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HomeMy WebLinkAbout2020.11.18_CCOA.p1_PFASMassLoadingProtocol CAPE FEAR RIVER PFAS MASS LOADING CALCULATION PROTOCOL Chemours Fayetteville Works Prepared for The Chemours Company FC, LLC 22828 NC Highway 87 Fayetteville, NC 28306 Prepared by Geosyntec Consultants of NC, PC 2501 Blue Ridge Road, Suite 430 Raleigh, NC 27607 Project Number TR0795 Version 1: August 31, 2020 Version 2: November 13, 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 11/18/2020 Geosyntec Consultants NC P.C. RESPONSES TO NCDEQ COMMENTS Chemours Fayetteville Works TR0795 November 2020 On October 5, 2020, Chemours received comments from the North Carolina Department of Environmental Quality (NCDEQ) on the protocol document “Cape Fear River PFAS Mass Loading Calculation Protocol (Version 1)” submitted by Chemours on August 31, 2020 as required under Paragraph 1 (a) and (b) of the Addendum to Consent Order Paragraph 12. The table below summarizes the comments received by NCDEQ, Chemours’ responses to those comments, and the subsequent changes made in this second version of the protocol document. Comment # Protocol Document Comment Description Response Section Edit 7 Cape Fear River Mass Loading OLDOF-1, this sampling location is approximately 500' upstream from the confluence with the CFR. Sampling should take place closer to the mouth unless it can be demonstrated that the CFR is interfering with sampling between the designated location and the 'mouth' of the old outfall 002 channel. Chemours does not recommend moving the old outfall sample location closer to the Cape Fear River based on the following: • The current sample location represents the overwhelming majority flows from the Old Outfall channel that will reach the river. The stretch of channel downstream of the current sampling location and the river was investigated on November 6, 2020, and Chemours’ contractors identified only one area with seepage. The seepage was estimated to be less than 100 milliliters per minute (“drips”) which would be equivalent to ~0.004% of total flow in the Old Outfall. • Chemours does not own this property. Closer to the river the ground is less stable and safe access would require improvements. The area near the river has poison ivy present. Chemours cannot unilaterally alter the land to address these issues; • The area closer to the river is low lying and is prone to inundation; • Portions of the channel closer to the river mouth become similar to a braided stream where flows are not all in the same channel. Sampling from this environment will not be representative of the entire channel flow; • Placing the sampling infrastructure (an autosampler) closer to the mouth of the Old Outfall increases the likelihood of the sampler being vandalized as it brings the sampler closer to a more publicly accessible area. -- 8 Cape Fear River Mass Loading The FRO discovered two seeps at the boat ramp below L&D#3 draining into the river. They sampled the seeps and the results are attached. The loading from these seeps should somehow be captured in the sampling plan. • Chemours contractors identified and sampled an offsite seep near the Lock and Dam in March 2020, which is likely the ‘West Seep 31’ identified by FRO. Chemours’ contractors have gone out multiple times (most recently in October 2020) and have not observed a seep on the east side (East Seep 32). It is postulated that surface water runoff from a recent rainfall occurred in the days preceding DEQ sampling (July 2020) and this residual flow was identified as East Seep 32. Chemours will include sampling and estimation of flow measurements of the west side seep (West Seep 31) when water flow is present. • Previously Chemours had requested one time access to the Lock and Dam Seep from the United States Army Corps of Engineers (USACE). Chemours is presently arranging a longer- term access agreement with the USACE to facilitate collecting samples from West Seep 31 (i.e. the Lock and Dam Seep) as part of this protocol. The mass discharge from this seep will be included in the Mass Loading Model. • In the six month period after protocol approval, Chemours will observe the east side of the boat launch area monthly and take photographs and, if possible, measure flow, collect a grab samples, and estimate loading of the East Seep 32. At the end of the six month period, Chemours will discuss the need for continued sampling of East Seep 32 with DEQ. Sections 2.4 and 4.4.4.1 9 Cape Fear River Mass Loading Section 4.2: Equation 6 is used to estimate the mass of PFAS at the intakes for the two water treatment plants downstream of Chemours (Bladen Bluffs and Kings Bluff). We understand the equation, except Chemours does not explain why the flow recorded at the W.O. Huske Dam needs to be adjusted for travel time for the Bladen Bluffs plant using Equation 7. The text has been clarified to note that a time offset is applied to the flow data to account for travel time for the flow passing the W.O. Huske Dam to reach the Bladen Bluffs. River flow passing the W.O. Huske Dam is estimated to have a travel time between 2 and 12 hours to reach Bladen Bluffs depending on river flow (e.g., the flow rate passing W.O. Huske Dam at 8 am will arrive at Bladen Bluffs at 11 am for a 3 hour travel time). Section 4.2 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Geosyntec Consultants NC P.C. RESPONSES TO NCDEQ COMMENTS Chemours Fayetteville Works TR0795 November 2020 Comment # Protocol Document Comment Description Response Section Edit 10 Cape Fear River Mass Loading Chemours should provide an example dataset for the equations presented in the protocol, along with the spreadsheets planned for calculating the mass loads and mass discharges (the spreadsheets could be populated with the example dataset). This would further aid in understanding the formulas and also provide a mechanism to check for errors. An excel work product was submitted on August 31,2020 with the protocol documents, as required by the Consent Order Addendum. Files were re-sent to NCDEQ on October 7, 2020. -- 13 Cape Fear River Mass Loading Section 4.4 does not include loading from the floodplain deposits adjacent to the Cape Fear River: The PFAS mass loading model does not account for PFAS loading of the river from groundwater contamination or contaminants in soil of the vadose zone. Loading of PFAS from the floodplain deposits to the river will occur until the extraction well system and/or barrier wall are constructed. Chemours should clarify why PFAS loading from the floodplain deposits are not included. 1. The Floodplain Deposits are not always in hydraulic connection with the Cape Fear River as this layer is above the water line and the Floodplain Deposits have an order of magnitude lower hydraulic conductivity.  The mass discharge from the Floodplain Deposits was estimated using the same method that was used to estimate the mass discharge from the Black Creek Aquifer.  Using data from the Q2 2020 sampling event, the mass discharge from the Floodplain Deposits and the Black Creek Aquifer were estimated to be 0.06 mg/sec and 3.9 mg/sec, respectively. Therefore, the loading from Floodplain Deposits is 1.5% of the Black Creek Aquifer loading value, and 0.3% of the total modeled mass discharge, which does not meaningfully impact the results of the model.  As part of the groundwater remedy pre-design investigation, data from passive flux meters is being used to better understand this differential.  Chemours will include an estimate of mass discharge from the Floodplain Deposits into an annual sensitivity analysis. 2. The vadose zone is where water infiltrates primarily vertically under gravitational forces to the water table. Therefore, we expect limited contributions from the vadose zone directly to the Cape Fear River and do not recommend including in the model. Section 4.4.4.2 and Appendix D 14 Cape Fear River Mass Loading Section 4.4.1: The equation labelled “[1]” should perhaps be labelled the 9th equation presented in the body of the text. Chemours also does not have an equation #8 in the protocol. The text has been clarified. Sections 4.2, 4.3, and 4.4.1 15 Cape Fear River Mass Loading Section 4.4.4: Pathway TP-5 is the upwelling of PFAS from the Black Creek Aquifer into the River at 8 segments of the river bank. Mass discharge for each segment will be determined using the cross-sectional area, the hydraulic gradient for the groundwater surface near the river and the hydraulic conductivity (K) estimated from slug tests performed on individual wells screened in the Black Creek Aquifer. In general, K values estimated from multiple well aquifer pumping tests are preferred over those estimated from slug tests. Kruseman and de Ridder (1994) note that “…slug tests cannot be regarded as a substitute for conventional pumping tests” and that a slug test “…determines the characteristics of a small volume of aquifer material surrounding the well, and this volume may have been disturbed during the drilling and construction.” Chemours has indicated that pumping tests are planned during the design phase for building of the groundwater extraction system and barrier wall. Chemours is presently conducting pumping tests (also known as aquifer yield tests) to better establish hydraulic properties near the Cape Fear River. As noted in Section 4.5, these enhanced hydrogeological data will be incorporated into the mass loading model as they become available. -- 16/17 Cape Fear River Mass Loading [#16] Section 4.4.6 references Appendix D, which has an equation for the total PFAS discharged from groundwater adjacent to Chemours (east side of river) and downstream of Chemours within a 1-mile distance of the river. Wells with contaminated groundwater were detected within the 1-mile width on either side of the river. The equation includes a unitless “scaling factor” which is a ratio of the length of the river adjacent to the site + downstream [#17] Based upon our review, it appears more appropriate to input “land areas” into the ratio instead of “river length” units. Chemours includes a figure that shows the off-site land areas underlain by impacted groundwater and the river lengths. The figure shows a width that extends greater than 1 mile on either side of the river, based on comparing the mapped widths to the bar scale. Length was used as the method for scaling downstream offsite loadings since the river is in direct contact with the land it is passing through. Using land area adds unnecessary complexity as it is unclear how the distance of land from the river should be considered in the land area calculation; i.e., land further away from the river will not have the same contribution effect. An assessment comparing both approaches showed that the two approaches yielded roughly similar scaling outcomes of 0.38 and 0.55 for the length and area methods, respectively. Chemours will include an estimate of loading from adjacent and downstream groundwater using the land area scaling method into an annual sensitivity analysis. Regarding Figure D1, the widths on either side of the river are indeed one mile. There was an issue with the scale bar on this figure, which has now been corrected. Section 4.4.6 and Appendix E DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Geosyntec Consultants NC P.C. RESPONSES TO NCDEQ COMMENTS Chemours Fayetteville Works TR0795 November 2020 Comment # Protocol Document Comment Description Response Section Edit 18 Cape Fear River Mass Loading The Draft Mass Loading Assessment Summary dated Dec. 6, 2019 determined hypothetical mass loading scenarios of HFPO-DA as reductions occurred at the facility. To continue this modeling and confirm these predictions PFAS samples should be taken below Outfall 002 (outside the mixing zone as determined by the dilution model) and below Outfall 003 when samples are taken upstream. The protocol document specifies that downstream samples are being collected at CFR- TARHEEL, which is sufficiently downstream of the Facility such that PFAS inputs into the river from the Facility are well mixed throughout the water column. Sampling requirements pertaining to Outfall 003 and Outfall 002 permits are being arranged by Chemours and NCDEQ separate from this Cape Fear River PFAS Loading Protocol. -- Additional Comment A Cape Fear River Mass Loading What will be the timeframe for establishing the Cape Fear River PFAS Baseline? This protocol document describes development of the Cape Fear River PFAS Mass load Baseline in Section 4.1. The baseline period began on March 28, 2020 and will conclude on March 28, 2021. The date of March 28, 2020 is when the autosampler at CFR-TARHEEL was put into service and Chemours began regular collection of samples at this location. Pursuant to the Consent Order and the Consent Order Addendum, three PFAS transport pathways require compliance demonstrations relative to a defined baseline: 1. Air Emissions reductions addressed under Paragraphs 8 and 9 of the Consent Order; 2. Long-Term Seep Remediation Objective addressed under Consent Order Addendum Paragraph 2(c) and described in the Onsite Seeps Long-Term Loading Calculation Plan submitted by Chemours on October 30, 2020 (Geosyntec, 2020a); and 3. The Cape Fear River PFAS Mass Load Baseline required pursuant to Paragraph 16 of the Consent Order and specified in this Cape Fear River PFAS Mass Loading Calculation Protocol (Geosyntec, 2020b). Section 4.1.1 Additional Comment B Cape Fear River Mass Loading Please provide an example of how the load of PFAS reduced by the remedies will be calculated in the estimation of the PFAS baseline load calculation? The protocol document has been updated. Section 4.1.3 and Appendix B DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 ii November 2020 TABLE OF CONTENTS 1 INTRODUCTION ................................................................................................ 1 2 DESCRIPTION OF PFAS MASS LOADS ......................................................... 2 2.1 Mass Loading Terminology......................................................................... 2 2.2 Cape Fear River PFAS Mass Load .............................................................. 2 2.3 Bladen Bluffs and Kings Bluff PFAS Sampling ......................................... 2 2.4 Cape Fear River PFAS Mass Loading Model ............................................. 3 3 SAMPLING AND MEASUREMENT LOCATIONS AND FREQUENCIES ... 4 3.1 Cape Fear River PFAS Mass Load Sampling ............................................. 4 3.2 Bladen Bluffs and Kings Bluff PFAS Sampling ......................................... 