Cut, Porter Creek, and DCUT11). Pre -Mod Alt L data were
compared to post -Mod Alt L data for each creek. If only one year of data was available,
values represent data from that year and if multiple years of data were available, values
represent average data across the multiple years for each metal and each creek. Figure 11-
E2 (a — d), Figure II-E3 (bar chart), and Figure II-E4 (a - b; line graph) show sediment metals
averages combined into various categories for comparison. When all creeks with pre- and
post -Mod Alt L data were combined and all years were combined into either pre- or post -
Mod Alt L years, of the 10 metals included in the evaluation, three (Ag, Mo, Se) were
significantly higher statistically in the post, three (Al, Cr, Zn) were significantly lower, and
four (As, Cd, Cu, Fe) showed no significant post -Mod Alt L change (Table II-E1).
Also of note: only one creek may have served as a control creek, pre -Mod Alt L non -
control creek, or post -Mod Alt L non -control creek for a given year (Table II-E2). Eleven (11)
years and seven creeks comprise the post -Mod Alt L period, and many of the creeks do
exhibit some variability in metals values, often due to more or less sand in the samples from
year to year, particularly in Huddles Cut.
Evaluation of metals within each individual creek resulted in the following statistically
significant differences between pre- and post -Mod Alt L data sets (p=<0.05): Jacks Creek —
increase in Ag and Se, decrease in Al and Cr; Jacobs Creek — increase in Ag, Cd, Mo, and
Se; Drinkwater Creek — increase in Ag, Mo, and Se, decrease in Zn; Tooley Creek —
increase in Ag, Mo, and Se, decrease in Al, Cr, Cu, Fe, and Zn; Huddles Cut — increase in
Ag; Porter Creek — increase in Ag, Cd, and Se; and DCUT11 — no statistically significant
differences (Table II-E1). Seven impact creeks showed post -Mod Alt L increases for Ag, six
for Se, and four for Mo; however, it is important to note that for many years of the entire data
set and almost all of the post -Mod Alt L years for these creeks, Ag Cd, and Mo
concentrations used in the analysis were the LOQs. Therefore, statistically significant
elevations reflect changes in the LOQ rather than changes in detected concentrations for
these three metals. Unlike Ag and Mo, Se detections occurred in most creeks most years;
but no ERL or ERM exist for either Mo or Se. Sediment from Jacobs Creek and Porter
Creek had statistically significant elevations in average concentrations of Cd for post -Mod L
years compared to pre -Mod L years. Concentrations for Cd and Mo for all of these creeks
were below the LOQs in 2020. Average concentrations of Se were higher in all post -Mod Alt
L years compared to pre -Mod Alt L years. Average concentrations of Se were also higher in
all control creeks when pre- and post -Mod Alt L years for each impact creek were used to
divide control creek data for comparison. Se increased in 12 creeks in 2020 relative to 2019
(six impact creeks: Jacks, Jacobs, Drinkwater, Tooley, Porter, and DCUT11 and six control
creeks: Little, Long, Muddy, PA2, DCUT19, and Duck).
Although metal variability can make detection of statistically significant differences
more challenging, average concentrations of all metals across the years and creeks have
stayed about the same or decreased in post -Mod Alt L years relative to pre -Mod Alt L years
and relative to control creeks except for Ag, Cd, Mo, and Se. Average Ag, Cd, Mo, and Se
concentrations increased from 2016-2020 (post -Mod Alt L years for most creeks) relative to
II-E-2

