Loading...
The URL can be used to link to this page
Your browser does not support the video tag.
Home
My WebLink
About
NC0039586_Corrective Action Plan_20190829
1, 4., DUKE Tanya M.Hamilton Vice President ENERGY Harris Nuclear Plant 5413 Shearon Harris Rd New Hill, NC 27562-9300 AUG 2 9 2019 Serial: RA-19-0348 Certified Mail Number: 7014 2120 0003 3196 5770 RECEIVED/NQ/DWR Return Receipt Requested SEP 0 3 2019 Ms. Linda Culpepper, Director WaterQuali NC DEQ Division of Water Resources Permitting Section 1617 Mail Service Center Raleigh, NC 27699-1617 Subject: Duke Energy Progress, LLC - Shearon Harris Nuclear Power Plant (HNP) NPDES Permit No. NC0039586 Part I (A)(9) - Schedule of Compliance (Outfall 006), Wake County Dear Ms. Culpepper: On August 29, 2016, NC DEQ DWR issued NPDES Permit NC0039586 with an effective date of September 1, 2016. Contained within this permit were new effluent limit requirements for copper and zinc for Outfall 006 (Combined Outfall for Internal Outfalls 001-005) serving HNP. Part I (A)(9)1 of the permit requires Duke Energy Progress, LLC (Duke Energy), submit to the Division of Water Resources a Corrective Action Plan (CAP) which summarizes the actions to be taken to achieve the total copper and total zinc limits at Outfall 006 and a schedule of actions to be taken to implement the plan. The CAP was submitted to the Division on September 1, 2017. Part I (A)(9)2 requires and annual report summarizing activities in Year 2 of the permit and the Year 2 report was submitted on August 27, 2018. This Year 3 report is being submitted in accordance with Part I (A)(9)3 of the permit which requires reporting to the Division summarizing actions taken in accordance with the CAP. As described in the attached report, we have conducted a Water Effect Ratio Study for copper, met with DWR staff and received comments. DWR staff have requested further dilution studies and additional WER testing and Duke Energy will work out detailed approaches to these studies with DWR staff as we move forward to address these comments. Duke Energy will be contacting DWR permitting staff future to set up a meeting to review and discuss these comments and our path forward. If you have any questions regarding this matter or wish to discuss in further detail, please do not hesitate to contact Mr. Bob Wilson, HNP Site Environmental Professional, at(919) 362-2444. Division of Water Resources Serial: RA-19-0348 / Page 12 l certify, under penalty of law, that this document and all attachments were prepared under my direction or supervision in accordance with a system designed to assure that qualified personnel properly gather and evaluate the information submitted. Based on my inquiry of the person or persons who manage the system, or those persons directly responsible for gathering the information, the information submitted is, to the best of my knowledge and belief, true, accurate, and complete. l am aware that there are significant penalties for submitting false information, including the possibility of fines and imprisonment for knowing violations. Sincerely, v) trK - Tanya M. Hamilton Enclosure: Technical Memorandum — NC0039586 Compliance Update Water Effect Ratio (WER) Study— Copper Report Reasonable Potential Analysis — Spreadsheet Calculations cc: Ms. Julie Grzyb, Supervisor, NPDES Complex Permitting Supervisor, Certified Mail Number: 7014 2120 0003 3196 5787 Mr. Rick Bolich, Interim Water Resources Regional Supervisor, NC DEQ DWR Raleigh Regional Office Certified Mail Number: 7014 2120 0003 3196 5794 Ms. Cyndi Karoly, Chief, Water Sciences Section, NC DEQ DWR Certified Mail Number: 7014 2120 0003 3196 5800 NC DEQ DWR Central Files Certified Mail Number: 7014 2120 0003 3196 5817 Division of Water Resources Serial: RA-19-0348 Enclosure Harris Nuclear Plant and Harris Energy and Environmental Center NPDES Permit Number NC0039586 Technical Memorandum — NC0039586 Compliance Update (167 pages including cover) I � Final Technical Memorandum Corrective Action Plan for Copper and Zinc for Harris Nuclear Plant NPDES Permit Year 3 Activities Report RECE VED/NCDEQ/DWR SEP 0 3 2019 Water Quality Permitting Section Prepared for Duke Energy Progress, LLC Shearon Harris Nuclear Plant NPDES Permit No. NC0039586 August 2019 CARQ�� . t1.:Q�0FES3lp�:9 • JACOBS R,,,,,,,,,,, CH2M HILL North Carolina, Inc. 111 Corning Rd, Suite 116 Cary, NC 27518 TECHNICAL MEMORANDUM JACOBS Corrective Action Plan for Copper and Zinc for Harris Nuclear Plant NPDES Permit — Year 3 Activities Report RECEIVED/NCDEQ/DWR PREPARED FOR: Shearon Harris Nuclear Plant(HNP) Duke Energy-Progress LLC(Duke Energy) SEP 0 3 2019 COPY TO: Bob Wilson/Duke Energy-HNP Don Safrit, PE/Duke Energy Water Quality Permitting Section PREPARED BY: Jennifer Bell, PE/CH2M HILL North Carolina, Inc. (Jacobs) DATE: August 19, 2019 REVISION NO.: Version 01- Final Executive Summary The 2016 National Pollutant Discharge Elimination System (NPDES) permit for the Shearon Harris Nuclear Plant(HNP) included effluent limits—effective September 30, 2021—for copper and zinc for Outfall 006 and a compliance schedule requiring development of a Corrective Action Plan (CAP) and reports on annual progress towards compliance through September 1, 2020.The CAP was submitted on September 1, 2017 (Year 1 of the permit) and the Year 2 Report was submitted to North Carolina Division of Water Resources (DWR) on August 27, 2018. Year 3 activities proposed in the Year 2 Report included: 1)continued characterization efforts, 2)completion of a Water Effect Ratio(WER)study, 3)meeting with DWR to discuss the WER study, and 4)potential initiation of a mixing zone study. All activities have been accomplished except for initiation of a mixing zone study,which is proposed for completion in Year 4.Table ES-1 below summarizes activities completed in Years 1-3, as well as proposed activities for Year 4. Table ES-1.Summary of Compliance Activities for NPDES Permit Years 1-4 Year 1 Activities Year 2 Activities Year 3 Activities Year 4 Activities-Proposed (9/1/16-8/31/17) (9/1/17-8/31/18) (9/1/18-8/31/19) (9/1/19-8/31/20) • CAP Development • Effluent • Completion of WER • DWR Meetings • Effluent Characterization, Study • Dilution studies using a Characterization Continued • DWR Meetings mixing zone model • WER Study • Effluent Characterization, • Additional WER testing, • Water Chemistry Continued as needed Management • Water Chemistry • Effluent Characterization, Management, Continued Continued • Water Chemistry Management, Continued On June 5, 2019, Duke Energy representatives met with DWR to discuss the results of the effluent characterization results and WER study for copper submitted on May 5, 2019.The report indicated that water chemistry management activities had reduced zinc levels so that compliance was no longer an issue at the limits included in the current NPDES permit or at recalculated limits based on effluent CH2M HILL NORTH CAROLINA,INC. 1 CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT-YEAR 3 ACTIVITIES REPORT hardness. Copper compliance could be attained if the permit limits were adjusted based on the effluent characterization of hardness and the final WER developed through the study. DWR provided comments on the WER Study on July 16, 2019 requesting that a dilution study be conducted, as well as additional WER testing. Based on this feedback and discussions from June 5tn Duke Energy anticipates Year 4 activities to include: • Planning efforts and meeting with DWR on detailed approaches and procedures for dilution studies and additional WER testing • Dilution studies involving use of a mixing zone model • Additional WER testing, if necessary • Further meetings with DWR to discuss results and determine a path forward to NPDES permit compliance Year 3 CAP Activities Report The purpose of this report is to present to DWR the actions that have be taken by HNP in accordance with the CAP submitted September 1, 2017, and the Year 2 Report submitted on August 27, 2018,to achieve compliance with effluent limitations for copper and zinc for discharge through Outfall 006, as included in NPDES Permit NC0039586.The requirement for yearly progress reports is included in Part I(A)(9)of the NPDES Permit. Background The NPDES Permit issued to HNP,effective September 1, 2016, includes limits for total recoverable copper and total recoverable zinc from Outfall 006 based on dissolved copper and zinc criteria that were calculated using default a hardness concentration of 25 milligrams per liter(mg/L) as calcium carbonate (CaCO3)and default WER of 1 due to a lack of historical data available for Outfall 006 discharges when the permit was developed. Table 1.Total recoverable copper and zinc limits included in HNP NPDES Permit issued September 1,2016 Metal Monthly Average Limit Daily Maximum Limit Copper 7.9 p.g/L 10.5 µg/L Zinc 126 µg/L 126 µg/L The 2016 permit included a schedule of compliance for the effluent limits for copper and zinc,as specified in Part I(A)(9).The schedule includes the following milestones: 1. Within 1 year from the effective day of the permit,the permittee will submit to DWR a CAP summarizing the actions to be taken to achieve compliance with the total copper and total zinc limits at Outfall 006 and a schedule of activities to implement the plan.The CAP may include mixing zone studies and site-specific studies. Methods for conducting site-specific studies must be approved by DWR. 2. Within 2 years from the effective date of the permit,submit a report to DWR summarizing actions taken in accordance with the CAP. 3. Within 3 years from the effective date of the permit, submit a report to DWR summarizing actions taken in accordance with the CAP. 2 CH2M HILL NORTH CAROLINA,INC. CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT-YEAR 3 ACTIVITIES REPORT 4. Within 4 years from the effective date of the permit, submit a report to DWR summarizing actions taken in accordance with the CAP. 5. Achieve compliance with total copper and total zinc limits by September 30, 2021. The CAP was developed and submitted to DWR August 31, 2017; it included results of the effluent characterization that began in April 2017 and is ongoing, as well as a recommendation to complete a WER study and to evaluate potential water chemistry management options. Results of the ongoing effluent characterization are summarized in this report as well as continuing water chemistry management activities.The WER study was completed in early 2019 and submitted to DWR on May 5, 2019. A meeting was held with DWR on June 5, 2019 and comments were received on July 16 requesting additional studies. Planned Year 4 activities are listed based on the comments received. Effluent Characterization and Monitoring Monthly effluent characterization efforts continue to focus on hardness,copper, and zinc. Results through June 2019 are included in Attachment 1. Hardness Characterization Effluent hardness data were collected since permit limits are based water quality criteria that vary based on hardness.They were also developed based on 100%effluent with no dilution. For the sampling period beginning in 2017 the average hardness is 43.6 mg/L as CaCO3,which is above the default value of 25 mg/L.With average effluent hardness concentration greater than the default 25 mg/L hardness used to calculate the limits in the NPDES permit, recalculation of the zinc and copper limits is appropriate. Potential limits are shown below. Table 2.Current vs.Potential Recalculated Limits based on Site-specific Effluent Hardness data Current NPDES Limits Potential Recalculated Limits Monthly Average Daily Maximum Monthly Average Daily Maximum Copper 7.9 µg/L 10.5 µg/L 12.7 µg/L 17.7 µg/L Zinc 126 µg/L 126 µg/L 203 µg/L 201 µg/L Zinc Concentrations Zinc concentrations during this period did not exceed the monthly average or daily maximum limits (both 126 µg/L) as defined in the NPDES permit as written. If the median effluent hardness from 2017 to 2019 is considered when calculating the dissolved water quality criteria, a limit of 201 µg/L zinc would be appropriate. Under current operational procedures, HNP will remain in compliance with either the current or recalculated zinc limits. HNP is continues to achieve compliance with zinc limits as a result of the facility eliminating use of a zinc-based corrosion inhibitor in its cooling tower. Copper Concentrations Copper concentrations during the characterization and monitoring period exceeded the limits, both current and recalculated based on effluent hardness.The current daily maximum limit (10.5 µg/L) was exceeded on 49 of 76 sampling days and the recalculated daily maximum limit (17.7 µg/L)on 26 of these days (see Attachment 1, Figure 3). Since mid-November 2018,the current daily maximum was exceeded on 3 of 23 sampling days and the recalculated daily maximum limit was exceeded only once. Monthly average concentrations exceeded the current monthly average limit(7.9 µg/L) in 24 of 28 months during the characterization and monitoring and exceeded the recalculated monthly average limit(12.7 µg/L) in 19 of those months(see Attachment 1, Figure 4). Starting from December 2018,the current monthly CH2M HILL NORTH CAROLINA,INC. 3 CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT-YEAR 3 ACTIVITIES REPORT average limit was exceeded in 4 of those months, and the recalculated copper limit was exceeded in 2 of those months. HNP has continued water chemistry evaluations to determine if there are ways of minimizing copper in the effluent,as recommended in the CAP as well as proceeding with a WER study for copper. Water Chemistry Management In addition to the WER study,water chemistry management within the facilities at HNP are being considered as a complimentary means of achieving compliance. One of the reasons that compliance with the zinc effluent limits is no longer an issue is because of the use of an alternative anticorrosion agent that does not include zinc. Use of this alternative agent began in January 2017, and zinc levels have been dramatically reduced since that time. It is believed that zinc levels that are measured in the effluent are either residual zinc in the system, corrosion of zinc from galvanized materials, and zinc that is in the lake water that is cycled up (concentrated) in the cooling process. Copper was not an initial focus of the water chemistry management efforts; HNP does not believe copper is being added from any water treatment additives. Concentration of the intake water by cooling tower cycling has been identified as a contributor to elevated levels. Corrosion of plant components that contain copper is also a potential issue. HNP has been working with chemical suppliers to evaluate the potential sources of copper and determine whether copper levels can be reduced through further management of water chemistry. The current view is that neither water chemicals nor system corrosion are significant sources of copper in the Outfall 006 discharge. Rather, it is believed that observed copper levels, which predominantly between 10 µg/L and 30 µg/L(with a few results above this up to a maximum of 47 µg/L) and are primarily a result of cooling tower cycling up of lake levels of copper. Beginning in mid-November 2018 all samples fell within a range of 5 µg/L to 20 µg/L. The 2017 Environmental Monitoring Report(Duke Energy, 2018)submitted to DWR in December 2018 showed that lake levels for total copper averaged less than 1.0 ug/L at all stations and that maximum values were 1.1 to 1.3 ug/L.These values are all below the dissolved criterion for copper of 2.7 ug/L based on a hardness of 25 ug/L.Average lake hardness in 2017 ranged from 22 to 26 ug/L at the lake stations. WER Study A WER study was completed from July through September 2018 with three rounds using a primary species (Ceriodaphnia dubia) and a fourth round using a secondary species(Pimephales promelas)for both total recoverable and dissolved