4 3.3 Cape Fear River PFAS Mass Loading Model Sampling ............................. 5 3.4 Potential Adjustments to Sampling Program............................................... 6 4 CALCULATION METHODOLOGIES ............................................................... 6 4.1 Cape Fear River PFAS Mass Load Calculation Methodology .................... 6 4.1.1 Baseline Mass Load Calculation Methodology .............................. 7 4.1.2 In-River Mass Load Calculation Methodology .............................. 7 4.1.3 Captured Mass Load Calculation Methodology ........................... 11 4.2 Bladen Bluffs and Kings Bluff Intake Calculation Methodology ............. 11 4.3 Cape Fear River PFAS Mass Loading Model Calculation Methodology . 12 4.4 PFAS Mass Loading Model Pathways ...................................................... 13 4.4.1 Upstream Cape Fear River (Transport Pathway 1) ....................... 13 4.4.2 Tributaries – Willis Creek, Georgia Branch Creek, and Old Outfall 002 (Transport Pathways 2, 7 and 9) ........................................................ 14 4.4.3 Aerial Deposition to the Cape Fear River (Transport Pathway 3) 15 4.4.4 Onsite Groundwater (Transport Pathways 5 and 6) ...................... 15 4.4.5 Outfall 002 (Transport Pathway 4) ............................................... 16 4.4.6 Adjacent and Downstream Offsite Groundwater (Transport Pathway 8) ................................................................................................ 16 4.5 Potential Adjustments ................................................................................ 17 5 REPORTING ...................................................................................................... 17 6 REFERENCES ................................................................................................... 18 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 iii November 2020 LIST OF TABLES Table 1: PFAS Analytical Methods and Analyte list Table 2: Surface Water, Seep and River Sampling Locations and Flow Measurement Methods Table 3: Groundwater Monitoring Well Sampling and Water Level Measurement Locations LIST OF FIGURES Figure 1: Potential PFAS Transport Pathways to the Cape Fear River from Site Figure 2: Cape Fear River Watershed and Downstream Drinking Water Intakes Figure 3: Groundwater Monitoring Well Sampling and Water Level Measurement Locations Figure 4: Surface Water, Seep and River Water Sampling and Flow Measurement Locations Figure 5: Cape Fear River Sample Locations LIST OF APPENDICES Appendix A: Field Methods Appendix B: Captured Mass Load Calculation Methodology Appendix C: Supporting Calculations – Direct Aerial Deposition on Cape Fear River Appendix D: Supporting Calculations – Onsite Groundwater Appendix E: Supporting Calculations – Adjacent and Downstream Offsite Groundwater DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 v November 2020 LIST OF ABBREVIATIONS CFR Cape Fear River CFR-BLADEN Bladen Bluffs CFR-KINGS Kings Bluff CFR-TARHEEL Tar Heel Ferry Road bridge CO Consent Order DEQ Department of Environmental Quality DSI Dynamic Solutions International EFDC Environmental Fluid Dynamics Code kg Kilograms L/s liters per second mg/s Milligrams per second Mass Loading Protocol PFAS Mass Loading Protocol NC North Carolina ng/L nanograms per liter PFAS Per- and polyfluoroalkyl substances SOP Standard Operating Procedures USGS United States Geological Survey DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 1 November 2020 1 INTRODUCTION Geosyntec Consultants of NC, PC (Geosyntec) has prepared this per- and polyfluoroalkyl substances (PFAS) Mass Loading Protocol (“Mass Loading Protocol”) on behalf of The Chemours Company FC, LLC (Chemours) pursuant to the requirements of Paragraph 1 (a) and (b) of the Addendum to Consent Order Paragraph 12 (CO Addendum). The objective of this Mass Loading Protocol document is to describe the sampling and measurement activities, calculation methods and reporting requirements associated with the following mass loading programs:  Cape Fear River PFAS Mass Load Sampling;  Bladen Bluffs and Kings Bluff PFAS Sampling; and  Cape Fear River PFAS Mass Loading Model Pathway Sampling.  The CO Addendum specifies that PFAS mass loading calculations estimate the mass loading for each of the PFAS compounds listed in Attachment C of the CO (February 25, 2019). The calculations presented in this document are suitable for evaluating the mass loads of any given set of selected PFAS. For the purposes of calculations and reporting for Paragraph 1 of the CO Addendum, the set of PFAS will be those listed in Attachment C of the Consent Order and listed in Table 1. The remainder of this document is organized as follows:  Section 2 – Description of PFAS Mass Loads which presents an overview of the three types of PFAS Mass Loading quantities described by this protocol document;  Section 3 – Sampling and Measurement Locations and Frequency which presents the sampling requirements for the mass loads;  Section 4 – Calculations which present the protocol by which the mass loads will be calculated; and  Section 5 – Reporting which describes how the results of the protocol will be reported. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 2 November 2020 2 DESCRIPTION OF PFAS MASS LOADS This section provides first an overview of terms used in this document and then an overview of each of the sampling, calculation and reporting activities for the three mass loading programs. 2.1 Mass Loading Terminology The following mass loading terms are used in this document:  Mass Load – the quantity in kilograms (kg; mass) of PFAS present in a pathway over a period of time (e.g., 5 kg from a pathway over a certain number of days). This quantity is used to assess the total amount of PFAS that have reached the Cape Fear River;  Mass Discharge – the quantity in milligrams per second (mg/s; mass over time) of PFAS present in a pathway at a specific point in time. This quantity is used for assessing the relative loadings from the different pathways in the Mass Loading Model and the loading of PFAS at Bladen Bluffs and Kings Bluff raw water intakes. 2.2 Cape Fear River PFAS Mass Load The Cape Fear River PFAS Mass Load focuses on PFAS mass loads measured in the river, and loads prevented from reaching the Cape Fear River from the Fayetteville Works Facility. Specifically, three loads are assessed: 1. The “In-River Mass Load” which is the total measured in-river PFAS mass load that reached the river as measured in kg over a period of time based on time- weighted concentrations of PFAS from samples collected at the Tar Heel Ferry Road bridge (CFR-TARHEEL) and Cape Fear River flow volumes; 2. The “Captured Mass Load” which is the PFAS mass load, measured in kg, prevented from reaching the Cape Fear River by remedies implemented by Chemours; and 3. The “Baseline Mass Load” which is the sum of the River Mass Load and the Captured Mass Load. The Baseline Mass Load will be used to assess PFAS Mass Loading reductions to surface water achieved over time. 2.3 Bladen Bluffs and Kings Bluff PFAS Sampling The Bladen Bluffs and Kings Bluff PFAS sampling will collect monthly samples to measure PFAS loadings in the Cape Fear River adjacent to the Bladen Bluffs and Kings DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 3 November 2020 Bluff points in time from discrete water samples. The loadings are expressed as mass per unit time, i.e., mg/s. 2.4 Cape Fear River PFAS Mass Loading Model The Cape Fear River PFAS Mass Loading Model will estimate the mass discharge of PFAS from nine potential PFAS transport pathways to the Cape Fear River. The potential pathways are listed below, and are shown on the conceptual diagram provided in Figure 1:  Transport Pathway 1: Upstream Cape Fear River and Groundwater – This pathway is comprised of contributions from non-Chemours related PFAS sources on the Cape Fear River and tributaries upstream of the Site, and upstream offsite groundwater with PFAS present from aerial deposition;  Transport Pathway 2: Willis Creek – Groundwater and stormwater discharge and aerial deposition to Willis Creek and then to the Cape Fear River;  Transport Pathway 3: Direct aerial deposition of PFAS on the Cape Fear River;  Transport Pathway 4: Outfall 002 – Comprised of (i) water drawn from the Cape Fear River and used as non-contact cooling water, (ii) treated non- Chemours process water, (iii) Site stormwater, (iv) steam condensate, and (v) power neutralization discharge, which are then discharged through Outfall 002;  Transport Pathway 5: Onsite Groundwater – Direct upwelling of onsite groundwater to the Cape Fear River from the Black Creek Aquifer;  Transport Pathway 6: Seeps – Onsite groundwater seeps A, B, C and D and the Lock and Dam Seep, which are above the Cape Fear River water and discharge into the Cape Fear River;  Transport Pathway 7: Old Outfall 002 – Groundwater discharge to Old Outfall 002 and stormwater runoff that flows into the Cape Fear River;  Transport Pathway 8: Adjacent and Downstream Offsite Groundwater – Offsite groundwater adjacent and downstream of the Site upwelling to the Cape Fear River; and,  Transport Pathway 9: Georgia Branch Creek – Groundwater, stormwater discharge and aerial deposition to Georgia Branch Creek and then to the Cape Fear River. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 4 November 2020  Results of the mass loading model assessments are expressed as both the PFAS mass discharge (in mg/s) per pathway and the relative estimated mass discharge per pathway. 3 SAMPLING AND MEASUREMENT LOCATIONS AND FREQUENCIES This section describes sampling and measurement locations and frequencies for the mass loading programs. The field methods to be used for the sampling programs is provided in Appendix A. 3.1 Cape Fear River PFAS Mass Load Sampling To assess the Cape Fear River PFAS In-River and Baseline Mass Loads (Section 2.2), a 24 hour composite sample of the Cape Fear River will be collected twice per week using an autosampler placed at CFR-TARHEEL (Figure 2). Additional sampling will be conducted within 24 hours of rain events when these rain events are predicted two days before and with at least a 70% likelihood and to be of 1 ½ inches or greater in a 24 hour period. Such additional sampling will be conducted up to twice per month for any month in which there are two or more such rain events. River flow volumes corresponding to collected samples will be determined using Cape Fear River flows as reported by the United States Geological Survey (USGS). Remedies implemented or to be implemented by Chemours (e.g. onsite seeps interim remedies, Outfall 002 remedy) will prevent PFAS mass loads from reaching the Cape Fear River. For certain remedies, specific sampling frequency and methods and flow measurements will be specified in sampling plans or other sampling requirements (e.g. NPDES permits) for such remedy. Sampling will be conducted for a period of five years. At the end of each reporting year, Chemours may apply to DEQ for modification of this protocol. 3.2 Bladen Bluffs and Kings Bluff PFAS Sampling To sample the PFAS mass loading near the Bladen Bluffs and Kings Bluff Intakes (Section 2.3), grab samples will be collected on a monthly basis from the Cape Fear River adjacent to both intakes (Figure 2). For the Bladen Bluffs Intake sample location, flows as reported by the United States Geological Survey (USGS) river gauging station at the W.O. Huske Dam will be used to determine river flow volumes corresponding to collected samples. For the Kings Bluff Intake sample location, flows as reported by the USGS river gauging station at Cape Fear River Lock & Dam #1 will be used to determine river flow volumes corresponding to collected samples. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 5 November 2020 Sampling will be conducted for a period of five years. At the end of each reporting year, Chemours may request to DEQ for modification of the protocol. 3.3 Cape Fear River PFAS Mass Loading Model Sampling To assess the relative mass loading of PFAS to the Cape Fear River from the potential PFAS mass loading pathways (Figure 1), pathway inputs to the Mass Loading Model will be sampled. The following pathways and locations will be sampled (Figures 3 and 4)1,2:  Transport Pathway 1: Upstream Cape Fear River;  Transport Pathway 2: Willis Creek;  Location: Intake River Water at Facility;  Transport Pathway 4: Outfall 002;  Transport Pathway 5: Onsite Groundwater (Table 2)3;  Transport Pathway 6: Onsite Seeps (Seeps A through D) and Lock and Dam Seep;  Transport Pathway 7: Old Outfall 002;  Transport Pathway 9: Georgia Branch Creek; and  Location: CFR-TARHEEL; Where Site access and Site conditions permit, samples will be collected as 24-hour composite samples. Flow rates will be measured after sample collection at seep and creek locations specified in Table 2. Flow rates will be measured using flumes at the seeps and using flow velocity gauging at the Lock and Dam Seep, Willis Creek and Georgia Branch Creek. Flow will then be used to calculate volumetric flow rates. Flow data for the Intake River Water at Facility location and Outfall 002 will be obtained from facility discharge monitoring reports. Flow data, adjusted for travel time, recorded at the USGS river gauge at the W.O. Huske Dam will be used for CFR-TARHEEL and CFR-BLADEN. Flow 1 Transport pathway 3, direct aerial deposition, is estimated based on modeling calculations and therefore is not sampled. 2 Transport pathway 8, adjacent and downstream groundwater, is estimated based on transport pathway 1, upstream Cape Fear River and is therefore not sampled for pathway estimation purposes. The downstream river is sampled to evaluate the PFAS mass loading to the Cape Fear River. 3 This list of groundwater wells to be sampled is derived from the Corrective Action Plan (Geosyntec, 2019b) with wells INSITU-02 and BLADEN-1S removed as these wells are perennially dry. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 6 November 2020 data recorded at the USGS river gauge at Cape Fear Lock and Dam #1 will be used for CFR-KINGS. The travel time adjustment calculations were based on a calibrated hydrodynamic model using the Dynamic Solutions International (DSI) version of the Environmental Fluid Dynamics Code (EFDC). The model domain runs from downtown Fayetteville, North Carolina to Lock and Dam #1 near Kelly, North Carolina. The model was calibrated to flow data from the USGS gauges at W. O. Huske Dam and Lock and Dam #1 and water surface elevation data (from the USGS Gauges at Fayetteville, NC and the W. O. Huske Dam) for two periods: January-February 2017 and May-June 2018. To estimate travel times from W. O. Huske Dam to the Bladen Bluffs Intake, a dye release was modeled for 5 hours from Huske Dam at the following flow rates based on real flow data from calendar year 2017. Travel times were estimated based on first arrival as defined by the point where the concentration at the arrival point reaches 10% of the maximum concentration at the indicated location. The travel time to river flow relationships to locations CFR-BLADEN, CFR-TARHEEL and CFR-KINGS (i.e., regressions) had R2 values of 0.997, 0.997, and 0.943, respectively. The sampling of the inputs to the Mass Loading Model will be conducted for a period of one year on a monthly basis and then for the next four years on a quarterly basis. At the end of each reporting year, Chemours may apply to DEQ for modification of the protocol. 3.4 Potential Adjustments to Sampling Program Planned sampling outlined in this protocol document will be conducted where locations are safely, logistically and legally accessible. The sampling and measurement protocols described in this section have been outlined based on the present understanding of Site conditions. If conditions change, modifications may need to be made to this protocol. Additionally, during a field program, the field team may need to modify the sampling program outlined in this protocol. Modifications to the sampling protocol will be described in submitted reports described in Section 5. 4 CALCULATION METHODOLOGIES This section presents the calculation methodologies to be applied to estimate the mass loading quantities for the three mass loading programs. 4.1 Cape Fear River PFAS Mass Load Calculation Methodology This subsection presents the calculation methodology for calculating the Cape Fear River PFAS Baseline Mass Load, In-River Mass Load and Captured Mass Load. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 7 November 2020 4.1.1 Baseline Mass Load Calculation Methodology The Cape Fear River PFAS Baseline Mass Load period will be a period of one year. The baseline period began on March 28, 2020 and will conclude on March 28, 2021. The date of March 28, 2020 is when the autosampler at CFR-TARHEEL was put into service and Chemours began regular collection of samples at this location. The Cape Fear River PFAS Baseline will be calculated as the sum of both the measured In-River PFAS Load and the Remedy Captured PFAS Load as described below in Equation 1, with further details presented in Sections 4.1.2 and 4.1.3, respectively. Equation 1: Total PFAS Baseline Mass Load 𝑀஼ிோ = 𝑚஼ிோ +𝑚ோ௘௠௘ௗ௜௘௦ where, 𝑀஼ிோ = is the Baseline Mass Load of PFAS compounds in the Cape Fear River, including the mass load prevented from reaching the Cape Fear River by implemented remedies, measured in kg; 𝑚஼ிோ = is the River Mass Load estimated using PFAS concentrations in samples taken in the Cape Fear River downstream of the Site where the river is well mixed and using measured river flow volumes; and 𝑚ோ௘௠௘ௗ௜௘௦ = is the Captured Mass Load prevented from reaching the Cape Fear River by remedies implemented by Chemours. There have been numerous interim and permanent actions taken to limit PFAS reaching the Cape Fear River prior to this baseline period, i.e., air abatement measures (installation of the thermal oxidizer and carbon beds, etc.), grouting of the terracotta pipe, sediment removal from channels, among others, and these may not be captured in this baseline load calculation methodology but should be considered in the overall assessment of PFAS reductions. 4.1.2 In-River Mass Load Calculation Methodology The In-River Mass Load is the estimated mass, in kilograms, that has reached the Cape Fear River over a period of time. The River Mass Load, 𝑚஼ிோ, is calculated using primarily composite samples from the Cape Fear River and corresponding river flow volumes. The In-River Mass Load is calculated for a given time period following Equation 2 below: DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 8 November 2020 Equation 2: In-River Mass Load 𝑚஼ிோ = ෍ ෍ 𝐶஼ிோ,௡,௜ × 𝑉஼ிோ,௡ ୍ ௜ୀଵ ே ௡ୀଵ where, 𝑚஼ிோ = is the Total PFAS mass load estimated from PFAS concentrations in samples taken in the Cape Fear River downstream of the Site where the river is well mixed and measured river flow volumes;  𝑛= represents individual time intervals during a monitoring period;  𝑁= is the total number of time intervals in a monitoring period; i = represents each of the PFAS constituents being evaluated; I = represents total number of PFAS constituents included in the summation; 𝑐஼ிோ,௡,௜ = is the measured or estimated concentration of PFAS for each baseline mass loading time interval based on samples collected from the Cape Fear River; and 𝑉஼ிோ,௡ = is the volume of Cape Fear River water that flowed passed the sampling point during the baseline mass loading time interval. 4.1.2.1 Calculation of Time-Weighted Average Concentrations During a time period, multiple samples will be collected, most of them being composite samples and some potentially being grab samples. The calculation methodology outlined here considers all collected samples in the time period, including cases where samples are collected contemporaneously with each other and cases where composite sample collection events do not occur successively, as is the case with twice weekly 24 hour composite samples. To facilitate this calculation, the overall time period is separated into discrete time intervals with corresponding time-weighted concentrations calculated for each interval. The time intervals are defined as the duration in time between two sampling events, where sampling events consist of:  Beginning of a composite sample collection;  End of a composite sample collection; or  Collection of a grab sample. Equation 3 shows the formula used to calculate the total flow volume for each interval. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 9 November 2020 Equation 3: Mass Load Time Interval Concentration  𝐶஼ிோ,௡,௜ = ∑𝐶஼ிோ,௡,௜,௞ × 𝑤௞௄௞ୀଵ  = ∑𝐶஼ிோ,௡,௜,௞ ೟೙ ೟ೖ ∑೟೙ ೟ೖ ಼ೖసభ ௄௞ୀଵ  where,  𝐶஼ிோ,௡,௜ = is the measured or estimated concentration of PFAS for each baseline mass loading time interval based on samples collected from the Cape Fear River;  𝑛= represents individual time intervals during a monitoring period; i = represents each of the PFAS constituents being evaluated;  k = represents a concentration sample considered in the mass load time interval;  K = is the total number of concentration samples considered in the mass load time interval;  𝐶஼ிோ,௡,௜,௞ = is the measured concentration of PFAS for each sample result considered in calculating the time-weighted average concentration for a mass load time interval; and  𝑤௞ = is the weighting factor calculated for and applied individually to each concentration, where,  𝑡௡ = the length of time of the mass load time interval; and  𝑡௞ = the length of time of the collected sample. For composite samples, 𝑡௞ is the total length of the composite sample collection period. If 𝑡௞ <𝑡௡, i.e., the composite sample collection time is less than the interval time, or a grab sample was collected, then 𝑡௞ is set to equal the interval time for the purposes of concentration weighting. 4.1.2.2 Calculation of Travel Time Adjusted Flow Volumes To calculate the mass load, river flow volumes are calculated for each time interval using United States Geological Survey (USGS) reported flows at the W.O. Huske Dam. A time offset is applied to the flow data to account for travel time for the flow passing the W.O. Huske Dam to reach the CFR-TARHEEL location. River flow passing the W.O. Huske is estimated to have a travel time between 2 and 12 hours to reach CFR-TARHEEL depending on river flow (e.g., the flow rate passing W.O. Huske Dam at 8 am will arrive at CFR-TARHEEL at 11 am for a 3 hour travel time). Travel times are estimated based DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 10 November 2020 on the results of a numerical model of the Cape Fear River which developed a regression curve between the USGS reported gage heights at W.O. Huske Dam and travel times. Equation 4 shows the formula used to calculate the time offset. The total volume of flow for each mass loading interval is calculated as the sum of all individual flow measurements for an interval where each measurement multiplied by its corresponding 15-minute time duration. Equation 5 shows the formula used to calculate the total flow volume for each interval. Equation 4: Travel time offset W.O. Huske Dam to Tar Heel Ferry Road Bridge 𝑡௢௙௙௦௘௧ = 13,422 ∙𝑄ௐைு஽ିଵ + 2.019 where, 𝑡௢௙௙௦௘௧ = is the travel time flow in the Cape Fear River takes in hours to pass from the W.O. Huske Dam to CFR-TARHEEL based on the measured flow in the Cape Fear River at the W.O. Huske Dam; 𝑄ௐைு஽ିଵ = is the inverse of the measured flow rate of the Cape Fear River at W.O. Huske Dam for a given point in time in cubic feet per second (ft3/s); and 13,422 𝑎𝑛𝑑 2.019 = are constant values, which correspond to the slope and intercept of the regression line, respectively.  Equation 5: Cape Fear River Flow Volume per Interval  𝑉஼ிோ,௡ = ∑𝑄ௐைு஽,௡,௠ା௧೚೑೑ೞ೐೟ × (𝑡௡,௠ −𝑡௡,௠ିଵ)ெ௠ୀଵ where, 𝑉஼ிோ,௡ = is the volume of Cape Fear River water that flowed past the sampling point during the baseline mass loading time interval; n = represents the baseline mass loading time intervals number for which the volume is being calculated; m = represents a 15-minute flow measurement recorded by the USGS station at W.O. Huske Dam during a baseline mass loading time interval “n”; M = the total number of 15-minute flow measurements recorded by the USGS station at W.O. Huske Dam during a baseline mass loading time interval “n”; 𝑄ௐைு஽,௡,௠ା௧೚೑೑ೞ೐೟ = is the Cape Fear River flow rate (units of volume per time) at Tar Heel Ferry Road bridge based on the recorded values at W.O.Huske Dam and adjusted for travel time as described in Equation 4; and DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 11 November 2020 𝑡௡,௠ −𝑡௡,௠ିଵ = is the length of time for the flow measurement durations (units of time reported typically in 15-minute intervals by USGS). 4.1.3 Captured Mass Load Calculation Methodology Remedies implemented or to be implemented by Chemours (e.g., onsite seeps interim remedies, Outfall 002 remedy, etc.) will prevent PFAS mass loads from reaching the Cape Fear River. The loading reductions attained by a remedy will be calculated using a methodology appropriate for that given remedy. The goal of such calculations will be to estimate, for a given time period, the PFAS mass diverted from reaching the Cape Fear River by the remedy that would have otherwise reached the Cape Fear River. Presently, the Seeps Interim flow-through cell remedies and the Old Outfall capture and treatment remedies are sufficiently advanced to describe how the load reductions associated with these remedies will be calculated. Appendix B presents the calculation methodology for these two remedial measures. 4.2 Bladen Bluffs and Kings Bluff Intake Calculation Methodology This subsection presents the methodology used to calculate PFAS mass discharge at Bladen Bluffs and Kings Bluff Intakes. Total PFAS mass is calculated following Equation 6 below: Equation 6: Mass at Bladen Bluffs and Kings Bluff Intakes 𝑀஻஻/௄஻ = ෍ 𝑀௜ =෍ 𝐶௜ × 𝑄 ூ ௜ୀଵ ூ ௜ୀଵ where, MBB/KB = Total PFAS mass discharge in the downstream river locations (Bladen Bluffs or Kings Bluff Intakes) measured in mass per unit time [MT-1], typically mg/s; i = represents each of the PFAS constituents being evaluated; I = represents total number of PFAS constituents included in the summation of Total PFAS concentrations; Mi = mass load of each PFAS constituent i with measured units in mass per unit time [MT-1], typically mg/s; Ci = concentration of each PFAS constituent i with measured units typically in nanograms per liter; and DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 12 November 2020 Q = volumetric flow rate with measured units in volume per time [L3T-1], typically liters per second (L/s). For Bladen Bluffs, the volumetric flow recorded at W.O. Huske Dam is adjusted for travel time using Equation 7. Similar to CFR-TARHEEL, a time offset is applied to the flow data to account for travel time for the flow passing the W.O. Huske Dam to reach Bladen Bluffs. River flow passing the W.O. Huske is estimated to have a travel time between 2 and 12 hours to reach Bladen Bluffs depending on river flow (e.g., the flow rate passing W.O. Huske Dam at 8 am will arrive at CFR-TARHEEL at 11 am for a 3 hour travel time). Travel times are estimated based on the results of a numerical model of the Cape Fear River which developed a regression curve between the USGS reported gage heights at W.O. Huske Dam and travel times. Equation 7 shows the formula used to calculate the time offset. Equation 7: Travel time offset W.O. Huske Dam to Bladen Bluffs 𝑡௢௙௙௦௘௧ = 8,826 ∙𝑄ௐைு஽ିଵ + 1.530 where, 𝑡௢௙௙௦௘௧ = is the travel time flow in the Cape Fear River takes in hours to pass from the W.O. Huske Dam to Bladen Bluffs Intake location based on the measured flow in the Cape Fear River at the W.O. Huske Dam; 𝑄ௐைு஽ିଵ = is the inverse of the measured flow rate of the Cape Fear River at W.O. Huske Dam for a given point in time in cubic feet per second; and 8,826 𝑎𝑛𝑑 1.530 = are constant values, which correspond to the slope and intercept of the regression line, respectively. 4.3 Cape Fear River PFAS Mass Loading Model Calculation Methodology This subsection presents the Mass Loading Model methodology for estimating the mass discharge of PFAS from the potential PFAS transport pathways to the Cape Fear River. The Total PFAS mass discharge entering the Cape Fear River is defined in this model as the combined mass per unit time or mass discharge (e.g., mg/s) from potential pathways. Total PFAS mass load entering the Cape Fear River is calculated following Equation 8 below: Equation 8: Cape Fear River Estimated Mass Discharge from Mass Loading Model 𝑀𝐷஼ிோ = ෍෍ 𝑀𝐷௣,௜ =෍෍൫𝐶௡,௜ × 𝑄௡൯ ூ ௜ୀଵ ଽ ௣ୀଵ ூ ௜ୀଵ ଽ ௣ୀଵ DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 13 November 2020 where, MDCFR = Total PFAS estimated mass discharge entering the Cape Fear River, measured in mass per unit time [MT-1], typically mg/s; p = represents each of the 9 potential PFAS transport pathways described further in Section 4.4. To facilitate model construction, the Seeps (Transport Pathway 6) were further discretized as Seep A (Transport Pathway 6A), Seep B (Transport Pathway 6B), Seep C (Transport Pathway 6C), Seep D (Transport Pathway 6D), and Lock and Dam Seep (Transport Pathway 6E); i = represents each of the PFAS constituents being evaluated; I = represents total number of PFAS constituents included in the summation of Total PFAS concentrations; MDp,i = mass load of each PFAS constituent i from each potential pathway p with measured units in mass per unit time [MT-1], typically mg/s; Cp,i = concentration of each PFAS constituent i from each potential pathway p with measured units in mass per unit volume [ML-3], typically nanograms per liter (ng/L); and Qn = volumetric flow rate from each potential pathway n with measured units in volume per time [L3T-1], typically L/s. 4.4 PFAS Mass Loading Model Pathways The nine potential pathways representing compartments to the PFAS Mass Loading Model are described below. These pathways were identified as potential contributors of PFAS to river PFAS concentrations. 