pre -Mod Alt L years. Since 2016, there has been a general increase of Se in all creeks
including most control creeks; therefore, the increase in post -Mod Alt L Se was likely due to
the addition of post -Mod Alt L years for Porter Creek in 2016 and for DCUT11 in 2018.
However, 2020 Se concentrations were the highest detected in twelve creeks; impact creeks
included Jacks and Porter at 6.00µg/g, Jacobs and DCUT11 at 5.50 µg/g, Drinkwater at 5.10
µg/g, and Tooley at 4.90 µg/g. Concentrations of Se in 2020 were also the highest ever
detected in each of six control creeks: SCUT1 and DCUT19 at 4.30 µg/g, Little at 5.00 µg/g,
Long at 4.90 µg/g, Muddy at 5.20 µg/g, and Duck at 5.60 µg/g. In Jacks, Jacobs,
Drinkwater, Tooley, and Porter these concentrations represent statistically significant
differences between averages for pre -Mod Alt L years and post -Mod Alt L years.
Comparison of averages for the same years in control creeks (Muddy for Jacks and Tooley
creeks, PA2 for Jacobs and Drinkwater creeks, and Duck for Porter Creek) showed similar
statistically significant differences in each comparison with the exception of Tooley Creek.
Tooley Creek had a statistically significant higher concentration of Se compared to Muddy
Creek for the same pre -Mod Alt L and post -Mod Alt L years. As previously noted, reported
concentrations of Ag, Cd, and Mo were below the LOQs in 2020, so the actual
concentrations of these metals are unknown. As noted in the 2015 and subsequent reports,
the 2015 value for Zn in Jacks Creek was well above both its ERL (150 µg/g) and ERM (410
µg/g), but Zn detections never exceeded the ERL or ERM before or since. As previously
mentioned, all creeks had higher concentrations of Mo in post -Mod Alt L years relative to
pre -Mod Alt L years, with statistically significant elevations reported for Jacobs Creek,
Drinkwater Creek, and Tooley Creek; however, no Mo detections have occurred since 2015
or earlier in all creeks except Huddles Cut whose last detection was in 2016. There are no
published ERL or ERM values for Mo, but a search of the literature suggests values > 1,000
µg/g as a no effect concentration (Heijerick et al., 2012), which is higher than any LOQ for
Mo in any year in this study.
Figures II E2a-d display average sediment metal concentrations: pre -Mod Alt L years
compared to control creeks (Figure II-E2a) post -Mod Alt L years compared to control creeks
(Figure II-E2b), post -Mod Alt L creeks compared to control creeks for 2020 only (Figure II-
E2c), and pre -Mod Alt L years compared to post -Mod Alt L years (impact creeks combined).
Although it is not possible to do statistical analyses on 2020 data for individual creeks as
there was only one replicate per creek, Figure II-E2c illustrates that metal concentrations in
control creeks were equal to or slightly exceeded metal concentrations in post -Mod Alt L
creeks, with the exception of Cr and Zn, which are slightly higher (but not statistically higher)
in post -Mod Alt L creeks. A summary chart of sediment metal and TOC averages combined
into four categories: all years (impact and control creeks), all pre -Mod Alt L years (impact
creeks only), all post -Mod Alt L years (impact creeks only), and all control creek years is
shown in Figure II-E3. Note that TOC was first measured in 2013; therefore, pre -Mod Alt L
values for TOC are limited to two years in Jacks Creek, one year in Jacobs Creek, three
years in Porter Creek, and five years in DCUT11.
For sediment metals, summary combined information for all creeks by three
categories was also compared across the course of the study for six metals for which ERLs
and ERMs have been determined (Table II-E2). Average concentrations for all previous
years (2019 and earlier) for all six metals were below the ERLs for pre -mod Alt L creeks,
post -mod Alt L creeks, and control creeks with two exceptions. Post -mod Alt L and control
creeks Cd exceeded the ERL but were below the ERM and Zn exceeded the ERL and ERM
in post -mod Alt L creeks. For 2020, samples average concentrations were below the ERLs
for all previous years for pre -mod Alt L creeks, post -mod Alt L creeks, and control creeks.
II-E-3

