SAMPLING AND ANALYSIS PLAN (SAP) ADDENDUM

For

FINGERPRINT ANALYSIS OF
POLYCYCLIC AROMATIC HYDROCARBON

LOWER DARBY CREEK AREA (LDCA) SITE
CLEARVIEW LANDFILL - OPERABLE UNIT 1 (OU-1)

PHILADELPHIA AND DELAWARE COUNTIES,
PENNSYLVANIA

EPA Contract Number EP-S3-07-04
EPA Work Assignment Number 061-RDRD-D366
Tetra Tech Project Number 07477

For

U.S. ENVIRONMENTAL PROTECTION AGENCY

REGION 3

APRIL 2016


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1.0 INTRODUCTION

This is an addendum to the August 2015 Sampling and Analysis Plan (SAP) and was prepared to collect
environmental samples and perform a forensic hydrocarbon "fingerprint" analysis using an expanded set of
polycyclic aromatic hydrocarbon (PAHs) and alkylated homolog analytes in surface and subsurface soils,
sediments and groundwater as part of the remedial design (RD) being conducted forthe Lower Darby Creek
Area (LDCA) site, Operable Unit 1 (OU1) - Clearview Landfill Waste and Contaminated Soils. Unless
tables from the August 2015 OU1 SAP are included or updated in this addendum, the content from the
August 2015 OU1 SAP is sufficient and applies to this investigation. Several PAHs are contaminants of
concern (COCs) for surface and subsurface soils at OU1. PAH soil cleanup levels to protect both ecological
and human receptors were selected in the 2014 Record of Decision (ROD). These cleanup levels and the
specific PAHs to which they apply are listed in the August 2015 OU1 SAP.

The purpose of this fingerprint analysis is to determine if PAHs detected in portions of the Eastwick Regional
Park (City Park) and the adjacent Eastwick neighborhood are attributable to OU1, some other source(s)
(e.g. aerial deposition, flood events, combustible engine exhaust, and contaminated fill), or a combination
thereof. This SAP addendum describes the field sampling activities, laboratory activities and analyses that
will be conducted for this investigation. Tetra Tech will implement that field sampling. An EPA contracted
lab will perform the majority of the sample analyses. Battelle (via a contract with EPA's Office of Research
and Development) will perform analysis of all groundwater samples and any sediment samples with oil
and/or sheen present. All samples will be analyzed for the expanded PAH list and alkylated homologs.
Battelle will evaluate the data from the sampling effort using a variety of methods including primary
component analysis (PCA) and write a letter report on the results of their evaluation consistent with the
objective of the project.

2.0 SAMPLING LOCATIONS AND ANALYSIS

OU1 is located in both Delaware (Darby Township) and Philadelphia Counties. The Clearview Landfill is
adjacent to the City Park and Eastwick neighborhood located in southwest Philadelphia. In addition to
landfilling activities that were conducted in the 1950s - 1970s, the Eastwick area was subjected to
numerous activities and natural processes that may have contributed to PAHs that are present today in the
City Park and Eastwick neighborhood. This includes, but is not limited to, historical residential development
and activities, demolition and placement of additional fill/dredge sediments as part of the Eastwick
"redevelopment" in the 1970s, flood events depositing PAH-laden sediments from the adjacent creeks
(Darby and Cobbs), aerial deposition from combustible engine exhaust, etc.

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Samples of various media, including groundwater, surface and subsurface soil, oils/sheens, and sediment
in adjacent creeks, will be collected and analyzed for the expanded list of PAHs and alkylated homologs.
Rationale for media to be sampled and sample locations is provided in the following sections. The
expanded PAH and alkylated homolog analytes selected for this investigation are provided in Table 1. The
EPA Contract Laboratory Program (CLP) laboratory will analyze soil and sediment samples, whereas
groundwater samples and select soil and sediment samples exhibiting visual evidence of sheens or oils will
be sent to the Battelle laboratory. Table below summarizes a total number of samples planned for this
investigation. Details regarding the number of co-located, laboratory replicate samples, etc. can be found
in later sections of this Addendum.

Media

Number of

No. of Co-
located Field
Samples

Total Number of

Samples

Samples

Groundwater/Sheen

2

11

3

Sediment

9

7

16

Surface Sediment

O

O

£

Oil/Sheen

J

J

0

Soil - Discrete Boring

121

17

138

Soil - ISM
(new)

3

22

5

Soil - ISM

O

fi

O

(previously collected)

J

u

o

1	- Technically a duplicate sample, not co-located.

2	- Technically a field triplicate sample, not co-located.

2.1 Groundwater Sampling

Two grab groundwater samples will be collected from monitoring wells MW-4 and MW-12 (Figure 1) that
exhibited a visible oily sheen and/or evidence of non-aqueous phase liquid (NAPL) during remedial
investigation (Rl). A duplicate grab groundwater sample will be collected from MW-12. The purpose of the
duplicate sample being to evaluate contaminant concentration variability within the groundwater in the
monitoring well and subsequent representativeness of the analytical results obtained.

The potential for NAPL was based primarily in the form of sheens or strong odors noted during the Rl. To
date, measurable levels of oils or NAPLs accumulating on the top or bottom of the water column have not
been observed in any borings or monitoring wells. If elevated levels of PAHs are detected in these wells,
it may be potentially related to petroleum based products or other materials historically disposed of in the
landfill which could have been released while at the surface of the landfill. Groundwater is also known to
discharge through seeps along the creek bank and through upwelling in the creek bottom. Oils, sheens
and PAHs present in groundwater potentially could be migrating to the landfill creek bank orstreambed and

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impacting sediments and surface water. As is discussed further below, oil and sheens have been noted in
several landfill creek bank seeps at low tide. These areas will be sampled and the resulting "fingerprints"
compared to one another and to other media such as these groundwater samples to determine if they are
potentially related. This same evaluation will be conducted for additional sediment samples collected
upstream and downstream of OU1 and surface and subsurface soil samples from the landfill, City Park and
Eastwick neighborhood.

A representative sample of the sheen/groundwater will be collected using a peristaltic pump, a bailer, or
other appropriate sampling methods. Approximately 20 to 30 milliliters (mL) of oily water will be collected
into a 40-mL vial and sent to the Battelle laboratory for expanded PAH forensic "fingerprint" analysis.

2.2 Sediment & Oil/Sheen Sampling

Sediment samples will be collected upstream, adjacent and downstream of OU1 in both Darby and Cobbs
Creeks. Darby Creek is tidally influenced up to approximately the confluence with Cobbs Creek. Collection
of sediment samples from these locations are intended to provide insight into the PAH "fingerprint" in
surface sediments both upstream and downstream that could be contributing some portion of the PAHs
(either now or in the past) that have been identified in low lying areas throughout OU1. During large flood
events when creek waters overtop the stream banks, it is expected that sediments from the adjacent creeks
are deposited in the City Park and neighborhood. These sediments could contain PAHs which could
subsequently be contributing to the PAHs being detected in surface soils within the floodplain, including in
the City Park and neighborhood. The specific areas of the creeks that could be contributing sediments
deposited on or around OU1 during such events is influenced by numerous factors including tidal stage,
precipitation rates and duration, creek flow velocity, etc. There is also substantial mixing of materials in
creek and flood waters and there have been numerous storm events of varying sizes overthis area's history.
Therefore, it is likely impossible to discern any one specific stretch of creek bank that has contributed
sediments to OU1 surface soils. However, comparing the PAH "fingerprints" from different portions of the
creeks and the landfill bank itself may provide insight into major contributors to PAH concentrations, how
OU1 is influencing the creek sediments and vice versa.

Sediment sample locations for this investigation were selected based on the data obtained during the
previous Rl activities, proximity to other potential sources of PAHs upstream and downstream of the
Clearview Landfill, and the EPA Office of Research and Development (ORD) Excel program Fingerprint
Analysis of Leachate Contaminants (FALCON). A full description of how the FALCON analysis was
conducted as well as the conclusions are included as an appendix to this sampling and analysis plan. In
summary, the FALCON technique uses the coefficient of determination (r-squared, r2) from regression
analysis as a means to quantify the similarity between the multi-analyte patterns from two different samples.