copper according to the US EPA's Interim Guidance on Determination and Use of Water Effect Ratios for Metals(EPA, 1994).A copy of the submittal to DWR is included as Attachment 2. The North Carolina Water Quality Standard for copper is based on dissolved copper, although WER values were determined both for dissolved and total recoverable copper.The final WER for dissolved copper(fWER=4.9996)was applied when calculating potential water quality criteria and effluent limits. Additionally,the fWER for total recoverable copper(5.9789) was found to be higher than the dissolved fWER, so use of the dissolved fWER is appropriately conservative. DWR Meeting and Comment Letter Duke Energy met with DWR on June 5, 2019,to discuss the results of the WER.A meeting summary and presentation materials are included as Attachment 3. Copper was the focus of the conversation. Discussion centered on the type of WER completed and the application of both a WER and site-specific hardness values into the limit calculation.All WER tests were Type 1 tests conducted using 100% 4 CH2M HILL NORTH CAROLINA,INC. CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT—YEAR 3 ACTIVITIES REPORT effluent and, as such,the resulting final WER was determined using the lowest WER calculated from the three tests and represents a 'worst case scenario.' Including a Type 2 test in the calculation of the WER would likely result in a higher value than currently calculated. There was also some discussion of the use of the secondary test results and when they confirmed the primary tests. DWR pointed out that the interim guidance indicated that the ratio of WER values from secondary and primary tests should be 3 based on the EPA Interim Guidance and some of the ratios exceeded this value(EPA, 1994). Review of this issue indicated that the ratio of the WER values for primary and secondary species tests should not exceed 3 for simultaneous tests. In that comparison,the ratio was 8.20(Ceriodaphnia WER)/2.66 (Fish WER) =3.08. A value of 3.08 is statistically equivalent to 3, and therefore does not exceed the recommended value. Also,the ratio of the fish WER to the fWER (about 5) is less than 2. During discussion of the application of the WER and hardness results, DWR indicated that some type of mixing zone analysis may be necessary. DWR provided a July 10, 2019 letter response to the items discussed at the meeting, also included in Attachment 3.This substance of this letter is as follows: • DWR requests that a dye dispersion study or dilution model study be conducted so that the WER Study can be conducted in accordance with Appendix F of the EPA Interim Guidance for flowing- water situations • DWR requested that the primary species used for the WER study be fathead minnows since this provides more conservative results than the primary species used in the 2018 tests. • DWR also noted that Appendix A of the EPA Interim Guidance (EPA, 1994)allowed WER values to consider dilution provided in the mixing zone but this dilution could not be considered for the criteria Duke Energy has developed planned Year 4 activities based on these comments and will work with DWR to assure there is a consensus before proceeding with activities.We do believe the request to use fathead minnows as the primary species is inconsistent with the EPA Interim Guidance (page 147)to use an appropriate sensitive species(EPA, 1994). Ceriodaphnia dubia is the 2nd most sensitive species in the list of species mean acute values (SMAV) in the 2007 EPA Copper Criteria Document(EPA, 2007). Fathead minnows (Pimephales promelas) is 19`h in the list with an LC/EC50 value, more than 10 times that of Ceriodaphnia.This was also reflected in our tests, where the LC50 values for Ceriodaphnia(in lab water) ranged from 10 to 23 µg/L and for fathead minnows was about 170 µg/L.While it provides a lower WER value, fathead minnows do not qualify as a sensitive species. Bob Kelley with ETT discussed the use of fathead minnows with Joel Hansel of EPA Region 4 on July 26, 2019. He is aware of only one case in Region IV where fathead minnows were used as a primary species for WER testing and did not remember which pollutant was evaluated.This issue will be resolved with DWR during plan development and discussions for Year 4 activities discussed below. Year 4 Activities In addition to continued water chemistry management efforts, Duke Energy anticipates Year 4 activities to include continued WER studies and dilution studies.These planning efforts will be coordinated with DWR to ensure consensus before progressing.These Year 4 actions are to include: • Planning efforts and meeting with DWR on detailed approaches and procedures for dilution studies and additional WER testing • Dilution studies involving use of a mixing zone model (based on mixing zone study results) CH2M HILL NORTH CAROLINA,INC. 5 CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT-YEAR 3 ACTIVITIES REPORT • Additional WER testing if necessary • Further meetings with DWR to discuss results and determine a path forward to permit compliance Duke Energy is continuing on the path for NPDES permit compliance for Outfall 006 and is actively planning for Year 4 efforts as part of that progress. References U.S. Environmental Protection Agency(EPA). 1994. Interim Guidance on Determination and Use of Water-Effect Ratios for Metals.Washington, DC: Office of Water,Office of Science and Technology. U.S. Environmental Protection Agency(EPA). 2007.Ambient Water Quality Criteria for Copper—2007 Revision.Washington, DC:Office of Water, Office of Science and Technology. 6 CH2M HILL NORTH CAROLINA,INC. Attachment 1 Results of Ongoing Effluent Characterization Efforts CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT-YEAR 3 ACTIVITIES REPORT This page is intentionally left blank. CH2M HILL NORTH CAROLINA,INC. CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT-YEAR 3 ACTIVITIES REPORT • 006 Effluent -006 Effluent Average(43.6 mg/L) 70 60 • $ • 50 I • • •• • • • • • 40 • • IN • NOS• �•• U, 2 30 • = 20 • 10 0 r p1 `rri i `9 � s. i� �p1‹ i'1/ i1�� � i6� i6 is% ��� 1i cp cp cpNpNp jNpcp c0, 1j 1> 1j 01, 1 1cp 16, 16, 16, 04 19 19 19 19 Figure 1.Outfall 006 effluent hardness observed during the effluent characterization and continued monitoring showing the overall average of the data. Limit(at default 25 mg/L hardness) -----Limit(at 43.6 mg/L hardness) • 006 Effluent 250 200 150 c 100 • • • N •• • 50 • • • 0 1104k11.401 ~1 •. $ in,. Me•'••w Iftsegybig i ri i 9i 11 ji `i Si i `2- 1.l 1i a'i `:i -i 1, '�p �'p_� 1�p i 1� 1 16��p �s��p ��,�-p ii� �1_�p 1cp 1 1p_�p 1, 1j 1j 01, Id, Id) 1d, 16) Id) 01cp 79 19 19 19 Figure 2.Outfall 006 effluent zinc observed during the effluent characterization and continued monitoring compared to current and recalculated limits. CH2M HILL NORTH CAROLINA,INC. CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT—YEAR 3 ACTIVITIES REPORT Daily Max Limit(at default 25 mg/L hardness) -----Limit,Ac.(at 43.6 mg/L hardness) • 006 Effluent-Daily Value 50 45 0 • 40 • 0 0 J 35 0 = 30 0 0 0 p a`, Z5 000 pO 0 O� 0 O 0 20 ----•—� ••----� 0 O4 4 15 i®l.,• 0 �t•' ,Q 0 0 e 8 -o__-16 ti6 Gb 5 �` 0 --- s, `ri i 9i 11 'li �'i si i `5i 1,i 1i `ci `ri 1--,3si1i �Oi �8i -2j 76' 2)i CS" `�`S' T),.? 1.) cl1 ')i `)11 20i 1j 1- 1> 01, 1� 1� 1CP 1CP 1d, 018 19 19 19 1y Figure 3.Outfall 006 effluent copper observed during the effluent characterization and continued monitoring compared to current daily maximum and recalculated acute limits. Monthly Ave Limit(at default 25 mg/L hardness) -----Limit,Chr.(at 43.6 mg/L hardness) • 006 Effluent-Monthly Ave 35 30 0 0 25 • -72 6.0 20 0 0 0 0 0 a 15 Q Q__1J • • U 10 3 O 5 ?4 9 410 �` �� -9 s O 2 O ✓d P 4 1 17 r4 .<' 1 4. O 1/ O .mod P 470 7 y 410 1 ✓4 �G d�. 'Oi� ` 7 �� Gbo �°b �'!` �L PC '� 6 d,. 'br dy '� �v Gao P.O ('l` OL Nc` � 6 dam. '�i� dy � �� '�1 jp1,1-1 jp1 Ol,�'p1 j p1').0 1.-> 1 j p1 j01�'p1,—1�plc p qed,1�01c�p1cp�p4 p1��'p1d,p1,01�pj.��19 p19�019p1,9 .2 Figure 4.Outfall 006 monthly average effluent copper observed during the effluent characterization and continued monitoring compared to current monthly average and recalculated chronic limits. CH2M HILL NORTH CAROLINA,INC. CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT-YEAR 3 ACTIVITIES REPORT Attachment 2 WER study Submittal to DWR on May 3,2019 CH2M HILL NORTH CAROLINA,INC. CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT-YEAR 3 ACTIVITIES REPORT This page is intentionally left blank. CH2M HILL NORTH CAROLINA,INC. Tanya M.Hamilton DUKE Vice President VC ENERGY Harris Nuclear Plant 5413 Shearon Harris Rd New Hill,NC 27562-9300 MAY 0 3 2019 Serial: RA-19-0161 Certified Mail Number: 7006 0100 0006 4208 4774 Return Receipt Requested Ms. Linda Culpepper, Director NC DEQ Division of Water Resources 1617 Mail Service Center Raleigh, NC 27699-1617 Subject: Duke Energy Progress, LLC - Shearon Harris Nuclear Power Plant (HNP) NPDES Permit No. NC0039586 Part I (A)(9) - Schedule of Compliance (Outfall 006), Wake County Dear Ms. Culpepper: On August 29, 2016, NC Department of Environmental Quality (NC DEQ) Division of Water Resources (DWR) issued NPDES Permit NC0039586 with an effective date of September 1, 2016. Contained within this permit were new effluent limit requirements for copper and zinc for Outfall 006 (Combined Outfall for internal outfalls 001-005) serving HNP. The permit included a schedule for meeting the new limits for copper and zinc, as well as milestones. In accordance with permit requirements, Duke Energy Progress, LLC (Duke Energy), prepared a plan summarizing the proposed actions to meet the new metal limits at Outfall 006 and a timeline to implement this approach. The plan, submitted on August 31, 2017 (Letter HNP-17- 071), included steps consistent with EPA guidance for the new limits: 1. Conduct a detailed characterization of the effluent to understand the variability in metals concentrations as well hardness. 2. Examine issues associated with water treatment chemicals. 3. Initiate studies to determine site specific characteristics of the effluent which influence - the toxicity of metals. 4. Identify additional studies and steps to take to address the new limits. In addition to the plan, Duke Energy submitted the second annual progress update to DWR on August 27, 2018 (Letter RA-18-0152). That progress update indicated that zinc can meet the zinc limit based on changes that the HNP staff had implemented regarding water treatment chemicals, and hardness evaluations conducted at the site. The purpose of this letter is to provide results of the finalized Water Effects Ratio (WER) study and updated effluent characterization results for both zinc and copper through January 2019. These are presented in the attached technical memorandum (TM). The report documenting the Water Effects Ratio (WER) study for copper is included as an attachment. Division of Water Resources Serial: RA-19-0161 /page 2 The TM summarizes effluent data and shows there is a reasonable potential to meet effluent limits for zinc in the HNP Outfall 006 discharge. For copper, the WER study supports a final WER(EWER)for dissolved copper of 5.0. The data also indicates that there is a reasonable potential to meet copper criteria at Outfall 006 discharge using recalculated permit limits based on the actual effluent hardness and the dissolved fWER value. Duke Energy will be contacting Ms. Julie Grzyb, of your NPDES permitting staff, to set up a meeting to discuss the effluent characterization results and WER study. If you have any questions regarding this matter or wish to discuss in further detail, please do not hesitate to contact Mr. Bob Wilson, HNP Site Environmental Professional, at(919) 362- 2444. I certify, under penalty of law, that this document and all attachments were prepared under my direction or supervision in accordance with a system designed to assure that qualified personnel properly gather and evaluate the information submitted. Based on my inquiry of the person or persons who manage the system, or those persons directly responsible for gathering the information, the information submitted is, to the best of my knowledge and belief, true, accurate, and complete. I am aware that there are significant penalties for submitting false information, including the possibility of fines and imprisonment for knowing violations. Sincerely, C:14) /74(1, e- • Tanya M. Hamilton Enclosure: Technical Memorandum - NC0039586 Compliance Update Water Effect Ratio (WER) Study- Copper Report Reasonable Potential -Analysis Spreadsheet Calculations Y P cc: Ms. Julie Grzyb, Supervisor, NPDES Complex Permitting Supervisor, Certified Mail Number: 7006 0100 0006 4208 4750 Mr. Rick Bolich, Interim Water Resources Regional Supervisor, NC DEQ DWR Raleigh Regional Office Certified Mail Number: 7006 0100 0006 4208 4767 Ms. Cyndi Karoly, Chief, Water Sciences Section, NC DEQ DWR Certified Mail Number: 7006 0100 0006 4208 4743 NC DEQ DWR Central Files Certified Mail Number: 7014 2102 0003 3197 7087 Division of Water Resources Serial: RA-19-0161 /page 2 bcc: Della Allen Jim Eayres Kyle Kelly Don Safrit John Williamson Bob Wilson Darlene Wallace Nuclear Records Division of Water Resources Serial: RA-19-0161 Enclosure Harris Nuclear Plant and Harris Energy and Environmental Center NPDES Permit Number NC0039586 Technical Memorandum —NC0039586 Compliance Update (124 pages plus cover) JI%COBS Technical Memorandum 14120 Ballantyne Corporate Place Suite 200 Charlotte, North Carolina 28277 +1.704.544.4040 +1.704.544.4041 www.jacobs.com Subject Shearon Harris Nuclear Plant-Permit NC0039586 ••..