DEQp00020680

SAMPLING PLAN
Date: September 15, 2017
To: North Carolina Department of Environmental Quality ("DEQ")
From: The Chemours Company FC, LLC ("Chemours")
Re: Wastewater Sampling Plan
I. INTRODUCTION
Chemours has prepared this Sampling Plan for collecting and analyzing wastewater
samples at Chemours' Fayetteville, North Carolina facility "Fayetteville Works" to respond to
DEQ's request for certain wastewater sampling. Specifically, this Plan responds to DEQ's
September 10, 2017 email requesting that Chemours prioritize sampling for the following
constituents: "pH, TSS, COD, PFOA, PFOS, manufacturing operations specific organics,
metals, all the chemicals on the handout provided to DEQ on the July 27, 2017 site visit, PFECA
compounds and PFESA byproducts" (hereinafter, "DEQ's Requested Analytes").
Chemours discussed an outline of this Sampling Plan with DEQ during a September 13,
2017 teleconference, during which DEQ provided initial comments, including comments
regarding the scope of samples to be collected and analyzed. This Sampling Plan reflects the
comments DEQ provided during the September 13th teleconference and provides further details
of the wastewater sampling that will be conducted.
II. FIELD SAMPLING PLAN
DEQ plans to be at the Fayetteville Works the morning of Monday, September 18, 2017,
to collect samples from Outfalls 001 and 002 at the Fayetteville Works, as well as the following
portions of the Chemours' process that currently discharge into the Fayetteville Works'
wastewater treatment plant (designated with green dots on the process schematic Chemours
previously produced as CH -FW -DEQ -0057683 and included herein as Figure 1):
• Common Waste Tank
• Cell Lab Effluent
• DEG Tank
• Hydrolysis Waste Sump
• Products Sump
• Alkaline Waste Tank
• Waste Acid Tank
• Tank Farm Sump (Safety Showers, Steam Condensate, Rain)
During the September 13th teleconference, DEQ requested that Chemours sample the combined
effluent from some of the units listed above. However, upon further review, Chemours has
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determined that it is not feasible to sample the combined effluent from these units and so instead
will sample each of the units individually. In addition, during the September 13th
teleconference, DEQ requested that Chemours sample the effluent from "Sulfuric Acid/KOH
Addition." This effluent is either 93% sulfuric acid or nominally 20% KOH that is added to the
common waste tank for pH adjustment. Accordingly, Chemours has removed the Sulfuric
Acid/KOH Addition from this Sampling Plan.
In addition and contemporaneous to collecting a sample from, these locations for DEQ,
Chemours will collect four duplicates to be analyzed or retained as set forth below.
Under this Sampling Plan, only the following samples will be analyzed at this time: (1)
Outfall 001; (2) Outfall 002; (3) Common Waste Tank; and (4) Cell Lab Effluent (collectively,
"Phase 1 Sample Set"). The remaining samples collected hereunder (collectively, "Phase 2
Sample Set") will be retained and, depending on the results of the Phase 1 Sample Set, may be
analyzed. After receipt of all of the results of the Phase 1 Sample Set, Chemours will prepare a
supplemental Sampling Plan regarding the analysis of the Phase 2 Sample Set and will provide
this supplemental Sampling Plan to DEQ.
III. ANALYTICAL METHOD
As noted above, only the Phase 1 Sample Set will be analyzed under this Sampling Plan.
For purposes of this Sampling Plan, Chemours has divided DEQ's Requested Analytes into the
three categories shown in Table 1 (Conventional Pollutants, PFOA, PFOS, and HFPO Dimer
Acid), Table 2 (Products), and Table 3 (Potential Byproducts or Impurities) of this Sampling
Plan.'
Below addresses how each of the Phase 1 Sample Set will be analyzed for the compounds
listed in Tables 1, 2, and 3.
A. Table 1 - Conventional Pollutants, PFOA, PFOS, and HFPO Dimer Acid
During the September 13th teleconference, DEQ indicated that the existing sampling data
Chemours has provided for Outfalls 001 and 002 satisfy DEQ's requests for pH, TSS, COD, and
manufacturing operations specific organics, but DEQ requested that Chemours run a full scan for
metals in samples from Outfalls 001 and 002. Chemours provided a full set of metals analysis in
its April 2016 permit application for Outfalls 001 and 002. Per DEQ's August 18, 2017 letter
states that "Historical sampling data, no later than 4.5 years old, may be submitted provided it is
representative of the current wastewaters being discharged." Chemours believes the metals data
submitted along with its April 2016 permit application are representative of the metals content in
its current wastewater discharges.