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The assumption is that samples having similar or identical fingerprint patterns are more likely to have the
same or similar contaminant sources than samples having very different patterns. Two samples having
similar multi-analyte profiles have a higher r2 (up to a maximum of 1.000 for identical patterns). Two samples
having very different multi-analyte profiles will have a lower r2 (to a minimum of 0.000 for completely different
patterns). An evaluation of the OU1 historic sediment and seep data indicated that the pattern at sediment
sample location SD24 did not match either the "seep" or "leachate" samples particularly well, with none of
the r-squared values above 0.90. The SD24 pattern somewhat matches patterns from the following boring
samples having high total PAH concentrations. GP120D and GP243M show the best pattern agreement (r2
= 0.97 and 0.96, respectively).

Based on this information, nine (9) sampling stations (included SD24 which is now identified as Sample #3)
were selected (Figure 1).

Oily or Visible Sheen Sediment Samples

Currently, three locations (stations #3, #4, and #5 on Figure 1) along the landfill creek bank have been
identified with oily or visible sheens during low tide. These sheens/oils are originating from seeps in the
landfill creek bank that are exposed at low tide and/or oil material is seeping up through the sediment at
low tide. At these three stations, two samples will be collected. The first sample will be comprised of an
oil and/or sheen sample that is coating/covering surface sediment or water that is pooled on the surface of
the sediment. This oil/sheen sample will be collected using a medical gauze pad (likely 6" x 6" or 8" by 8").
The medical gauze pad will be placed in a 4 oz. glass sample jar. The Battelle laboratory will extract the
oil/sheen from these pads for analysis. An unused pad will also be subjected to extraction to serve as a
blank and to determine if any of the gauze pad contents are contributing to quantified levels of PAHs.

A second sample will be collected from all 3 stations at a depth of 2 cm below the sediment surface.
Sediment samples will be collected using a disposable Terra Core® sampler. These samplers can collect
approximately either 5 grams (g) or 10g of soil/sediment, depending on the size of the sampler used,
composition and water content of the matrix. The extraction mass needed for the expanded PAH and
alkylated homolog analysis is 20g. The Terra Core® sampler will be used to collect 2 or 4 (depending on
the size used) Terra Core® barrel volumes, each weighing approximately 5g or 10g and totaling at least
20g. EPA will coordinate with the lab to determine if up to 5g greater than the target mass, i.e., 25g, is
acceptable and can be completely extracted and analyzed. If the 10g sampler is used, the two barrel
volumes will be collected immediately adjacent to one another. If the 5g sampler is used, four barrel
volumes are needed and they will be collected in a square pattern immediately adjacent to one another.
The sediments will be placed in a 4 oz. glass jar and weighed to confirm a sample mass of at least 20g.
The entire mass in the sample jar (approximately 20g) will be extracted and analyzed by the lab. In addition,

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for every 20g sediment sample, a paired 5g sediment sample will be collected from each subsurface
sediment sample station and used to determine the percent (%) solids by the laboratory. This sample will
be collected in the same manner with the disposable Terra Core® sampler from the same depth interval,
but a new sampler will be used to collect it. Targeted thickness for the subsurface sediment sample is 2-
3 cm. The 5g Terra Core ® collects a 2 cm deep sample, while the 10g version collects a 3 cm deep
sample. The same Terra Core ® sampler size will be used for all sediment and soil samples to ensure
consistent sample depth and sample support. The one exception involves submerged sediment sample
locations which are discussed in further detail below.

At Station #5, two (2) co-located field samples (2 plus the original sample location) will be collected from
the oil/sheen on the surface and the subsurface sediments. These co-located samples shall have a
distance between them of no more than twelve inches (12"). The intent of co-located discrete samples is
to evaluate spatial variability and subsequent representativeness of results. Additional percent solids
samples do not need to be collected for the co-located field samples due to their close proximity to the initial
sample.

At Station #3, one (1) co-located field sample will be collected from the oil/sheen on the surface and the
subsurface sediment. A matrix spike and matrix spike duplicate (MS/MSD) sample (20g each) will also be
collected from Station #3.

This will result in a total of six (6) oil/sheen samples plus one gauze "blank", six (6) subsurface sediment
samples, three (3) % solids samples and one (1) MS/MSD sample that will be collected from these three
(3) locations (Stations #3-#5).

Non-Oil/Sheen Sediment Samples

Six (6) additional sediment sampling locations have been identified upstream and downstream of OU1.
These sediment samples will be targeted towards depositional areas. Areas that are exposed at low tide
(if within a tidal portion of the creek) are acceptable for sampling. Collection of sediment samples at these
locations shall be in the same manner as described above. That is, an approximate 20g sample (at least
20g) and 5g %solids sample. The targeted sample depth is the top 2-3 cm of sediment. Each will be
collected with a new Terra Core® sampler and placed in separate 4 oz. jars. Stations #6 through #9 are
above the tidally influence areas of Darby and Cobbs Creeks. Thus, it is likely that depositional areas of
the creek will be submerged. In these cases, collection of the sediment samples using the procedures may
not be practical and effective at obtaining a representative sediment sample from the top 2-3 cm. An
attempt will be made to use the Terra Core ® samplers from these submerged areas. If ineffective, a 2-3
cm (depending on the final size of Terra Core ® sampler being used) scoop will be collected from the

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surface sediment using a square bottomed scoop. The surface area of the square bottomed scoop shall
be greater than the surface area of two or four (depending on the final size of the Terra Core ® sampler
being used) adjacent sample cores. The sampling crew shall place a hand over the top of the sediment-
laden scoop as it is removed from the water to ensure sediment disturbance/loss is minimized. A Terra
Core ® sampler shall than be used to collect two or four sediment volumes (again, depending on which
size Terra Core ® sampler is being used) from the scoop of sediment and placed in a 4 oz. jar. The sample
volume shall be approximately 20 g (at least 20g). A 5g sample will also be collected for percent moisture
analysis.

At Station #9 two (2) co-located field samples (2 plus the original sample location) will be collected with a
distance of no more than twelve (12") inches between them. At Stations #1 and #7 one (1) co-located field
sample will be collected with a distance of no more than twelve (12") inches between them. The intent of
co-located samples is to evaluate spatial variability and subsequent representativeness of results.
Additional percent solids samples do not need to be collected for the co-located field samples due to their
close proximity to the initial sample.

This will result in a total often (10) sediment samples will be collected from these six (6) locations.

Samples containing oil/sheen gauze pads will be sent to the Battelle laboratory and all other samples will
be sent to a CLP laboratory. The table below summarizes proposed sediment sampling locations.

Station
No.



No. of



Location

Sediment

Comment



Samples









One surface sediment sample and

1

Darby Creek, Downstream.

Just upstream from Sunoco pipeline
crossing, in-line with tank farm.

2

one co-located sample.

Near the location of known past
release from the Sunoco pipeline.







One surface sediment sample.

2

Darby Creek, Downstream.
Upstream from Sunoco tank farm.

1

Upstream from the location of known
past release from the Sunoco
pipeline.







One oil/sheen gauze and one co-



Darby Creek, Landfill Creekbank.



located sample.

3

Oily sheen/leachate seep observed
at low tide.

4

One subsurface sediment sample
and one co-located sample.

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Leachate seep location near
monitoring well MW-3, known for
having a sheen/NAPL

4

Darby Creek, Landfill Creekbank
Oily sheen/leachate seep observed
at low tide.

2

One oil/sheen gauze and one
subsurface sediment sample.

Landfill leachate seep location

5

Darby Creek, Landfill Creekbank
Oily sheen/leachate seep observed
at low tide.

6

One oil/sheen gauze sample and two
co-located samples.

One subsurface sediment sample
and two co-located samples.

Landfill leachate seep location







One surface sediment sample.

6

Darby Creek, Upstream

1

Rl sediment sample location SD05.
Total PAH concentration between
16,000 and 32,000 pg/Kg.







One surface sediment sample and
one co-located sample.

7

Darby Creek, Upstream

2

Rl sediment sample location SD01.
Total PAH concentration between
16,000 and 32,000 pg/Kg.







One surface sediment sample.

8

Cobbs Creek, Upstream

1

Rl sediment sample location SD16.
Total PAH concentration between
32,000 and 64,000 pg/Kg.







One surface sediment sample and
two co-located samples.

9

Cobbs Creek, Upstream

3

Rl sediment sample location SD11.
Total PAHs concentration greater
than 64,000 |jg/Kg.

