The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

PFAS NON-TARGETED ANALYSIS AND
METHODS DEVELOPMENT PLAN
Process and Non-Process Wastewater and StormwaterPrepared by
The Chemours Company FC, LLC
1007 Market Street
PO Box 2047
Wilmington, DE 19899
andGeosyntec Consultants of NC, P.C.
2501 Blue Ridge Road, Suite 430
Raleigh, NC 27607
Geosyntec Project Number TR0726
January 30, 2019

The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

TABLE OF CONTENTS
1INTRODUCTION ................................................................................................ 11.1 Non-Targeted Analytical Background ......................................................... 1
1.2 Scope and Rationale..................................................................................... 12SAMPLING PLAN ............................................................................................... 3
2.1 Sampling Locations ..................................................................................... 3
2.2 Sampling Schedule ...................................................................................... 3
2.3 Sampling Procedures ................................................................................... 3
2.4 Sample Shipping and Chain of Custody ...................................................... 3
2.5 Quality Assurance/ Quality Control ............................................................ 43NON-TARGETED LABORATORY ANALYSIS .............................................. 53.1 Sample Preparation ...................................................................................... 5
3.2 Instrumental Analysis .................................................................................. 5
3.2.1 Liquid Chromatography .................................................................. 5
3.2.2 Quadrupole Time of Flight Mass Spectrometry .............................. 53.3

Compound Identification ............................................................................. 5
3.3.1 Initial Assessment ........................................................................... 5
3.3.2 Enhanced Assessment ..................................................................... 63.4

Test Method Development........................................................................... 64

REPORTING ........................................................................................................ 75

REFERENCES ..................................................................................................... 8ii

30-Jan-2019

The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

LIST OF TABLES
Table 1: Description of Sampling Locations
Table 2: Sampling Containers and Preservation
LIST OF FIGURES
Figure 1: Site Location
Figure 2: Sample Locations
Figure 3: Proposed Non-Targeted Analysis Schedule
ACRONYMS AND ABBREVIATIONSCFRW – Cape Fear River Watch
DEQ – Department of Environmental Quality
NCCW – non-contact cooling waterng/L – nanograms per liter
PFAS – per- and polyfluoroalkyl substances
PPA – polymer processing aid
Q-TOF-MS – quadrupole time of flight mass spectrometry
SPE – solid phase extractioniii

30-Jan-2019

The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

1

INTRODUCTION

This plan (the Plan) has been prepared by The Chemours Company FC, LLC (Chemours) andGeosyntec Consultants of NC, P.C. (Geosyntec) to provide information to support thecharacterization of additional per- and polyfluoroalkyl substances (PFAS) in aqueous samples
collected from process and non-process wastewater (i.e., non-contact cooling water [NCCW]) andstormwater at the Chemours Fayetteville Works, North Carolina site (the Facility; Figure 1). This
Plan identifies the locations for samples to be collected, a schedule, and describes the approachthat will be used to identify PFAS compounds. The analytical approach selected for screening theaqueous samples collected is referred to as a non-targeted analysis and this is described more below
in Section 1.1. For any new PFAS identified through the non-targeted analysis Chemours plans todevelop a schedule for developing test methods and laboratory standards.
This Plan is intended to address requirements specified in Paragraph 11 subpart (a) in the proposed
Consent Order dated 21 November 2018 between Chemours and the North Carolina Departmentof Environmental Quality (DEQ) with the Cape Fear River Watch (CFRW) as intervenor. Other
parts of the Consent Order will be addressed separately by Chemours. Aside from collection ofsamples for non-targeted analysis, at present Chemours plans to perform all other effort andreporting described in this Plan. This Plan was prepared under the direction of Dr. Lam Leung, ananalytical chemist, of The Chemours Company. The purpose of the work described in this Plan isto identify previously unidentified (i.e. additional) PFAS that may be present in water and develop
standards and methods to facilitate the quantitative analysis of these PFAS.
1.1

Non-Targeted Analytical BackgroundNon-targeted analysis for PFAS will be conducted using liquid chromatography coupled to highresolution quadrupole time of flight mass spectrometry (Q-TOF-MS). Q-TOF-MS accurately
measures the mass to charge ratio of unknown analytes (i.e. candidates) facilitating thedetermination of their chemical formulas. Relevant structural information can be interpreted byfragmenting ions via tandem mass spectrometry, where candidates that do not fit the fragmentation
requirements for a particular structure are eliminated so that the tentative structure for the moleculecan be assigned. After tentative identification, the structural identity of an analyte can be further
assessed by comparing the analyte’s chromatographic retention time and mass spectrometryfragmentation patterns to those of an authentic standard.
1.2