4.4.1 Upstream Cape Fear River (Transport Pathway 1) The upstream PFAS mass discharge contribution to Cape Fear River will be estimated using measured Cape Fear River PFAS concentrations and flow rates. One water sample will be collected immediately upstream of the Site and Willis Creek at River Mile 76 to estimate upstream PFAS mass discharge contribution to Cape Fear River. River water samples will be collected at the thalweg (i.e., deepest point of the river transect) at mid- depth in the water column. Volumetric flow rates for the Cape Fear River were measured at the USGS flow gauging station located at the W.O. Huske Dam, approximately 0.5 river miles downstream of the Site. The volumetric flow rate immediately upstream of the Site (River Mile 76) will be DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 14 November 2020 estimated using a volumetric budget accounting for flows between River Mile 76 and the W.O. Huske Dam. The volumetric flow rate at River Mile 76 will be estimated by subtracting inflows from Willis Creek, upwelling groundwater, seeps to the river, and Outfall 002 and by adding the river water intake from Chemours to the flow rate measurement from the W.O. Huske Dam (Equation 9). Equation 9: Flow at Upstream Cape Fear River and Groundwater 𝑄௎௣௦௧௥௘௔௠ = 𝑄ௐைு஽ − ൫𝑄ௐ஼ +𝑄ைி଴଴ଶ +𝑄ை௡௦௜௧௘ ீௐ +𝑄ௌ௘௘௣௦൯ + 𝑄ூ௡௧௔௞௘ where, 𝑄௎௣௦௧௥௘௔௠ = is the flow volume at River Mile 76; 𝑄ௐைு஽ = is the flow volume at W.O. Huske Dam, as reported by the USGS; 𝑄ௐ஼ = is the flow volume at Willis Creek, as measured by the point velocity method; 𝑄ைி଴଴ଶ = is the flow volume at Outfall 002 as reported in Facility Discharge Monitoring Reports; 𝑄ை௡௦௜௧௘ ீௐ = is the flow volume for onsite groundwater, as calculated based on the cross-sectional area, hydraulic gradient, and hydraulic conductivity for segments of the Black Creek Aquifer along the Cape Fear River Frontage; 𝑄ௌ௘௘௣௦ = is the summed flow volume for onsite seeps A, B, C, and D and the Lock and Dam Seep using measured flow rates; and 𝑄௜௡௧௔௞௘ = is the flow volume at the Facility intake, as reported in the Facility DMRs. 4.4.2 Tributaries – Willis Creek, Georgia Branch Creek, and Old Outfall 002 (Transport Pathways 2, 7 and 9) The PFAS mass discharge contribution to the Cape Fear River from tributaries to the Cape Fear River (Willis Creek, Georgia Branch Creek and Old Outfall 002) will be estimated using PFAS concentrations and flow rate data. PFAS samples will be collected at each tributary at a location near the discharge point to the Cape Fear River, but still far enough upstream in the tributary where they are not potentially influenced by the Cape Fear River. Since analytical sample locations are near the discharge point to the Cape Fear River, model input for tributaries will account for loading from groundwater discharging to the tributary, onsite surface water runoff into the tributary, and direct aerial deposition on these tributaries Volumetric discharge rates for the tributaries will be measured using a flume at Old Outfall 002 and flow velocity gauging at the creeks as outlined in the Seeps and Creeks DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 15 November 2020 Investigation Report (Geosyntec, 2019a). Detailed methods for flow measurements are presented in Appendix A. 4.4.3 Aerial Deposition to the Cape Fear River (Transport Pathway 3) The PFAS mass discharge from direct aerial deposition of PFAS to the Cape Fear River will be estimated using air deposition modeling results for HFPO-DA from the Site (ERM, 2018). Average deposition rates to the Cape Fear River will be estimated based on the reported aerial extent and deposition contours. Estimated deposition rates will be combined with the average river surface area and estimated residence time of flowing Cape Fear River water to estimate a mass discharge from aerial deposition. The mass discharge of PFAS compounds will be estimated by using the relative concentration ratios of other PFAS to HFPO-DA based on measured concentrations from offsite wells. Supporting documentation for this estimation is included in Appendix C. The 2018 emissions reduction scenario outlined in the ERM report (ERM, 2018) is likely a conservative assumption as further air emission reductions controls have been implemented compared to the modeled scenario. As assessment of air emissions controls continues, the bases of estimating PFAS mass discharge to the river from this pathway may be updated. 4.4.4 Onsite Groundwater (Transport Pathways 5 and 6) The Mass Loading Model describes two groundwater PFAS transport pathways to the Cape Fear River. First, the indirect pathway of groundwater to the onsite seeps which discharge to the Cape Fear River, and second, the direct pathway of Black Creek aquifer groundwater discharging directly to the river. 4.4.4.1 Indirect Pathway – Onsite Groundwater to Seeps (Onsite and Lock and Dam) to River (Transport Pathway 6) Four seeps at the Site have been identified that discharge directly to the Cape Fear River: Seep A, Seep B, Seep C, Seep D, and Lock and Dam Seep (Figure 4). The PFAS mass discharge from these seeps to the Cape Fear River will be estimated using measured PFAS concentrations and volumetric discharged rates. Volumetric discharge rates will be calculated using flumes as detailed in Appendix A. 4.4.4.2 Direct Pathway – Groundwater Discharge to River (Transport Pathway 5) The PFAS mass discharge of onsite groundwater discharge from the Black Creek Aquifer to the Cape Fear River will be estimated by calculating the sum of the PFAS mass discharge for eight segments of the Black Creek aquifer along the Cape Fear River frontage. PFAS mass discharge for each segment will be calculated based on the following parameters: DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 16 November 2020  The cross-sectional area of the Black Creek Aquifer for each segment, as determined from a three-dimensional hydrostratigraphic model of the Site;  The hydraulic gradient for each segment, as determined from groundwater level contours in the vicinity of the river frontage;  The hydraulic conductivity for each segment, as determined from slug tests conducted on monitoring wells representative of the Black Creek Aquifer; and  PFAS concentrations detected in monitoring wells in the vicinity of each segment. Groundwater discharge from the Floodplain Deposits to the Cape Fear River will also be evaluated on an annual basis as part of an overall model sensitivity analysis. The Floodplain Deposits are not always in hydraulic connection with the Cape Fear River as this layer is above the water line and the Floodplain Deposits have an order of magnitude lower hydraulic conductivity. As such, the contribution of the Floodplain Deposits is a small percentage of the overall loading to the Cape Fear River. As part of the groundwater remedy pre-design investigation, data from passive flux meters are being used to assess this differential. Further, the groundwater remedy at the Site will reduce the mass discharge from both the Floodplain Deposits and the Black Creek Aquifer because the Floodplain Deposits are downgradient of the Black Creek Aquifer and hydraulically connected to the Black Creek Aquifer. Further details on the onsite groundwater discharge term and associated calculations are provided in Appendix D. 4.4.5 Outfall 002 (Transport Pathway 4) The PFAS mass discharge of PFAS from Outfall 002 to the Cape Fear River will be estimated using measured PFAS concentrations and measured Outfall 002 volumetric flow rates. The concentration of PFAS compounds for Outfall 002 will be adjusted for PFAS already present in the sample collected at the Intake River Water at Facility before being input into the model. The PFAS present in intake water are already accounted for in the Mass Loading Model in pathways 1, 2, and 3 (Upstream River, Willis Creek and Direct Aerial Deposition). Daily volumetric discharge from Outfall 002 to the Cape Fear River is recorded and will be used to calculate the volumetric flow rate. 4.4.6 Adjacent and Downstream Offsite Groundwater (Transport Pathway 8) The PFAS mass discharge from adjacent (i.e., across or on the east side) and downstream offsite groundwater to the Cape Fear River will be calculated based on estimated upstream groundwater loading described in Section 4.4.1. PFAS detected in offsite groundwater originate from aerial deposition which has occurred in all directions from DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 17 November 2020 the Site (Geosyntec, 2019b). These aerially deposited PFAS have subsequently infiltrated to groundwater and migrate towards the Cape Fear River where they lead to upstream, adjacent and downstream offsite groundwater PFAS mass. The upstream offsite groundwater PFAS mass discharge will be estimated relatively simply by using measured river flows and concentrations at River Mile 76 upstream of the Site. Here only the upstream offsite groundwater PFAS mass discharge is present in the river at this location. Conversely, the adjacent and downstream offsite groundwater PFAS mass discharge is difficult to measure directly since many PFAS mass discharges from all other pathways are present in the river where these offsite groundwater contributions join the river. Additionally, adjacent and downstream offsite groundwater have a relatively small component of the Total PFAS mass discharge making their additional contributions to the total discharge difficult to distinguish from other discharges already present. Therefore, since PFAS mass discharge from offsite groundwater both upstream and downstream of the Site follow the same dynamics (deposition, infiltration, migration, discharge), the adjacent and downstream PFAS mass discharge will be scaled from the upstream offsite groundwater mass discharge estimate. The downstream offsite groundwater loadings are scaled to the upstream offsite groundwater loadings based on the length of river downstream of the Site known to be in contact with offsite groundwater containing PFAS compared to the length of the river upstream also in contact with offsite groundwater containing PFAS. A description of these calculations is presented in Appendix E. Potential Adjustments 4.5 Potential Adjustments The calculation methodologies described in this section have been outlined based on the present understanding of Site conditions. If conditions or methods change, modifications may need to be made to this protocol. For example, two components of the pre-design investigation, anticipated in Q3 and Q4 2020, includes installation of passive flux meters in wells along the Cape Fear River and aquifer tests in extraction wells adjacent to the Cape Fear River. Both investigations will provide a better understanding of the connection between the Black Creek Aquifer and the Cape Fear River. Accordingly, the Mass Loading Model may be modified to incorporate findings from these investigations. Modifications to the calculation methodologies will be described in submitted reports described in Section 5. At the end of each reporting year, Chemours may request to DEQ a modification of the protocol. 5 REPORTING The data and results from the three mass loading sampling programs (Cape Fear River Mass Loads, Bladen Bluffs and Kings Bluff Intakes Mass Discharge, and the Cape Fear DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TR0795 18 November 2020 River Mass Loading Model) will be provided to NCDEQ on a quarterly basis where outputs for the previous quarter are provided within ninety (90) days of the end of the previous quarter. 6 REFERENCES Geosyntec, 2019a. Seeps and Creeks Investigation Report. Chemours Fayetteville Works. 26 August 2019. Geosyntec, 2019b. Corrective Action Plan. Chemours Fayetteville Works. December 31, 2019. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TABLES DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TABLE 1 PFAS ANALYTICAL METHODS AND ANALYTE LIST Chemours Fayetteville Works, North Carolina Geosyntec Consultants NC P.C. Analytical Method Common Name Chemical Name CASN Chemical Formula HFPO-DA*Hexafluoropropylene oxide dimer acid 13252-13-6 C6HF11O3 PEPA Perfluoro-2-ethoxypropionic acid (Formerly Perfluoroethoxypropyl carboxylic acid)267239-61-2 C5HF9O3 PFECA-G Perfluoro-4-isopropoxybutanoic acid 801212-59-9 C12H9F9O3S PFMOAA Perfluoro-2-methoxyacetic acid 674-13-5 C3HF5O3 PFO2HxA Perfluoro-3,5-dioxahexanoic acid (Formerly Perfluoro(3,5-dioxahexanoic) acid)39492-88-1 C4HF7O4 PFO3OA Perfluoro-3,5,7-trioxaoctanoic acid (Formerly Perfluoro(3,5,7-trioxaoctanoic) acid)39492-89-2 C5HF9O5 PFO4DA Perfluoro-3,5,7,9-tetraoxadecanoic acid (Formerly Perfluoro(3,5,7,9-tetraoxadecanoic) acid)39492-90-5 C6HF11O6 PMPA Perfluoro-2-methoxypropionic acid (Formerly 2,3,3,3-Tetrafluoro-2-(trifluoromethoxy)propanoic) 13140-29-9 C4HF7O3 PFO5DA Perfluoro-3,5,7,9,11-pentaoxadodecanoic acid 39492-91-6 C7HF13O7 PS Acid (Formerly PFESA-BP1)Ethanesulfonic acid, 2-[1-[difluoro[(1,2,2-trifluoroethenyl)oxy]methyl]-1,2,2,2-tetrafluoroethoxy]-1,1,2,2- tetrafluoro- (Formerly PFESA-BP)29311-67-9 C7HF13O5S Hydro-PS Acid (Formerly PFESA-BP2)Ethanesulfonic acid, 2-[1-[difluoro(1,2,2,2-tetrafluoroethoxy)methyl]-1,2,2,2-tetrafluoroethoxy]-1,1,2,2- tetrafluoro- (Formerly PFESA-BP2)749836-20-2 C7H2F14O5S PFHpA*Perfluoroheptanoic acid 375-85-9 C7HF13O2 Notes: * - HFPO-DA and PFHpA are also analyzed by EPA Method 537 Mod. EPA - Environmental Protection Agency PFAS - Per- and Polyfluoroalkyl substances SOP - Standard Operating Procedure Table 3+ Lab SOP TR0795 Page 1 of 1 November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TABLE 2 SURFACE WATER, SEEP AND RIVER SAMPLING LOCATIONS AND AND FLOW MEASUREMENT METHODS Chemours Fayetteville Works, North Carolina Geosyntec Consultants of NC P.C. Location ID Location Description Sample Collection Method Flow Measurement Method OLDOF-1 Mouth of Old Outfall 002 24-hour composite Flume SEEP-A-1 Mouth of Seep A 24-hour composite Flume SEEP-B-1 Mouth of Seep B 24-hour composite -- SEEP-B-2 Tributary to Seep B --Flume SEEP-B-TR1 Tributary to Seep B --Flume SEEP-B-TR2 Tributary to Seep B --Flume SEEP-C-1 Mouth of Seep C 24-hour composite Flume SEEP-D-1 Mouth of Seep D 24-hour composite Flume WC-1 Mouth of Willis Creek 24-hour composite Velocity Probe GBC-1 Mouth of Georgia Branch Creek Grab Velocity Probe CFR-MILE-76 Cape Fear River Mile 76 Grab USGS Data CFR-BLADEN Cape Fear River at Bladen Bluffs Grab USGS Data CFR-KINGS Cape Fear River at Kings Bluff Raw Water Grab USGS Data TAR HEEL Cape Fear River at Tar Heel Ferry Road Bridge 24-hour composite USGS Data W.O. Huske Dam USGS Gauge Site No. 02105500 --USGS Data Intake River Water at Facility Water Drawn Through the Intake Sampled at the Power Area at the Site 24-hour composite Facility DMRs Outfall 002 Outfall 002 in open channel 24-hour composite Facility DMRs Notes: -- not applicable DMRs - discharge monitoring reports EPA - Environmental Protection Agency PFAS - per- and polyfluoroalkyl substances USGS - United States Geological Survey TR0795 Page 1 of 1 November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TABLE 3 GROUNDWATER MONITORING WELL SAMPLING AND WATER LEVEL MEASUREMENT LOCATIONS Chemours Fayetteville Works, North Carolina Geosyntec Consultants of NC, PC Area Hydrogeological Unit1 Well ID Adjacent Surface Water Feature Onsite Black Creek PIW-3D Cape Fear River Onsite Floodplain PIW-7S Cape Fear River Onsite Black Creek PIW-7D Cape Fear River Onsite Floodplain LTW-01 Cape Fear River Onsite Black Creek LTW-02 Cape Fear River Onsite Floodplain LTW-03 Cape Fear River Onsite Floodplain LTW-04 Cape Fear River Onsite Black Creek LTW-05 Cape Fear River Onsite Black Creek PZ-22 Cape Fear River Onsite Surficial PW-06 Georgia Branch Creek Onsite Surficial PW-07 Georgia Branch Creek Onsite Surficial PW-04 Old Outfall Onsite Black Creek PW-11 Old Outfall Onsite Black Creek PW-09 Willis Creek Onsite Surficial SMW-11 Willis Creek Onsite Surficial SMW-10 Willis Creek Onsite Black Creek SMW-12 Willis Creek Onsite Floodplain PIW-1S Cape Fear River / Willis Creek Onsite Surficial PIW-1D Cape Fear River / Willis Creek Offsite Black Creek Bladen-1D Georgia Branch Creek Notes: 1. Hydrogeologic units for existing wells determined based on boring log descriptions. TR0795 Page 1 of 1 November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 FIGURES DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 RainRain Cape F e ar Ri v e r Cape F e ar Ri v e r Perched Zo n e Surficial Aq u i f e r Black Cre e k Aquifer Groun d w a t e r ChemoursFayetteville WorksManufacturing Area ChemoursFayetteville WorksManufacturing Area Perched Zone Clay Black CreekConfining Unit Perched Zone Clay Black CreekConfining Unit Non-contact cooling water from river Non-Chemours treated process water Stormwater (4) Outfall 002 (Pipe to River) Groundwater Seep B Seep A Seep C Seep D (1) Upstream Cape Fear River (3) Aerial Deposition (9) G e orgi a Branch Creek (2) Willis Creek ( 7 ) Old Outfall 0 02(6) Seeps ( 5 ) OnSite Groundwater (8) Adjacentand Downstream (3) Aerial Deposition (9) G e orgi a Branch Creek (2) Willis Creek ( 7 ) Old Outfall 0 02(6) Seeps ( 5 ) OnSite Groundwater ( 8 ) A dja cent and W.O. Huske DamW.O. Huske Dam Upper Cape Fear Confining Unit(4) Outfall 002 (Pipe to River) (1) Upstream Cape Fear River Down stre a m Groundwater ( 8 ) A dja cent and Down stre a m Groundwater Groundwater (8) Adjacentand Downstream Raleigh, NC November 2020 Figure 1 Potential PFAS Transport Pathways to the Cape Fear River from Site Chemours Fayetteville Works, North Carolina Note: Image is conceptual and is not to scale DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 ^_Kings Bluff Intake Canal ChemoursFayettevilleWorks Start ofCape FearRiver Wilmington Fayetteville Raleigh Bladen BluffsIntake W.O. Huske Dam Greensboro Tar HeelFerry RoadBridge Virginia NorthCarolina SouthCarolina Cape Fear River Watershed and Downstream Drinking Water Intakes Chemours Fayetteville Works, North Carolina Figure Raleigh 2 ³Deep R i verH awRiv er LittleRiver CapeFearRiver 20 0 2010 Miles Note:Basemap sources: Esri, DigitalGlobe, GeoEye, EarthstarGeographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN, and the GIS User Community. Projection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US Legend ^_Chemours Fayetteville Works Upper Basin Middle Basin Lower Basin November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A CapeFearRi verSeep D Old Outfall 002 Seep C Seep B Seep A Willis Creek Georgi a B r a n c h C r e e k PIW-1D PW-04 PW-06 PW-07 SMW-11 LTW-01 LTW-03 LTW-04 PIW-1S PIW-7S Bladen-1D LTW-02 LTW-05 PIW-3D PIW-7D PW-09 PW-11 PZ-22 SMW-10 SMW-12 Groundwater Monitoring Well Samplingand Water Level Measurement Locations Chemours Fayetteville Works, North Carolina Figure 3Raleigh 1,000 0 1,000500 Feet ³Path: P:\PRJ\Projects\TR0795\Database and GIS\GIS\Baseline Monitoring Workplan\TR0795_BaselineGroundwaterMonitoringWellNetwork_Protocol.mxd; NBarNahoum; 8/20/2020November 2020 Projection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US Notes:1. Due to the scale of the map, pairs of wells that are in close proximity have been offset for visibility. Therefore, the placement of these wells on this map do not reflect their true geographic coordinates.2. The outline of Cape Fear River is approximate and is based on open data from ArcGIS Online and North Carolina Departmentof Environmental Quality Online GIS. 3. Basemap source: Esri, DigitalGlobe, GeoEye, Earthstar Geographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN, and the GIS User Community. Legend !'A Surficial Aquifer !'A Floodplain Deposits !'A Black Creek Aquifer Observed Seep Nearby Tributary Site Boundary DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 !( !( !( !( !( !( !( !( !( #* #* #* #* #* #* #* #* #* #* #* !(#*Ca p e F e a r R i v e r Lock-Dam Seep Intake River Water at Facility CFR-MILE-76 OUTFALL 002 SEEP-C-1 SEEP-D-1 OLDOF-1 SEEP-A-1 SEEP-B-1SEEP-B-2 SEEP-B-TR1 SEEP-B-TR2 WC-1 W.O. Huske DamOld Outfall 002 Willis Creek 1,250 0 1,250625 Feet ³Path: P:\PRJ\Projects\TR0795\Database and GIS\GIS\Baseline Monitoring Workplan\TR0795_StreamReaches_FlowMeasurements_April2020_Protocol.mxd Last Revised: 2020-11-10 Author: TIpProjection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US ³Legend #*Flow Measurement Location !(Sample Location Observed Seep Nearby Tributary Site Boundary Notes:1. The outline of Cape Fear River is approximate and is based onopen data from ArcGIS Online and North Carolina Department ofEnvironmental Quality Online GIS.2. Basemap sources: Esri, DigitalGlobe, GeoEye, Earthstar Geographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN,and the GIS User Community. !(#*GBC-1Ge o r g i a B r a n c h C r e e k ³ 1 0 10.5 Miles ³ 1 2 1 2 Surface Water, Seep and River WaterSampling and Flow Measurement Locations Chemours Fayetteville Works, North Carolina Figure 4Raleigh 1,000 0 1,000500 Feet November 2020 2,000 0 2,0001,000 Feet DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 !( !( !( CFR-BLADEN CFR-MILE-76 CFR-TARHEEL ³ Projection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US ³ Notes:1. The outline of Cape Fear River is approximate and is based onopen data from ArcGIS Online and North Carolina Department of Environmental Quality Online GIS.2. Basemap sources: Esri, DigitalGlobe, GeoEye, EarthstarGeographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN,and the GIS User Community. ³ 25 0 2512.5 Miles !( CFR-KINGS 1 ³ 2 0 21 Miles 2 - Downstream Cape Fear River Sample Locations Chemours Fayetteville Works, North Carolina Figure 5Raleigh 2 0 21 Miles November 2020 Legend !(Sample Location Site Boundary Cape Fear River 1 2 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 APPENDIX A Field Methods DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix A 1 November 2020 APPENDIX A FIELD METHODS This appendix describes the field methods and procedures that will be employed for collecting onsite seep and surface water samples, gauging stream flow, groundwater level measurements, water quality parameter assessment and sample collection. ONSITE SEEP AND SURFACE WATER SAMPLE COLLECTION METHODS Onsite Seep and Surface Water Composite Sampling Methods Autosamplers will be used to collect 24-hour integrated samples from various surface water bodies and onsite Seeps. The autosamplers will collect sample aliquots once per hour. The sample tubing from the autosampler will be positioned at minimum 2 inches above the bottom of the water body flow with the open end of the sample tubing pointed in the downstream direction to minimize the potential for sediment accumulation and uptake. Autosampler materials will be consisting of high- density polyethylene (HDPE) tubing, silicon tubing, and an HDPE sample reservoir. Water from the sample reservoir will be decanted into laboratory supplied bottles (e.g. 250-milliliter [mL] HDPE bottles for PFAS analysis) and then sent to an approved laboratory. Field parameters will be measured twice for composite samples: once during composite sampling (collected directly from the water stream), and once after composite sampling (collected from the autosampler reservoir). The following water quality parameters will be recorded: pH; Temperature (degrees Celsius [°C]); Specific Conductivity (microsiemens per centimeter [µS/cm]); Dissolved Oxygen (DO) (milligrams per liter [mg/L]); and, Oxidation-Reduction Potential (ORP) (millivolts [mV]) Creek and Seep Water Grab Sampling Methods Where composite sample collection is not feasible due to access or other field conditions, creek and seep water samples will be collected as grab samples. Laboratory-supplied 250 mL HDPE sample bottles will be lowered into the flowing water of the creek to collect the sample. The bottles will be lowered into the stream either using a properly decontaminated dip rod with bottle attached with a nylon zip tie, or in shallow streams, by hand. The bottle will be lowered into the stream with the cap removed, open and facing oncoming flow. Where possible, the sample will be collected from the middle of the stream. Care will be taken to avoid collecting suspended solids or other materials in the sample. The following water quality parameters will be measured after sample collection using water from the same location in the stream: pH; Temperature (°C); Specific Conductivity (µS/cm); DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix A 2 November 2020 DO (mg/L); and ORP (mV). Cape Fear River Water Grab Sampling Methods Cape Fear River water samples will be collected using a peristaltic pump and new dedicated HDPE tubing and dedicated silicone tubing for the pump head at each location. The tubing will be lowered to the specified sampling depth below the water surface using an anchor weight and the tubing fastened to the anchor pointing upwards. Surface water will be pumped directly from the submerged tubing through the pump head to a flow-through cell. Field parameters will be monitored over a 5-minute interval, then the flow-through cell will be disconnected, the tubing cut to provide a new, clean end and a grab sample will be collected from the discharge of the peristaltic pump in new 250 mL laboratory-supplied HDPE bottles. The following water quality parameters will be measured: pH; Temperature (°C); Specific Conductivity (µS/cm); DO (mg/L); and ORP (mV). FLOW GAUGING METHODS Flow velocity will be measured after sample collection at seep and creek locations specified in Table 2. Flow velocity will be measured using flumes where they exist, otherwise flow velocity will be measured via flow meters. Flumes Flumes are currently installed in Seep A, Seep B, Seep C, Seep D, and Old Outfall 002 under Nationwide Permit 38 (United States Army Corps of Engineers, June 2019). Where present, they will be used to calculate flow based on the data collected by the level logger installed in the flume. Flow Velocity Gauging Where flumes are not installed (i.e., Willis Creek and Georgia Branch Creek), the flow rate of the stream will be measured using a submersible flow meter. The flow meter will be placed beneath the flowing stream along the cross section of the stream at regular intervals (e.g. every six inches) and the height of the water will be recorded along with the recorded water velocity. These measurements will then be used to calculate the volumetric flow of water passing through the structure based on the regular geometry and measured flow rates. Flow will be measured using two to three transects to assess variability in estimated flow. Transects that have fairly uniform cross sections that could be gauged with minimal disturbance will be selected. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix A 3 Novmeber 2020 SYNOPTIC WATER LEVEL MEASUREMENTS Water level measurements for monitoring wells listed in Table 3 will be collected during a single synoptic event. At each location, notes on well condition, weather, date and time of collection, depth to bottom of well and depth to water level from top of casing will be recorded. GROUNDWATER SAMPLING METHODS Designated monitoring wells will be monitored as part of the quarterly monitoring activities. These wells are listed in Table 3 and Figure 3. The groundwater samples will be analyzed for the list of Table 3+ compounds listed in Table 1. Field equipment will be inspected by the program on-Site supervisor and calibrated daily prior to use according to the manufacturer’s recommended guidelines. Field parameters will be measured with a water quality meter after sample collection and will include the following: pH; Temperature (°C); Specific Conductivity (µS/cm); DO (mg/L); ORP (mV); Turbidity (nephelometric turbidity units [NTU]); and, Color. Non-dedicated or non-disposable sampling equipment will be decontaminated immediately before sample collection in the following manner: 1. De-ionized water rinse; 2. Scrub with de-ionized water containing non-phosphate detergent (i.e., Alconox®); and 3. De-ionized water rinse. Disposable equipment (e.g. gloves, tubing, etc.) will not be reused. New sample containers will be used for each sample. Groundwater samples will be collected, where possible, using low-flow sampling techniques as discussed in detail in the Long-term Groundwater Monitoring Plan (Parsons, 2018) and briefly summarized here. 1. New disposable or dedicated HDPE tubing will be placed at the midpoint of the well’s screened interval. 