• """ ""'• •.,_ Copper and Zinc Evaluation oOkl. ...... Date March 18, 2019 4—• O*E8$jp" Prepared for Duke Energy Prepared by Bill Kreutzberger—Jacobs Engineering Group, Inc. (Jacobs) / 7925 Muriel Steele,PhD, PE—Jacobs Project Name Shearon Hams Nuclear Plant NPDES Permit Assistance F�GME ' Project No. 680115 ,! : ' Executive Summary Additional characterization of the effluent for Shearon Harris Nuclear Plant's (HNP) Outfall 006 for hardness, copper and zinc were conducted as described in the Corrective Action Plan (CAP)and Year 2 Reports submitted to the Division of Water Resources (DWR)on or before the NPDES permit anniversary date in September 2017 and 2018, respectively. The purpose of this technical memorandum (TM) is to summarize the sampling results and progress towards achieving compliance. Hardness data indicated that applicable metals criteria should be calculated based on a hardness of about 43.8 milligrams per liter(mg/L)as calcium carbonate (CaCO3). Zinc data collected after elimination of a zinc-based corrosion control inhibitor indicated there is no longer a reasonable potential to exceed either the zinc limits in the NPDES permit or higher limits based on the effluent hardness. Copper data indicated that levels still exceeded limits calculated using the effluent hardness of 43.8 mg/L. A Water Effect Ratio (WER) study was conducted as laid out in the reports submitted to DWR. A final dissolved WER of 5.0 was determined based on these studies. There is no reasonable potential to exceed permit limits based on copper criteria adjusted based on effluent hardness and the final WER. 1. Background The NPDES Permit for the HNP, effective September 1, 2016, includes limits for total recoverable copper and total recoverable zinc from Outfall 006 (Table 1). These limits were based on the North Carolina water quality standards regulations (15A NCAC 2B .0211(c))that included the equations to calculate acute and chronic criteria based on hardness and a WER. For the HNP permit, the dissolved copper and Table 1. Copper&Zinc limits on HNP Outfall 006 zinc criteria that were calculated using default Metal Monthly Average Daily Maximum hardness concentration of 25 milligrams per liter (mg/L) as calcium carbonate (CaCO3)and default Total Copper 7.9 pg/L 10.5 pg/L WER of 1 due to a lack of historical data available Total Zinc 126 pg/L 126 Ng/L for Outfall 006 discharges when the permit was developed. The dissolved criteria were translated JACOBS® Shearon Harris Nuclear Plant-Permit NC0039586 Copper and Zinc Evaluation to total recoverable permit limits using approved EPA procedures and were also applied to the Outfall 006 discharge with no credit for dilution (meeting limits in 100% effluent). A CAP was developed and submitted to DWR August 31, 2017 in accordance with the schedule of compliance laid out in the permit.The CAP included effluent characterization for hardness, copper, and zinc that began in April 2017 and is ongoing, as well as a recommendation to complete a WER study. A Year 2 report was submitted to DWR on August 31, 2018 that included preliminary results. The WER study was completed ETT Environmental, Inc. in Greenville, South Carolina in 2018; the report from ETT is included as Attachment 1 and is summarized in this TM. 2. Effluent Characterization Starting in April 2017, composite samples were collected from Outfall 006 weekly for three months and has continued twice per month through the present; samples are analyzed for hardness (by calculation method)and total recoverable zinc and copper. Raw water samples were also collected from the intake at HNP and analyzed according to the same timeline as Outfall 006 in order to distinguish impacts of influent characteristics on the effluent(raw water data is not presented in this TM). The average and median hardness of Outfall 006 samples (n=48 for April 2017 through January 2019) are 43.8 and 44.0 mg/L as CaCO3, respectively(Figure 1). Values are consistently within the range of 35 to 60 mg/L as CaCO3; the only exception to this range is during a scheduled shutdown of HNP during April and May of 2018 when the hardness in the effluent fell to the 20 to 30 mg/L as CaCO3 range. • 006 Effluent —006 Effluent Average(43.8 mg/L) 70 0 60 • •. ®® CO 40 fs�® :sit ® *woo4. f ® ® ® ® s9900 30 a 20 E 10 CO = 0 �i 9i 1,j 1i �'i i �i �i 10 1N) 01> �O `�O <)O �1 OT 01 �O `-O �O >1 ) 1 dj 1, 1j 01, cQ 8 Id, 1� d(p 04 1d 9 Figure 1. Outfall 006 Effluent Hardness in mg/L as CaCO3 Sampling values during characterization (April 2017 to January 2019) Notes: HNP experienced a scheduled shutdown during April/May 2018 resulting in lower than normal hardness 2.1 Zinc Limits The results of the hardness evaluation from the effluent characterization were used to calculate water quality criteria (WQC)for dissolved zinc(Equations 1 and 2). The default US EPA translator for zinc (0.288)was then used to determine the corresponding total recoverable zinc limit for Outfall 006 (Table 2), similar to how DWR calculated the permit limit for the NPDES permit. Zinc results from the effluent characterization Zinc,Acute = WER x 0.978 x eo.8473On hardness)+0.884 efforts, as well as NPDES-required Zinc,Chronic = WER x 0.986 x eo.8473(ln hardness)+0.884 monitoring, were compared against the zinc limits in HNP's permit as well as the calculated limit based on site-specific hardness (Figure 2). Shearon Harris Nuclear Plant-Permit NC0039586 JACOBS Copper and Zinc Evaluation Table 2. Calculated Zinc Limits Calculated acute and chronic dissolved zinc WQC and corresponding total recoverable zinc effluent limits at the default and site-specific hardness concentrations Default hardness HNP Outfall 006 Average Hardness (25 mg/L as CaCO3) (43.8 mg/L as CaCO3) Water Quality Criterion for Acute 36.2 µg/L 58.2 µg/L Dissolved Zinc Chronic 36.5 µg/L 58.7 µg/L Calculated Effluent Limit for Acute 126 µg/L 202 µg/L Total Recoverable Zinc Chronic 126 µg/L 203 µg/L Limit(at default 25 mg/L hardness) Limit(at 43.8 mg/L hardness) • 006 Effluent 250 200 150 c 100 • Z • • 50 • • • o Ni�••, i •••, • qi•• i/!� • •sem • i `ri i 9i 1,j 1i `i - 6 di 10 1) 1,"(2 ��0 1�O ij1/., 6�`301 s'i•- 1p<) c'��0 19��0 il�ii, i���0 r01 •1j 1, 01, 8 1� 13 18 01� j8 Figure 2. Outfall 006 Effluent Total Recoverable Zinc, in pg/L Sampling values during characterization (April 2017 to January 2019) Notes:Calculated zinc limits at default and site-specific hardness concentrations are shown;acute and chronic limits for zinc are effectively equal,thus only the greater limit is shown 2.2 Copper Limits Similarly, hardness results from the effluent characterization were used to calculate WQC for dissolved copper(Equations 3 and 4)and the default US EPA translator for copper(0.348)was then used to determine the corresponding total recoverable copper limit for Outfall 006 (Table 3). Copper results from the effluent Copper,Acute = WER x 0.960 x e0.9422(tn hardness)-1.700 characterization efforts, as well as NPDES- Copper,Chronic = WER x 0.960 x e0.8545(In hardness)-1.702 required monitoring, were compared against the copper limits in HNP's permit as Equations 3 and 4 well as the calculated limit based on site- -,araress-1ependent water quality starcards calc.aation or ccpcer specific hardness(Figure 3). Table 3. Calculated Copper Limits Calculated acute and chronic dissolved copper WQC and corresponding total recoverable copper effluent limits at the default and site-specific hardness concentrations Default Hardness HNP Outfall 006 Average Hardness (25 mg/L as CaCO3) (43.8 mg/L as CaCO3) Water Quality Criterion for Acute 3.6 p.g/L 6.2 µg/L Dissolved Copper Chronic 2.7 µg/L 4.4 µg/L JACOBS Shearon Harris Nuclear Plant-Permit NC0039586 Copper and Zinc Evaluation Table 3. Calculated Copper Limits Calculated acute and chronic dissolved copper WQC and corresponding total recoverable copper effluent limits at the default and site-specific hardness concentrations Default Hardness HNP Outfall 006 Average Hardness (25 mg/L as CaCO3) (43.8 mg/L as CaCO3) Calculated Effluent Limit for Acute 10.5 µg/L 17.8 µg/L Total Recoverable Copper Chronic 7.9 µg/L 12.8 µg/L Daily Max Limit(at default 25 mg/L hardness) -----Limit,Ac.(at 43.8 mg/L hardness) • 006 Effluent-Daily Value 50 45 • • 40 • • • • 35 cuo 30 • • • a 25 •• • • • • • 0 105 ---- --•- �•-----� • ♦ %Zy-; 10Q ® ® _ ®® ®" • ••,li ts 5 • 0 i `> i 49i 1,j ji ai i 6i 10 • 1 �j/`O ��`O 10 /11�1 6/`)01 �i�>0 ���O ��<-) 1��0 /s)i /�i-) 1 1, j 0 •d' ' c c c 1� 1� 9 Figure 3. Outfall 006 effluent total recoverable copper daily maximum, in pg/L Sampling values during characterization (April 2017 to January 2019), compared to effluent limits as written and adjusted for site-specific hardness Monthly Ave Limit(at default 25 mg/L hardness) -----Limit,Chr.(at 43.8 mg/L hardness) • 006 Effluent-Monthly Ave 35 30 • • • 'LT 25 • • • • u`, 20 • • • • • 0 15 • • • • • v -S • • 10 —JR----- • 5 • 0 10 'Lid G� ✓4/ yG 4r,0 pce oG pPc.)0 ✓d' so6 47 to 47 ✓G, ✓4/ yG ,ew pc� 4LoL°c0 ✓0 10;�0;01;01��0 101.�01 �0 �01�01�10��01�01��01�01�01�.�0. �01�01 �01�01�019 Figure 4. Outfall 006 effluent total recoverable copper monthly averages, in pg/L, Sampling values during characterization (April 2017 to January 2019), compared to effluent limits as written and adjusted for site-specific hardness Shearon Harris Nuclear Plant-Permit NC0039586 JACOBS• Copper and Zinc Evaluation 3. Metals Compliance at Outfall 006 3.1 Zinc Results from the effluent characterization showed no values greater than the monthly average or daily maximum limits for total zinc(Figure 2), thus demonstrating compliance. Reasonable potential analysis was performed using the results of the characterization (see Attachment 2), including hardness and zinc calculations, and concluded that there is no reasonable potential to exceed the limits as included in the current NPDES permit or as calculated using the monitoring data for hardness. 3.2 Copper Results from the effluent characterization for copper, on the other hand, showed non-compliance in most cases with respect to both monthly average and daily maximum limits (Figures 3 and 4)as included in the current NPDES permit and as calculated using the monitoring data for hardness. A WER study was proposed to determine applicable dissolved copper criteria and corresponding total recoverable copper limits. WER Study A WER study was completed in 2018 from July through September with three rounds using a primary species (Ceriodaphnia dubia)and a fourth round using a secondary species (Pimephales promelas)for both total recoverable and dissolved copper according to the US EPA's Interim Guidance on Determination and Use of Water Effect Ratios for Metals. The report for this study is included as Attachment 1. Because the North Carolina Water Quality Standard for copper is based on dissolved copper, the final WER for dissolved copper(fWER =4.9996)was applied when calculating WQC and effluent limits. Additionally, the fWER for total recoverable copper(5.9789)was found to be higher than the dissolved fWER so use of the dissolved fWER is appropriately conservative. Again, results of the hardness Table 4. Calculated Copper Limits Adjusted for WER evaluation from the effluent Calculated acute and chronic dissolved copper WQC and characterization were used to corresponding total recoverable copper effluent limits at the calculate WQC for dissolved copper default and site-specific hardness concentrations and the default US EPA translator for HNP Outfall 006 copper was used to determine the Hardness=as 8 mgiL as CaCO corresponding total recoverable zinc WER=5.0 limit for Outfall 006, this time including Acute 30.9 /L the determined WER (Table 4). Water Quality Criterion for pg Dissolved Copper Chronic 22.E µg/L Results from the effluent characterization showed no values Calculated Effluent Limit for Acute 88.8 µ9/L greater than the calculated acute and Total Recoverable Copper Chronic 63.6 µg/L chronic effluent limits for total copper (Figures 5 and 6) based on effluent hardness and WER. Reasonable potential analysis was performed using the results of the characterization and WER study(see Attachment 2)and concluded that there is no reasonable potential to exceed the limits with adjustments based on hardness and WER. 4. Conclusions Analysis showed that there is no reasonable potential to exceed zinc WQC based on recent effluent data (since substitution of a zinc-based anti-corrosion inhibitor), therefore it is appropriate to remove the numerical zinc limits from HNP's NPDES permit and instead add a monitor and report requirement. A revised total recoverable copper limit was determined according to US EPA guidance using effluent hardness data and a WER, and analysis showed that there is no reasonable potential to exceed these limits. Therefore, the revised limits on copper should be adopted into HNP's NPDES permit or removed in lieu of a monitor and report requirement. JI COBS Shearon Harris Nuclear Plant-Permit NC0039586 Copper and Zinc Evaluation -----Limit,Ac.(at 43.8 mg/L hardness and WER=5.0) • 006 Effluent-Daily Value 100 80 J 0 60 • • Q 40 ® ® ® • v 20 •�®••fib ®•® • ®®® %s- •• 0 �� • • •� •N•D • i ri i 9, 11 1i `�'i i 6 8i 10 1<.)0 �j<3 � n3 1<3 1'7/ 6/V01 �i�01 �i3 ��<3 <3 1 C%3 V01 1> 1, dj 01) •8 8 1, 1cp 1� 015 1C 9 Figure 5. Outfall 006 Effluent Total Recoverable Copper—Daily Maximum Sampling values during characterization (April 2017 to January 2019), compared to effluent limits adjusted for site-specific hardness and WER -----Limit,Chr.(at 43.8 mg/L hardness and WER=5.0) • 006 Effluent-Monthly Ave 100 80 J 60 - 40 o • • • • • 20 • • ® •• • • • ® • ® ® ® ® • • 0 14. 44 ✓Gif7 ✓<'/ 9G j04, % +0 60c✓d7 c°6�d, 90.• 47d G7 ✓G/ 9G je °fie +0L 66' ✓dui 101�c0 j0;01°'10 �0 �01,�010;p1,101 201�01c�01d016,01��0.e�0.42 4 01101, •<9 Figure 6. Outfall 006 Effluent Total Recoverable Copper—Monthly Average Sampling values during characterization (April 2017 to January 2019), compared to effluent limits adjusted for site-specific hardness and WER Shearon Harris Nuclear Plant-Permit NC0039586 f,/■ACOBS Copper and Zinc Evaluation Attachment 1 Water Effect Ratio Study, Copper— Report ETT Environmental, Inc.—December 2018 Elronm],inc, (864)877-6942 . FAX(864)877-6938 P.O. Box 16414,Greenville, SC 29606 4 Craftsman Court,Greer,SC 29650 WATER EFFECT RATIO STUDY Duke Energy: Shearon Harris Nuclear Power Plant NPDES Permit # NC0039586 Metal: Copper Issued: December 2018 Test Reviewed and Approved By: Robert W. Kelley,Ph.D.:QA/QC Farhad Rostampour: Lab Manager neiac FL Certification#E87819 SCDHEC Certification #23104 Test results presented in this report conform to all requirements of NELAC,conducted under NELAC Certification#E87819 Florida Dept.of Health. NCDC' NR Certification#022 Included results pertain only to provided samples. Page 1 of 110 1.0 INTRODUCTION The Duke Energy Shearon Harris Nuclear Power Plant (SHNPP) discharges effluent to Harris Lake in Wake County,North Carolina. ETT Environmental has been retained to conduct a Water Effect Ratio for the facility to determine if permitted copper limits for the effluent discharge are unnecessarily overprotective of aquatic life. This is to be accomplished through the calculation of a water effect ratio (WER), comparing the acute effects of copper upon surrogate aquatic test organisms (the water flea Ceriodaphnia dubia and the Fathead Minnow Pimephales promelas)living in laboratory dilution water to the acute effects of copper to the same test species in simulated downstream receiving water. The SHNPP discharges effluent to Harris Lake under NPDES permit#NC 0039586. At sites with very low metal limits, a permittee may conduct a site-specific study to determine if the permit limit for copper should be modified to account for the unique characteristics of the receiving stream. This is done by determining a Water Effect Ratio(WER),which is multiplied against the state water quality criterion to calculate a site-specific criterion. Methodology for determining a WER is provided in the Interim Guidance on Determination and Use of Water-Effect Ratios for Metals (EPA-823- B-94-001). This report presents the results of three rounds of WER primary test determinations using acute tests with the invertebrate Ceriodaphnia dubia and a single round of WER secondary test determinations using acute tests with the vertebrate Pimephales promelas (Fathead Minnow). Using the Interim Guidance, a Final WER is determined and the site specific criterion is calculated. Duke Harris WER Study-Cu ETT Environmental,Inc.; 12/18 Page 2 of 110 2.0 METHODS 2.1 Overview As delineated in the EPA Interim Guidance, a minimum of three rounds of side-by-side tests with the primary test organism(Ceriodaphnia dubia)are required. Each round includes a 48 Hour acute definitive test in which copper is spiked into laboratory dilution water(DMW: Diluted Mineral Water)alongside a test where copper is spiked into simulated downstream water. A 48 Hour LC50 is calculated for each test, and a WER is determined based upon the ratio of the LC50 in simulated downstream water divided by the LC50 in laboratory dilution water. A final WER (EWER) is determined based upon all three individual WER values. A WER is also determined for a secondary species, which in this case is the Fathead Minnow - Pimephales promelas. Acute definitive tests (48 Hour) with the secondary species also are conducted as acute tests,with the endpoint being an LC5o• 2.2 Simulated Downstream Water Simulated downstream water was prepared using 100%effluent. 2.3 Measured Concentrations All calculations were based upon measured concentrations of copper in the laboratory water and downstream water. In acute tests with Ceriodaphnia dubia and Pimephales promelas measured concentrations of total copper were conducted for each test concentration at test initiation and at test termination. Dissolved copper also was measured at test initiation and test termination. 