The ERL is not a threshold of degradation; it represents a 10 percent likelihood of toxicity.
Elevated Zn in the 2019 and earlier average is related to the apparently anomalous 2015
value in Jacks Creek that has not been repeated in subsequent samples.
Data in Table II-E2 indicate that the long term average for metals detected in the
sediment samples in all control creeks was below the ERL for five of the six metals when
one standard deviation was applied; Cd was the exception at 0.18 µg/g above the ERL with
the standard deviation applied. All 2020 control creek average detections were below the
ERL with standard deviation applied (Ag and Cd were not detected). For the pre -Mod Alt L
creeks, the long term average was below the ERLs for five of the six metals with the
standard deviation applied; again Cd was the exception at 0.58 µg/g above the ERL with the
standard deviation applied. For post -Mod Alt L creeks, the long term average was below the
ERLs for four metals with the standard deviation applied; Cd exceeded the ERL by 0.29
µg/g with the standard deviation applied and the Zn long term average exceeded the ERM
by 108.09 µg/g (due to the aforementioned anomalously high Zn reading in 2015).
However, the 2020 seven -creek mean was below the ERL with standard deviation applied.
All long term pre- and post -Mod Alt L averages (alone and with standard deviations applied)
were well below the ERMs with the exception of Zn. On average, concentrations of all
metals in all creeks have remained about the same or declined over time, although yearly
fluctuations up and down have become more apparent as the dataset grows. The addition
of new creeks can also modify the seven -creek means of both pre- and post -Mod Alt L
years. Regardless, results indicate that metals in the sediment of the studied creeks are
unlikely to be associated with biological effects in exposed organisms as they are
consistently below the published ERMs.
For water column metals, 10 years of data have been collected as part of this study
compared to the 20 years for sediment metals. Figure II-E4 a-b show the pre -Mod Alt L
water column metal values combined and compared to post -Mod Alt L values. Figure II-E5a-
b illustrate the water column metal averages across the years and compare all creeks
averages combined to control creeks averages and other creek averages and show that
concentrations are similar among the creek types; no statistical differences were found
between water column metals in post -Mod Alt L creeks compared to controls (as was done
for the sediments, LOQs were used for all non -detects in these figures and analysis). When
post -Mod Alt L years were compared to pre -Mod Alt L years, no metal water column values
in post -Mod Alt L years were statistically significantly different relative to pre -Mod Alt L
years.
Table II-E3 shows the percentage of years for each creek where metals were below
the LOQ/CL/RL for the sediment and the water column. For some metals, the change in
methods in 2016 mentioned above did not seem to affect the percentage as the metal had
seldom been detected up to 2016; however, for other metals (e.g. Cr and Cu), it did seem to
affect detection. No sediment metals have been detected for every sample year in each
creek; As, Cr, Cu, and Zn were detected in most years in most creeks; Ag and Mo were
seldom detected. Within the water column, Ag has never been detected in any creek
sample and Cd and Mo were seldom detected (Cd has not been detected to date in either
DCUT19, Duck Creek, Broomfield Swamp Creek, or SCUT1).
Answer: Results show that with the exception of Zn in the sediment at Jacks
Creek in 2015, concentrations of sediment metals or concentrations of water column
metals in the studied creeks are not likely to be associated with detectable biological
I I-E-4

effects. No statistical differences and no obvious trends have been found to indicate
that mine continuation has changed either sediment or water column metal
concentration relative to changes observed in control creeks or relative to changes
observed pre -Mod Alt L in all creeks but Jacks Creek. In 2015, the first year for which
post -Mod Alt L was available for Jacks Creek, levels of Zn in the sediment exceeded
the ERL and ERM. Two samples from Jacks Creek in 2016 showed values for Zn
within the range of all years previous to 2015. The 2020 averages for all combined
post -Mod Alt L creeks, which includes Jacks Creek, were below both the ERL and
ERM.
II-E-5

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x Jacobs Post -Mod Alt L
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II-E-6

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Fiqure II-E2 a - d. Average sediment metals (µg/g) for all control creeks combined across years and creeks with both pre- and post -Mod Alt L data. a) Average sediment metals for pre -Mod Alt L creeks relative to control creeks.
b) Average sediment metals for post -Mod Alt L creeks relative to control creeks. c) Average sediment metals for post -Mod Alt L creeks relative to control creeks, 2020 concentrations only. d) Average sediment metals for pre -
Mod Alt L years relative to post -Mod Alt L years. When comparing combined creek data from pre -Mod Alt L years to post -Mod Alt L years, statistical (p < 0.05) elevations in average sediment metals for post -Mod Alt L years
occurred for Ag and Se.
I I-E-7

Sediment Metal Averages Wig) and TOC(g/kg)
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Pre- and Post -Mod Alt L Creeks
Water Column Metal Averages
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+ Pre -Mod
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Figure II-E4a. Combined pre -Mod Alt L water column metals
concentrations compared to combined post -Mod Alt L values with all
detected values and any <LOQs as detected values.
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Only detections at or above reporting limit used
Ag has never been detected
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f Post -Mod
Figure II-E4b. Combined pre -Mod Alt L water column metals
concentrations compared to combined post -Mod Alt L values with only
detections at or above LOQ.
II-E-9

Water Column Metal Averages All Years All Creeks
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Figure II-E5a. Water column metal means for all years (2011-2020) for all
creeks by type. LOQ/Reporting limit used as data point when metal was not
detected or detected below the limit.
Metal concentration pg/L
90
80
70
60
50
40
30
20
10
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Water Column Metal Averages All Years All Creeks
(without Fe)
11.1 • 1 1 . ■
Ag As Cd Cr Cu Mo Se Zn
All Creeks • Control Creeks Other Creeks
Figure II-E5b. Water column metal means compared for all years (2011-
2020) by type without Fe shown. LOQ/Reporting limit used as data point
when metal was not detected or detected below the limit.
II-E-10