Scope and Rationale

This Plan addresses requirements in Paragraph 11 subpart (a) as listed in the proposed ConsentOrder. Chemours plans to begin sample collection within thirty days of DEQ approval of this Plan.
In parallel to this non-targeted work, samples will also be collected and analyzed for PFAS using
existing laboratory methods as part of the Initial Characterization program described in theDecember 2018 Sampling Plan (Geosyntec, 2018). Non-targeted analysis will commence with130-Jan-2019

The Chemours Company
Fayetteville Works22828 NC Highway 87 W
Fayetteville, NC 28306

sample preparation by filtration, direct injection, or solid phase extraction (SPE) procedures,
followed by analysis by liquid chromatography coupled to Q-TOF-MS. Initial assessment will be
conducted for all additional PFAS, to determine each analyte’s empirical formula and identify
candidate molecular structures. Enhanced assessment will be conducted on a prioritized set of thehighest abundance additional PFAS, using authentic standards for confirmation of the analyte’sstructural identity. Test methods will then be developed for these analytes according to EPA’s
Protocol for Review and Validation of New Methods for Regulated Organic and Inorganic
Analytes in Wastewater under EPA’s Alternate Test Procedure Program (EPA, 2016). Chemours
plans to prepare a report documenting the findings of the non-targeted analysis and developmentof laboratory standards and test methods and plans to submit this report to the DEQ by June 30,
2020.

230-Jan-2019

The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

2SAMPLING PLAN

2.1

Sampling Locations

Aqueous samples will be collected during the non-targeted sampling events at locations shown on
Figure 2 and listed in Table 1. The six identified sample locations (4, 8, 15, 16, 17, and 20) are asubset of those proposed in the December 2018 Sampling Plan (Geosyntec, 2018). These locations
include water from process wastewater streams, non-process wastewater, and stormwater.
Process wastewater streams at the Chemours Monomers IXM Area (location 16) may vary
temporally based on campaigns being run at different times, therefore samples at this location will
be collected on a bimonthly basis for one year, concurrent with the Initial Characterization
sampling events outlined in the December 2018 Sampling Plan (Geosyntec, 2018). All other nontargeted samples will be collected one time during the first sampling event, because they are notexpected to show significant temporal variation.
Process wastewater at the Chemours PPA Area (location 17) is pumped in a closed loop directly
into trailers within secondary containment. The sample collection point for this PPA will bedetermined at a later date, but is expected to be a grab sample from each of the waste trailer tanks.
2.2

Sampling Schedule

The proposed sampling, analysis, evaluation and reporting schedule is provided in a Gantt Chart(Figure 3).
2.3

Sampling Procedures

Samples will be collected as part of the Initial Characterization sampling for the December 2018
Sampling Plan (Geosyntec, 2018). Samples will be collected according to the same procedures
outlined in the December 2018 Sampling Plan, including field parameter monitoring,decontamination procedures, and documentation. Sample collection procedures for non-targeted
analysis are summarized in Table 2.
2.4

Sample Shipping and Chain of Custody

Samples will be shipped under chain of custody in the same manner as described in the December
2018 Sampling Plan (Geosyntec, 2018). Coolers with samples for non-targeted analysis will beshipped to the following address:
The Chemours Company
Attn: Lam Leung
Experimental Station 402/5323
200 Powder Mill Road
Wilmington, DE 19803
USA
330-Jan-2019

The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

2.5

Quality Assurance/ Quality Control

A field duplicate will be collected at each sampling location shown on Figure 2 and listed in Table
1. The duplicates will be archived for potential future analysis to confirm analyte identities after
compound identification described below in Section 3.3.