2.4 Laboratory Water Due to the relatively low hardness of the receiving stream and effluent, 13%DMW(diluted mineral water at—50 mg/L hardness)was used as the laboratory water into which copper was spiked.Using dilution water with a hardness of 50 mg/L minimizes the hardness adjustment required to normalize the LC50 results to the site hardness. Duke Harris WER Study-Cu ETT Environmental, Inc.; 12/18 Page 3 of 110 2.5 Determination of Final Water Effect Ratio Type I WERs1 most accurately simulate design-flow conditions, so these values are used directlyin gn determination of the fWER. Type II WERs are not representative of the design flow conditions, but can be used in two ways. First, a Type II WER can be considered a conservative estimate of the WER at design flow conditions, since the WER will typically be lower for higher stream flows. Type II WERs are also used to calculate the highest WER (hWER) that would provide adequate protection under design flow conditions. The hWER incorporates the highest concentration of metal in the effluent (HCME) which will not cause the site specific criterion to be exceeded downstream. The HCME is then used to predict the hWER at design flow conditions. The HCME is calculated as follows; HCME= [CCC x WER x(eFLOW+uFLOW)] -[(uCONC)(uFLOW)] eFLOW where; CCC= criterion continuous concentration WER= the Type II WER which is experimentally determined eFLOW= effluent flow at time of sampling uFLOW= upstream flow at time of sampling uCONC= copper concentration upstream at time of sampling The hWER is calculated as follows; hWER= (HCME) x (eFLOWdf) + (uCONCdf) x (uFLOWdf) (CCC)x(eFLOWdf+uFLOWdf) where df indicates the value under design flow conditions. In this study all three of the primary WERs were Type I WERs. According to the Interim Guidance, when all WERs are Type I, the final water effect ratio (fWER) is the lowest Type I WER or the lowest hWER. Method 1 (determining WERs for areas in or near plumes),was used. The WERs were defined as Type 1 because the SHNPP effluent NPDES permit limitation for copper assumes and instream wastewater concentration of 100%. IA Type I WER is defined as a WER conducted when flow is<2 times the effluent design flow+7Q10 upstream flow(low flow)and a Type II WER is defined as a WER conducted when flow is 2-10 times the same value. Duke Harris WER Study-Cu ETT Environmental,Inc.; 12/18 Page 4 of 110 3.0 RESULTS 3.1 Determination of Type 1 vs. Type 2 Conditions In as much as all tests were conducted using 100%effluent, all tests were Type I tests. 3.2 Water Effect Ratios for Each Round of Tests The experimentally derived (hardness adjusted) WERs for total recoverable copper for acute testing with Ceriodaphnia dubia are summarized as follows; Total Cu Dis. Cu Date Species WER WER Round 1. 7/12/18 primary 5.9789 4.9996 Round 2 8/15/18 primary 10.8966 10.3127 Round 3 9/26/18 primary 8.2006 7.4639 Round 4 9/27/18 secondary 2.6644 2.8330 Because the WER for the secondary test was within a factor of five of the values in the primary test,the secondary test is considered to confirm the primary test results. 3.3 Calculation of Highest Concentration of Metal in Effluent(HCME)Values Calculations of HCME values are provided in Tables 1 and 2. HCME (total recoverable) values ranged from a low value of 32.625 ug/L in Round 1 to a high value of 61.269 µg/L in Round 2. Duke Hams WER Study-Cu ETT Environmental,Inc.; 12/18 Page 5 of 110 3.4 Calculation of hWER Values The experimentally derived (hardness adjusted) hWERs for total recoverable copper for acute testing with Ceriodaphnia dubia are summarized as follows; Total Cu Dis.Cu Date Species hWER hWER Round 1. 7/12/18 primary 5.9789 4.9996 Round 2 8/15/18 primary 10.8966 10.3127 Round 3 9/26/18 primary 8.2006 7.4639 Round 4 9/27/18 secondary 2.6644 2.8330 3.5 Calculation of Final Water Effect Ratio(EWER) As noted above,the Interim Guidance requires that the fWER be calculated as the lowest of a)the the lowest Type 1 WER or b) the lowest hWER. Calculations of the geometric means of the WERs were not needed.The results are summarized as follows; Lowest Type 1 WER Lowest hWER EWER Total Rec.Cu 5.9789 5.9789 5.9789 Dissolved Cu 4.9996 4.9996 4.9996 The WER values for acute tests with fathead minnows were not used in the calculations.According to the EPA Interim Guidance the secondary species WER(fathead minnow)is not incorporated in the fWER calculations but is used only to confirm the magnitude of the primary species WERs. Duke Harris WER Study-Cu ETT Environmental,Inc.; 12/18 Page 6 of 110 3.6 Calculation of Site Specific Continuous Concentration Criterion for Copper(CCC) The continuous concentration criterion(ccc)limit(average limit)for the proposed NPDES permit for the SHNPP effluent should be adjusted using the fWER as follows; Site Specific CCC =[(ccc)x(fWER)x(downstream flow)] -(upstr. Cu conc x upstr.flow) (Effluent flow) [5.4564A x 5.9789B x 7.9 mgd]—(0.0cx 0.0) (7.9 mgd) A:recalculated CCC 1(ug/L)at site hardness(average for the 3 rounds) B:lowest WER C:assigned upstream copper concentration =32.6 µg/L (using Total Recoverable Copper fWER) [5.4564A x 4.9996B x 7.9 mgd]c(0.0 x 0.0) (7.9 mgd) A:recalculated CCC1(ug/L)at site hardness(average for the 3 rounds) B:lowest WER C:assigned upstream copper concentration =27.3 µg/L(using Dissolved Copper EWER) 1 The CCC is calculated as 0.960 x[e^{0.8545(ln ay.site hardness)-1.702}] Duke Harris WER Study-Cu ETT Environmental,Inc.; 12/18 Page 7 of 1 10 3.7 Calculation of Site Specific Criterion Maximum Concentration (CMC)for Copper The criterion maximum concentration (cmc) limit (maximum limit) for the proposed NPDES permit for the SHNPP effluent should be adjusted using the EWER as follows; Site Specific CMC = [(cmc)x(fWER)x(downstream flow)] -(upstr.Cu conc x upstr.flovti) (Effluent flow) [7.7822A x 5.9789B x 7.9 mgd] —(0.0c x 0.0) (7.9 mgd) A:recalculated CMC1(ug/L)at site hardness(average for the 3 rounds) B:lowest WER C:assigned upstream copper concentration =46.5 µg/L(using Total Recoverable Copper fWER) [7.7822A x 4.9996B x 7.9 mgd]S(0.0 x 0.0) (7.9 mgd) A:recalculated CMC1at site hardness B:lowest WER C:assigned upstream copper concentration =38.9 µg/L (using Dissolved Copper fWER) The CMC is calculated as 0.960 x[e^(0.9422(ln ay.site hardness)-1.700}] Duke Harris WER Study-Cu ETT Environmental,Inc.; 12/18 Page 8 of 110 TABLE 1. DERIVATION OF TOTAL COPPER fWERS WITH HARDNESS ADJUSTMENT(Using Acute Tests) Facility: Harris Nuclear T-Cu nCMC= e(0.9422[In(hardness)]-1.700)x 0.96 nCCC= e(0.8545[In(hardness)]-1.702)x 0.96 Upstream Design Flow: 0 mgd 0.00% adj EC50= e(0.9422[In(site water hard-In(lab water hard)]) Effluent Design Flow: 7.9 mgd 100.00% Design hardness Upstream Design Conc.: 0 ppb Streamlined Interim WER Lab Water Site Water SMAV Hard.Adj. CMC @ CCC @ Upstream Effluent Upstream Effluent WER# Type Hardness LC50 Adj LC50 Hardness EC50 Adj EC50 WER WER site hard site hard Flow(mgd) Flow(mgd) Hardness Hardness HCME hWER 1:7/12/18 Design flow 50.0000 23.2080 25.8233 56.0000 154.3950 NA 11.1091_ 5.9789 7.7824 5.4567�_ 0.0000 7.9000 0.0000 56.0000 32.6250 5.9789 2:8/15/18 Design flow 50.0000 10.2360 11.7723 58.0000 128.2780 NA 8.9297 10.8966 8.0440 5.6228 0.0000 7.9000 0.0000 58.0000 61.2690 10.8966 3:9/26/18 Design flow 50.0000 20.3580 21.8891 54.0000 179.5040 NA 13.3660 8.2006 7.5202 5.2897 0.0000 7.9000 0.0000 54.0000 43.3790 8.2006 average average Lowest Type I WER 5.978914 7.7822 5.4564 Limits per Interim Guidance • EWER 5.9789 nCCC= 5.4564 IWC= 1.0000 CCC Eff Criterion= 32.6233 fWER 5.9789 nCMC= 7.7822 IWC= 1.0000 CMC Eff Criterion= 46.5292 Page 9 of 110 TABLE 2. DERIVATION OF DISSOLVED COPPER fWERS WITH HARDNESS ADJUSTMENT(Using Acute Tests) Facility: Harris Nuclear Dis-Cu nCMC= e(0.9422[In(hardness)1-1.700)x 0.96 nCCC= e(0.8545[In(hardness)1-1.702)x 0.96 Upstream Design Flow: 0 mgd 0.00% adj EC50= e(0.9422[In(site water hard-In(lab water hard)j) Effluent Design Flow: 7.9 mgd 100.00% Design hardness Upstream Design Conc.: 0 ppb Streamlined Interim WER Lab Water Site Water SMAV Hard.Adj. CMC @ CCC @ Upstream Effluent Upstream Effluent • WER# Type Hardness LC50 Adj LC50 Hardness EC50 Adj EC50 WER WER site hard site hard Flow(mgd) Flow(mgd) Hardness Hardness HCME hWER II 1:7/12/18 Design flow 50.0000 21.1090 23.4877 56.0000 117.4290 NA - 8.4493 4.9996 7.7824 5.4567 0.0000 7.9000 0.0000 56.0000 27.2812 4.9996 2:8/15/18 Design flow 50.0000 9.4020 10.8132 58.0000 111.5130 NA 7.7627. 10.3127 8.0440 5.6228 0.0000 7.9000 0.0000 58.0000 57.9861 10.3127 3:9/26/18 Design flow 50.0000 19.7480 21.2332 54.0000 158.4830 NA 11.8008 7.4639 7.5202 5.2897 0.0000 7.9000 0.0000 54.0000 39.4821 7.4639 average average Lowest Type I WER 4.9996 7.7822 5.4564 Limits per Interim Guidance EWER 4.9996 nCCC= 5.4564 IWC= 1.0000 CCC Eff Criterion= 27.2797 EWER 4.9996 nCMC= 7.7822 IWC= 1.0000 CMC Eff Criterion= 38.9079 PI ETT environmental,Inc. (864)877-6942 . FAX(864)877-6938 P.O. Box 16414, Greenville, SC 29606 Craftsman Court, Greer, SC 29650 APPENDIX A WATER EFFECT RATIO STUDY (Interim Guidance) Duke Energy Shearon Harris Nuclear Power Plant Primary Species - Round 1 Metal: Copper July 2018 07/18 ETT Environmental; Duke Harris-WER 1 Cu Page 11 of 110 TABLE OF CONTENTS 1.0 INTRODUCTION 2.0 METHODS 2.1 Experimental Design 2.2 Laboratory Dilution Water 2.3 Upstream and Effluent Sample Collection 2.4 Chemical Analyses 2.5 Preparation of Test Solutions 2.6 Test Organisms 3.0 RESULTS 3.1 Laboratory Water 3.2 Simulated Downstream Water 3.3 Upstream Waters 4.0 CALCULATION OF WATER EFFECT RATIO 5.0 DISCUSSION LIST OF APPENDICES Appendix Al. Reference Toxicant Quality Control Chart for Ceriodaphnia dubia Appendix A2. Survival Data for Acute Definitive Tests Appendix A3. Measured Concentrations of Total Recoverable Copper in Test Solutions Appendix A4. Water Chemistry Measurements for Acute Definitive Tests Appendix A5. Chain of Custody Records Appendix A6. Statistical Analysis Results Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 12 of 110 1.0 INTRODUCTION The Duke Energy Shearon Harris Nuclear Power Plant (SHNPP) discharges effluent into Harris Lake under NPDES Permit NC0039586. In cooperation with Jacobs Engineering,ETT Environmental has been retained to conduct a "site specific study" to determine if permitted copper limits for each effluent discharge are unnecessarily overprotective of aquatic life. This is to be accomplished through the calculation of a water effect ratio (WER), comparing the acute effects of copper upon the surrogate aquatic test organism Ceriodaphnia dubia living in laboratory dilution water to the acute effects of copper to the same test species in simulated downstream receiving water. The study used the methodology provided in the Streamlined Water-Effect Ratio Procedure for Discharges of Copper (EPA-822-R-01- 005). On July 10-11, 2018, SHNPP personnel collected a composite effluent water sample. Acute toxicity tests for the Water Effect Ratio study were initiated on July 12th,2018. Laboratory Location: ETT Environmental, Inc. 4 Craftsman Court Greer,SC 29650 SCDHEC Certification# 23104 Study Director: Robert W.Kelley,Ph.D. Study Scientist: Amy McMahon Study Technicians: Jennifer Christian Jonathon Gillespie Forrest Jackson Study Dates: July 12-14,2018 Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 13 of 110 2.0 METHODS 2.1 Experimental Design The design of the study involved spiking copper into test solutions and assessing the acute toxicity of the test solutions with 48 Hour Acute Definitive tests using the surrogate test organism Ceriodaphnia dubia. The two test solutions assessed were 1) laboratory dilution water, and 2) simulated downstream water at measured conditions on the day of sampling(100% effluent). Acute toxicity tests were set according to U.S. EPA protocols (EPA 821-R-02-012 Method 2002),modified according to the following parameters; Test type: Acute Static Temperature: 25°C±1 Light: 100 ft.-candles; 16 hr light/8 hr dark Test Chambers: 30 mL plastic cups Test Solution Volume: 25 mL Renewal of Test Solutions: None Test Organism Age: <24 hr #Neonates/Cup: 5 #Replicates/Concentration: 4 Feeding Regime: None Aeration: None Dilution Factor: 0.7 Test Duration: 48 Hours Endpoints: Survival 2.2 Laboratory Dilution Water The laboratory dilution water used in all tests was diluted mineral water(DMW). In this first round of tests the DMW was prepared at a hardness of 50.0 mg/L. This dilution water was prepared by adding Perrier water to ultra-pure water to obtain the desired final hardness. The procedure for the preparation of this water may be found in the EPA manual Short Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms(EPA 821-R-02-013). * Dilution water during the period of testing was prepared as follows; Amount Hardness Conductivity Alkalinity pH 20 L 50.0 mg/L 117 µmhos/cm 42.3 mg/L 8.0 Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 14 of 110 2.3 Sample Collection Sampling Locations The effluent discharges into Harris Lake. The effluent samples were collected as composite samples. As received the effluent was measured to have oxidizers (measured by the DPD method) of 0.90 mg/L. Although the DPD method is used to measure residual chlorine, in this effluent it is believed that manganate was the oxidizer which was measured. All samples were collected in half gallon plastic jugs and preserved in coolers at 0-6°C. Samples were shipped to ETT by overnight delivery. 2.4 Chemical Analyses Dissolved oxygen and pH were measured in one surrogate of each test concentration at the beginning and end of the test.Temperature was monitored in three surrogate test cups in the incubator daily. Dissolved Oxygen and pH were measured with the use of a Orion 4 Star meter. The meter is calibrated daily. Alkalinity, hardness, total suspended solids (TSS), total organic carbon (TOC), and specific conductance were measured on each laboratory water and effluent sample collected. Total recoverable copper was measured on each test solution at the beginning and end of the test. Dissolved copper also was measured for each test concentration at the beginning and end of the test. Copper analyses were conducted by ETT Environmental of Greer, SC using Standard Methods 18th Edition Method 3111 B (flame atomic absorption), and concentrated to achieve a detection limit of 10 ug/L(or lower with concentration). 2.5 Preparation of Test Solutions 2.5.1 Simulated Downstream Water A simulated downstream sample was prepared using 100%effluent. Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 15 of 110 2.5.2 Copper Spiking Copper was spiked as copper sulfate (CuSO4.5H2O) into laboratory water and the simulated downstream water. Prior to spiking the total recoverable copper in each effluent sample was measured. Each day a batch of simulated downstream water was prepared. An 12.72 mg/L stock solution of copper sulfate was prepared by adding 0.05 g of CuSO4.5H2O to one liter of demineralized water. A microliter syringe was used to add the correct volumes of the stock solution to each simulated effluent or control concentration to achieve the desired nominal concentration of copper. 2.6 Test Organisms The test organism used for this study was the daphnid Ceriodaphnia dubia. Test organisms were neonates of less than 24 hours in age which were obtained from individual cultures at ETT Environmental, Inc. These cultures are set weekly with reproduction of the first three broods tracked for all culture organisms. Only neonates from broods of eight or larger, produced by culture trays demonstrating less than 10% mortality and greater than a mean of 15 young per female(3 broods)are used for testing. Culture sensitivity is monitored through the use of semi-monthly reference toxicant testing. Voucher specimens from the culture are set aside on a monthly basis and taxonomically verified by a staff macroinvertebrate taxonomist. Culture organisms are subject to the same light,temperature, and feeding regimes as used for testing. Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 16 of 1 l0 3.0 RESULTS 3.1 Laboratory Water 3.1.1 Acute Toxicity Testing Results The acute definitive test with Ceriodaphnia dubia in laboratory water spiked with copper showed a 48 Hour LC50 of 23.208 ug/L Total Recoverable Copper and a 48 Hour LC50 of 21.109 ug/L Dissolved Copper. Due to the pattern of the data! the values were calculated using the probit method. The survival data at each concentration are summarized as follows; Nominal Concentration Mean Measured Conc. 48 Hour of Total Recoverable Cu of Total Recoverable Cu Mortality and(Dissolved Cu) 0 ug/L <1.0 ug/L(<1.0) 0% 4.2 ug/L 7.0 ug/L(5.7) 0% 6.0 ug/L 8.2 ug/L(6.8) 0% 8.6 ug/L 11.0 ug/L (7.4) 0% 12.3 ug/L 13.0 ug/L(9.9) 0% 17.5 ug/L 17.1 ug/L(15.7) 5% 25 ug/L 33.0 ug/L(30.0) 100% 35 ug/L 38.5 ug/L(38.5) 100% Survival data for the test may be found in Appendix A2. Results of measured concentrations of total recoverable and dissolved copper are provided in Appendix A3. Statistical analysis results are found in Appendix A6. 3.1.2 Chemical Analyses The pH in the spiked dilution water test ranged from a minimum of 7.9 to a maximum of 8.0. Dissolved oxygen was generally at the saturation point in all treatments throughout the test. 1 The probit method is used when there is only a single concentration with partial mortality. Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 17 of 1 10 3.2 Simulated Downstream Water 3.2.1 Acute Toxicity Testing Results The acute definitive test with Ceriodaphnia dubia in downstream water spiked with copper showed a 48 Hour LC50 of 154.395 ug/L Total Recoverable Copper and a 48 Hour LC50 of 117.429 ug/L of Dissolved Copper. Due to the pattern of the data, the value was calculated using the Trimmed Spearman Karber method.The survival data at each concentration are summarized as follows; Nominal Concentration Mean Measured Conc. 48 Hour of Total Recoverable Cu of Total Recoverable Cu Mortality and(Dissolved Cu) 0 ug/L 19.5 ug/L(11.5) 0% 25 ug/L 43.5 ug/L (29) 0% 35 ug/L 58 ug/L(43) 0% 50 ug/L 70.5 ug/L(51) 0% 71.4 ug/L 91.5 ug/L(60) 0% 102 ug/L 121 ug/L(85) 20% 143 ug/L 157.5 ug/L(113) 40% 204 ug/L 193 ug/L(166) 95% Measured concentrations were generally higher than nominal concentrations. A significant suppression in survival was noted at a nominal concentration of 143 ug/L of total copper. Survival data for the test may be found in Appendix A2. Results of measured concentrations of total recoverable and dissolved copper are provided in Appendix A3. Statistical analysis results are found in Appendix A6. 1 The Spearman Karber Method is used when there are at least two concentrations with partial mortality. Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 18 of 1 10 3.2.2 Chemical Analyses The pH in the simulated downstream water ranged from a minimum of 7.9 to a maximum of 8.6. Dissolved oxygen was generally near the saturation point in all treatments throughout the test. Other water chemistry parameters are summarized as follows; Parameter Effluent Total Recoverable Copper(ug/L) 19.5 Dissolved Copper(ug/L) 11.5 Alkalinity(mg/L) 56.3 Conductivity(umhos/cm) 397 Hardness(mg/L) 56.0 Total Organic Carbon(mg/L) 21.1 Total Suspended Solids(mg/L) 23.1 It may be seen that the effluent water was characterized by moderate alkalinity, hardness, TOC and TSS. 3.3 Upstream Waters Not applicable when downstream water is defined as 100% effluent; Parameter Result Total Recoverable Copper(µg/L) NA Dissolved Copper(µg/L) NA Total Organic Carbon(mg/L) NA Alkalinity(mg/L) NA Hardness(mg/L) NA Conductivity(µmhos/cm) NA Total Suspended Solids(mg/L) NA Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 19 of 110 4.0 CALCULATION OF WATER EFFECT RATIO As noted in the results section,acute testing indicated an LC50 of 23.208 ug/L of total recoverable copper in laboratory dilution water and an LC50 of 154.3950 ug/L of total recoverable copper in 100% SHNPP effluent.The laboratory dilution water LC50 values must be adjusted to downstream water hardness in order to calculate the Water Effect Ratio,using the EPA formula, as follows; LC50 x (downstream hardness/laboratory water hardness)o.9422 T-Cu: 23.208 ug/L x(56/50)0'9422= 25.8233 ug/L Dis-Cu: 21.109 ug/L x(56/50)0.9422= 23.4877 ug/L The Water Effect Ratio can thus be calculated as follows; Water Effect Ratio(WER) = LC50 in Effluent = 154.395 ug/L = 5.9789 (Total Recoverable Copper) LC50 in Lab Water 25.8233 ug/L Water Effect Ratio(WER) = LC10 in Effluent = 117.429 ug/L = 4.9996 (Dissolved Copper) LC50 in Lab Water 23.4877 ug/L A final water effect ratio(FWER)will be calculated using the individual WERs from three rounds of testing. Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 20 of 110 ROUND 1 -APPENDIX Al Reference Toxicant Quality Control Chart Ceriodaphnia dubia See Round 3 Appendix C l. Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 21 of 110 ROUND 1 -APPENDIX A2 Survival Data for Acute Definitive Tests Duke Harris-WER Round 1 Cu ETT Environmental,Inc.;07/18 Page 22 of 110 r Page 6p ofttr WER 48 Hour Acute Toxicity Test �'� Nominal I Initial# bloflality Measured Concentration I ( � N r I /� 1 fVl2tal Conc Pep Organisms 24 hi 48 hr initial Final Mean Facility: a A. `,\'t tr'.i _ i; AC� °lal t,,i,l lolul Sam Sample ID. r jS . 0% B J 0 Start Date: 7- I •ro Time: j,:3;J0 By: „Y c <) Dis Diii Di, End Date: Time: By D 0 Effluent Log tl: J --O( ''2 _ Upstream Log ft. A _) TEST ORGANISMS 0 I olal l 0161 l ula� B t ' Test Organism: 3-2( Y--k9 A- �� C 0 Die Di:: Dis fol Ceriodaphnia dubia) Source. r / i '� 75 D Date Removed; /- )1-1 6� I A _ 0 (alai To alai Betweent t c)and , incl B ....D. 0 for fathead minnows or mysids: 1--- C 5 6 Dis Dis Dis Source: Age: D 5 CJ Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles r.. A 5 0 Total Total Total Laboratory Water DMW/SSF ' , 50 mg/L hardness B 5 0 Downstream Water Preparation ,56 C .J 0 Dis Dis Dis % effluent volume mL Prep.Date: _ D 5 6 % upstream volume mL_Prep.by: A 5 0 1 Total Total Total 5oB 9 U Test Solution Preparation: Metal Salt: 0,1S01. C S. 0 Dis Die Dis Date: By: Stock.Soln:I2--12-013 II— I D 5 o Nominal Conc mL Stock Soln. Volume prepared A a) Total Total Total D 0 �93 rn� B 0 I'1.5 . 0 i 1{ 0/� �Jy - "1 l•1 C ✓ Dis Dis Dis 25 9 t-/ A 5 2 Total Total Total ✓O I•q lviq C 6 d Die Dls Dig I V 1 -l 11 i liil ill D S. C.) 11\5 • Cow- IL lilt;{' A 5 3 Total Total Total A Total Total Total irii V B 5 I B Iil5 C 5 fC Die Die Die ';Fr`:, Die Die Die a,,, D 5 3 D or. '01 \V A 5 .5-- Total Total Total A Total Total Total 1i , B 3' 5- B I �0 NI M C 5 51 Dis Dis Die C Die Dis Die Dit iir! 5LI D Ma •,., Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. U Test Method: per (EPA Interim l Guidance Zo t \ 8 r"Q l .Al'I 5"oM`" Page 23 of 110 i 1 le 60 of-i Page 61 of 100 Nominal Initial# Mortality Measured Concentration WER 48 HourAcute Toxicity Test Conc Rep Organisms 24 hr 48 hr Initial Final Mean , Facility: ___J7Aki)J Metal: ,f AJ ,,.,,,_ .. f� otal TotalSample ID 0% B —�) ? • Start DtIe -1 2-1 Time: G�`(:) By ..Y C J 0} Dos Dls End Date: Time: By: -.__ D �� f(fluent Log // Upstream Log t?: A � fatal iat,, TEST ORGANISMS B_ . 0 Test Organism: �j X -Z / �' Z C lJ1 as Dis for Ceriodaphnia dubia Source: ►-FVt— 6.--_ Dall Li Date Removed; J_ 1 _1 b� C--L— 7-J� rn;e` �; Gi j I J (Time) �- LA ) (Time) ! � / Total iotai total BCIWCeII I I(ilC' and Z B 1 0 for fathead minnows or mysids: 6,0 C 5 0 Die Die Die Source: Age: ..-..,�.. 0 Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles INIMINNEMMNI G A 0 Total Total Total Laboratory Water DMW/SSF A 50 mg/L hardness 7 �j-) B 1 0 Downstrea m Water Pre oration 6 n P I J 0 Dis Ds Dis effluent volume mL Prep.Date: D 5 0 % upstream volume mL Prep.by: r A ✓ b Total Total Total 1/- 2 B 5 0 Test Solution Preparation: Metal Salt: �i:�s\ J C � �l Die Die Dis Date: By: Stock.Soln:J 7_ 72_ rtq!/i D 5 00 Nominal Conc mL Stock kkk Soln. Volume prepared J A r5 Total Total Total Q /f ` J! Y' 1 ryi I, C S.. `-' Dis Dis Dis (e 6 Zi 5 ° a l 3{{ q A 5 S Total Total Total 11 5 . g il 7-1 B S 11.5 , 61 C .L--�DIs Dis Dis f t 9 g 5 s :3.5 1 .35 ]tat A 5 5 Total Total Total A Total Total Total B 5 5 B 'Is C 5 S DIs Dis Die C DIs Die Dis D S D tal A Total Total Total A Total Total Total B B s C DIs DIs Ds C Die Die Die D D Test solution volume:25 mL- Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. Test Method: per EPA Interim Guidance Page 24 of 1 10 ROUND 1 -APPENDIX A3 Measured Concentrations of Total Recoverable Copper in Test Solutions Duke Harris-WER Round 1 Cu ETT Environmental,Inc.;07/18 Page 25 of 110 Measured Total Recoverable and Dissolved Copper Duke Harris Plant-Primary Species Site Specific Study July 2018 Sample:S iked Dilution Water(Diluted DMW Initial Date:07/12/18 ominal Measured Total Recoverable Copper(µg/L) %of Measured Dis.Cu(µg/L) Total Cu Initial Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Mean 0 <1.0 Nominal Initial Day 2 Mean Dissolved <1.0 <1.0 <1.0 <1.0 <1.0 4.2 6.0 6.0 9.3 8.0 7.0 167% 8.0 3.3 5.7 81% 7.1 8.2 137% 7.7 6.0 6.8 83% 8.6 10.2 12.3 15.2 11.7 11.0 128% 11.7 3.1 7.4 67% 10.8 13.0 106% 15.6 4.2 9.9 76% 17.5 18.2 16.0 17.1 98% 23.0 8.4 15.7 92% 25.0 34.0 32.0 33.0 132% 28.0 32.0 30.0 91% 35.0 39.0 38.0 38.5 110% 39.0 38.0 38.5 100% Sample:Simulated Downstream-Duke Harris Initial Date:7/12/18 Nominal Measured Total Recoverable Copper(µg/L) %of Measured Dis.Cu(µg/L) Total Cu Initial Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Mean Nominal Initial Day 2 Mean Dissolved 0.0 19.7 I9.2 19.5 8.2 14.8 11.5 25.0 40.0 47.0 43.5 174% 29.0 29.0 29.0 67% 35.0 58.0 58.0 166% 43.0 31.0 43.0 74% 50.0 76.0 65.0 70.5 141% 51.0 34.0 51.0 72% 71.4 94.0 89.0 91.5 128% 60.0 54.0 60.0 66% • 102.0 123.0 119.0 121.0 119% 85.0 67.0 85.0 70% 143.0 156.0 159.0 157.5 110% 113.0 81.0 113.0 72% 204.0 198.0 188.0 193.0 95% 168.0 164.0 166.0 86% In the DMW test there was some indication of a substantial decrease in dissolved copper in the mid range concentrations at 48 hours, however,the decrease was not noted in the total copper concentrations and thus the data was deemed acceptable. Page 26 of 110 ROUND 1 -APPENDIX A4 Water Chemistry Measurements for Acute Definitive Tests Duke Harris-WER Round 1 Cu ETT Environmental,Inc.;07/18 Page 27 of 110 , 1 I ACUTE TOXICITY TEST - CHE�MISTR\' P 46 Hour R 16 Hour Rendinj;s eo Inilinl Readings 2a Hour Readings 24 Hour Readings ----n----� old o nr+•. nr�• nip CO nduru+�rn old old old Do so lr+Q DruoIs rd Drssols•rd Drssntvrd (Prn6asrtm)nr Dresalrrd cu P11 Clr1'f.rn rN n Otyr. Os pli or tirluurl U+Yrr„ pll U,)'fcn f mr(L . Efltr,nrI lPn I rn /L tngiL, mI:/L --� uno mg/L. t ra. Contcntn ���)�i�O .,„ ___Eii ,„ ....6_-_ _. __ _.. .. _________ _._. ... __________ .... -.1,„, ________ ______„ 1.,„ ____________ . , _____ i.. i�`'5 7— iti-1� . f _______ Datc, q Time: I350 13t,z I,• Initials: -r/ F I 1, f 72 Hour Readings 72 Hour Readings 96 Hour Readings I old old new old old new � IL! Dissolved Dissolved Dissolved Ii ' H Ony cr pH ' !,;f Effluent Oxygen PH Oxygca P I 1 Cooceutntion mg/L mg/L - 1 i, I . toi I ;Ili Date: — 1.0 } lit: Time: 1I ' Initials: llr t Ili ill r:PLab ID#; , Client: {I,y '/,, 'VIA C 0 5 7 d AF—Fn J 52013—t3 i 1� I.< ilk. --1. 'k � ,iliBI Page 28 of 110 i' ROUND 1 - APPENDIX A5 Chain of Custody Documentation S Duke Harris-WER Round 1 Cu ETT Environmental,Inc.;07/18 Page 29 of 110 .._..... ETri 4 I CHAIN OF CUSTODY RECORD i Fwito �'en o13er'itt PO Box 16414 Greenville,SC 29606-7414 Page —of_� (864)877-6942, (800)891-2325 Fex:(864)877 6938 Shipping Address:4 Craftsman Ct,Greer,SC 29850 W W W.ETTENV IRONM_NTAL.COM Client: 1' p /f — - Vt,Ji�L Conir-c,r�ed t�►-ill lrHM HIII N0�., ,„,„,IllAt Program Containers Preservative Parameters Facility: 1� J 1- �/12�1dR71'\• f Iaril-S MU C-1 eQr I rIC Whole Ernuent Taxiciry State: NC NPD]sue: NC003g5R1a Q Acute Chronic Test Organisms , 1 U O U _ 'o (Composite only) (Grab or Campos ht) _ U ,� U E .^ Sign,and Print b'zlow = '-HCL = °- _ < 5i E =' rj the dotted line U ,o • ; HNos = z �' .2 - . = i- o C ^ L.. h _ 4=NaOH c o 2 c = •y o O- ` ,.i 2 ° b o o n O U s=za4c u o _ = W Ci SAty(PLE ID Con,i;co;ic Sion Iron Time Simple Cntk I on al, Time Collected by U Co CO Z F. t7 > 6;Oilier < < U U ono. 2 .J, U = 5 .e Chemical Analysis&Other — :•o-; o O1 7-/I-;= o1 5 6, I ae►k, Cl� * 52 (3* ne co a 0 Special Instructions: t -h e t- 5 a-rri veal ay..'7 efor,r resul-tS -b Mu.riel- S'__ e@ 1_ ,cul * B+jrGgs arrived IOt.Ae. —ar, 11}03 � I ail$ Sample Custody Transfer Record Secure Receipt Sample Date`) Time Relinquished By/Organization Received By/Organization Area Temp`C Preserved? 7Jii, ig H- t y UPS F•rr-- 3{.‘1 COMPOSITE SAMPLING PROCEDURES TEMPERATURE MONITORING PROCEDURES HOLD TIME PROCEDURES Composite samples must be collected over a 24 hour period. Sample temperature during collection and transport must be between For toxicity testing the sample must first be used within 36 hours Time Proportional: I sample each hour for 24 hours.Equal volui 0.0 and 6.0'C.Samples must not be frozen.Use water ice in sealed bags. of sample collection(completion of composite sample). or at minimum I sample every 4 hours over 24 hours. Sample may not be used after 72 hours from sample collection. Flow Proportional:As 1aer instructions in NPDES oermit. ROUND 1 - APPENDIX A6 Statistical Analysis Results Duke Harris-WER Round 1 Cu ETT Environmental,Inc.;07/18 Page 31 of 110 ETT Environmental,Inc. SPEARMAN KARBER Test Conc. #dead Out of Client: ETT 0.1 0 20 Sample ID: DMW Dis Cu 7.4 0 20 Sample#: WER 9.9 0 20 Test Length: 48 hr acute def. 15.7 1 20 Test Organism: C dubia 30 20 20 Test Date: 7-12-18 38.5 20 20 LC50= 21.109 ucl 22.312 Icl 19.971 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Spearman Karber LC50 value. Page 32 of 110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 51 0 20 1.7076 0.5 60 0 20 1.7782 0.5 85 20 20 1.9294 4.16 113 40 20 2.0531 4.75 166 95 20 2.2201 6.64 1. Enter data in yellow boxes Test Type: WER Species: C dubia Sample ID Harris DisCu LC50 = Date: 7/12/18 117.429 • > entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact A value of 0 must be e e the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value. Page 33 of 110 ETT environmental,Inc. (864)877-6942 . FAX(864)877-6938 P.O. Box 16414, Greenville, SC 29606 Craftsman Court, Greer, SC 29650 APPENDIX B WATER EFFECT RATIO STUDY (Interim Guidance) Duke Energy Shearon Harris Nuclear Power Plant Primary Species - Round 2 Metal: Copper August 2018 Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 34 of 110 TABLE OF CONTENTS 1.0 INTRODUCTION 2.0 METHODS 2.1 Experimental Design 2.2 Laboratory Dilution Water 2.3 Upstream and Effluent Sample Collection 2.4 Chemical Analyses 2.5 Preparation of Test Solutions 2.6 Test Organisms 3.0 RESULTS 3.1 Laboratory Water 3.2 Simulated Downstream Water 3.3 Upstream Waters 4.0 CALCULATION OF WATER EFFECT RATIO 5.0 DISCUSSION LIST OF APPENDICES Appendix B1. Reference Toxicant Quality Control Chart for Ceriodaphnia dubia Appendix B2. Survival Data for Acute Definitive Tests Appendix B3. Measured Concentrations of Total Recoverable Copper in Test Solutions Appendix B4. Water Chemistry Measurements for Acute Definitive Tests Appendix B5. Chain of Custody Records Appendix B6. Statistical Analysis Results Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 35 of 110 1.0 INTRODUCTION The Duke Energy Shearon Harris Nuclear Power Plant (SHNPP) discharges effluent into Harris Lake under NPDES Permit NC0039586. In cooperation with Jacobs Engineering, ETT Environmental has been retained to conduct a "site specific study" to determine if permitted copper limits for each effluent discharge are unnecessarily overprotective of aquatic life. This is to be accomplished through the calculation of a water effect ratio (WER), comparing the acute effects of copper upon the surrogate aquatic test organism Ceriodaphnia dubia living in laboratory dilution water to the acute effects of copper to the same test species in simulated downstream receiving water. The study used the methodology provided in the Streamlined Water-Effect Ratio Procedure for Discharges of Copper (EPA-822-R-01- 005). On August 13-14, 2018, SHNPP personnel collected a composite effluent water sample. Acute toxicity tests for the Water Effect Ratio study were initiated on August 15th,2018. Laboratory Location: ETT Environmental,Inc. 4 Craftsman Court Greer,SC 29650 SCDHEC Certification# 23104 Study Director: Robert W.Kelley,Ph.D. Study Scientist: Amy McMahon Study Technicians: Jennifer Christian Jonathon Gillespie Forrest Jackson Study Dates: August 15-17,2018 Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 36 of 110 2.0 METHODS 2.1 Experimental Design The design of the study involved spiking copper into test solutions and assessing the acute toxicity of the test solutions with 48 Hour Acute Definitive tests using the surrogate test organism Ceriodaphnia dubia. The two test solutions assessed were 1) laboratory dilution water, and 2) simulated downstream water at measured conditions on the day of sampling(100% effluent). Acute toxicity tests were set according to U.S. EPA protocols (EPA 821-R-02-012 Method 2002),modified according to the following parameters; 1 Test type: Acute Static Temperature: 25°C±1 Light: 100 ft.