' In addition, DEQ requested that Chemours analyze the Phase 1 Sample Set for CF20 (CASRN 353-50-4) and CF2
(CASRN 2154-59-8). These substances, however, are unstable in the presence of water and are unlikely to be
detected. COF2 will hydrolyze to form carbon dioxide and hydrogen fluoride. CF2 is a very unstable intermediate
that will readily react in aqueous environment to form carbon monoxide and hydrogen fluoride. For these reasons,
Chemours does not intend to analyze for CF20 (CASRN 353-50-4) and CF2 (CASRN 2154-59-8) under this
Sampling Plan.
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In addition, on September 14, 2017, Chemours submitted analytical results for, among
other locations, an August 1, 2017 sample collected from Outfall 002 and analyzed for HFPO
Dimer Acid and the modified EPA Method 537 compounds (including PFOA and PFOS). These
results (and the prior BFPO Dimer Acid sampling results Chemours has produced to DEQ)
satisfy DEQ's request for HFPO Dimer Acid, PFOA, and PFOS data from Outfall 002.
These prior HFPO Dimer Acid results also satisfy DEQ's request for analytical results for
HFPO Dimer Acid ammonium salt, HFPO Dimer Acid potassium salt, BFPO Dimer Acid
Fluoride, as all three of these compounds dissociate in aqueous environment and exist as HFPO
Dimer anion. This HFPO Dimer anion is the same as what all testing labs are detecting (via
LC/MS/MS) as the HFPO Dimer Acid.
In light of these existing data, the remaining analysis for Table 1 compounds for the
sample locations comprising the Phase 1 Sample Set are as follows:
• Outfall 001 - PFOA, PFOS, and HFPO Dimer Aci&
• Common Waste Tank - all Table 1 compounds
• Cell Lab Effluent - all Table 1 compounds
In order to respond to DEQ's requests, Chemours already has collected and provided
these samples to external laboratories for analysis. Chemours anticipates being able to provide
these results to DEQ on a rolling basis beginning the week of September 18, 2017.
These existing samples and forthcoming results will satisfy DEQ's remaining requests to
analyze Outfalls 001 and 002, Common Waste Tank, and Cell Lab Effluent for the Table 1
compounds, and therefore Chemours will not analyze the Phase 1 Sample Set samples that will
be collected on Monday, September 18th for the Table 1 compounds unless and until requested
to do so by DEQ.
B. Table 2 - Products
For the Table 2 compounds, Chemours is unaware of any certified analytical methods for
identifying or quantifying these compounds in wastewater.
Therefore, in order to respond to DEQ's request for sampling data for these compounds,
Chemours will proceed as follows:
Chemours will collect a reference sample of the compound from the Fayetteville
Works' process.
Chemours' internal laboratory will then try to detect the compound in the Phase 1
Sample Set.
If the compound is not detected in the sample, Chemours will take no further action
with respect to analyzing the sample for the Table 2 compound.
2 As explained above, this also addresses DEQ's request for results for HFPO Dimer Acid ammonium salt, HFPO
Dimer Acid potassium salt, HFPO Dimer Acid Fluoride.
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• If the compound is detected, Chemours' internal laboratory will then attempt to
estimate the concentration of the Table 2 compound.
Please note that Chemours' methodology for Table 2 compounds is primarily associated
with the monitoring of process streams. In some cases, adjustments will be made to translate that
methodology to wastewater matrices. In addition, some of the Table 2 compounds would
undergo hydrolysis and those hydrolysis products would require a change in analytical
methodology. That work would be additive to what is currently described in the Sampling Plan
and ongoing progress would be shared during the weekly teleconferences with DEQ that
Chemours has proposed in its cover letter transmitting this Sampling Plan to DEQ.
In order to meet DEQ's request for expedited results, any results for the Table 2
compounds will be estimates subject to certain limitations that Chemours will detail further when
it provides the results to DEQ. Chemours anticipates being able to begin to provide the results
for the Table 2 compounds in the Phase 1 Sample Set on a rolling basis beginning the week of
September 25, 2017.