2.3 Soil Sampling

Prior to the cessation of landfilling activities at OU1, soil and wastes containing PAHs may have been
present on the landfill surface (both in the Delaware County and Philadelphia portions). The fate of these
contaminants could have been to stay on the landfill proper and/or be transported to the City Park and/or
Eastwick neighborhood. The landfill was partially covered and seeded by the Philadelphia Redevelopment
Authority in 1976. In addition, fill materials were brought in to level and grade the current neighborhood
prior to its construction. These cover and fill materials likely buried the former landfill surface and
subsequent contaminated soils. Further, the cover material and/or fill may have contained PAHs or other
contaminants as well. There are several layers of soil/fill materials (not including municipal trash) that have
been noted on the landfill, City Park, and/or neighborhood. This includes a topsoil layer, a silty or sandy

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loam soil mixed with varying amount of construction and demolition (C&D) debris, an apparent "clean fill
material" consisting of soils with higher clay content and varying amounts of C&D debris, a gray/black fine
sand, a brown fine sand and a "native" soil layer. These layers are not present everywhere and they are
not always present in the same sequence with depth. However, there is potential for these layers to be of
the same origin, even when found with significant distance between them. Based on the OU1 history,
potential historic and current contaminant transport pathways and contaminant data, the main goal for the
soil sampling portion of this investigation is to collect multiple samples from each of these layers throughout
OU1 and compare the subsequent PAH results to discern if the "fingerprints" from any soil/fill "layers" on
the landfill are the same as those found in the City Park or Eastwick Neighborhood.

The multiple sources of soil/fill materials overtime present a challenge in discerning the source(s) of PAHs
that have been detected in surface and subsurface soils in the City Park and Eastwick neighborhood.
Therefore, soil samples will be collected from several locations on the landfill surface (both at the crest and
the toe of the eastern slope) the City Park and Eastwick neighborhood. These samples are being collected
in areas that may be potential source areas for PAHs (either now or in the past), e.g., surface soils at the
crest of the landfill that can be transported downhill in storm runoff, imported fill from the 1970s
redevelopment era, as well as areas that could be acting as depositional zones from soil and sediment
particles laden with PAHs, e.g., low lying areas in the City Park or neighborhood, deeper soils that could
have been impacted when exposed during landfill operation. Multiple depths including surface soil and
near the horizon for other subsequent soil/fill "layers" that are identified in borings will be sampled.

Because of the OU1 history described above, a large portion of the soil samples collected will be from the
eastern side of Clearview Landfill, including the City Park and Eastwick neighborhood as they are potentially
impacted by surface runoff from the landfill during storm events. Surface water runoff during precipitation
events was/is likely a prominent migration pathway for contaminated soils on the eastern side of the landfill
to be transported to the City Park and potentially the Eastwick neighborhood. During the original Remedial
Investigation (Rl) for the Clearview Landfill, several surface water drainage basins were identified
throughout Landfill and surround areas (Figure 3-12 from the Rl Report). Seven distinct drainage basins
(Basins A through G) were identified at Clearview Landfill and the City Park. In general, stormwater west
of the ridge (Basins D, E, and F) drains toward Darby and Cobbs Creeks, while stormwater to the east of
the landfill ridge (Basins A, B, C, and G) drains toward the City Park (PD02 and PD03). Drainage from the
landfill is also collected in a low lying depression in the southern portion of the City Park (PD01). Ponding
in these depression areas was observed during periods of high precipitation.

Sampling locations were selected based on potential contamination transport pathways, the conceptual site
model and data obtained during previous Rl investigations. Samples relying on Rl data were biased

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towards borings with elevated concentrations of total PAHs as these could be indicative of PAH source
materials.

The proposed discrete soil sample and incremental soil sample (ISM) sampling locations are shown on
Figure 2 and listed in the table below. Estimated totals for field samples (including co-located samples)
and field replicates (in the case of ISM samples)) are provided in the table and are based on the number of
planned borings and assumed soil/fill layers above any layers containing municipal solid waste (MSW).
The actual number of field samples submitted may vary slightly based on the actual number of soil/fill layers
found in each boring.

Sampling Boring
No(s).

Focus Area

No. of
Borings

Estimated No. of
Soil Samples

No. of Co-located
Samples
(One/Two)

1 (GP227)

Western Side of
Landfill

1

2

0

2-7, 8 (GP219),
31-33, 37

Landfill Ridge

10

20

3/1

9-12

Eastern Side of
Landfill

4

8

13-18

Northern City Park

6

18

1/2

19-30

Eastwick
Neighborhood

12

40

4/1

34-36 (SU-1)

Suffolk Park
(background)

3

6

1/0

Discrete Samples
from SU049B,
SU081, SU108

City Park and
Eastwick
Neighborhood SUs

3 per SU
times 3 SUs

27 (up to 3 samples
per boring)

N/A

ISM samples from
SU049B, SU081,
SU108

City Park and
Eastwick
Neighborhood SUs

10

increments
per SU

6 (3 new and 3
archived samples
per SU)

N/A

Discrete Samples

Samples will be collected from soil cores using a direct push technology (DPT). Each boring outside of
landfill footprint will be advanced until "native' soil is encountered (approximately 10 feet below ground
surface [bgs]). Collection of soil/fill samples from the DPT soil cores shall be in the same manner as
described above for sediments with no oil/sheen visible. That is, an approximate 20g sample (at least 20g)
and 5g %solids sample collected using a Terra Core® disposable sampler. The disposable samplers will
be advanced into the center line of the DPT soil core. If the 10g sampler is used, the two barrel volumes
will be collected immediately adjacent to one another. If the 5g sampler is used, four barrel volumes are
needed and will be collected in a straight line down the center line of the DPT soil core immediately adjacent
to one another. Each sample location (not each individual 5 or 10g plug) will be collected with a new Terra
Core® sampler and placed in separate 4 oz. jars.

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Two (2) samples will be collected from each boring installed on the landfill and City Park (borings 1 through
12 and 31-33). One sample will be collected from the surface soil (veneer (0-2 cm)) and the other sample
from a representative soil underlying vegetative cover (typically be limited to top 2 feet). There is a distinct
ridge of large C&D debris that runs along the top of the eastern landfill slope. It is unclear if precipitation
falling on the "plateau" of the landfill will actually runoff in an easterly direction towards the City Park and
Eastwick Neighborhood. Therefore samples both from above and below this C&D ridge will be collected
for comparison. Out of borings 2-12 and 31-33 two (2) sets of co-located field sample pairs (2 plus the
original sample location) will be collected at one boring. Three other borings will have a single co-located
field sample collected. Two of the single co-located samples shall be from the surface veneer soils (0-2
cm). The other three (3) co-located samples (one pair and one single) will be collected from the soil layer
underlying the surface veneer soils with vegetative cover at the same depth. Co-located samples will have
a distance of no more than twelve (12") inches between them. The intent of co-located samples is to
evaluate spatial variability and subsequent representativeness of results. Additional percent solids samples
do not need to be collected for the co-located field samples due to their close proximity to the initial sample.

Borings installed in the northern City Park and Eastwick neighborhood (borings 13 through 30) will have
three (3) samples collected from each distinct layer - surface (veneer, 0-2 cm), fill material, and "native"
material. Two (2) of the borings in the City Park shall also have a sample collected from the gray/black fine
sand and the brown fine sand layers. Out of borings 13-18 two sets of co-located field sample pairs (2 plus
the original sample location) will be collected at two (2) different borings to be determined in the field. One
pair of these co-located samples shall be from the gray/black fine sand layer at the same depth. The other
pair of co-located field samples will be from the soil layer underlying the surface veneer soils with vegetative
cover at the same depth. One other boring from locations 13-18 will have a single co-located field sample
collected. This co-located sample shall be collected from the soil layer underlying the vegetative cover at
the same depth.

Out of borings 19-30, one set of co-located field sample pairs (2 plus the original sample location) will be
collected at one (1) boring location to be determined in the field. These co-located samples will be taken
from the surface veneer soils (0-2 cm). Four (4) other borings from locations 19-30 will have a single co-
located field sample collected. These co-located field samples will be from the soil layer underlying the
vegetative cover at the same depth. As with previous samples, co-located samples will have a distance of
no more than twelve (12") inches between them. The intent of co-located samples is to evaluate spatial
variability and subsequent representativeness of results. Additional percent solids samples do not need to
be collected for the co-located field samples due to their close proximity to the initial sample.