430-Jan-2019

The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

3NON-TARGETED LABORATORY ANALYSIS

3.1

Sample Preparation

Preparation of water samples for non-targeted PFAS analysis may be accomplished by filtration,
direct injection, or SPE procedures. Direct injection will be conducted first, and SPE will be used
if enhanced sensitivity is required. SPE is widely used to extract, clean up, and concentratecomplex water samples for detection of PFAS at nanogram per liter (ng/L) levels (Nakayama etal., 2010). Various SPE sorbent materials will be evaluated to optimize the SPE extraction
efficiency in the water samples.
3.2

Instrumental Analysis

3.2.1

Liquid Chromatography

All analytes in extracted samples will be separated by liquid chromatography. Liquid
chromatography enables separation of analytes in complex sample matrices based on their relative
affinity for the solid phase and liquid phase of the chromatographic column, significantly
improving selectivity and sensitivity when coupled to mass spectrometry. Chromatographic
conditions and column materials will be optimized to further improve the current detection
methodology.
3.2.2

Quadrupole Time of Flight Mass Spectrometry

Following separation by liquid chromatography, the mass to charge ratio of individual analytes
will be determined by Q-TOF-MS: samples are ionized, then analytes pass through a series ofquadrupoles that select for one mass to charge ratio at a time. Analytes then undergo further
focusing in a time of flight chamber, so that ions of different mass to charge ratios reach thedetector at different times.
3.3

Compound Identification

All detectable additional PFAS will be tentatively identified through an initial assessment. The
molecular identity of select compounds will then be confirmed through enhanced assessment.
3.3.1

Initial Assessment

The spectra obtained from Q-TOF-MS analysis will be used to quantify known analytes withauthentic standards and determine the empirical formula for unknown analytes. Because fluorine
has a unique negative mass defect, the presence and empirical formula for fluorinated compounds
can be determined with a high level of confidence.
Structural information will also be interpreted for unknown compounds by performing tandem
mass spectrometry: following initial mass to charge separation, precursor ions are broken down
(fragmented) into product ions, and the spectra for the product ions can provide information on thestructure of the precursor ions. Through this method, tentative molecular structures will beassigned.
530-Jan-2019

The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

3.3.2

Enhanced Assessment

Chemours will prioritize unknowns with the highest abundance for enhanced assessment, wherethe structural identity of the analyte will be assessed by preparing and analyzing an authenticstandard. The retention times and spectra for the tentatively identified analytes will be comparedto those of the authentic standard to confirm their chemical identity. If standards for a given
compound are not commercially available, standards will be synthesized by Chemours or acontract laboratory. If the spectra for a standard does not match an unknown analyte’s spectra,
alternative structures will be considered.
3.4

Test Method Development

Test methods will be developed for additional PFAS compounds identified by the non-targetedassessment. Test methods will be developed according to EPA’s Protocol for Review andValidation of New Methods for Regulated Organic and Inorganic Analytes in Wastewater under
EPA’s Alternate Test Procedure Program (EPA, 2016). Depending on the number of additional
PFAS identified through the non-targeted analysis and the availability of authentic standards forthe additional PFAS, test method development may continue past the planned report submission
date of June 30, 2020 discussed below in Section 4.

630-Jan-2019

The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

4REPORTING

Chemours plans to submit a report to the DEQ by June 30, 2020. The report will summarize thefindings of the non-targeted analysis and identify any additional PFAS detected in processwastewater, non-process wastewater, and stormwater at the Facility, and provide copies of the test
methods that have been developed. The schedule of activities described in the report is shown in
Figure 3.

730-Jan-2019

The Chemours Company
Fayetteville Works
22828 NC Highway 87 W
Fayetteville, NC 28306

5REFERENCES(EPA) United States Environmental Protection Agency, 2016. Protocol for Review and Validationof New Methods for Regulated Organic and Inorganic Analytes in Wastewater Under
EPA’s Alternate Test Procedure Program.
https://www.epa.gov/sites/production/files/2016-03/documents/chemical-new-methodprotocol_feb-2016.pdf; Accessed January 17, 2019.
Geosyntec Consultants, 2018. PFAS Characterization Sampling Plan. December 28, 2018.
Nakayama, S. F.; Strynar, M. J.; Reiner, J. L.; Delinsky, A. D.; Lindstrom, A. B. “Determinationof Perfluorinated Compounds in the Upper Mississippi River Basin.” Environ. Sci.
Technol. 2010, 44 (11), 4103−4109.