-candles; 16 hr light/8 hr dark Test Chambers: 30 mL plastic cups Test Solution Volume: 25 mL 1 Renewal of Test Solutions: None Test Organism Age: <24 hr #Neonates/Cup: 5 #Replicates/Concentration: 4 1 Feeding Regime: None Aeration: None I Dilution Factor: 0.7 Test Duration: 48 Hours Endpoints: Survival 2.2 Laboratory Dilution Water 1 The laboratory dilution water used in all tests was diluted mineral water (DMW). In this first round of tests the DMW was prepared at a hardness of 50.0 mg/L. This dilution water was prepared by adding Perrier water to ultra-pure water to obtain the desired final hardness. The procedure for the preparation of this water may be found in the EPA manual Short Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms(EPA 821-R-02-013). * Dilution water during the period of testing was prepared as follows; Amount Hardness Conductivity Alkalinity �H 20 L 50.0 mg/L 107 µmhos/cm 42.9 mg/L 7.8 Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 37 of 110 2.3 Sample Collection Sampling Locations The effluent discharges into Harris Lake. The effluent samples were collected as composite samples. As received the effluent was measured to have oxidizers (measured by the DPD method) of 0.20 mg/L. Although the DPD method is used to measure residual chlorine, in this effluent it is believed that manganate was the oxidizer which was measured. All samples were collected in half gallon plastic jugs and preserved in coolers at 0-6°C. Samples were shipped to ETT by overnight delivery. 2.4 Chemical Analyses Dissolved oxygen and pH were measured in one surrogate of each test concentration at the beginning and end of the test.Temperature was monitored in three surrogate test cups in the incubator daily. Dissolved Oxygen and pH were measured with the use of a Orion 4 Star meter.The meter is calibrated daily. Alkalinity, hardness, total suspended solids (TSS), total organic carbon (TOC), and specific conductance were measured on each laboratory water and effluent sample collected. Total recoverable copper was measured on each test solution at the beginning and end of the test. Dissolved copper also was measured for each test concentration at the beginning and end of the test. Copper analyses were conducted by ETT Environmental of Greer, SC using Standard Methods 18th Edition Method 3111B (flame atomic absorption), and concentrated to achieve a detection limit of 10 ug/L(or lower with concentration). 2.5 Preparation of Test Solutions 2.5.1 Simulated Downstream Water A simulated downstream sample was prepared using 100%effluent. Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 38 of 110 1 1 1 1 1 2.5.2 Copper Spiking 1 Copper was spiked as copper sulfate (CuSO4.5H2O) into laboratory water and the 1 simulated downstream water. Prior to spiking the total recoverable copper in each 1 effluent sample was measured. Each day a batch of simulated downstream water was prepared. An 12.72 mg/L stock solution of copper sulfate was prepared by adding 0.05 g of CuSO4.5H2O to one liter of demineralized water. A microliter syringe was used to add the correct volumes of the stock solution to each simulated effluent or control concentration to achieve the desired nominal concentration of copper. 2.6 Test Organisms The test organism used for this study was the daphnid Ceriodaphnia dubia. Test organisms were neonates of less than 24 hours in age which were obtained from individual cultures at ETT Environmental, Inc. These cultures are set weekly with reproduction of the first three broods tracked for all culture organisms. Only neonates from broods of eight or larger, produced by culture trays demonstrating less than 10% mortality and greater than a mean of 15 young per female (3 broods) are used for testing. Culture sensitivity is monitored through the use of semi-monthly reference toxicant testing. Voucher specimens from the culture are set aside on a monthly basis and taxonomically verified by a staff macroinvertebrate taxonomist. Culture organisms are subject to the same light,temperature,and feeding regimes as used for testing. Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 39 of 110 3.0 RESULTS 3.1 Laboratory Water 3.1.1 Acute Toxicity Testing Results The acute definitive test with Ceriodaphnia dubia in laboratory water spiked with copper showed a 48 Hour LC50 of 10.236 ug/L Total Recoverable Copper and a 48 Hour LC50 of 9.402 ug/L Dissolved Copper. Due to the pattern of the data the values were calculated using the Probit method. The survival data at each concentration are summarized as follows; Nominal Concentration Mean Measured Conc. 48 Hour of Total Recoverable Cu of Total Recoverable Cu Mortality and(Dissolved Cu) 0 ug/L <1.0 ug/L (<1.0) 0% 4.2 ug/L 5.0 ug/L(5.1) 0% 6.0 ug/L 6.0 ug/L(5.8) 0% 8.6 ug/L 6.3 ug/L (7.3) 45% 12.3 ug/L 14.4 ug/L(11.6) 95% 17.5 ug/L 18.3 ug/L(15.7) 100% 25 ug/L 24.5 ug/L(23.0) 100% 35 ug/L 34.0 ug/L (23.5) 100% Survival data for the test may be found in Appendix B2. Results of measured concentrations of total recoverable and dissolved copper are provided in Appendix B3. Statistical analysis results are found in Appendix B6. 3.1.2 Chemical Analyses The pH in the spiked dilution water test ranged from a minimum of 7.8 to a maximum of 8.1. Dissolved oxygen was generally at the saturation point in all treatments throughout the test. 1 The Probit Method is used when there are at least two test concentrations with partial mortality. Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 40 of 1 10 3.2 Simulated Downstream Water 3.2.1 Acute Toxicity Testing Results I The acute definitive test with Ceriodaphnia dubia in downstream water spiked with copper showed a 48 Hour LC50 of 128.278 ug/L Total Recoverable Copper and a 48 Hour LC50 of 111.513 ug/L of Dissolved Copper. Due to the pattern of the data the value was calculated using the Trimmed Spearman Karber method. The survival data at each concentration are summarized as follows; I Nominal Concentration Mean Measured Conc. 48 Hour of Total Recoverable Cu of Total Recoverable Cu Mortality and(Dissolved Cu) 0 ug/L 29.3 ug/L(22.7) 0% 25 ug/L 50 ug/L(32.5) 0% 35 ug/L 55 ug/L(40) 0% 50 ug/L 67.5 ug/L(64) 5% 71.4 ug/L 87.5 ug/L (77) 20% 102 ug/L 123.5 ug/L(109.5) 45% 143 ug/L 163 ug/L(136.5) 75% 204 ug/L 216.5 ug/L(186) 90% Measured concentrations were generally higher than nominal concentrations. A significant suppression in survival was noted at a nominal concentration of 143 ug/L of total copper. Survival data for the test may be found in Appendix B2. Results of measured concentrations of total recoverable and dissolved copper are provided in Appendix B3. Statistical analysis results are found in Appendix B6. 1 The Probit method is used when there are at least two test concentrations with partial mortality. Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 41 of 110 3.2.2 Chemical Analyses The pH in the simulated downstream water ranged from a minimum of 7.9 to a maximum of 8.6. Dissolved oxygen was generally near the saturation point in all treatments throughout the test. Other water chemistry parameters are summarized as follows; Parameter Effluent Total Recoverable Copper(ug/L) 29.3 Dissolved Copper(ug/L) 22.7 Alkalinity(mg/L) 58.1 Conductivity(umhos/cm) 402 Hardness(mg/L) 58.0 Total Organic Carbon(mg/L) 25.1 Total Suspended Solids(mg/L) 54.4 It may be seen that the effluent water was characterized by moderate alkalinity, hardness, and TOC and elevated TSS. 3.3 Upstream Waters Not applicable when downstream concentration is defined as 100%effluent; Parameter Result Total Recoverable Copper(µg/L) NA Dissolved Copper(µg/L) NA Total Organic Carbon(mg/L) NA Alkalinity(mg/L) NA Hardness(mg/L) NA Conductivity(µmhos/cm) NA Total Suspended Solids(mg/L) NA Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 42 of 110 1 4.0 CALCULATION OF WATER EFFECT RATIO As noted in the results section,acute testing indicated an LC50 of 9.5500 ug/L of total recoverable copper in laboratory dilution water and an LC50 of 144.544 ug/L of total recoverable copper in 1 100% SHNPP effluent.The laboratory dilution water LC50 values must be adjusted to downstream water hardness in order to calculate the Water Effect Ratio,using the EPA formula, 1 as follows; 1 0 9a22 LC50 x (downstream hardness/laboratory water hardness) T-Cu: 10.236 ug/L x(58/50)0.9422= 11.7723 ug/L Dis-Cu: 9.402 ug/L x(58/50) 0.9422= 10.8132 ug/L The Water Effect Ratio can thus be calculated as follows; Water Effect Ratio(WER) = LC50 in Effluent = 128.278 ug/L = 10.8966 (Total Recoverable Copper) LC50 in Lab Water 11.7723 ug/L Water Effect Ratio(WER) = LC50 in Effluent = 111.513 ug/L = 10.3127 (Dissolved Copper) LC50 in Lab Water 10.8132 ug/L A final water effect ratio(FWER)will be calculated using the individual WERs from three rounds of testing. 1 Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 43 of 110 ROUND 2 -APPENDIX B1 Reference Toxicant Quality Control Chart Ceriodaphnia dubia See Round 3 Appendix Cl Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 44 of 110 ROUND 2 - APPENDIX B2 Survival Data for Acute Definitive Tests Duke Harris-WER Round 2 Cu ETT Environmental,Inc.;08/I8 Page 45 of 110 IP Page 64 c.tat Nominal Initial# Mortality Measured Concentration WER 48 Hour Acute Toxicity Test Conc Rep Organisms 24 hr 48 hr_Initial Final Mean Facility: 3: (1\UL) Metal: cAk --7.! A r? 0 Total Total Total Sample ID: , , 0% B 5 0 Start Date: 8 15 i g Time: 1300 By: /1M 110 C 5 0 Dis Die Die End Date: j 17 a Time:.13 Z— BY: rtM III D 5— 0 Effluent Log it: _Upstream Log#: tit r A 5- Q Total Total rota, TEST ORGANISMS it Z B 6- n Test Organism: A.F 8.10 1 G".�, t+t , C ( 0 DIG DIs eta for Ceriodaphnia dubia Source: fVr g cj, 8 r0 tft D Date Removed; 8 t{ 1 HI - • • n - - - P...1t.,...... !--Inc) (Time and '27.9J) /"rim,.... b B y Q for fathead minnows or mysids: u C 0 , Die Die Dis Source: Age: if D 1 n Temperature 24-26 C. Light 16 hr If/8 hr kd;50-100 ft candles I A S Z Total Total Total Laboratory Water MW/SSF @ 50 mg/L hardness ,: i B 5 3 Downstream Water Preparationtl t C 6. 2 DI5 ot5 Ole %effluent volume mL Prep.Date: t D 6 .� % upstream volume mL Prep.by: , ', A y Total Total Total ion: Metal Salt: 'S e aratt I� Solution Pr LD Test �t,t� �1 B � p y 12� C S DIG Dis Dis Date: 1 is lb' BY Stock. Soln: 12--72 L 4 I D Nominal Conc mL Stock Saki. Volume prepared 6%1 A Total Total Total L\•2" '/7 . 'P O „l i B s zy 9 I t ,lj \� C V , Die Ds Ole 0 •3y i i4 l A 6 6- Total Total Total I f•7 '401 li il l B 6 .s Z •Id, ; j C -� b3pC D 4js i,l; ID 6I '!{t A 6 5 Total Total Total A Total Total Tot 11 I i i] '0l 3 B t 5 B ih Ij .1i C ,") Dls DIG Die C Ole Ole DI: D D r,ii •i r'r ,ri {II A Total Total Total A Total Total Tot I �l B B 1 :l C Die Dis Dls C Dis Dis Di: t.I. D D Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. Test Method: per EPA Interim Guidance 5 i. ill. Page 46of110 V64Qt1 Page 65 of 100 t No Initial# Mortality Measured Concentration WER 48 Hour Acute Toxicity Test Cent Rep Organisms 24 hr 48 hr Initial Final Mean Facility: 1 u - kto.4-(�('S/ Metal:ctiu A A Total Total Total Sample ID: Q(A-A-"I O C - I 0% B ,� 0 Start Date: ?-I5'18 Time: 13 00 By: AM 1 _ C 5 0 DIs DID Ols End Date: Sl171f1 Time: /3Z5" By: 4/17 ire D S Effluent Log It: 2 t Z l Upstream Log#: 1 .—„ t A 5- 0 Total Total Total TEST ORGANISMS --1 B .S 0 Test Organism: A-F 4'•!o, 6 Li d f) �.r� 2 5 C 0 DIs Ols DIs M`P tl• / .s-k p vo - 5- for Ceriodaphnia dubia Source: D , 4- 0 Date Removed; J'•/y.« rr L F' w• ,al - - beiweel I j 7ot (Time)and -—64:1p- (Time) ( 3 B .S t!`)., for fathead minnows or mysids: -�.1• C 5 ��0ll Ols Us Dis Source: Age: I D 5- V Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles A 5- 0 Total Total Total Laboratory Water DMW/SSF @ 50 mg/L hardness 1 j 5D B - / Downstream Water Preparation C 5 0 Dis DIs DIs % effluent 1000 volume 1/000 mL Prep.Date:8IS'/j i D o i % upstream volume , mL Prep.by: AM �/ .—}T , t� A 7 z Total Total Total B S / . Test Solution Preparation: Metal Salt: Cu SO Y•5// 22) i I 0 Dis Ells DIs Date: '8-��tr By: AYE Stock.Soln: 1 Z,7Zn'ij/ D Nominal Conc mL Stock Soln. Volume prepared A S Total Total Total 25 Q}� `�� v» I t7 (OZ.. B 5- 1 35 I-38 c 3 ( �1 '._ Ols DIs DIs. 5-1) �,� D 3 ?)- A loz 11. , 5 Total Total Total ( 143 B s 1y3 S,62 C 5- 3.. Ols DIs DIs vVL1 1.v7., I 1 D 5- 3 �— A 5-- ,5--* Total Total Total A Total Total Total I �t B s B C / Dis DIs DIs C Ols DIs DIs I p 51 Y D t A Total Total Total A Total Total Total I ii ii B B 1 a C Dis DIs DIs C DIs DIs DIs I . D D O•Test solution volume:zsmL. Test vessels,oz.plastic cups.Transfer volume 0.osmL. Test Method: per EPA Interim Guidance . I I Page 47 of 110 I r - ROUND 2 -APPENDIX B3 Measured Concentrations of Total Recoverable Copper in Test Solutions Duke Harris-WER Round 2 Cu ETT Environmental, Inc.;08/10 Page 48 of 110 I 1 1 1 I I Measured Total Recoverable and Dissolved Copper Duke Harris Plant-Primary Species Site Specific Study I August 2018 1 I Sample:S iked Dilution Water(Diluted DMV1 Initial Date:08/15/18 ominal Measured Total Recoverable Copper(µg/L) %of Measured Dis.Cu(µg/L) % I Total Cu Initial Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Mean Nominal Initial Day 2 Mean Dissolved 1 0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 4.2 4.6 5.3 5.0 119% 4.9 5.2 5.1 102% 6.0 no data 6.0 6.0 100% 5.8 no data 5.8 97% _ 8.6 7.3 5.3 6.3 73% 9.6 5.0 7.3 116% 12.3 14.7 14.1 14.4 117% 15.4 7.7 11.6 81% 1 17.5 20.1 16.4 18.3 105%" 17.4 14.0 15.7 86% 25.0 25.0 24.0 24.5 98% 23.0 23.0 23.0 94% 1 35.0 39.0 29.0 34.0 97% 23.0 28.0 d 23.5 69% 1 I Sample:Simulated Downstream-Duke Harris Initial Date:8/15/18 Nominal Measured Total Recoverable Copper(µg/L) %of Measured Dis.Cu(µg/L) % 1 Total Cu Initial Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Mean Nominal Initial Day 2 Mean Dissolved 1 0.0 27.7 30.8 29.3 21.5 23.8 22.7 25.0 50.0 no data 50.0 200% 24.0 41.0 32.5 65% 1 35.0 55.0 no data 55.0 157% 43.0 37.0 40.0 73% 1 50.0 60.0 75.0 67.5 135% 59.0 69.0 64.0 95% 71.4 85.0 90.0 _ 87.5 123% 76.0 78.0 77.0 88% 1 102.0 121.0 126.0 _ 123.5 121% 110.0 109.0 109.5- 89% 143.0 161.0 165.0 _ 163.0 114% 137.0 136.0 136.5 84% 1 204.0 218.0 215.0 216.5 106% 185.0 187.01 186.0 86% Page 49 of 110 ROUND 2 - APPENDIX B4 Water Chemistry Measurements for Acute Definitive Tests Duke Harris-WER Round 2 Cu ETT Environmental,Inc.;08/18 Page 50 of 110 (l EV Er 4 AC>rl`i.iJ -TTIXIC("1-l' TCS�� - Ci-1I"q\'I l;Till' N„r —_____ ___ "— 4b'hour�c ?J Hour Rradrngi Jb'Hour fiendin!s it Initial Initial Readings 14!lour 11 rn riinlr) nr" iCI�:' old old ^,:. old nld nr" nr" Cnodon, nDusoly.d OwnI,cd l)r snlvr<I IkIlil (7itsul•,rtl (runhnslrmlo� U�ad•rd ,II Orygrn n, ill C1ryt�n P II Oryl•,rn t PII IJ PII <,r 1, n�ii Orll: mt./I. (Cfl_ nl rl't:r' ml./I. rat'./L __ `\ Cone—`_ __e 1— ------. _- oo 1p 8lD-31 II iu,l. Date p' " "lb �3� tYi'rlHI, Time. ` )� III ly l,l. Initials. tillfilli 72 Hour Readings 71 Hour Readings 96 Hour Readings 11171'f.!ILi old o{d nc"' nc>+' old old Dissolved Dissolved Dissolved I€LIIIII'I Elilucnt Oxygen pH Oxygen pHOxygen p31 �t- IkL+El.INI Cooccotrrtioo mg/L m�' I1C11Bilu 12illllllii 91ilttlf k, I1111illlll -- MHO, Mtu:altII , IH111111 IP . ➢KIWI, ilIHIIIII.I Date: win Time: NI1111liII initials: tlllti111EI E IJIIIIII Lab 1D#: ullaul!rl Client: 1/4A \\�l1, (/+ 1�7�'L2 1 Ililg11lu 3 �f IIITIllli.. V 01 1 1 BUlllliv Page 51 of 110 ROUND 2 - APPENDIX B5 Chain of Custody Documentation Duke Harris-WER Round 2 Cu ETT Environmental,Inc.;08/18 Page 52 of 110 se ET, 7 i CHAIN OF CUSTODY RECORD sI,::. .en ViTOIl unri,`i Page 0I PO Box 16414,Greenville,SC 29606-7414 f (864)877-6942, (800)891-2325 Fax:(864)877 6938 Shipping Address:4 Craftsman Ct,Greer,SC 29650 W W W.ETTE NvI RO NM ENTAL.COM Client: ,f <_� -.. tJ bi.s� L._.fl' t�"i `' � Program Containers Preservative Parameters Facility: L,/ _ . a r%r J Whole Effluent Toxicir State: A l `' , NPDES f: acute Chronic Test Organisms i tj ci d p o U (Composite only) (Grab or Composite) o _ _ i j V o_ — t+ Z • ' U = U = _ 1=H2SO4 •:n = � E. = •E _ �" Sign,and Print below > 8 =o ?