In addition, three discrete borings will be advanced (up to 2 feet bgs) within the 0.01-acre background
sampling unit (SU) in Suffolk Park that was previously sampled (Figure 3). Two (2) samples will be

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collected from each boring; the surface (veneer, 0-2 cm) and top 2-feet layer of native soil beneath
vegetative cover. One (1) boring from locations 34-36 will have a single co-located field sample collected.
Results from these samples will be included in the "fingerprint" evaluation.

All of these discrete samples will be submitted to the CLP lab.

Evaluation of ISM Sample Utility for PAH "Fingerprinting"

In order to evaluate the potential utility of employing incremental soil sampling (ISM) for PAH forensic
"fingerprint" analysis, Tetra Tech will re-sample three (3) existing SUs that were originally sampled during
the initial phase of the PDI (SU049B, SU081, and SU108) in the manner described in the August 2015
SAP. Samples from these original SU samples (0-1' and 1 '-2' depth intervals) are currently archived at the
EPA Region 10 Laboratory. These ISM samples were processed by the Region 10 lab (drying, sieving,
grinding) but have been stored at room temperature. Therefore, there is potential that microbial degradation
of PAHs in these samples has continued since the samples were collected in November 2015. Both the
original archived ISM samples and the new ISM samples from these SUs will be analyzed for the expanded
PAH analytes and alkylated homologs to determine if there has been any change in PAH concentrations,
potentially due to microbial degradation.

One incremental sampling method sample from the 0 to 1 foot interval will be collected from SU049B,
SU081, and SU108. These SUs will be sampled using the same methodology included in the August 2015
PDI SAP. Three (3) field replicate samples will be collected from SU049B, processed and analyzed for
expanded PAHs and alkylated homologs. One of these field replicates will be sub-sampled in triplicate by
the laboratory and each analyzed. A laboratory triplicate sub-sample will also be collected from the
archived SU049B sample and analyzed for the expanded PAHs and alkylated homologs. These field and
laboratory triplicates will be used to evaluate variability due soil and contaminant heterogeneity as well as
laboratory processing and sub-sampling error.

There is also uncertainty regarding whether an ISM sample can be utilized for PAH "fingerprinting" because,
by definition, the ISM samples are made up of soil increments distributed evenly throughout a sampling unit
(SU). Thus, if there are varying levels of PAHs or different sources of PAHs present in the SU, the collection
of the sample via numerous increments could mask these factors. To evaluate this potential scenario, each
of these SUs that are being resampled for ISM samples will also include three (3) discrete borings that will
be sampled using the same sampling approach as described above for the other discrete borings. Each
boring will have a sample collected from the surface (veneer, 0-2 cm) soil as well as up to 2 samples from
each soil layer (within the top 0-1' interval) beneath the vegetative cover/veneer soils. The discrete samples
that will be collected throughout OU1 and within these SUs, will be the exact mass needed for analysis

11


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(20g) of the expanded PAHs and alkylated homologs. As such, these samples do not require any of the
standard "processing" that is conducted for ISM (drying, sieving, grinding and sub-sampling to create a sub-
sample aliquot for analysis). However, because the purpose of this facet of the investigation is to evaluate
the utility of ISM for PAH "fingerprinting" and the original ISM samples from the PDI have already been
processed, the new ISM that will be collected as part of this effort samples will be processed using the
standard ISM method. The SOP from Region 10 for performing ISM processing is included with this
addendum.

The PAH "fingerprint" of these discrete results will be compared to both the original and new ISM samples
from these SUs to determine what, if any, changes occurred.

ISM samples will be processed and subsampled (or re-subsampled in the case of the three (3) archived
samples from the first round of the PDI) at the EPA Region 10 laboratory, and will be shipped to a CLP
laboratory for expanded PAH and alkylated homolog analysis. Discrete samples will be shipped directly to
the CLP laboratory for expanded PAH and alkylated homolog analysis.

12


-------
Tables and Figures


-------
Table 1. PAHs with Twenty-two Additional Analytes and Cx Alkylated Homologues and Special
Reporting Requirements

Method Source: SOM02.3 Method: Semivolatiles by SIM

Matrix: Soil and Sediment

Summary of Modification

The purpose of this modified analysis is to analyze soil and sediment samples by Semivolatiles SIM
analysis for the specific PAH analytes and Cx alkylated homologues at the specified CRQLs in Section I
below.

I. Analyte Modifications Not
applicable D

Analyte

CAS Number
or Analyte
Code

Soil CRQL

(ug/kg)

Quantitation
Ion

Conf. Ions

*1 -Methylnaphthalene

90-12-0

3.3

142

141

2-Methylnaphthalene

91-57-6

3.3

142

141

*2,6-Dimethylnaphthalene

581-420

3.3

156

141

*2,3,5-Tri methylnaphthalene

2245-38-7

3.3

170

155

*1 -Methyldibenzothiophene

31317-07-4

3.3

198



*2/3-Methyldibenzothiophene

30995-64-3
/16587-52-3

3.3

198



*4-Methyldibenzothiophene

7372-88-5

3.3

198



*1 -Methylphenanthrene

832-69-9

3.3

192

191

*2-Methylphenanthrene

2531-84-
2/832-64-4

3.3

192

191

*3-Methylphenanthrene

832-71-3

3.3

192

191

*4/9-Methylphenanthrene

883-20-5

3.3

192

191

*2-Methylanthracene

613-12-7

3.3

192

191

*Retene

483-65-8

3.3

234



*C30 17L(H), 21p(H)-hopane

33281-23-1

3.3

191



*Biphenyl

92-52-4

3.3

154

153

*Dibenzofuran

132-64-9

3.3

168

139

*Decalin

91-17-8

3.3

138



**C1-Decalins

DE1

3.3

151



**C2-Decalins

DE2

3.3

166



**C3-Decalins

DE3

3.3

180



**C4-Decalins

DE4

3.3

194



*Dibenzothiophene

132-65-0

3.3

184



**C1-Dibenzothiophenes

D1

3.3

198



**C2-Dibenzothiophenes

D2

3.3

212



**C3-Dibenzothiophenes

D3

3.3

246



**C4-Dibenzothiophenes

D4

3.3

260



*Naphthobenzothiophenes

205-43-6

3.3

234



**C1 -Naphthobenzothiophenes

NBT1

3.3

248



**C2-Naphthobenzothiophenes

NBT2

3.3

262



**C3-Naphthobenzothiophenes

NBT3

3.3

276



**C4-Naphthobenzothiophenes

NBT4

3.3

290



Naphthalene

91-20-3

3.3

128

127

**C1 -Naphthalenes

N1

3.3

142

141

**C2-Naphthalenes

N2

3.3

156

141


-------
**C3-Naphthalenes

N3

3.3

170

155

**C4-Naphthalenes

N4

3.3

184

169

Acenaphthylene

208-96-8

3.3

152

153

Acenapthene

83-32-9

3.3

154

153

Fluorene

86-73-7

3.3

166

165

**C1 Fluorenes

F1

3.3

180

165

**C2-Fluorenes

F2

3.3

194

179

**C3 Fluorenes

F3

3.3

208

193

Phenanthrene

85-01-8

3.3

178

176

Anthracene

120-12-7

3.3

178

176

**C1 -Phenanthrenes/Anthracenes

PA1

3.3

192

191

**C2-Phenanthrenes/Anthracenes

PA2

3.3

206

191

**C3-Phenanthrenes/Anthracenes

PA3

3.3

220

205

**C4-Phenanthrenes/Anthracenes

PA4

3.3

234

219

Fluoranthene

206-44-0

3.3

202

101

Pyrene

129-00-0

3.3

202

101

**C1 -Fluoranthenes/Pyrenes

FP1

3.3

216

215

**C2-Fluoranthenes/Pyrenes

FP2

3.3

230

215

**C3-Fluoranthenes/Pyrenes

FP3

3.3

244

229

**C4-Fluoranthenes/Pyrenes

FP4

3.3

258



Benzo(a)anthracene

56-55-3

3.3

228

226

Chrysene

218-01-9

3.3

228

226

**C1 Chrysenes

C1

3.3

242

241

**C2 Chrysenes

C2

3.3

256

241

**C3 Chrysenes

C3

3.3

270

255

**C4 Chrysenes

C4

3.3

284

269

Benzo(b)fluoranthene

205-99-2

3.3

252

253, 125

Benzo(k)fluoranthene

207-08-9

3.3

252

253, 125

*Benzo(a)fluoranthene

50-32-8

3.3

252

253, 125

*Benzo(e)pyrene

192-97-2

3.3

252

253

Benzo(a)pyrene

50-32-8

3.3

252

253, 125

*Perylene

198-55-0

3.3

252

253

lndeno(1,2,3-cd)pyrene

193-39-5

3.3

276

277, 138

Dibenzo(a,h)anthracene

53-70-3

3.3

278

279, 139

Benzo(g,h,i)perylene

191-24-2

3.3

276

277, 138

*Designated as additional non-SOW target analyte.