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II-E-11

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Jacks Creek
Jacks Creek
Jacks Creek
Jacks Creek
Huddles Cut
Huddles Cut
Huddles Cut
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ND= non detected
II-E-12

Table II-E3. Percent of samples for each creek where metals were not detected (below LOQ/CL/RL)
in sediment (a) or the water column (b). The data set varies by creek from 20 years for Muddy Creek
sediment to one year for Broomfield Swamp Creek and SCUT1 sediment and water column; number
of sample years are shown in parens next to creek name.
Percent of sample years in each creek where metals were below detection (<LOQICLJRL)
a. sediment
Metal (µg/g; % for Fe)
Creek
Broomfield (2)
SCUT1 (2)
Jacks (17)
Little (10)
Jacobs (10)
PA2 (10)
Drinkwater (10)
Long (10)
Tooley (14)
Muddy(20)
Huddles Cut (17)
Porter (10)
DCUT11 (8)
❑CUT19 (8)
Duck (10)
Al Ag As Cd Cr Cu Fe Mo Se Zn
0.0 100.0 0.0 100.0 0.0 0.0 0.0 100.0 0.0 0.0
0.0 100.0 0.0 100.0 0.0 0.0 0.0 100.0 0.0 0.0
5.9 47.1 0.0 17.6 0.0 0.0 5.9 47.1 0.0 0.0
10.0 90.0 0.0 30.0 0.0 0.0 10.0 80.0 10.0 0.0
10.0 80.0 0.0 40.0 0.0 0.0 10.0 90.0 0.0 0.0
10.0 90.0 0.0 30.0 0.0 0.0 10.0 80.0 10.0 0.0
10.0 90.0 0.0 30.0 0.0 0.0 10.0 90.0 10.0 0.0
10.0 80.0 0.0 30.0 0.0 0.0 10.0 90.0 0.0 0.0
7.1 57.1 0.0 21.4 0.0 0.0 7.1 64.3 0.0 0.0
5.0 35.0 0.0 15.0 0.0 0.0 5.0 40.0 0.0 0.0
11.8 52.9 23.5 29.4 5.9 29.4 11.8 47.1 35.3 5.9
10.0 80.0 0.0 30.0 0.0 0.0 10.0 90.0 0.0 0.0
12.5 87.5 0.0 50.0 0.0 0.0 12.5 87.5 0.0 0.0
12.5 100.0 12.5 50.0 0.0 0.0 12.5 75.0 12.5 0.0
0.0 90.0 0.0 60.0 0.0 0.0 0.0 60.0 0.0 0.0
b. water column (per the plan, Al is not measured)
Metal (pg/L)
Creek Al Ag As Cd Cr Cu Fe Mo Se Zn
Broom field (2) NA 100.0 100.0 100.0 100.0 100.0 50.0 100.0 100.0 100.0
SCUT1 (2) NA 100.0 100.0 100.0 100.0 100.0 0.0 100.0 100.0 100.0
Jacks (10) NA 100.0 50.0 90.0 50.0 50.0 40.0 90.0 50.0 80.0
Little (10) NA 100.0 50.0 90.0 50.0 50.0 50.0 80.0 60.0 70.0
Jacobs (10) NA 100.0 50.0 90.0 50.0 50.0 50.0 90.0 50.0 70.0
PA2 (10) NA 100.0 30.0 90.0 50.0 50.0 60.0 80.0 40.0 70.0
❑rinkwater (10) NA 100.0 60.0 90.0 50.0 50.0 50.0 80.0 40.0 80.0
Long (10) NA 100.0 50.0 90.0 50.0 50.0 60.0 70.0 50.0 70.0
Tooley (10) NA 100.0 60.0 90.0 50.0 40.0 60.0 90.0 50.0 70.0
Muddy (10) NA 100.0 50.0 90.0 50.0 50.0 60.0 80.0 40.0 70.0
Huddles Cut (10) NA 100.0 50.0 90.0 50.0 50.0 30.0 80.0 50.0 70.0
Porter (10) NA 100.0 60.0 90.0 50.0 40.0 60.0 90.0 40.0 70.0
DCUT11 (8) NA 100.0 62.5 87.5 62.5 50.0 25.0 75.0 62.5 62.5
DCUT19 (8) NA 100.0 62.5 100.0 62.5 62.5 50.0 87.5 50.0 62.5
Duck (10) NA 100.0 60.0 100.0 60.0 50.0 40.0 90.0 40.0 70.0
Note: Laboratory equipment changed once and laboratory methods changed twice over the course of
the study to date.
II-E-13