2. Water will be purged through a flow-through cell attached to a water quality meter capable of measuring pH, temperature, specific conductivity, dissolved oxygen, and ORP. 3. Water will be pumped using a peristaltic pump, with dedicated silicone tubing for the pump head, at wells with water level less than 30 feet. A submersible pump will be used for wells with water level deeper than 30 feet. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix A 4 November 2020 4. Groundwater will be pumped directly from submerged tubing through the pump head to a flow-through cell until field parameters (pH, temperature, specific conductivity, DO, ORP) and will be stabilized within ±10% over three consecutive readings within a five-minute interval. If field parameters stabilized, but turbidity remains stable yet elevated greater than 20 NTU, field personnel will purge five well volumes prior to sample collection. 5. Water levels in the designated wells will be monitored during purging so that minimum draw-down of the water column was maintained. 6. Once flow-through cell readings are stable, the flow-through cell will be disconnected, the tubing cut to provide a new clean end and samples will be collected from the discharge of the peristaltic pump in new 250 mL laboratory-supplied HDPE bottles. 7. Sample identification information (e.g., well/sample identification number, sample time and date, samplers’ names, preservative, and analytical parameters) will be recorded on the bottle label with permanent ink after the sample will be collected. Sample Packing and Shipping Upon sample collection, each containerized sample will be placed into an insulated sample cooler. Wet ice will be placed around the sample containers within heavy-duty plastic bags within the sample cooler. A chain-of-custody form was completed by the field sample custodian for each sample shipment. Sample locations, sample identification numbers, description of samples, number of samples collected, and specific laboratory analyses will be recorded on the chain-of-custody form. Field QA/QC Samples Field quality assurance/ quality control (QA/QC) samples will be collected as discussed in detail in the Long-term Groundwater Monitoring Plan (Parsons, 2018) and summarized below: 1. For samples collected to be analyzed by Method EPA 537 Modified, three blind duplicate samples will be collected. 2. For samples collected to be analyzed by Method Table 3+, three blind duplicate samples will be collected. 3. For samples collected to be analyzed by EPA 537, three Modified Matrix Spike and Matrix Spike Duplicate (MS/MSD) samples will be collected. 4. For samples collected to be analyzed by Method Table 3+, three MS/MSD samples will be collected. 5. For groundwater samples, equipment blanks and field blanks will be collected daily. 6. For surface water samples, three equipment blanks will be collected. REFERENCES Parsons, 2018. Long-term Groundwater Monitoring Plan. September 28, 2018. Parsons, 2020. Fayetteville Works Health and Safety Plan. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix A 5 November 2020 United States Army Corps of Engineers. Nationwide Permit 6. 19 March 2017. http://saw- reg.usace.army.mil/NWP2017/2017NWP06.pdf. Accessed 30 January 2019. United States Army Corps of Engineers. Nationwide Permit 36, 06 June 2019. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 APPENDIX B Captured Mass Load Calculation Methodology DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix B 1 November 2020 APPENDIX B CAPTURED MASS LOAD CALCULATION METHODOLOGY INTRODUCTION AND OBJECTIVE The objective of this appendix is to present the calculation methodology for the Captured Mass Load term in Equation 1 below: Equation 1: Total PFAS Baseline Mass Load 𝑀஼ிோ = 𝑚஼ிோ + 𝑚ோ௘௠௘ௗ௜௘௦ where, 𝑀஼ிோ = is the Baseline Mass Load of PFAS compounds in the Cape Fear River, including the mass load prevented from reaching the Cape Fear River by implemented remedies, measured in kg; 𝑚஼ிோ = is the River Mass Load estimated using PFAS concentrations in samples taken in the Cape Fear River downstream of the Site where the river is well mixed and using measured river flow volumes; and 𝑚ோ௘௠௘ௗ௜௘௦ = is the Captured Mass Load prevented from reaching the Cape Fear River by remedies implemented by Chemours. Remedies implemented or to be implemented by Chemours (e.g., onsite seeps interim remedies, Outfall 002 remedy, etc.) will prevent PFAS mass loads from reaching the Cape Fear River. The loading reductions for each remedy will be calculated using a methodology appropriate for that given remedy. The goal of such calculations will be to estimate, for a given time period, the PFAS mass diverted from reaching the Cape Fear River by the remedy that would have otherwise reached the Cape Fear River. This appendix presents the calculation methodology for the Seeps Interim flow-through cell remedies and the Old Outfall capture and treatment remedies. APPROACH Presently, the Seeps Interim flow-through cell remedies and the Old Outfall capture and treatment remedies are sufficiently advanced to describe how the load reductions associated with these remedies will be calculated. Equation 2 presents the calculation of the Remedy Captured PFAS Mass Load term for these two remedies. Equation 2: Calculation of Remedy Captured Mass Load 𝑚ோ௘௠௘ௗ௜௘௦ = 𝑚௦௘௘௣௦ூெ + 𝑚ை௟ௗைி + 𝑚௢௧௛௘௥௦ where, 𝑚ோ௘௠௘ௗ௜௘௦ = is the Captured Mass Load prevented from reaching the Cape Fear River by remedies implemented by Chemours; DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix B 2 November 2020 𝑚௦௘௘௣௦ூெ = is the mass load, measured in kg, captured by the seep interim flow-through cell remedies; 𝑚 ை௟ௗைி = is the mass load, measured in kg, captured by the Old Outfall 002 capture and treat remedy; 𝑚௢௧௛௘௥௦ = is the mass load of other remedies to potentially be estimated in the future, such as the stormwater capture and treat system required by CO Addendum paragraph 4(a). For both the Seeps and the Old Outfall treatment systems, the mass loads will be evaluated using sampling collected pursuant to: CO Addendum Paragraph 2(a)(iii) requirements for interim seep flow-through cell remedy performance monitoring sampling; Outfall 003 NPDES permit for the Old Outfall treatment system performance monitoring; CO Paragraph 2(a)(iii) seeps wet weather sampling following rainfalls greater than 0.5 inches; and Seeps baseline period sampling being performed pursuant to CO Addendum paragraph 2(c)(i) as described in the Onsite Seeps Long-Term Loading Calculation Plan submitted (Geosyntec, 2020) The mass loads for both the Seeps interim remedies and the Old Outfall 002 will follow the same general approach by which Cape Fear River In-River mass loads are calculated. Both of these remedies involve influent and effluent samples taken at regular periods and high-resolution flow data. These data enable a calculation of the Total PFAS mass entering and exiting the systems, allowing for a calculation of the mass differential, i.e., the mass captured and removed by the system. For any given evaluation time period, the influent and effluent sampling periods will be discretized into time intervals. The Remedy Captured Mass Loads for the Seeps interim flow-through cells and Old Outfall 002 system will be calculated following Equation 3 below. Equation 3: Seeps Flow-Through Cells and Old Outfall Capture and Treatment Remedy Captured Mass Loads 𝑚௦௘௘௣௦ூெ + 𝑚ை௟ௗைி = ෍൫𝑚௥ ௜௡௙ − 𝑚௥ ௘௙௙൯ ோ ௥ୀଵ = ෍ቆ෍ ෍ ൣ𝑐௥,௡,௜ ௜௡௙ 𝑉௥,௡ ௜௡௙൧ ୍ ௜ୀଵ ே ௡ୀଵ − ෍ ෍ ൣ𝑐௥,௡,௜ ௘௙௙ 𝑉௥,௡ ௜௡௙൧ ୍ ௜ୀଵ ே ௡ୀଵ ቇ ோ ௥ୀଵ where, DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix B 3 November 2020 𝑚௦௘௘௣௦ூெ + 𝑚ை௟ௗைி = is the mass load, measured in kg, captured by the seep interim flow- through cell remedies and the Old Outfall 002 capture and treat remedy during a monitoring period; r = represents each remedy being evaluated; 𝑅 = represents the total number of remedies being evaluated, e.g., five (5) interim flow- through cells at Seeps A, B, C and D, and the ex situ capture and treatment system at the Old Outfall; 𝑚௥ ௜௡௙ = is the mass load of PFAS at the influent of the treatment system during a monitoring period; and 𝑚௥ ௘௙௙ = is the mass load of PFAS at the effluent of the treatment system during a monitoring period. 𝑛 = represents individual time intervals during a monitoring period; 𝑁 = is the total number of time intervals in a monitoring period; i = represents each of the PFAS constituents being evaluated; I = represents total number of PFAS constituents included in the summation; 𝑐௥,௡,௜ ௜௡௙ = is the measured or calculated influent concentration for a given remedy r, time interval n and PFAS constituent i; 𝑐௥,௡,௜ ௘௙௙ = is the measured or calculated effluent concentration for a given remedy r, time interval n and PFAS constituent i; and 𝑉௥,௡ ௜௡௙ = is the volume of water that flowed into the treatment system for a given remedy r and time interval1 n. During a given monitoring period (e.g., typically three months or one quarter), multiple samples will be collected from each remedy’s influent and effluent. Most of these samples will be composite samples and some could be grab samples. The calculation methodology outlined here considers all collected samples during a given monitoring period, including cases where two or more samples may be collected contemporaneously, and cases where composite sample collection events do not occur successively, i.e., there is a period of time where no sample is being collected. To facilitate this calculation, the overall time period is separated into discrete time intervals with corresponding time-weighted concentrations calculated for each interval. The time intervals are defined as the duration in time between two sampling elements, where a sampling element can be: Beginning of a composite sample collection; End of a composite sample collection; or 1 The influent volume is applied to the effluent concentration to calculate the mass load at the effluent for two reasons. First, the flow-through cells only measure flow at the influent. Second, the Old Outfall treatment system effluent may include flows from other remedies such as the interim groundwater extraction remedy. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix B 4 November 2020 Collection of a grab sample. For each time interval the influent and effluent concentration is calculated following Equation 4 below. Equation 4: Remedy Influent and Effluent Mass Load Time Interval Concentration 𝑐௥,௡,௜ௌ௖௘௡௔௥௜௢ = ෍𝐶௥,௡,௜,௞ௌ௖௘௡௔௥௜௢ × 𝑤௞ ௄ ௞ୀଵ = ෍𝑐௥,௡,௜,௞ ௌ௖௘௡௔௥௜௢ 𝑡௡𝑡௞ ∑𝑡௡ 𝑡௞ ௄௞ୀଵ ௄ ௞ୀଵ where, 𝑐௥,௡,௜ௌ௖௘௡௔௥௜௢ = is the measured or calculated scenario (influent or effluent scenario) concentration for a given remedy r, time interval n, and PFAS constituent i; 𝑟 = represents each remedy being evaluated; 𝑛 = represents individual time intervals during a monitoring period; i = represents each of the PFAS constituents being evaluated; k = represents a concentration sample considered in the mass load time interval; K = is the total number of concentration samples considered in the mass load time interval; 𝑐௥,௡,௜,௞ ௌ௖௘௡௔௥௜௢ = is the scenario-specific (influent or effluent scenario) concentration for a given remedy r, time interval n, PFAS constituent i, and sample k used in calculating the time- weighted average concentration for a remedy captured mass load time interval; and 𝑤௞ = is the weighting factor calculated for and applied individually to each concentration, where, 𝑡௡ = the length of time of the mass load time interval; and 𝑡௞ = the length of time of the collected sample. For composite samples, 𝑡௞ is the total length of the composite sample collection period. If 𝑡௞ < 𝑡௡, i.e., the composite sample collection time is less than the interval time or a grab sample was collected, then 𝑡௞ is set to equal the interval time for the purposes of concentration weighting. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix B 5 November 2020 REFERENCES Geosyntec, 2020. Onsite Seeps Long-Term Loading Calculation Plan. Chemours Fayetteville Works. October 30, 2020. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 APPENDIX C Supporting Calculations – Direct Aerial Deposition on Cape Fear River DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix C 1 November 2020 APPENDIX C SUPPORTING CALCULATIONS – DIRECT AERIAL DEPOSITION ON CAPE FEAR RIVER INTRODUCTION AND OBJECTIVE Nine pathways (Figure 1) are identified as potentially contributing to observed Cape Fear River per- and polyfluoroalkyl substances (PFAS) concentrations. These pathways include direct PFAS aerial deposition to the Cape Fear River. This pathway is identified as Transport Pathway Number 3 in the PFAS mass loading model. The mass discharge (mass per unit time measured in milligrams per second [mg/s]) from direct aerial deposition of PFAS to the Cape Fear River will be estimated by scaling air deposition modeling results for Hexafluoropropylene oxide dimer acid (HFPO-DA; ERM, 2018). The objective of this appendix is to present the calculations for estimating aerially deposited PFAS directly on the Cape Fear River during a mass loading event. APPROACH HFPO-DA mass loading directly to the Cape Fear River will be estimated using the reported aerial extent and deposition contours modeled for October 2018 (ERM, 2018). As depicted in (Table C1), the HFPO-DA air loading data (micrograms per meters squared [µg/m2]) provided from ERM (2018) will be used to calculate the net hourly deposition rate (nanograms per meters squared per hour [ng/m2/hr]) using Equation 1 below: Equation 1: Net Hourly Deposition Rate 𝐷𝑅ோ் = 𝑀𝐿஺ூோ 𝑡஺ூோ where: 𝐷𝑅ோ் = Net hourly deposition rate with units of mass per area per time (M L-2 T-1), typically in ng/m2/hr; 𝑀𝐿஺ூோ = Air mass loading of HFPO-DA with units of mass per area (M L-2), typically µg/m2; and 𝑡஺ூோ = time that air mass loading was modeled (T), typically hours. Depositional area along the river will be calculated using available data for river width and computed river lengths where deposition contours were modeled (ERM, 2018). Average river width in meters (m) along sections of the Cape Fear River will be estimated in GIS. As depicted in Figures C1 through C5, five sections along the Cape Fear River (Center, Up River Sections 1 and 2, and Down River Sections 1 and 2) with HFPO-DA concentrations contours ranging from 40 to 640 µg/m2 have been identified and the length of the Cape Fear River along each of the sections will be measured. For each section, the average river width and lengths between contours shown in Figures C1 through C5 will be used to calculate cross-sectional areas (in m2) as described in Equation below: DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix C 2 November 2020 Equation 2: Cape Fear River Surface