830-Jan-2019

TablesTABLE 1
DESCRIPTION OF SAMPLING LOCATIONS
Chemours Fayetteville Works, North Carolina

Geosyntec Consultants

Sample Category
SampleNumberSample Location Description

Sampling Method

Combined stormwater discharge from Kuraraynorthern leased area and Chemours PPA area
Outfall 001 non-Chemours treated process wastewater
discharge to open channel to Outfall 002
Combined stormwater and NCCW discharge fromeastern portion of the Facility
Chemours Monomers IXM Area combined processwastewater

TemporalCompositeTemporal
Composite
TemporalComposite



Grab

17

Chemours PPA Area combined process wastewater

Grab

20*

Outfall 002 to Cape Fear River

4*815*
16

TemporalComposite

Outfall

Process
Wastewater

Non-processwastewater (i.e.,NCCW)

Stormwater









Notes
Sample numbers refer to locations identified in Figure 2 and correspond to locations identified in the December 28, 2018 Sampling Plan (Geosyntec, 2018).
NCCW - non-contact cooling water
PPA - polymer processing aid* - sample must be collected during a rain event

January 2019

TABLE 2SAMPLING CONTAINERS AND PRESERVATION
Chemours Fayetteville Works, North Carolina
Analytical Method
Non-targetedanalysis

Container Type andNumber of Containers
Volume250 mL HDPE

4Geosyntec Consultants

Preservation
None

Notes:HDPE - high density polyethylene

January 2019

Figures³Chemours
PPA Area

Chemours Monomers IXM Area
Kuraray America
Leased Areas

Chemours
Former Teflon
Production Area

Wastewater
Treatment
Plant
Dupont / Dow
Leased Area

Path: E:\TR0726\Saved Keep\TR0726_SiteLocationRaleigh.mxd; JK; 12/18/2018

Legend750375

0750 Feet

Drainage Network
Site Boundary
Areas at Site
Chemours Monomers IXM Area
Chemours PPA Area
Dupont / Dow Leased Area
Chemours Former Teflon Production Area
Kuraray America Leased Area
Wastewater Treatment Plant
Notes:
Basemap Source: Esri, DigitalGlobe, GeoEye, Earthstar Geographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN, and the GIS User Community

Site Location
Chemours Fayetteville Works, North Carolina

FigureRaleighJanuary 20191

Legend
Ditch Types
Wood Lined Trench
Waste Water Treatment Plant Discharge

17

Cooling Water Channel
Open Channel to Outfall 002
DuPont Area Ditches

820: Outfall 002 Pipe to Cape Fear River

164*Sample Location

16: Chemours Monomers IXM Area
Combined Process Water Sampling
17: Chemours PPA Area Combined
Process Water Sampling* - Samples must be collected during rain event
Sample numbers correspond to locations identified
in the December 28, 2018 Sampling Plan
(Geosyntec, 2018)

15*
820*

Outfall 002 Pipe to Cape Fear River
500

250

0500 Feet

Primary Ditches
Samplein SiteLocations
Drainage Network
Chemours Fayetteville Works, North Carolina

Figure2Basemap Source: Esri, DigitalGlobe, GeoEye, Earthstar Geographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN, and the GIS User Community

RaleighJanuary 2019

Project Milestone/Deliverable
Approval of Sampling Plan
Sampling EventSample Preparation
Instrumental Analysis
Initial Data Assessment
Enhanced Assessment
Test Method Development
Report Submission

2020

2019
0102


03

04




05

06







07

08


♦




♦

09

10


♦




♦
‡

11

12



♦
‡




♦
‡

01

02

03

04

05

06


♦
‡



♦
‡



♦
‡


‡





×Notes:This schedule is based on the assumption that this Sampling Plan will be approved on February 1, 2019, and will be modified accordingly if the approval date changes.



♦‡

×Approval of Sampling Plan.
Bimonthly sampling event, to occur concurrently with Initial Characterization sampling events outlined in the December 2018 Sampling Plan (Geosyntec, 2018). Sample locations 4,8, 15, 17, and 20 will be sampled once, during the first sampling event. Sample location 16 will be sampled bimonthly for one year. This schedule assumes that a storm event, asdefined in C.F.R. 122.21(g)(7)(ii), will occur resulting in enough rain such that water is present at all sampling locations in the stormwater drainage network for the proposed
sampling event.
Sample preparation by filtration, direct injection or solid phase extraction (SPE) procedures.
Instrumental analysis of samples by liquid chromatography coupled to quadrupole time of flight mass spectrometry (Q-TOF-MS).
Initial assessment to determine the empirical formulas and tentative structural information for unknown analytes.
Enhanced assessment to confirm structural identity of select analytes following preparation of authentic standards.
Test method development for additional PFAS identified by non-targeted analyses. Test method development is expected toProposed Non-Targeted Analysis Schedule
be an ongoing process that may require additional time beyond June 2020.
Chemours Fayetteville Works, North Carolina
Report submission.
FigureRaleigh

January 20193