"Designated as Cx alkylated PAH homologue.

Bolded analytes are the SOW SVOA SIM target analytes. The two analytes that are bold with an
asterisk are routine SVOA target analytes included in this MA for SVOA SIM analysis.

II. Calibration and QC Requirements	Not

applicable ~	

The Laboratory shall

•	Analyze the low point ICAL standard at 0.10 ng/uL concentration for each target analyte except
analytes with ** in Section I.

•	Perform a five-point initial calibration to establish the linear calibration ranges on GC/MS for the
target analytes except analytes with ** in Section I. The recommended ICAL standard

	concentrations are at 0.10, 0.20, 0.40, 0.80 and 1.6 ng/uL.	


-------
•	Add the same DMC solution specified for SVOA SIM analysis in the SOW at the same
concentrations 0.10, 0.20, 0.40, 0.80 and 1.6 ng/uLto the ICAL standards.

•	Add the same Internal Standard (IS) solution specified for SVOA SIM analysis at concentration
of 0.40 ng/uLto all ICAL standards.

•	Perform the Continuing Calibration Verification (CCV) consisting of mid-point ICAL standard
(CS3) for the analytes except analytes with ** in Section I at the same frequency as specified in
the SOW.

•	Optionally, perform the same ICAL and CCV standards specified for the SVOA analysis in the
SOW plus the additional target analytes with * in Section I at the specified concentrations.

•	Note that ICAL/CCV RRF for the target analytes with * in Section I shall be greater than or equal
to 0.010. ICAL Percent Relative Standard Deviation (%RSD) for the target analytes with * in
Section I shall not exceed 25.0%. CCV %D for the target analytes with * in Section I shall be in
the inclusive range of+/-25.0% for the opening CCV and +/-40.0% for the closing CCV,
respectively.

•	Note that the ICAL and CCV technical acceptance criteria for all SOW SVOA SIM target
analytes in Section I and the associated DMCs shall remain the same as specified in the SOW.

•	Analyze a Standard Reference Material (SRM), NIST SRM 2779, Gulf of Mexico crude oil, after
the opening CCV prior to sample analysis, in each analytical sequence per run batch.

•	Note that the SRM 2779 solution should be analyzed initially using GC/MS full scan to establish
the retention time windows for the alkylated PAH homologues to create the SVOA SIM
descriptors. The standard reference oil must be analyzed after the opening CCV standard and
prior to sample analysis using GC/MS SVOA SIM to verify that the SVOA SIM descriptors are
appropriate for the detection of the alkylated PAH homologues.

•	Note that the peak resolution of analytes 9-Methylphenathrene and 1-Methylphenathrene in the
SRM 2779 shall be greater than 80%. %D for each target analyte in Section I shall be within
+/-20.0% of NIST 95% uncertainty range for analytes within the quantitation range. Up to 2
analytes may exceed the 20.0% limits; but the average %D must be less than 35.0%.

•	Prepare and analyze the method blank at the same frequency and sequence as specified in the
SOW. The concentration of any analyte in Section I shall not exceed the CRQL in the method
blank.

•	Perform MS/MSD analyses, if requested, as specified for SVOA SIM analysis in the SOW.

•	Add the same DMC solution at the specified concentration specified for SVOA-SIM analysis in
the SOW to the samples, MS/MSD (if requested) and blanks. DMC %R technical acceptance
criteria specified in the SOW shall remain in effect.

•	Perform any required dilutions as specified in SOW for any of the 17 SOW PAH target analytes
and the additional target analytes when exceeding the calibration range (this does not apply to
alkylated PAH homologue series).

•	Note that all other technical acceptance criteria for ICALs, CCVs, blanks, MS/MSD and samples
remain the same as specified in the SOW.

III. Preparation and Method Modifications	Not applicable

	~	

The Laboratory shall:

•	Perform a MDL study for the target analytes in Section I except analytes with **.

•	Perform GPC clean up procedure as specified in the SOW.

•	Note the GC column requirements: A 30-m x 0.25-mm (5% Phenyl)-methylpolysiloxane capillary
column with 0.33 or 0.50 jjm film thickness, such as an Agilent DB-5MS, Ultra-2, Rtx-5MS, HP-
5MS, or a PTE-5 which is certified for GC/MS analysis with improved inertness, signal to noise
ratio and sensitivity, shall be used for this analysis. Substitution of a different gas


-------
chromatography column will result in data that may not be comparable to those data that this
modified analytical protocol can achieve and that have been generated previously for this study.

•	Note the recommended gas chromatographic conditions:

Injection Volume: 1-|jL injection volume into a 2 or 4mm ID glass liner. Carrier Gas: Helium
Electronic Pressure Control (EPC) Gas Program: Initial Pressure: 30 psi; Initial Time: 1 min;
Ratel: 99 psi/min; Final Pressure: Constant Flow (1 mL/min); Vacuum Compensation: On;
Injection Port: 300°C; Transfer Liner: 280°C; Initial Temp: 40°C; Initial Hold: 1 minute; Ramp
Rate: 6°C/min; Final Temp: 320°C; Final Hold: 20 minutes or until Benzo(g,h,i)perylene elutes.

•	Note that other GC conditions may be used, as appropriate, to achieve the
chromatographic separation and response requirements of the Modified Analysis
request.

•	Note that the Mass Spectrometer Conditions specified in the SOW shall remain the same.

•	Note that a minimum of 5 SVOA SIM scans will be acquired during the elution of each analyte.
Document the retention time references of the SVOA SIM descriptor groups to identify
the SVOA SIM acquisition ion groups and SVOA SIM acquisition windows for the PAH
target analytes and the alkylated PAH homologue series.

•	Verify that the GC and SVOA SIM MS conditions and the SVOA SIM windows have been
identified as required. The length of the time required for performing each sample and standard
analysis is about one hour; therefore, the Laboratory shall verify that the instrument meets
the DFTPP criteria every 12 hours.

•	Note the following criteria for analyte identification: The pattern of each group and the retention
time window for the group is established by the analysis of the SRM 2779. Relative Retention
Time (RRT) is useful to inter-compare the identity of analytes in samples and reference
standard that elute within like alkylated PAH homologue groupings.

•	Note that the alkylated PAH homologue groupings (e.g. C3-Naphthalene) appear as clusters or
groups of isomers and must be integrated as individual groups in their entirety. The total
response of each group of alkylated homologues is used in the quantitative determination of the
concentration of the entire group.

•	Note that the characteristic masses of each analyte of interest must be in the same scan or
within one scan of each other. The retention time must fall within +/- 0.2 min of the retention
time of the authentic parent analytes that define each alkylated homologue grouping
determined by the analysis of the daily calibration check or reference oil standard, respectively.

•	Note that the relative peak heights of the primary mass ion, compared to the confirmation or
secondary mass ion, must fall within 30% of the relative intensities of the masses in a reference
mass spectrum. The reference mass spectrum is obtained from the continuing calibration
solution or the SRM 2779 for the parent analytes and alkylated homologues, respectively.
Supportive data may be included in some instances for an analyte that does not meet
secondary ion confirmation criteria but is determined to be present in a sample after close
inspection of the data by a qualified mass spectrometrist.

•	Note that the mass spectra of an alkylated PAH group in a real sample quantified below
reporting limits may not be definitive and subject to distortion by interfering peaks from non-
target analytes, especially when dominated by spectra of non-target analytes present at high
concentrations. Consequently, the relative peak heights of primary mass-ion to the confirmation
ion will not always be within 30% of the relative intensities of the masses in a reference mass
spectrum.

•	Follow the internal standard method for analyte quantitation as defined in the SOW. Relative
Response factors for the alkylated PAH homologues are presumed equal to the RRF of the
respective un-substituted (parent) analyte.


-------
• Quantify and report total alkylated (Cx) Naphthalenes (as specified in Section I), total alkylated
(Cx) Fluorenes and total (Cx) alkylated Chrysenes and the rest Cx PAH in Section I. The
alkylated Phenanthrenes + Anthracenes must be reported as total alkylated (Cx)
Phenanthrenes/Anthracenes. Similarly, alkylated Fluoranthenes + Pyrenes will be quantitated
using the RRF of the parent analyte Fluoranthene and the final concentration shall be reported,
as total alkylated (Cx) Fluoranthenes/Pyrenes.