Area for Each Section 𝐴௦ = 𝐿௦ × 𝑊௦ where, 𝐴௦ = total spatial area over which deposition occurs between contours (L2) in section “s”, typically in m2; s = section along the Cape Fear River with HFPO-DA concentrations contours ranging from 40 to 640 µg/m2 (five sections in total); 𝐿 = total length of river within section “s”, typically in m; and 𝑊௦ = average river width in section “s”, typically in m. Start and end deposition rates (ng/m2/hr) for each section along the Cape Fear River will be estimated based on the deposition contours and corresponding net hourly deposition rate (Table C1); a combined deposition rate for each section will be calculated as the average of the start and end deposition rates. River velocity (meters per hour [m/hr]) will be estimated from measured flow rates from USGS (2020) and the calculated river cross sectional area. Section lengths will be used to calculate HFPO-DA travel time based on the estimated river velocities. The combined deposition rate (ng/m2/hr) from Table C1, section area (m2), and travel time (hr) will be used to calculate mass HFPO-DA deposited (ng) as follows in Equation 3 below. Equation 2: Total HFPO-DA Mass Discharge to Cape Fear River 𝑀𝐷ுி௉ைି஽஺ = ෍𝐷𝑅஺௏ீ,௦ × 𝐴௦ × 𝑡௦ ௌ ௦ୀଵ where, 𝑀𝐷ுி௉ைି = total mass discharge of HFPO-DA into the river across all sections, with units of mass per time (M T-1), typically mg/s; s = section along the Cape Fear River with HFPO-DA concentrations contours ranging from 40 to 640 µg/m2; S = total number of sections along the Cape Fear River with HFPO-DA concentrations contours ranging from 40 to 640 µg/m2, five in total; 𝐷𝑅஺௏ீ,௦ = average deposition rate based from the ERM model (2018) in section “s”, typically in ng/m2/hr; 𝐴௦ = spatial area over which deposition occurs in section “s”, typically in m2; and 𝑡௦ = travel time through the river length in section “s”, typically in hr. As reported in the Corrective Action Plan (Geosyntec 2019), ten offsite groundwater seeps south of Old Outfall 002 (Seeps E to M) were identified on the west bank of the Cape Fear River south of the Site. Seeps E to M were sampled in October 2019 and Seeps E to K were sampled in March DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix C 3 November 2020 2020. The results of both sampling events indicate that Seeps E to M show an aerial deposition PFAS signature (concentrations decrease in seeps more distant from the Site). Accordingly, the offsite seep data will used to build a relationship, i.e., scaling factor, between HFPO-DA and other PFAS compounds (Figure B6). This scaling factor will be used to estimate mass discharge of Total PFAS compounds to the Cape Fear River as shown in Equation 4. Equation 4: Mass Discharge to Cape Fear River 𝑀𝐷௉ி஺ௌ = 𝑀𝐷ுி௉ைି × 𝑅 where, 𝑀𝐷௉ி஺ௌ = total mass discharge of PFAS compounds into the river, typically in mg/s; 𝑀𝐷ுி௉ைି = total mass discharge of HFPO-DA into the river, typically in mg/s; and 𝑅 = average ratio of measured HFPO-DA to PFAS compounds across the nine offsite seeps. REFERENCES ERM, 2018. Modeling Report: HFPO-DA Atmospheric Deposition and Screening Groundwater Effects. 27 April 2018. Geosyntec, 2019. Corrective Action Plan. Chemours Fayetteville Works. December 31, 2019. USGS, 2020. USGS 02105500 Cape Fear River at Wilm O Huske Lock near Tarheel, NC. Available at: https://waterdata.usgs.gov/nwis/uv?site_no=02105500 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Length (m): 903.00 Measurement of Cape Fear River Length at Center Section Chemours Fayetteville Works, North Carolina Figure Notes:HFPO-DA - Hexafluoropropylene oxide dimer acid; or dimer acid; or GenX µg / m2/yr - micrograms per square meter per year HFPO-DA deposition model contours for October 2018 from ERM, 2018, Modeling Report: HFPO-DA Atmospheric Deposition and Screening Groundwater Effects. 27 April 2018. 1 0 10.5 Miles ³ Projection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US Legend ite Boundary 40 µg/m2/yr 80 µg/m2/yr 160 µg/m2/yr 320 µg/m2/yr 640 µg/m2/yr C1 Modeled Deposition Contours, October 2018 Scenario Raleigh, NC November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Length (m): 489.90 Measurement of Cape Fear River Length at Up-River Section 1 Chemours Fayetteville Works, North Carolina Figure Notes:HFPO-DA - Hexafluoropropylene oxide dimer acid; or dimer acid; or GenX µg /m2/yr - micrograms per square meter per year HFPO-DA deposition model contours for October 2018 from ERM, 2018, Modeling Report: HFPO-DA Atmospheric Deposition and Screening Groundwater Effects. 27 April 2018. 1 0 10.5 Miles ³ Projection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US Legend Site Boundary Modeled Deposition Contours, October 2018 Scenario 40 µg/m2/yr 80 µg/m2/yr 160 µg/m2/yr 320 µg/m2/yr 640 µg/m2/yr C2November 2020Raleigh, NC DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Length (m): 908.05 Measurement of Cape Fear River Length at Up-River Section 2 Chemours Fayetteville Works, North Carolina Figure Notes:HFPO-DA - Hexafluoropropylene oxide dimer acid; or dimer acid; or GenX µg / m2/yr - micrograms per square meter HFPO-DA deposition model contours for October 2018 from ERM, 2018, Modeling Report: HFPO-DA Atmospheric Deposition and Screening Groundwater Effects. 27 April 2018. 1 0 10.5 Miles ³ Projection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US Legend Site Boundary Modeled Deposition Contours, October 2018 Scenario 40 µg/m2/yr 80 µg/m2/yr 160 µg/m2/yr 320 µg/m2/yr 640 µg/m2/yr C3November 2020Raleigh, NC DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Length (m): 586.39 Measurement of Cape Fear River Length at Down-River Section 1 Chemours Fayetteville Works, North Carolina Figure Notes:HFPO-DA - Hexafluoropropylene oxide dimer acid; or dimer acid; or GenX µg /m2/yr - micrograms per square meter per year HFPO-DA deposition model contours for October 2018 from ERM, 2018, Modeling Report: HFPO-DA Atmospheric Deposition and Screening Groundwater Effects. 27 April 2018. Raleigh, NC 1 0 10.5 Miles ³ Projection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US Legend Site Boundary Modeled Deposition Contours, October 2018 Scenario 40 µg/m2/yr 80 µg/m2/yr 160 µg/m2/yr 320 µg/m2/yr 640 µg/m2/yr C4November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Length (m): 564.68 Measurement of Cape Fear River Length at Down-River Section 2 Chemours Fayetteville Works, North Carolina Figure Notes:HFPO-DA - Hexafluoropropylene oxide dimer acid; or dimer acid; or GenX µg /m2/yr - micrograms per square meter per year HFPO-DA deposition model contours for October 2018 from ERM, 2018, Modeling Report: HFPO-DA Atmospheric Deposition and Screening Groundwater Effects. 27 April 2018. Raleigh, NC 1 0 10.5 Miles ³ Projection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US Legend Site Boundary Modeled Deposition Contours, October 2018 Scenario 40 µg/m2/yr 80 µg/m2/yr 160 µg/m2/yr 320 µg/m2/yr 640 µg/m2/yr C5November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 !( !( !( !( !( !( !( !(!(Cape Fear RiverSEEP-E SEEP-F SEEP-G SEEP-H SEEP-I SEEP-J SEEP-K SEEP-LSEEP-M Old Outfall 00 2 Willis Creek Georgi a B r a n c h C r e e k Figure C6Raleigh ³Path: P:\PRJ\Projects\TR0795\Database and GIS\GIS\Baseline Monitoring Workplan\TR0795_Offsite_Seep_Locations.mxd Last Revised: 7/30/2020 Author: jkasunicNovember 2020 Projection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US 1,000 0 1,000500 FeetLegend Observed Seep Nearby Tributary Site Boundary Notes:1. Seep E to M samples were collected where the seeps enteredthe Cape Fear River. Their locations on this figure have beenslightly adjusted to facilitate interpretation so that they do notappear to be in the Cape Fear River.2. The outline of Cape Fear River is approximate and is basedon open data from ArcGIS Online and North CarolinaDepartment of Environmental Quality Online GIS (MajorHydroshapefile).3. Basemap Source: Esri, DigitalGlobe, GeoEye, EarthstarGeographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN,and the GIS User Community Chemours Fayetteville Works, North Carolina Southwestern Offsite Seeps Locations DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TABLE C1 NET HOURLY HFPO-DA DEPOSITION RATE Chemours Fayetteville Works, North Carolina Geosyntec Consultants NC P.C. Air Loading (µg/m2) Air Loading (ng/m2) Time (year) Time (hour) Net Hourly Deposition Rate (ng/m2/hr) River Sections Within Air Loading Zones 40 40,000 1 8,760 4.6 Up River Section 2 Down River Section 2 80 80,000 1 8,760 9.1 Up River Section 1 Up River Section 2 Down River Section 1 Down River Section 2 160 160,000 1 8,760 18.3 Center Up River Section 1 Down River Section 1 320 320,000 1 8,760 36.5 Not used in calculations 640 640,000 1 8,760 73.1 Not used in calculations Notes: 1. HFPO-DA model values are from ERM (2018). Modeling Report: HFPO-DA Atmospheric Deposition and Screening Groundwater Effects. 27 April 2018. 2. Air deposition contours are shown in Figures J-2 through J-6. 3. Net hourly deposition rates are used in the mass discharge calculations, Table J5. Abbreviations: HFPO-DA: Hexafluoropropylene oxide dimer acid; or dimer acid. µg/m2: micrograms per meter square. ng /L: nanograms per liter. ng/m2/hr: nanograms per meter square per hour. Page 1 of 1 November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 APPENDIX D Supporting Calculations – Onsite Groundwater Pathway DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix D 1 November 2020 APPENDIX D SUPPORTING CALCULATIONS – ONSITE GROUNDWATER PATHWAY INTRODUCTION AND OBJECTIVE The objective of this appendix is to provide calculations for estimating PFAS mass loading from onsite groundwater discharge based on calculated PFAS mass flux for segments of the Black Creek Aquifer along the river frontage. Based on the conceptual site model, the Black Creek Aquifer and the Floodplain Deposits at the riverbank are the primary hydrogeologic units that are potentially in hydraulic connection with the Cape Fear River. The Cape Fear River stage is lower than the top of the Black Creek Aquifer, except during peak rainfall or flooding, indicating that the Cape Fear River is a discharge boundary for the aquifer. The Floodplain Deposits are not always in hydraulic connection with the Cape Fear River as this layer is above the water line and the Floodplain Deposits have an order of magnitude lower hydraulic conductivity. As such, the contribution of the Floodplain Deposits is a small percentage of the overall loading to the Cape Fear River. Therefore, onsite groundwater from the Black Creek Aquifer discharging to the Cape Fear River is considered the potential pathway for per- and polyfluoroalkyl substances (PFAS) mass loading to the Cape Fear River. This pathway was identified as Transport Pathway Number 5 in the PFAS mass loading model. APPROACH The PFAS mass loading from onsite groundwater discharge will be estimated as follows: 1. The Cape Fear River frontage will be divided into 8 segments (Figure D1). Each segment includes at least one groundwater monitoring well that is considered representative of the Black Creek Aquifer and that is included in the Corrective Action Plan (Geosyntec, 2019b). 2. The thickness of the Black Creek Aquifer (h) will be estimated for each segment based on the segment length and the cross-sectional area of the Black Creek Aquifer, as determined by the three-dimensional hydrostratigraphic model of the Site, constructed using CTech’s Earth Volumetric Studio (EVS) software (Geosyntec, 2019b): ℎ = 𝐴 𝑙 where h is the Black Creek Aquifer thickness [ft]; A is the cross-sectional area of the Black Creek Aquifer [ft2]; and l is the segment length [ft]. The EVS model output for each segment is presented in Figure D2. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix D 2 November 2020 3. The hydraulic gradient (i) will be derived based on the groundwater level contour map. For each segment, the gradient will be estimated based on the distance between contour lines in the vicinity of the river frontage: 𝑖= 𝛥ℎ 𝑑 where i is the hydraulic gradient [ft/ft]; Δh is the head difference between two contour lines [ft]; and d is the estimated distance between the contour lines [ft]. This approach is considered to best represent the likely groundwater fluxes discharging from the Black Creek Aquifer to the Cape Fear River. Based on hydrographs from wells along the river presented in Figure D3 hydraulic gradients in the aquifer are relatively constant over time. With the exception of large changes in the river level (over ten feet), these wells respond to river level fluctuation in a subdued manner. 4. The hydraulic conductivity (K) will be estimated for each segment using the results of slug tests conducted for select monitoring wells representative of the Black Creek Aquifer. The range of slug test results for LTW-02, LTW-03, and LTW-05 will be used to determine the hydraulic conductivity of segments 3,4, and 7, respectively since these wells are located in the corresponding segments. For other segments where no slug tests are performed, the range of slug test results for the entire Black Creek Aquifer will be used to determine the hydraulic conductivity. In both cases, the minimum hydraulic conductivity and the geometric mean hydraulic conductivity will be used to calculate a range of mass flux values. Table D1 provides the results of the slug tests and the minimum and geometric mean hydraulic conductivities for each segment. 