That said, analyzing for Table 2 compounds requires developing new analytical methods,
as there are no certified analytical methods for detecting or quantifying the Table 2 compounds
in wastewater. This Sampling Plan may need to be updated as Chemours undertakes this
analysis and obtains a better understanding of these analytical methods. Chemours will continue
to keep DEQ updated on Chemours' progress in analyzing for the Table 2 compounds and
recommends doing so on the weekly teleconferences with DEQ that Chemours proposed in its
cover letter transmitting this Sampling Plan to DEQ.
C. Table 3 - Potential Byproducts or Impurities
As with the Table 2 compounds, Chemours is unaware of any certified analytical
methods for identifying or quantifying the Table 3 compounds in wastewater. Earlier this week,
Chemours received a SOP from EPA for analyzing several of the Monether PFECAs listed in
Table 3 and, although Chemours still is reviewing this SOP, Chemours likely will attempt to
duplicate this method.
In order to respond to DEQ's request for sampling data for the Table 3 compounds,
Chemours will proceed as follows:
• Chemours will commission either its internal laboratory or an external, third -party
laboratory to analyze each of the Phase 1 Sample Set to try to detect the presence of
substances that appear to be similar to the Table 3 compounds.
• If the compound is not detected in the sample, the laboratory will take no further
action with respect to analyzing the sample for the Table 3 compound.
• If the compound is detected, the laboratory will then attempt to estimate the
concentration of the Table 3 compound by using best available methods.
In order to meet DEQ's request for expedited results, any results for the Table 3
compounds will be estimates subject to certain limitations that Chemours will detail further when
it provides the results for the Table 3 compounds to DEQ. Chemours anticipates being able to
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begin to provide the results for the Table 3 compounds in the Phase 1 Sample Set on a rolling
basis beginning the week of October 2, 2017.
That said, analyzing for Table 3 compound requires developing new analytical methods,
as there are no certified analytical methods for detecting or quantifying the Table 3 compounds
in wastewater. This Sampling Plan may need to be updated as Chemours undertakes this
analysis and obtains a better understanding of these analytical methods. Chemours will continue
to keep DEQ updated on Chemours' progress in analyzing for the Table 3 compounds and
recommends doing so on the weekly teleconferences with DEQ that Chemours proposed in its
cover letter transmitting this Sampling Plan to DEQ.
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TABLES
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Table 1: Conventional Pollutants ,
PFOA, PFOS, and BFPO Dimer Acid
Name
CASRN, if applicable
H
N/A
Total Suspended Solids (TSS)
N/A
Chemical Oxygen Demand (COD)
N/A
PFOA
335-67-1
PFOS
1763-23-1
Manufacuning operations specific organics N/A
Metals
N/A
HFPO Dimer Acid3
13252-13-6
3 For 3 compounds (HFPO Dimer Acid ammonium salt, HFPO Dimer Acid potassium salt, HFPO Dimer Acid
Fluoride), they all dissociate in aqueous environment and exist as HFPO Dimer anion. This HFPO Dimer anion is
the same as what all testing labs are detecting (via LC/MS/MS) as the HFPO Dimer Acid. As such, the results for
HFPO Dimer Acid will also cover HFPO Dimer Acid ammonium salt, HFPO Dimer Acid potassium salt, and HFPO
Dimer Acid Fluoride.
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Table 2: v Pioucts _ .
Name
CASRN, if applicable
E2
3330-14-1
EVE
63863-43-4
BFPO
428-59-1
MMF
69116-71-8
PEVE
10493-43-3
PMVE
1187-93-5
PPVE
1623-05-8
PSEPVE
16090-14-5
RSU
677-67-8
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Table 3: Potential B " roducts
or Impurities
DEQ's Categories from
August 16"h Letter
Formula
CASRN, if applicable
Monoether PFECAs
C3H F5O3
674-13-5
C4HF7O3
377-73-1
CsHF9O3
863090-89-5
C7HF13O3
174767-10-3
C8HF15O3
N/A
Polyether PFECAs
C7HF13O7
39492-91-6
C6HF11O6
39492-90-5
C5HF9O5
39492-89-2
C4HF7O4
39492-88-1
PFESAs
C7HF13O5S
66796-30-3 or
29311-67-9
C7112F14O5S
1 749836-20-2
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FIGURE
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