IV. Special Reporting Requirements Not
	applicable ~	

The Laboratory shall:

•	Report the CRQLs listed in Section I, adjusted according to the equation listed in Exhibit
D, even if the level of the corresponding target analytes in the low-point calibration
standard is below the CRQLs listed in Section I.

•	Submit the MDL study results for all target analytes in Section I except those with ** as specified
in the SOW. If the Laboratory has not previously submitted MDL results during the current
contract year for the target analytes in Section I except those with ** above, compliant MDL
study results shall be submitted concurrently with the deliverables for this MA to the recipients
specified in SOW Exhibit B, Table 1, Row G.

•	Modify all applicable hardcopy forms to include all required the target analytes in Section I and
the required DMCs, ISs as appropriate. This includes Forms 1, 2, 3, 6, 7 and 8.

•	Note that the Analysis/Analyte and AnalysisGroup/Analyte node(s), including the Peak node(s)
for each, of the parent analyte in the EDD must be copied and reported using the 'Analyte Code'
(see Section I) as the CASRegistryNumber data element of each Cx alkylated PAH homologue
being quantitated from the parent analyte.

•	Note that the PeakID field shall be reported with the "Quantitation Ion" information in Section I
for all analytes including those with **.

•	Report the SRM 2779 with the EPA sample number of "SRM2779##" where ## is the
alphanumerical value in both EDD and on hardcopy form. Report the QCType of
"Continuing_Calibration_Verification" under IQC in the EDD for the SRM.

•	Report the SRM2779## on a modified Form 7 to include retention time information for analytes
and alkylated PAH homologues in Section I as appropriate.

•	Include the peak resolution of the analytes 9-Methylphenathrene and 1-Methylphenathrene in
the SRM 2779 on this modified Form 7 as well.

•	Note that applicable Lab Qualifiers specified in the SOW shall remain the same.

•	Note that TICs are not required to be reported for the analysis, however, full, detailed
quantification reports showing baseline integrations are required.

•	Include the same information on the EDD as in the hardcopy.

•	Provide hardcopies of the initial Cal Level 3 standard and continuing calibration standard
chromatograms so that the 17 SOW target PAH analytes, their isomers, 1-Methylnaphthalene
and 2- Methylnaphthalene are 75 - 100% of full scale.

•	Include the hard copy chromatogram and results of the SVOA full scan analysis of the SRM
2779 that was used to determine the homologue descriptors for the SVOA SIM analysis in the
data package. The chromatogram of the full scan analysis of the SRM must be scaled so the
chromatographic peaks with the greatest peak heights are 90% of full scale.


-------
SAP Worksheet #12 - Measurement Performance Criteria Table - Field QC Samples

QC Sample

Analytical Group

Frequency

Data Quality Indicators
(DQIs)

Measurement Performance
Criteria (MPC)

QC Sample
Assesses Error for
Sampling (S),
Analytical (A) or
both (S&A)

Field Triplicate
(ISM)

Expanded PAHs and
alkylated homologs

1 field triplicate for 3
sampling units (SUs)

Precision /
Comparability /
Representativeness

<25% Relative Standard
Deviation (RSD).

S

Co-located
Samples
(Discrete Soil,
Sediment and
Oil/Sheen)

Expanded PAHs and
alkylated homologs

Soil -14 co-located
samples for 121 initial
samples

Sediment - 7 co-
located samples for 9
initial samples

Oil/Sheen - 3 co-
located samples for 3
initial samples

Comparability /
Representativeness

Not applicable as only aliquot
extraction mass is being
collected from each sample
location

S

Duplicate

Sample

(Groundwater)

Expanded PAHs and
alkylated homologs

1 duplicate for 2 initial
samples

Comparability /
Representativeness

< 25% Relative Standard
Deviation (RSD)

S

Gauze Sampler

Blank

(Oil/Sheen)

Expanded PAHs and
alkylated homologs

1 blank (medical
gauze)

Accuracy / Sampler
Purity

Same as Method/SOP QC
Limits.

No target PAH compounds
detected

A

Matrix

Spike/Matrix
Spike Duplicate

Expanded PAHs and
alkylated homologs

1 per 20

environmental

samples

Precision/Accuracy/Bi
as

Same as Method/SOP QC
Limits.

A

Submission of Quality Control Samples

To establish the precision, accuracy, and representativeness of data obtained from the sampling effort, QC samples will be submitted to the
laboratories for chemical analysis. The QC samples include co-located samples, field triplicates (ISM only), duplicates (groundwater only), matrix
spikes/matrix spike duplicates (MS/MSDs) and a sampler blank (medical gauze only).


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SAP Worksheet #19 - Analytical SOP Requirements

Matrix

Analytical
Group

Concentration
Level

Analytical
Method1

Sample
Volume

Containers
(number, size,
and type)

Preservation
Requirements (chemical,
temperature, light
protected)

Maximum
(preparation/
analysis)

Soil - ISM

PAHs

Trace

8330B/SOM02.3 SIM
MA 2585.0

> 1 kg

32 - 64 oz. glass
jar

Cool to <6°C

10 days to extraction,
40 days to analysis

Soil - Discrete

PAHs

Trace

SOM02.3 SIM
MA2585.0

20 grams

(g)

1 - 4 oz. amber
glass jar with
Teflon® -lined lid

Cool to <6°C

14 days to extraction,
40 days to analysis

Groundwater

PAHs

Trace

Modified 8270D

2 Liters

2 - 1L amber
glass bottles

Cool to 4±2°C

7 days to preparation,
40 days to analysis

Sediment/Oil
and/or Sheen

PAHs

Trace

Modified 8270D

20g

1 - 4 oz. amber
glass jar with PTFE-
lined lid

Cool to 4±2°C

14 days to extraction, 40
days to analysis


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SAP Worksheet #20 - Field Quality Control Sample Summary Table

Matrix

Analytical
Group

Cone.
Level

Analytical and

Preparation
SOP Reference

No. of
Sampling
Locations

No. of
Samples
Collected per
Location

No. of
Co-located
Samples1

No. of ISM

Field
Triplicates2

No. of
Duplicate
Samples3

Total No.
of

Samples
to Lab

Groundwater/
Sheen

Expanded
PAHs &
Alkylated
Homologs
(EPAHs &
AHs)

Trace

SOM02.3 SIM
MA2585.0

2

1

N/A

N/A

1

3

Sediment

EPAHs &
AHs

Trace

SOM02.3 SIM
MA2585.0

9

1

7

N/A

N/A

16

Surface

Sediment

Oil/Sheen

EPAHs &
AHs

Trace

SOM02.3 SIM
MA2585.0

3

1

3

N/A

N/A

6

Soil - Discrete

EPAHs &
AHs

Trace

SOM02.3 SIM
MA2585.0

45

1-4

17

N/A

N/A

138

Soil - ISM
(new)

EPAHs &
AHs

Trace

8330B/SOM02.3S
IM MA2585.0

3

1

N/A

1

N/A

5

Soil - ISM
(previously
collected)

EPAHs &
AHs

Trace

8330B/SOM02.3
SIM

3

1

0

N/A

N/A

3

1	- Co-located samples apply to discrete sediment and soil locations. Co-located samples are not "replicates."

2	- Applies only to ISM samples.

3	- Applies only to groundwater/sheen samples.


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SAP Worksheet #28 - Laboratory QC Samples Table

Matrix

Soil/Sediment



Analytical Group

PAHs

Concentration Level

Trace / Low

Sampling SOP

SA-1.3

Analytical Method

SOM02.3 SIM

Sampler's Name

TBD

Field Sampling
Organization

Tt

Analytical
Organization

TBD

No. of Samples

162

QC Sample:

Frequency/
Number

Method/SOP QC
Acceptance Limits

Corrective Action

Person(s)
Responsible
for Corrective
Action

Data Quality
Indicator (DQI)

Measurement
Performance
Criteria

Method Blank

One per analytical
batch. Not to
exceed 20 field
sample.

No target compounds
>CRQL, except common
lab contaminants which
should be <5xCRQL.

Re-clean, retest, re-extract,
reanalyze blank. Reanalyze all
sample associated with
unacceptable blank.