5. The total PFAS concentration for each segment will be determined based on grab samples collected from monitoring wells within a given monitoring period. For segments with two wells, the average PFAS concentration will be used. 6. Mass flux for each segment, representing the PFAS mass loading to the river from groundwater, will be determined as follows: 𝑄=𝑙ℎ𝐾𝑖𝐶𝑓 where Q is the mass flux [mg/s]; l is the segment length [ft]; h is the Black Creek Aquifer thickness [ft]; K is the hydraulic conductivity of the aquifer [ft/s]; DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix D 3 November 2020 i is the hydraulic gradient [ft/ft]; C is the total PFAS concentration [ng/L]; and f is the conversion factor between cubic feet and liters and between ng and mg. 7. The total mass flux for the groundwater pathway will be calculated as the sum of the individual mass flux results for the 8 segments. SENSITIVITY For purposes of comparison, the mass discharge from the Floodplain Deposits was estimated using the same method that was used to estimate the mass discharge from the Black Creek Aquifer. Using data from the Q2 2020 sampling event (Geosyntec, 2020), the mass discharge from the Floodplain Deposits and the Black Creek Aquifer were estimated to be 0.06 mg/sec and 3.9 mg/sec, respectively. Therefore, the mass discharge from the Floodplain Deposits was 1.5% of the mass discharge from the Black Creek and 0.3% of the total modeled mass discharge, which suggests that the mass discharge from the Floodplain Deposits does not meaningfully impact the results of the mass loading model. The groundwater discharge from the Floodplain Deposits to the Cape Fear River will continue to be evaluated on an annual basis as part of an overall model sensitivity analysis. Further, the groundwater remedy at the Site will reduce both the mass discharge from both the floodplain deposits and the black creek aquifer as the floodplain deposits are both downgradient of the black creek aquifer and hydraulically connected to the black creek aquifer. POTENTIAL FUTURE METHODOLOGY MODIFCATIONS Periodically, adjustments to this calculation methodology may be required based on changes in conditions or refinement of Site knowledge. REFERENCES Geosyntec, 2019. Corrective Action Plan. Chemours Fayetteville Works. December 2019. Geosyntec, 2020. Cape Fear River PFAS Mass Loading Assessment – Second Quarter 2020 Report. Chemours Fayetteville Works. September 2020. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 PPPPPPPPPPPPPPPP !'A !'A !'A !'A !'A !'A !'A !'A !'A !'A CapeFear RiverSeep D Old Outfall 002 Seep C Seep B Seep A Willis Creek PIW-1D LTW-03 PIW-1S PIW-7S LTW-02 LTW-05 PIW-7D PW-11 PZ-22 PIW-3D Segment 1 Segment 2 Segment 3 Segment 4 Segment 5 Segment 6 Segment 7 Segment 8 ³Path: P:\PRJ\Projects\TR0795\Database and GIS\GIS\Baseline Monitoring Workplan\TR0795_Black CreekAquiferSegmentsforGroundwaterPathway.mxd Last Revised: 7/29/2020 Author: jkasunicProjection: NAD 1983 StatePlane North Carolina FIPS 3200 Feet; Units in Foot US Black Creek Aquifer Segmentsfor Groundwater Pathway Chemours Fayetteville Works, North Carolina Figure D1RaleighNovember 2020 1,000 0 1,000500 Feet Notes: 1. Due to the scale of the map, pairs of wells that are in close proximity have been offset for visibility. Therefore, the placement of these wells on this map do not reflect their true geographic coordinates.2. The outline of Cape Fear River is approximate and is based on open data from ArcGIS Online and North Carolina Department of Environmental QualityOnline GIS.3. Basemap source: Esri, DigitalGlobe, GeoEye, Earthstar Geographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN, and the GIS User Community. Legend !'A Surficial Aquifer !'A Floodplain Deposits !'A Black Creek Aquifer Observed Seep Nearby Tributary Site Boundary Transect Line 0.5 0 0.50.25 Miles ³ DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 FigureD2Cross-Sections Along Cape Fear River Transect LineChemours Fayetteville Works, North CarolinaRaleighNovember 2020Elevation (feet NAVD88)50403020100PIW-1S/D-1002505007501,000Elevation (feet NAVD88)50403020100-100250500750PIW-3DLTW-01Elevation (feet NAVD88)50403020100-100250500750LTW-02Segment 1Elevation (feet NAVD88)50403020100-100250500750LTW-03Elevation (feet NAVD88)50403020100-100250500LTW-04PZ-22Elevation (feet NAVD88)50403020100-100250500PIW7S/DElevation (feet NAVD88)50403020100-100250500750Elevation (feet NAVD88)50403020100PW-11-1002505007501,000 1,2501,5001,7502,000Segment 2Segment 3Segment 4Segment 5Segment 6Segment 7Segment 8Units(2)Floodplain DepositsBlack Creek Confining UnitBlack Creek AquiferUpper Cape Fear Confining UnitLegendWell screen(1)Notes:NAVD88 – feet North America Datum of 1988 Vertical Exaggeration = 10x1. Wells are projected onto the cross-section.Segment 1Segment 3Segment 2Segment 4Segment 5Segment 6Segment 7Segment 8Distance Along Transect Line (feet)Distance Along Transect Line (feet)Distance Along Transect Line (feet)Distance Along Transect Line (feet)Distance Along Transect Line (feet) Distance Along Transect Line (feet)Distance Along Transect Line (feet)Distance Along Transect Line (feet)NorthSouthNorthSouthNorthSouthNorthSouthNorthSouthNorthSouthNorthSouthLTW-05NorthSouthCape Fear RiverDocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 \\projectsitesb.geosyntec.com@SSL\DavWWWRoot\5\FWConsentOrder\Shared Documents\34 - P16 Quarterly Reports\2020 Q1\Report\Appendices\Appendix H - Onsite Groundwater Gradients\[Figure H-4 - Hydrographs.xlsx]FigureH4Hydrograph for Select Onsite Groundwater Monitoring Wells and W.O Huske Dam Chemours Fayetteville Works, North Carolina Figure D3 Raleigh November 2020 0 10 20 30 40 50 60 0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 27-Nov-201828-Dec-201828-Jan-201928-Feb-201931-Mar-20191-May-20191-Jun-20192-Jul-20192-Aug-20192-Sep-20193-Oct-20193-Nov-20194-Dec-20194-Jan-20204-Feb-20206-Mar-20206-Apr-20207-May-20207-Jun-2020W.O Huske Dam River Elevation (ft NAVD88)Groundwater Elevation (ft NAVD88)Date LTW-01 LTW-02 LTW-05 PIW-1D PIW-2D PIW-3D PIW-4D PIW-7D PIW-7S PIW-8D W.O. Huske Dam Notes: ft - feet NAVD88 - North American Vertical Datum of 1988 NAVD88 - North American Vertical Datum of 1988 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TABLE D1 HYDRAULIC CONDUCTIVITY RESULTS Chemours Fayetteville Works, North Carolina Geosyntec Consultants of NC P.C. Segment Well Slug Test Observed Hydraulic Conductivity (ft/sec) Minimum Hydraulic Conductivity (ft/sec) Geometric Mean Hydraulic Conductivity (ft/sec) --BCA-01 T1 2.1E-04 2.1E-04 2.8E-04 T1*3.7E-04 T2 2.2E-04 T2*3.7E-04 T3 2.1E-04 T3*3.6E-04 T4 2.2E-04 T4*3.9E-04 --BCA-02 T1 4.6E-04 3.1E-04 5.4E-04 T1*1.0E-03 T2 4.2E-04 T2*9.1E-04 T3 3.4E-04 T3*7.4E-04 T4 3.3E-04 T4*7.4E-04 T5 3.1E-04 T5*6.8E-04 --BCA-04 T1 1.1E-03 1.1E-03 1.4E-03 T1*1.6E-03 T2 1.1E-03 T2*1.7E-03 T3 1.1E-03 T3*1.6E-03 T4 1.1E-03 T4*1.7E-03 T5 1.2E-03 T5*2.3E-03 3 LTW-02 T1 3.0E-04 3.0E-04 4.0E-04 T1*4.8E-04 T2 3.2E-04 T2*4.9E-04 T3 3.1E-04 T3*4.7E-04 T4 3.9E-04 T4*5.5E-04 T5 3.0E-04 T5*4.5E-04 4 LTW-03 T1 6.5E-05 2.00E-05 4.6E-05 T2 2.4E-05 T3 2.6E-05 T4 2.6E-04 T5 2.0E-05 7 LTW-05 T1 2.4E-05 1.8E-05 4.8E-05 T1*8.0E-05 T2 1.8E-05 T2*3.5E-05 T4 7.4E-05 T4*1.3E-04 Remaining Segments (1, 2, 5, 6, and 8) All BCA Wells ----1.8E-05 3.2E-04 Notes * - Screen length used for aquifer thickness BCA - Black Creek Aquifer ft/sec - feet per second TR0795 Page 1 of 1 November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 APPENDIX E Supporting Calculations –Adjacent and Downstream Offsite Groundwater DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix E 1 November 2020 APPENDIX E ADJACENT AND DOWNSTREAM OFFSITE GROUNDWATER This appendix presents the methodology for calculating the PFAS mass discharge from adjacent and downstream offsite groundwater to the Cape Fear River. PFAS detected in offsite groundwater originate from aerial deposition which has occurred in all directions from the Site (CAP Geosyntec, 2019g). These aerially deposited PFAS have subsequently infiltrated to groundwater and migrate towards the Cape Fear River where they lead to upstream, adjacent and downstream offsite groundwater PFAS mass. The upstream offsite groundwater mass discharge is estimated relatively simply by using measured river flows and concentrations at River Mile 76 upstream of the Site. Here, only the upstream offsite groundwater mass discharge is present in the river at this location. Conversely, the adjacent and downstream offsite groundwater PFAS mass discharge is difficult to measure directly since many Table 3+ PFAS mass discharges from all other pathways are present in the river where these offsite groundwater contributions join the river. Additionally, downstream offsite groundwater has a relatively small component of the Total PFAS mass discharge making its additional contributions to the total discharge difficult to distinguish from other discharges already present. Therefore, since PFAS mass discharge from offsite groundwater upstream, adjacent, and downstream of the Site follow the same dynamics (deposition, infiltration, migration, discharge) the adjacent and downstream PFAS mass discharge is scaled from the upstream offsite groundwater mass discharge estimate. The downstream offsite groundwater loadings are scaled to the upstream offsite groundwater loadings based on the length of river adjacent and downstream of the Site known to be in contact with offsite groundwater containing PFAS compared to the length of the river upstream also in contact with offsite groundwater containing PFAS. The volume of river flow is assumed to be constant immediately upstream and downstream of the Site for the purposes of this calculation. This adjacent and downstream offsite mass discharge will be calculated using Equation 1 below: Equation 1: Total PFAS Mass Discharge Adjacent and Downstream Offsite Groundwater 𝑀𝐷௔ௗ௝ିௗି௚௪ = ෍൫𝐶௨௣ି௚௪,௜ × 𝑄஼ிோ൯ × 𝑓௔ௗ௝ିௗ ூ ௜ୀଵ where, 𝑀𝐷௔ௗ௝ିௗି௚௪ = represents the Total PFAS discharge from adjacent and downstream offsite groundwater to the Cape Fear River, units in mass per unit volume [ML-3], typically milligram per second; i = represents each of the PFAS constituents listed in Table 1; DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix E 2 November 2020 I = represents total number of PFAS constituents included in the summation of Total PFAS concentrations, e.g., 12 constituents listed in Table 1; 𝐶௨௣ି௚௪,௜ = represents the upstream concentration of each PFAS constituent i from measured units in mass per unit volume [ML-3], typically nanograms per liter; 𝑄஼ிோ = represents the volumetric flow in the Cape Fear River as reported by the United States Geological Survey gage at the W.O. Huske Dam, station ID 02105500 with units used in the equation expressed as volume per time [L3T-1], typically liters per second; and 𝑓௔ௗ௝ିௗ = represents the unitless scaling factor to adjust offsite upstream groundwater mass discharge to offsite adjacent and downstream mass discharge. Where 𝑓௨௣ି௔ௗ௝ିௗ is calculated following Equation 2 below: Equation 2: Offsite Upstream Groundwater to Adjacent and Downstream Offsite Groundwater Mass Discharge Scaling Factor 𝑓௔ௗ௝ିௗ = 𝑙஼ிோି௔ + 2𝑙஼ிோିௗ 2𝑙஼ிோି௨௣ where, 𝑙஼ிோି௔ௗ௝ = represents the length of the Cape Fear River adjacent to the Site (i.e., the east bank of the Cape Fear River opposite the Site) where PFAS have been detected in offsite groundwater within one mile of the river. 2𝑙஼ிோିௗ = represents the length of the Cape Fear River downstream of the Site where PFAS have been detected in offsite groundwater within one mile of the river. This quantity is multiplied by two (2) as the river has two downstream sides (east and west) from which groundwater discharge can reach the Cape Fear River (adjacent only has one side, east). 2𝑙஼ிோି௨ = represents the length of the Cape Fear River upstream of the Site where PFAS have been detected in offsite groundwater within one mile of the river. This quantity is multiplied by two (2) as the river has two upstream sides (east and west) from which groundwater discharge can reach the Cape Fear River (adjacent only has one side, east). Figure E1 displays the quantities used in calculating the scaling factor 𝑓𝑎𝑑𝑗−𝑑 on a map of the Cape Fear River and Table E1 provides a calculation of 𝑓𝑎𝑑𝑗−𝑑. Sensitivity Assessment A potential alternative scaling factor for adjacent and downstream offsite groundwater loadings is using land area instead of river length. The land area upstream, adjacent and downstream of the Site would be estimated using the extent of detections in offsite residential wells (Figure E1). However, using land areas adds additional complications because it is unclear how the distance of land from the river should be considered in the land area calculation; land further away will not have the same contribution effect. To compare the two scaling factor approaches (length versus DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 Appendix E 3 November 2020 area), the two scaling factors were calculated and yielded roughly similar scaling factors of 0.38 and 0.55 for the river length and land area methods, respectively. This alternative scaling method will be evaluated on an annual basis as part of an overall model sensitivity analysis. DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 !5 !5 !5 ChemoursFayettevilleWorks Tar Heel Ferry Road Bridge CFR-BLADEN Mile 76 4.5 Miles Downstream of Old Outfall 14.2 Miles Upstream of Site 1.6 Miles Adjacent of Site Estimated Extents of Offsite Groundwater Contributions to Cape Fear River PFAS Mass Loads Chemours Fayetteville Works, North Carolina Figure E1Raleigh Path: P:\PRJ\Projects\TR0795\Database and GIS\GIS\Baseline Monitoring Workplan\TR0795_1MileResidentialDetects.mxd; jkasunic; 07/27/2020November 2020 ³ 2 0 21 Miles Notes:Basemap sources: Esri, DigitalGlobe, GeoEye, Earthstar Geographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN, and the GIS User Community. Projection: WGS 1984 Web Mercator Auxiliary Sphere; Units in Meter Legend Offsite Groundwater Sampling Location with Detected Result !5 Selected Prior Cape Fear River Sampling Locations Detected Results within 1 mile of Cape Fear River Chemours Fayetteville Works Cape Fear River DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029 TABLE E1 ADJACENT AND DOWNSTREAM OFFSITE GROUNDWATER MASS DISCHARGE SCALING FACTOR Chemours Fayetteville Works, North Carolina Geosyntec Consultants of NC, PC Item Value Unit 𝑙_(𝐶𝐹𝑅−𝑢𝑝) 14.2 miles 𝑙_(𝐶𝐹𝑅−𝑎𝑑𝑗) 1.7 miles 𝑙_(𝐶𝐹𝑅−𝑑) 4.5 miles 𝑓_(a𝑑𝑗−𝑑) 0.38 -- Calculation Notes for Offsite Upstream Groundwater to Adjacent and Downstream Offsite Groundwater Mass Discharge Scaling Factor 𝑓௔ௗ௝ିௗ = 𝑙஼ிோି௔ௗ௝ + 2𝑙஼ிோିௗ 2𝑙஼ிோି௨௣ where, 𝑓௔ௗ௝ିௗ =represents the unitless scaling factor to adjust offsite upstream groundwater mass discharge to adjacent and downstream offsite groundwater mass discharge. 𝑙஼ிோି௔ = represents the length of the Cape Fear River adjacent to the Site (i.e. the east bank of the Cape Fear River opposite the Site) where PFAS have been detected in offsite groundwater within one mile of the river. 2𝑙஼ிோିௗ = represents the length of the Cape Fear River downstream of the Site where PFAS have been detected in offsite groundwater within one mile of the river. This quantity is multiplied by two (2) as the river has two downstream sides (east and west) from which groundwater discharge can reach the Cape Fear River (adjacent only has one side, east). 2𝑙஼ிோି = represents the length of the Cape Fear River upstream of the Site where PFAS have been detected in offsite groundwater within one mile of the river. This quantity is multiplied by two (2) as the river has two upstream sides (east and west) from which groundwater discharge can reach the Cape Fear River (adjacent only has one side, east). Page 1 of 1 November 2020 DocuSign Envelope ID: 5786C4B4-CBA2-41C7-8849-31F176D22029