Analyst,
Supervisor

Bias /

Contamination

Same as Method/SOP
QC Limits.

DMC

At least 3 per
sample

See Table 5 of Method.

Up to three DMCs per sample
may fail to meet the recovery
limits in Table 5. Check
calculations, DMC spiking
solutions, and instrument
performance and then reanalyze
sample.

Analyst,
Supervisor

Accuracy / Bias

Same as Method/SOP
QC Limits.

IS

3 per sample

Retention time must be
within + 20 seconds; quant
ion area must be within
50-200% of the mid-point
(L3) of the calibration
curve.

Check calculations, spike
solution, and instrument
performance. Take Corrective
Action to technical acceptance
criteria. Narrate.

Analyst,
Supervisor

Precision /
Accuracy / Bias

Same as Method/SOP
QC Limits.

MS/MSD

One per 20

environmental

samples

%R requirements in
method tables.

Recalculate, check spike
solutions, or recalibrate if
necessary.

Analyst,
Supervisor

Precision /
Accuracy / Bias

Same as Method/SOP
QC Limits.

Laboratory Triplicate
Sub-sample

One set per 10 ISM

< 25% RSD

Collect new sub-sample aliquots
and reanalyze

Analyst,
Supervisor

Precision /
Accuracy/
Representativeness

< 25% RSD


-------
Matrix

Groundwater



Analytical Group

PAHs

Concentration Level

Trace

Sampling SOP

SA-1.3

Analytical Method

SOM02.3 SIM

Sampler's Name

TBD

Field Sampling
Organization

Tt

Analytical
Organization

TBD

No. of Samples

3

QC Sample:

Frequency/
Number

Method/SOP QC
Acceptance Limits

Corrective Action

Person(s)
Responsible
for Corrective
Action

Data Quality
Indicator (DQI)

Measurement
Performance
Criteria

Method Blank

One per analytical
batch. Not to
exceed 20 field
sample.

No target compounds
>CRQL, except common
lab contaminants which
should be <5xCRQL.

Re-clean, retest, re-extract,
reanalyze blank. Reanalyze all
sample associated with
unacceptable blank.

Analyst,
Supervisor

Bias /

Contamination

Same as Method/SOP
QC Limits.

DMC

At least 3 per
sample

See Table 5 of Method.

Up to three DMCs per sample
may fail to meet the recovery
limits in Table 5. Check
calculations, DMC spiking
solutions, and instrument
performance and then reanalyze
sample.

Analyst,
Supervisor

Accuracy / Bias

Same as Method/SOP
QC Limits.

IS

2 per sample

Retention time must be
within + 20 seconds; quant
ion area must be within
50-200% of the mid-point
(L3) of the calibration
curve.

Check calculations, spike
solution, and instrument
performance. Take Corrective
Action to technical acceptance
criteria. Narrate.

Analyst,
Supervisor

Precision /
Accuracy / Bias

Same as Method/SOP
QC Limits.

LCS/LCSD

One per extraction
batch of 20 or less

Qualitative criteria in
Tables 2 and 9; %R within
limits listed in Table 6.

Re-extract and reanalyze if low
recovery. Flag associated
samples.

Analyst,
Supervisor

Precision /
Accuracy / Bias

Same as Method/SOP
QC Limits.


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Matrix

Oil/Sheen (Gauze)



Analytical Group

PAHs

Concentration Level

Trace

Sampling SOP

SA-1.3

Analytical Method

SOM02.3 SIM

Sampler's Name

TBD

Field Sampling
Organization

Tt

Analytical
Organization

TBD

No. of Samples

7

QC Sample:

Frequency/
Number

Method/SOP QC
Acceptance Limits

Corrective Action

Person(s)
Responsible
for Corrective
Action

Data Quality
Indicator (DQI)

Measurement
Performance
Criteria

Method Blank

One per analytical
batch. Not to
exceed 20 field
sample.

No target compounds
>CRQL, except common
lab contaminants which
should be <5xCRQL.

Re-clean, retest, re-extract,
reanalyze blank. Reanalyze all
sample associated with
unacceptable blank.

Analyst,
Supervisor

Bias /

Contamination

Same as Method/SOP
QC Limits.

DMC

At least 3 per
sample

See Table 5 of Method.

Up to three DMCs per sample
may fail to meet the recovery
limits in Table 5. Check
calculations, DMC spiking
solutions, and instrument
performance and then reanalyze
sample.

Analyst,
Supervisor

Accuracy / Bias

Same as Method/SOP
QC Limits.

IS

2 per sample

Retention time must be
within + 20 seconds; quant
ion area must be within
50-200% of the mid-point
(L3) of the calibration
curve.

Check calculations, spike
solution, and instrument
performance. Take Corrective
Action to technical acceptance
criteria. Narrate.

Analyst,
Supervisor

Precision /
Accuracy / Bias

Same as Method/SOP
QC Limits.

LCS/LCSD

One per extraction
batch of 20 or less

Qualitative criteria in
Tables 2 and 9; %R within
limits listed in Table 6.

Re-extract and reanalyze if low
recovery. Flag associated
samples.

Analyst,
Supervisor

Precision /
Accuracy / Bias

Same as Method/SOP
QC Limits.


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7 (SD/SW01)

l9;(sd/sw,ii)

6 (SD/5WQ5)

8 (SD/SW16)

W	V1

-/«>cT- -*3 -

r>*SlaJ

sif _ §

_ p. * ^

~ • 1 \r*r

r i *

7*

J tr,J M

' a

•. >>'

Wit /«

. • *inv1 r /. • .

HfiH

HHviR

1 1 /

~

Legend

Sediment Sample





MF

~ •

~

GW Sample









~

County Boundary Line









^jmr ^WK^psM^gitalSeE

HKEmsSiibti^ll)Sl|®ill

P1 S® 1 SSl&Bofefeaitl1Bl^|-^|

o

Historical Extent of Clearview Landfill











Stream

Source: Aerial photography - Bing Map, City Planning Commission (PCPC)
Department - GIS Division, 2008.

S:\03-Projects\Federal\EPA R3 RAC Assignments\Lower Darby\112G07477 - LDCA OU1 RD\Documents\Plans\SAP\Appnedix B - Figures\GIS\PAH Fingerprinting\Figure 1 - GW SD Locations.mxd

It

Approximate Site Location = I
¦

Lower Darby Creek Area Site - Clearview Landfill
Delaware and Philadelphia Counties, Pennsylvania

Figure 1

Proposed Groundwater and Sediment Sampling Locations

TETRATECH

Project Number
103IG2570014.0000.0320

Map created on February 5, 2016
by V. Petrov, Tetra Tech, Inc.


-------
H£E0B®

B

SU049B

SU108

Basin A

21(GP109)

19(GP301)

25(GP.007)



Source: Aerial photography - Bing Map, City Planning Commission (PCPC)
Department - GIS Division, 2008.

Legend

@ Soil Sample

ISM/Discrete Sample
Drainage Basins on Clearview Landfill
County Boundary Line
Historical Extent of Clearview Landfill

1,000
I Feet

S:\03-Projects\Federal\EPA R3 RAC Assignments\Lower Darby\112G 0747 7 - LDCA OU1 RD\Documents\Plans\SAP\Appnedix B - Figures\GIS\PAH Fingerprinting\Figure 2 - Soil Locations.mxd

It

Approximate Site Location = I
Pennsylvania

£3

Lower Darby Creek Area Site - Clearview Landfill
Delaware and Philadelphia Counties, Pennsylvania

Figure 2

Proposed Soil Sampling Locations

TETRATECH

Project Number
103IG2570014.0000.0320

Map created on February 5, 2016
by V. Petrov, Tetra Tech, Inc.


-------


jMM

S:\03-Projects\Federal\EPA R3 RAC Assignments\Lower Darby\112G07477 - LDCA 0U1 RD\Documents\Plans\SAP\Appnedix B - Figures\GIS\PAH Fingerprinting\Figur© 3 - Background Locations.mxd

It

sun

Legend

Soil Sample

sq.iii rLGe^i^ia a i ta I mo	Ie

0.01 -acre SU

Suffo k Park SU

Source: Aerial photography - Bing Map, City Planning Commission (PCPC)
Department - GIS Division, 2008.

Approximate Site Location = I
Pennsylvania

£3

Lower Darby Creek Area Site - Clearview Landfill
Delaware and Philadelphia Counties, Pennsylvania

Figure 3

Suffolk Park Sampling Locations

TETRATECH

Project Number
103IG2570014.0000.0320

Map created on March 3 L 2016
by V. Petrov, Tetra Tech, Inc.


-------
GP081,GP081

GP082

GP043

GP083

GP019
GP033D GP020.

GP211

GP002

GP021
GP021

GP103 /V

GP080

nDn ,SP°m:



GP247
GF037 GP037



GPOO!

G3036 GP039

GP007

GP005i

GP008

2S7050G

Grid in PA State Plane South (ft)

¦ Sampled 2003
A Sampled 2004
© Sampled 2006
I | HHRA Zone 1
I HHRA Zone 2
HHRA Zone 3
Clearview Landfill

1:4,800 1 inch equals 400 feet

Tetra Tech Delaware

Phone: (302) 738-7551
Toll Free: (800) 462-0910
www.tetratech-de.com
www.tetratech.com

T47111.0109

Figure 3-2
Soii Boring Locations
2003 - 2006
Clearview Landfill
Philadelphia, PA

This map is provided by Tetra Tech solely for display and reference purposes and
is subject to change without notice. No claims, either real or assumed, as to the
absolute accuracy or precision of any data contained herein are made by Tetra
Tech, nor will Tetra Tech be held responsible for any use of this document for
purposes other than which it was intended.


-------
Grid in PA State Plane South (ft)

Legend

1,000 2,000

4,000
I Feet

1:24,000 1 inch equals 2,000 feet
Historical Extent of Clearview Landfill

Sampled in 2002
Sampled in 2002/2005

Tetra Tech Delaware

Phone: (302) 738-7551
Toll Free: (800) 462-0910
www.tetratech-de.com
www.tetratech .co m

Figure 3-5

Surface Water and Sediment
Sampling Locations
Lower Darby Creek Area
Pennsylvania

This map is provided by Tetra Tech solely for display and reference purposes and
is subject to change without notice. No claims, either real or assumed, as to the
absolute accuracy or precision of any data contained herein are made by Tetra
Tech, nor will Tetra Tech be held responsible for any use of this document for
purposes other than which it was intended.


-------
Grid in PA State Plane South (ft)

PD - Pond

CS - Combined Sewer

400 200
1:4,800 1 inch = 400 feet

400

800
~ Feet

Tetra Tech Delaware

Phone: (302) 738-7551
Toll Free: (800) 462-0910
www.tetratech-de.co m
www.tetratech. co m

Figure 3-12

Drainage/Recharge Basins and
Stormwater Sample Locations
Clearview Landfill
Pennsylvania

This map is provided by Tetra Tech solely for display and reference purposes and
is subject to change without notice. No claims, either real or assumed, as to the
absolute accuracy or precision of any data contained herein are made by Tetra
Tech, nor will Tetra Tech be held responsible for any use of this document for
purposes other than which it was intended.


-------
APPENDIX
FALCON Signature Tracing


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Use of EPA ORD's FALCON Procedure to Compare PAH "Signature" Patterns

Prepared by Deana Crumbling, 19Feb2016 for Josh Barber, R3

EPA ORD described a technique to evaluate the degree of similarity or difference between the
"fingerprint" patterns for different samples. This technique can be used for multi-analyte classes
of contaminants, such as PAHs, PCBs and dioxins. The ORD technique is called Fingerprint
Analysis of Leachate Contaminants (FALCON, USEPA 2004). The technique uses the
coefficient of determination (r-squared or r2) from regression analysis as a means to quantify the
similarity between the multi-analyte patterns from two different samples. The assumption is that
samples having similar or identical fingerprint patterns are more likely to have the same or
similar contaminant sources than samples having very different patterns. Two samples having
similar multi-analyte profiles have a higher r2 (up to a maximum of 1.000 for identical patterns).
Two samples having very different multi-analyte profiles will have a lower r2 (to a minimum of
0.000 for completely different patterns).

For historical LDCA samples, PAHs was the multi-analyte class of compounds. All LDCA
samples had results for the same set of 15 specific PAH compounds. (Dibenz(a)anthracene was
not analyzed, or was nondetect, for nearly all of the LDCA samples, therefore that PAH
compound was excluded from FALCON analysis.) PAH profiles were compared for sediment
samples from Darby and Cobbs Creeks and landfill samples. Because the way these r2 values
were used to look for anomalies (rather than attribute "sources"), the term "signature" pattern or
profile will be used instead of the term "fingerprint." The signature findings are summarized
below:

Darby Creek: When the PAH profile of the most upstream sample of Darby Creek was compared
to the other 9 downstream Darby Creek samples, the r2 (rounded to 2 decimal places) for each of
the 9 signature comparisons ranged between 0.98 to 1.00, showing very high similarity among
the PAH profiles of all Darby Creek sediment samples.

Cobbs Creek: When the PAH profile of the most upstream sample of Cobbs Creek was
compared to the 9 Cobbs Creek samples, the r-squareds of those 9 signature comparisons ranged
between 0.94 to 0.99. Although there is high similarity among the PAH profiles of all Cobbs
Creek sediment samples, there are places along Cobbs Creek where pattern similarity dropped,
then rebounded. Since these samples were collected around 10 years ago, it is difficult to say
now what explanation there could be.

•	It could be conjectured that the Darby Creek profile represents the "purest" form of a
Phila. non-point source "urban PAH background" stormwater runoff signature.

•	Examination of current GoogleEarth satellite photos show the presence of a fuel oil
retailer and car repair shops near the Cobbs Creek shoreline, but no similar potential
sources along Darby Creek.

•	It is easy to imagine that storm drains carrying oily fuel and automotive leakage from
such point sources could enter Cobbs Creek and somewhat change the PAH composition
of sediments just downstream of those particular storm drain outfalls.

•	Storm drain outfalls solely carrying non-point source PAH runoff entering Cobbs Creek
below potential point-sources could re-establish the "urban background" runoff signature.


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The most interesting finding from signature comparisons was a sudden drop in similarity for one
of the sediment sampling locations (#24) in the stream bordering the landfill after the confluence
of Darby and Cobbs Creeks. Comparing the first Darby Creek sample to samples taken along the
western side of the landfill (#21 through #26 Or #27) shows a drop at #24, with gradual recovery
of similarity with "urban PAH background profile" by #26.









1 VS 21



1 vs 22



1 vs 23



1 vs 24



1 vs 25



1 vs 26

SD01

Darby #1 vs 21 thru 38



0.99



0.94



0.96



0.72



0.89



0.98

The same pattern is seen for the last sample of Darby Creek (#10), and the first sample of Cobbs
Creek (#11).





10 vs. 21 10 vs 22 10 vs 23



10 vs 24

10 vs 25



10 vs 26



10 vs 27

SD10

Darby #10 vs. #21 thru 38



1.00

0.91

0.93



0.65

0.8^



0.96



0.95









11 vs 21



11 vs 22



11 vs 23



11 vs 24



11 vs 25



11 vs 26

SD11

1st Cobbs (#11) vs. 21 thru 38

0.93



0.99



0.99



0.87



0.96



0.98

The pattern at sediment sample #24 did not match either the "seep" or "leachate" samples
particularly well, with none of the r-squareds above 0.90.









SD24 vs seep 2

24 vs seep 3

24 vs seep 4

24 vs seep 5

24 vs seep 6

SD24

SD24 vs all seeps



0.85



0.71



0.78



0.82



0.80











SD24 vsLSD01

SD24 vs LSD02

SD24 vs LSD03

SD24 vs LSD04

SD24vsLSD05

SD24 vs LSD 15

SD24

SD24vs all leachates



0.72



0.89



0.72



0.89



0.83



0.86



The SD#24 pattern somewhat matches patterns from the following boring samples having high
total PAH concentrations. GP120D and GP243M show the best pattern agreement (r2 = 0.97 and
0.96, respectively):







GP120D (94K)

GP121D (104K)

GP218D (1.6M) GP222D (360K)

GP228M (426K)

GP232D (510K)

GP243M (228K)

SD24 SD24vs boring samples



0.97

0.94

0.94 0.95

0.87



0.86



0.96



These boring

samples have total PAH conc. greater than about 100K ppm (actual cone in parentheses)













Reference:

Plumb, R. H.; Fingerprint Analysis of Contaminant Data: A Forensic Tool for Evaluating
Environmental Contamination; May 2004; (EPA/600/5-04/054); available online at
http://www.epa.gov/sites/production/files/2015-06/documents/plumb20Q4.pdf


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