=t-a. 2 — 2 _ SI — —', _ _ _ > I the dotted line _ E E v o a= on ' ' o = s y r p I c _ f .o _ n - o c = o. —_ o c 6 o,•o = = 6 8 i=zn.4c v c) — _ - > w SAMPLE ID EE Composite Start Date lime SampleCotlection Date Time Collected In u rn :n z T. a U > e=rj . < < v U u Ir Z n = v - 3 Chemical Analysis&Other C e { �n aaa(1w On(2) ^1,u ��0,3� a r)rt,rn t ay aLA i w! 0 -,i; 0 Special Instructions: Sample Custody Transfer Record Secure Receipt I Sample Date Time Relinquished By I Organizati n Received By/Organizatig / Area Temp`C Preserved? U'�K It dV..3Ll di iL4 fili �/ii/i ' Imo° - , �(� 0.i COMPOSITE SAMPLING PROCEDURES TEMPERATURE MONITORING PROCEDURES HOLD TIME PROCEDURES Composite samples must be collected over a 24 hour period. Sample temperature during collection and transport must be between For toxicity testing the sample must first be used within 36 hours Time Proportional:I sample each hour for 24 hours.Equal volut 0.0 and 6.0'C.Samples must not be frozen.Use water ice in sealed bags. of sample collection(completion of composite sample). or at minimum I sample every 4 hours over 24 hours. Sample may not be used after 72 hours from sample collection. Flow Proportional:As per instructions in NPDES permit. ROUND 2 - APPENDIX B6 Statistical Analysis Results Duke Harris-WER Round 2 Cu ETT Environmental,Inc.;08/18 Page 54 of 110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 5 0 20 0.6990 0.5 6 0 20 0.7782 0,5 6.3 45 20 0.7993 4.87 14.4 95 20 1.1584 6.64 18.3 100 20 1.2625 8.09 1. Enter data in yellow boxes Test Type: Acute Definitive 48 Hour Species: C dubia Sample ID DMW T Cu LC50 = Date: 8/15/18 10.236 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value Page 55 of 110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 5.1 0 20 0.7076 0.5 5.8 0 20 0.7634 0.5 7.3 45 20 0.8633 4.87 11.6 95 20 1.0645 6.64 15.7 100 20 1.1959 8.09 1. Enter data in yellow boxes Test Type: Acute Definitive 48 Hour Species: C dubia Sample ID DMW Dis Cu LC50 = Date: 8/15/18 9.402 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value Page 56 of 110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 67.5 5 20 1.8293 3.36 87.5 20 20 1.9420 4.16 123.5 45 20 2,0917 4,87 163 75 20 2.2'122 5.67 216.5 90 20 2.3355 6.28 1. Enter data in yellow boxes Test Type: Acute Definitive 48 Hour Species: C dubia Sample ID Duke Harris T Cu LC50 = Date: 8/15/18 128.278 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value Page 57 of 110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 64 5 20 1.8062 3.36 77 20 20 1.8865 4.16 109.5 45 20 2.0394 4.87 136.5 75 20 2.1351 5.67 186 90 20 2.2695 6.28 1. Enter data in yellow boxes Test Type: Acute Definitive 48 Hour Species: C dubia Sample ID Duke Harris Dis Cu LC50 = Date: 8/15/18 111.513 A value of>0 must be entered for the control concentration,thus a nominal value of 0.l is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value Page 58 of l l0 I ET Elronm !inc. (864)877-6942 . FAX(864)877-6938 P.O. Box 16414, Greenville. SC 29606 Craftsman Court, Greer, SC 29650 APPENDIX C I WATER EFFECT RATIO STUDY (Interim Guidance) Duke Energy Shearon Harris Nuclear Power Plant Primary Species - Round 3 Metal: Copper September 2018 Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 59 of 110 TABLE OF CONTENTS 1.0 INTRODUCTION 2.0 METHODS 2.1 Experimental Design 2.2 Laboratory Dilution Water 2.3 Upstream and Effluent Sample Collection 2.4 Chemical Analyses 2.5 Preparation of Test Solutions 2.6 Test Organisms 3.0 RESULTS 3.1 Laboratory Water 3.2 Simulated Downstream Water 3.3 Upstream Waters 4.0 CALCULATION OF WATER EFFECT RATIO 5.0 DISCUSSION LIST OF APPENDICES Appendix Cl. Reference Toxicant Quality Control Chart for Ceriodaphnia dubia Appendix C2. Survival Data for Acute Definitive Tests Appendix C3. Measured Concentrations of Total Recoverable Copper in Test Solutions Appendix C4. Water Chemistry Measurements for Acute Definitive Tests Appendix C5. Chain of Custody Records Appendix C6. Statistical Analysis Results Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 60 of 110 1.0 INTRODUCTION The Duke Energy Shearon Harris Nuclear Power Plant (SHNPP) discharges effluent into Harris Lake under NPDES Permit NC0039586. In cooperation with Jacobs Engineering, ETT Environmental has been retained to conduct a "site specific study" to determine if permitted copper limits for each effluent discharge are unnecessarily overprotective of aquatic life. This is to be accomplished through the calculation of a water effect ratio P comparing aring the acute effects of copper upon the surrogate (WER), aquatic test organism Ceriodaphnia dubia living in laboratory dilution water to the acute effects of copper to the same test species in simulated downstream receiving water. The study used the methodology provided in the Streamlined Water-Effect Ratio Procedure for Discharges of Copper (EPA-822-R-01- 005). On September 24-25, 2018, SHNPP personnel collected a composite effluent water sample. Acute toxicity tests for the Water Effect Ratio study were initiated on September 26th,2018. Laboratory Location: ETT Environmental, Inc. 4 Craftsman Court Greer, SC 29650 SCDHEC Certification# 23104 Study Director: Robert W. Kelley, Ph.D. Study Scientist: Amy McMahon Study Technicians: Jennifer Christian Jonathon Gillespie Forrest Jackson Study Dates: September 26-28,2018 Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 61 of 110 2.0 METHODS 2.1 Experimental Design The design of the study involved spiking copper into test solutions and assessing the acute toxicity of the test solutions with 48 Hour Acute Definitive tests using the surrogate test organism Ceriodaphnia dubia. The two test solutions assessed were 1) laboratory dilution water, and 2) simulated downstream water at measured conditions on the day of sampling(100% effluent). Acute toxicity tests were set according to U.S. EPA protocols (EPA 821-R-02-012 Method 2002),modified according to the following parameters; Test type: Acute Static Temperature: 25°C±1 Light: 100 ft.-candles; 16 hr light/8 hr dark Test Chambers: 30 mL plastic cups Test Solution Volume: 25 mL Renewal of Test Solutions: None Test Organism Age: <24 hr #Neonates/Cup: 5 #Replicates/Concentration: 4 Feeding Regime: None Aeration: None Dilution Factor: 0.7 Test Duration: 48 Hours Endpoints: Survival 2.2 Laboratory Dilution Water The laboratory dilution water used in all tests was diluted mineral water (DMW). In this first round of tests the DMW was prepared at a hardness of 50.0 mg/L. This dilution water was prepared by adding Perrier water to ultra-pure water to obtain the desired final hardness. The procedure for the preparation of this water may be found in the EPA manual Short Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms(EPA 821-R-02-013). * Dilution water during the period of testing was prepared as follows; Amount Hardness Conductivity Alkalinity pH 20 L 50.0 mg/L 108 µmhos/cm 44.3 mg/L 7.8 Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 62 of 110 2.3 Sample Collection Sampling Locations The effluent discharges into Harris Lake. The effluent samples were collected as composite samples. As received the effluent was measured to have oxidizers (measured by the DPD method) of 0.19 mg/L. Although the DPD method is used to measure residual chlorine, in this effluent it is believed that manganate was the oxidizer which was measured. All samples were collected in half gallon plastic jugs and preserved in coolers at 0-6°C. Samples were shipped to ETT by overnight delivery. 2.4 Chemical Analyses Dissolved oxygen and pH were measured in one surrogate of each test concentration at the beginning and end of the test.Temperature was monitored in three surrogate test cups in the incubator daily. Dissolved Oxygen and pH were measured with the use of a Orion 4 Star meter.The meter is calibrated daily. Alkalinity, hardness, total suspended solids (TSS), total organic carbon (TOC), and specific conductance were measured on each laboratory water and effluent sample collected. Total recoverable copper was measured on each test solution at the beginning and end of the test. Dissolved copper also was measured for each test concentration at the beginning and end of the test. Copper analyses were conducted by ETT Environmental of Greer, SC using Standard Methods 18th Edition Method 3111B (flame atomic absorption), and concentrated to achieve a detection limit of 10 ug/L (or lower with concentration). 2.5 Preparation of Test Solutions 2.5.1 Simulated Downstream Water A simulated downstream sample was prepared using 100%effluent. Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 63 of 110 2.5.2 Copper Spiking Copper was spiked as copper sulfate (CuSO4.5H20) into laboratory water and the simulated downstream water. Prior to spiking the total recoverable copper in each effluent sample was measured. Each day a batch of simulated downstream water was prepared. An 12.72 mg/L stock solution of copper sulfate was prepared by adding 0.05 g of CuSO4.5H20 to one liter of demineralized water. A microliter syringe was used to add the correct volumes of the stock solution to each simulated effluent or control concentration to achieve the desired nominal concentration of copper. 2.6 Test Organisms The test organism used for this study was the daphnid Ceriodaphnia dubia. Test organisms were neonates of less than 24 hours in age which were obtained from individual cultures at ETT Environmental, Inc. These cultures are set weekly with reproduction of the first three broods tracked for all culture organisms. Only neonates from broods of eight or larger, produced by culture trays demonstrating less than 10% mortality and greater than a mean of 15 young per female (3 broods) are used for testing. Culture sensitivity is monitored through the use of semi-monthly reference toxicant testing. Voucher specimens from the culture are set aside on a monthly basis and taxonomically verified by a staff macroinvertebrate taxonomist. Culture organisms are subject to the same light,temperature,and feeding regimes as used for testing. Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 64 of 110 3.0 RESULTS 3.1 Laboratory Water 3.1.1 Acute Toxicity Testing Results The acute definitive test with Ceriodaphnia dubia in laboratory water spiked with copper showed a 48 Hour LC50 of 20.358 ug/L Total Recoverable Copper and a 48 Hour LC50 of 19.748 ug/L Dissolved Copper. Due to the pattern of the data the values were calculated using the probit method. The survival data at each concentration are summarized as follows; Nominal Concentration Mean Measured Conc. 48 Hour of Total Recoverable Cu of Total Recoverable Cu Mortality and(Dissolved Cu) 0 ug/L <1.0 ug/L(<1.0) 0% 4.2 ug/L 3.6 ug/L(3.3) 0% 6.0 ug/L 6.7 ug/L (6.6) 0% 8.6 ug/L 8.4 ug/L(7.1) 0% 12.3 ug/L 11.3 ug/L (10.6) 0% 17.5 ug/L 15.3 ug/L (15.5) 5% 25 ug/L 22.5 ug/L (26.0) 75% 35 ug/L 33.5 ug/L (27.5) 100% Survival data for the test may be found in Appendix C2. Results of measured concentrations of total recoverable and dissolved copper are provided in Appendix C3. Statistical analysis results are found in Appendix C6. 3.1.2 Chemical Analyses The pH in the spiked dilution water test ranged from a minimum of 7.6 to a maximum of 7.8. Dissolved oxygen was generally at the saturation point in all treatments throughout the test. The Probit method is used when there are at least two test concentrations with partial mortality. Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 65 of 110 3.2 Simulated Downstream Water 3.2.1 Acute Toxicity Testing Results The acute definitive test with Ceriodaphnia dubia in downstream water spiked with copper showed a 48 Hour LC50 of 179.504 ug/L Total Recoverable Copper and a 48 Hour LC50 of 158.483 ug/L of Dissolved Copper. Due to the pattern of the data the value was calculated using the probit method. The survival data at each concentration are summarized as follows; Nominal Concentration Mean Measured Concs. 48 Hour of Total Recoverable Cu of Total Recoverable Cu Mortality and(Dissolved Cu) 0 ug/L 22.9 ug/L(20.2) 0% 25 ug/L 50 ug/L (32) 0% 35 ug/L 63.5 ug/L(40) 0% 50 ug/L 68 ug/L(51.5) 0% 71.4 ug/L 85.5 ug/L(72.5) 0% 102 ug/L 113 ug/L (103) 5% 143 ug/L 152 ug/L (140) 20% 204 ug/L 224 ug/L(189) 55% Measured concentrations were generally higher than nominal concentrations.A significant suppression in survival was noted at a nominal concentration of 204 ug/L of total copper. Survival data for the test may be found in Appendix C2. Results of measured concentrations of total recoverable and dissolved copper are provided in Appendix C3. Statistical analysis results are found in Appendix C6. The Probit method is used when there are at least two test concentrations with partial mortality. Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 66 of 110 3.2.2 Chemical Analyses The pH in the simulated downstream water ranged from a minimum of 7.9 to a maximum of 8.6. Dissolved oxygen was generally near the saturation point in all treatments throughout the test. Other water chemistry parameters are summarized as follows; Parameter Effluent Total Recoverable Copper(ug/L) 22.9 Dissolved Copper(ug/L) 20.2 Alkalinity(mg/L) 50.6 Conductivity(umhos/cm) 347 Hardness(mg/L) 54.0 Total Organic Carbon(mg/L) 26.0 Total Suspended Solids(mg/L) 13.3 It may be seen that the effluent water was characterized by moderate alkalinity, hardness, TOC and TSS. 3.3 Upstream Waters Not applicable when effluent is 100%of downstream flow. Parameter Result Total Recoverable Copper(µg/L) NA Dissolved Copper(µg/L) NA Total Organic Carbon(mg/L) NA Alkalinity(mg/L) NA Hardness(mg/L) NA Conductivity(µmhos/cm) NA Total Suspended Solids(mg/L) NA Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 67 of 110 4.0 CALCULATION OF WATER EFFECT RATIO As noted in the results section,acute testing indicated an LC50 of 20.358 ug/L of total recoverable copper in laboratory dilution water and an LC50 of 179.504 ug/L of total recoverable copper in 100% SHNPP effluent.The laboratory dilution water LC50 values must be adjusted to downstream water hardness in order to calculate the Water Effect Ratio,using the EPA formula, as follows; LC50 x (downstream hardness/laboratory water hardness)°.9422 T-Cu: 20.358 ug/L x(54/50)°9422= 21.8891 ug/L Dis-Cu: 19.748 ug/L x(54/50)°.9422= 21.2332 ug/L The Water Effect Ratio can thus be calculated as follows; Water Effect Ratio(WER) = LC50 in Effluent = 179.504 ug/L = 8.2006 (Total Recoverable Copper) LC50 in Lab Water 21.8891 ug/L Water Effect Ratio(WER) = LCs0 in Effluent = 158.483 ug/L = 7.4639 (Dissolved Copper) LC50 in Lab Water 21.2332 ug/L A final water effect ratio(FWER)will be calculated using the individual WERs from three rounds of testing. Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 68 of 110 ROUND 3 -APPENDIX Cl Reference Toxicant Quality Control Chart Ceriodaphnia dubia Reference Toxicant Chart 2017/18 Acute /NaCI / Ceriodaphnia dubia 2.75- __ —_ _— __ __ __ -- __ -_. _— __ __ _— __ __ __ __ __ ._. __ __ __ __ 2.50 - - -2. • 2. - - - - — — — - -- -- - - �.?�2. L. 2. 9 2.t 2. 2. 2. 3 2. — . 2. 7 2. t 2.' 2.'S U 2. 2 2. ca2.2 - - -- -- - -- -- - -- -- - — - -- - -- -- — C- 1. 1.4 -1 1.-e 1.75 -- - - - - - -� ' - t :t • 1, 1. 1.,4 1. 1.50 Dec1917 Ja' '18 Feb27 18 Faar222`18 Apr2418 May3O 8 Jun25`48 JLtM`18 Aug.29 18 Sep24�8 Jan318 Feb1718 Mart18 Apr218 May8.18 Jart518 Jut3"18 Auge'18 Sep1O18 0ct298 Upper Lower -LC 50 *Mean - -Control -A-Control Limit Limit 'JCL&LCL are+1-2 standard deviations from mean(respec ivey) Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 69 of 110 ROUND 3 -APPENDIX C2 Survival Data for Acute Definitive Tests 1 1 1 1 1 1 1 1 1 1 1 1 Duke Harris-WER 3 Cu ETT Environmental;09/18 1 1 1 Page 70 of 110 1 1 Page 70 of 1pp Nominal Initial It Mortality Measured Concentration WER 48 Hour Acute Toxicity Test a1 j---- r Nor Cone Reit Organisms 24 hr 48 hr Initial Pinal Mean Facility: 1IA.V. Metal: %t Ct A t ,„,„, ,,," iota Sample: ID. cz 1 0% B _ 0 Start Date: t 6, !.� Time: \.-71(,Y) By: J(i C 5 () DIO Diu Ds End Date: 1-2`(1-n' Time: 150 By d: D r� () Effluent Log#: Upstream Loc:tl: ... ,1 A 5 ,,,,,,, ,,,,,,: Ini,„ TEST ORGANISMS I r B 5 0 Test Organism: I- 11-H, Cif �61 0 , `_) Cr 1 1 fk_2 Z C 0) Dls Coi Dis f "i.Cenoclaphnia dubia 1 Source: l D J 0 -bate Removed; - (s, A H 0 Mal Total Total - Between ;-71Y) (-rime)and Z (Time) B _I 0 for fathead minnows or mysids: C 5 r) Dis Dls Dis Source: Age: '3 D 5 0 Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles 1 , I A n Total Total Total Laboratory Water DMW / SSF © 50 mg/L hardness / B 5 0Downstream Water Preparation g (tn 1 G C O ols Dls Ds % effluent volume mL Prep.Date: i L. D 5 0 % upstream volume mL Prep.by: A ' ) 0 Total Total Total fZ 3 B 5 0 Test Solution Preparation: Metal Salt: C.)501-51-0 C 5 0 Dls ots Dis Date: By: Stock.Soln: 12.72-011:k It- ( D 5 0 Nominal Conc mL Stock Soln. Volume prepared A 5 1 Total Total Total 0 0 5C0 ovt L I C 5 O Dts Dis Die 0 ,z9 D ////5 0 Z.' .3ry 1 A 5 Total Total Total (�-3 O ZS B 5 �Al 1/5 '(/p g 11 C 5 �t Dis Dls Dis ��► 1 D 5 3 ) I. Z A 5 5 Total Total Total A Total Total Total 5 B 5j 5 B C ✓ 5 Os Dis Dis C Dls Dis Dis D5 5 D ....... A Total Total Total A Total Total Total B B I C Dls Dis Dls C Dis DIs DIs D D Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. Test Method:per EPA Interim Guidance Test soy ii, „i Page 71 of 110 I r 3e)Q Page 71 of 100 I t N°ttittnl 1 Initial it VILER Mortality Measured Concentration ER 48 Hour Acute Toxicity Test Rep Organisms 24 hr 48 hr Initial Fins! Mean , Facility / �/a ( jo c°„t: Yl�Y t t� .Y i �� Metal L l A (-5 i i,,,, 1,..,„ 1 Sample. ID ,��'�. 1 B `) _1) Start Date: (-(-�(r_�j : Time: . By: Y . c 1 C " J () Dr Ols Dis End Date c �� '(R" Time: ;510 BY Effluent Log . ✓ 1,1 1L"�kt m; Upstrea Log#t. A \-') ( ) ,ut.,, im,,l lula, TEST ORGANISMS 1 I L B 5 (-- Test Orgattisnm: _13,0. S_ . , (. Os Dis Dis for(eriodaphnia dubi�t .- Source: I D C 0 \ Date Removed; (4 -2 '1� TimA1 >� TirnPl anCl , 6�)(i (Time) A` �� �` R�t nic.an I /'y l B J JO for fathead minnows or mysids: 35 C (_� Dis Dio Dis Source; Ache ri 0 D 0Temperature 24-26 C. Light 16 hr It/8 fir kd;50-100 h candles I i A 5 �n1 Total Total Total Laboratory Water DMW I SSF @ 50 rng/L hardness IB 5 t f Downstream Water Preparation ' l 1 O C GS 0 ols Din Dln %effluent I o volume( mL Prep.Date: D J 0 % upstream volume mL Prep.by: A 5 0 Total Total Total ' . B S 0 Test Solution Preparation: Metal Salt: T''A C 5 Os DIs Ols Date: By: Stock. Soln: D S 0 Nominal Conc mL Stock Spin. Volume prepared A ✓ 1 Tvtai Total Total ( t 0 500 I /�o� r)5 0 25 .15 C ✓ 6 Ols ols DIs 35 I-38' D 5 0 50 I -q1 A 5 i 27� Total Total Total 11 B 5 , i Inz 1.....o1 C 5 O DIs Ms DIs 115 ,6 2/' D I ' OZ �� 1 i A / 3 Total Total Total A Total Total Total B B j5C3 Ms Dis DIs C Ols Dls Dis , D D A Total Total Total A Total Total Total B B 1 C DIs Os DIs C Dis DIs DIs D D Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. Test Method: per EPA Interim Guidance Page 72 of 110 ROUND 3 - APPENDIX C3 Measured Concentrations of Total Recoverable Copper in Test Solutions Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 73 of 110 Measured Total Recoverable and Dissolved Copper Duke Harris Plant-Primary Species Site Specific.Study September 2018 Sample:Spiked Dilution Water(Diluted DMWlnitial Date:09/26/18 Nominal Measured Total Recoverable Copper(AWL) „r Measured Dis.Cu(µg/L) % Total Cu Initial Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Mean \„,„,,,.,i Initial Day 2 Mean Dissolved 0 <1.0 <1.0 I 1.6 I.(1 <1.0 4.2 2.2 4.8 3.6 86% 3.6 3.0 3.3 92% 6.0 4.6 8.8 6.7 112% 7.6 5.5 6.6 99% 8.6 7.4 9.4 8.4 98% 8.0 6.3 7.1 85% 12.3 8.1 14.4 11.3 92% 11.2 9.9 10.6 94% 17.5 14.8 15.7 15.3 87% 15.4 15.7 15.5 101% 25.0 18.0 27.0 22.5 90% 23.0 29.0 26.0 116% 35.0 32.0 35.0 ;3 5 96% 26.0 29.0 27.5 82% Sample:Simulated Downstream-Duke Harris Initial Date:9/26/18 Nominal Measured Total Recoverable Copper(µg/L) %of Measured Dis.Cu(µg/L) Total Cu Initial Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Mean Nominal Initial Day 2 Mean Dissolved 0.0 23.4 22.4 22.9 20.2 20.2 25.0 50.0 50.0 50.0 200% 41.0 23.0 32.0 64% 3'5.0 64.0 63.0 63.5 181% 48.0 32.0 40.0 63% 50.0 66.0 70.0 68.0 136% 54.0 49.0 51.5 76%_ 71.4 85.0 86.0 85.5 120% 76.0_ 69.0 72.5 85% _ 102.0 116.0 109.0 113.0 111% 108.0 98.0 103.0 91% 143.0 151.0 152.0 152.0 106% 152.0 127.0 140.0 92% 204.0 228.0 221.0 224.0 110% 208.0 169.0 189.0 84% It is not known why measured concentrations of copper in DMW were higher on Day 2 than at start of test, however,the mean values used for statistical analysis were close to the nominal values. Page 74 of 110 ROUND 3 -APPENDIX C4 Water Chemistry Measurements for Acute Definitive Tests Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 75 of 110 1 i • • - , . A C LIT I TOXICITY TEST - CH E-IN 4 1 STR 1.) , • Initial Reading:i 24 Hour Readingi 24 Hour Readings ._ 4ii Hour Read:tr dig.t _____•48,1-,,luur Readings Coorloriom old old) old onv or» Pll 131olvrtl. 1 D Ipmh rn oOr )01 essol%rd Olcolvrd Cltsl,olvcd DI s sol y•atj. v! C010011 01 rtc-ri p 1 01 S11001) 01 Irr0 pl I Olytco p I I Oxyu. pll Oltytco pll corcou,lmo nwL (PI) mt/L mt/l. "'IA mt/L • !--------, 00/ ------ ; -;• 2-^ • 061.--- F ----•---------_ - C1'111-: •'--.7 — ----- --------------------------6— g• -------, ' ____--- -._ I _ ___---•_ ——----- ----•--------- Datc. _ Initials. . • 72 Hour Readings 72 Hour Readings 96 Hour Readings ' old old new new old cid Dissolved Dissolved Dissolved Elnuent Oxygen pH Osygco pH Oxygen p14 Concentration ang/L tog/L eng/L .... . • Date: Time: Initials: Client: , '--120t 115- cu, Lab IDt4: .: . • 0 0 1. 2.0 . .. Page 76 of 110 ROUND 3 -APPENDIX C5 Chain of Custody Documentation Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 77 of 110 i'Ll ,...:,' : k CHAIN I F CUSTODY RECORD PO Sox 16414,Greenville,SC 29606-7414 (864)877-6942, (800)891-2325 Fax:(864)877 6938 Shipping Address:4 Craftsman Ct,Greer,SC 29650 W W W.ETTEN V IRONMENTAL.COM Cltent: JJ I, -------- }" `r accs Program • Containers 'Preservative l' i�i� J.� 6 a-amctcrs , Facility: �__ - — __-- l' ° whole Effluent Tonicity - State ,i r. NPDES 4: ___________. _I Acute Chronic Test Organisms \ J — C ; {{ — (Composite only) (Grab or Composite) . - - ; ? - `� _ _ Z Sign,and Print below 5 _ al = ?=IKCL n = 1- a _ ca ' - _ _ _ j _ the dotted line -F. " = & U o E s=HNo:; ' = ' - _ = s r 'o - El' `� C ej O O t: ^ P., 3=Zaie o o i T _ SAMPLE IDComposite Stan Dote Time Sample Collection Date Time Collected by U CA Z E v > 6=otter < < i v t j C ^ 5 7. T. U _ 5 G Chemical Analysis&Other CC U-+ O_ii ' -:i1-t-d4 , _ `i-. -rl � �_ L0 t?19) 1(, ✓ 5 / j ficet� [L mil•-lie Ail(,_r- I �F� tt Zn �5��}�3 J O O i i q t k Special Instructions: a Sample Custody Transfer Record - Secure Receipt Sample Date Time Relinquished By/Organization Received gvtOrganization ,e. Area 1 Temp°C ! Preserved? 1 Z5-A 1030 f }� �� () era- ,3 r "�y" °j,J, 'c =-'' � f 1 �'' 9/ 6118 3° '-- o'' \ �f- 04.1,-,. en" I O. COMPOSITE SAMPLING PROCEDURES TEMPERATURE MOArITORIAJC PROCEDURES HOLD TIME PROCEDURES Composite samples must be collected over a 24 hour period. Sample temperature during.collection and transport must be between For toxicity resting the sample must first be used within 36 hours Time Proportional: I sample each hour for 24 hours.Equal volut 0.0 and 6.0°C.Samples must not be frozen.Use water ice in sealed bags. of sample collection(completion of composite sample). or at minimum I sample every 4 hours over-24 hours. Sample may not be used after 72 hours from sample collection. Flow Proportional:As per instructions in NPDES permit. ROUND 3 -APPENDIX C6 Statistical Analysis Results Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 79 of 110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 8.4 0 20 0.9243 0.5 11.3 0 20 1.0531 0.5 15.3 5 20 1.1847 3.36 22.5 75 20 '1.3522 5.67 33.5 100 20 1.5250 8.09 1. Enter data in yellow boxes Test Type: WER Acute Species: C dubia Sample ID DMW T-Cu LC50= Date: 9/26/18 20.358 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value Page 80of110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 7.1 0 20 0.8513 0.5 10.6 0 20 '1.0253 0.5 15.5 5 20 '1.1903 3,36 26 75 20 1.4150 5.67 27.5 100 20 1.4393 8.09 1. Enter data in yellow boxes Test Type: WER Acute Species: C dubia Sample ID DMW Dis-Cu LC50= Date: 9/26/18 19.748 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value Page 81 of 110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality_ Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 85.5 0 20 1.9320 0.5 113 5 20 2.0531 3.36 152 20 20 2.1818 4.16 224 55 20 2.3502 5.13 320 100 20 2.5051 8.09 1. Enter data in yellow boxes Test Type: WER Acute Species: C dubia Sample ID Harris T-Cu LC50= Date: 9/26/18 179.504 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value The highest concentration run showed only 55%mortality.The concentration factor used in the test was 0.7.Therefore it was assumed that had the next higer concentration been run(which would have been 224/0.7=320 ug/L),that all the test organisms would have died(most conservative-worst case scenario). Page 82 of 110 P RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 72.5 0 20 1.8603 0.5 103 5 20 2.0128 3.36 140 20 20 2.1461 4.16 '189 55 20 2.2765 5.13 270 100 20 2.4314 8.09 1. Enter data in yellow boxes Test Type: WER Acute Species: C dubia Sample ID Harris Dis-Cu LC50= Date: 9/26/18 158.483 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value. Low dissolved copper values as compared to higher total zinc values may reflect adherence of copper ions to particulates in the effluent. The highest concentration run showed only 55%mortality.The concentration factor used in the test was 0.7.Therefore it was assumed that had the next higer concentration been run(which would have been 189/0.7=270 ug/L),that all the test organisms would have died(most conservative-worst case scenario). Page 83 of 110 environmental,Inc. (864)877-6942 . FAX(864)877-6938 P.O. Box 16414, Greenville, SC 29606 Craftsman Court, Greer, SC 29650 APPENDIX D WATER EFFECT RATIO STUDY (Interim Guidance) Duke Energy Shearon Harris Plant Secondary Species - Round 4 Metal: Copper September 2018 Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 84 of 110 TABLE OF CONTENTS 1.0 INTRODUCTION 2.0 METHODS 2.1 Experimental Design 2.2 Laboratory Dilution Water 2.3 Upstream and Effluent Sample Collection 2.4 Chemical Analyses 2.5 Preparation of Test Solutions 2.6 Test Organisms 3.0 RESULTS 3.1 Laboratory Water 3.2 Simulated Downstream Water 3.3 Upstream Waters 4.0 CALCULATION OF WATER EFFECT RATIO 5.0 DISCUSSION LIST OF APPENDICES Appendix Dl. Reference Toxicant Quality Control Chart for Pimephales promelas Appendix D2. Survival Data for Acute Definitive Tests Appendix D3. Measured Concentrations of Total Recoverable Copper in Test Solutions Appendix D4. Water Chemistry Measurements for Acute Definitive Tests Appendix D5. Chain of Custody Records Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 85 of 110 1.0 INTRODUCTION The Duke Energy Shearon Harris Nuclear Power Plant (SHNPP) discharges effluent into Harris Lake under NPDES Permit NC0039586. In cooperation with Jacobs Engineering,ETT Environmental has been retained to conduct a "site specific study" to determine if permitted copper limits for each effluent discharge are unnecessarily overprotective of aquatic life. This is to be accomplished through the calculation of a water effect ratio (WER), comparing the acute toxicity of copper upon the surrogate aquatic test organisms Ceriodaphnia dubia and Pimephales promelas in laboratory dilution water to the acute toxicity of copper to the same test species in simulated downstream receiving water.The study used the methodology provided in the Streamlined Water-Effect Ratio Procedure for Discharges of Copper (EPA-822-R-01-005). This round of testing was conducted using the secondary test organism Pimephales promelas (fathead minnow). On September 24-25, 2018, SHNPP personnel collected a composite effluent water sample. Acute toxicity tests for the Water Effect Ratio study were initiated on September 27th,2018. Laboratory Location: ETT Environmental,Inc. 4 Craftsman Court Greer, SC 29650 SCDHEC Certification# 23104 Study Director: Robert W.Kelley,Ph.D. Study Scientist: Amy McMahon Study Technicians: Jennifer Christian Jonathon Gillespie Forrest Jackson Study Dates: September 27-29,2018 Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 86 of 110 2.0 METHODS 2.1 Experimental Design The design of the study involved spiking copper into test solutions and assessing the acute toxicity of the test solutions with 48 Hour Acute Definitive tests using the surrogate test organism Pimephales promelas. The two test solutions assessed were 1) laboratory dilution water, and 2) simulated downstream water at 100% concentration. Acute toxicity tests were set according to U.S. EPA protocols (EPA 821-R-02-012 Method 2000), modified according to the following parameters; Test type: Acute Static Temperature: 25°C+1 Light: 100 ft.-candles; 16 hr light/8 hr dark Test Chambers: 300 mL plastic cups Test Solution Volume: 200 mL Renewal of Test Solutions: None Test Organism Age: <24 hr #Organisms/Cup: 10 #Replicates/Concentration: 2 Feeding Regime: None Aeration: None Dilution Factor: 0.7 Test Duration: 48 Hours Endpoints: Survival 2.2 Laboratory Dilution Water The laboratory dilution water used in all tests was diluted mineral water (DMW). In this first round of tests the DMW was prepared at a hardness of 50.0 mg/L. This dilution water was prepared by adding Perrier water to ultra-pure water to obtain the desired final hardness. The procedure for the preparation of this water may be found in the EPA manual Short Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms(EPA 821-R-02-013). Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 87 of 110 *Dilution water during the period of testing was prepared as follows; Amount Hardness Conductivity Alkalinity �H 20 L 50.0 mg/L 108 µmhos/cm 44.3 mg/L 7.8 2.3 Upstream and Sample Collection Sampling Locations The effluent discharges into Harris Lake. The effluent samples were collected as composite samples. As received the effluent was measured to have a oxidizer concentration of 0.19 mg/L(likely permanganate rather than chlorine). All samples were collected in halfgallonplastic jugs and preserved in coolers at 0-6°C. Jg Samples were transported to ETT by overnight delivery. 2.4 Chemical Analyses Dissolved oxygen and pH were measured in one surrogate of each test concentration at the beginning and end of the test.Temperature was monitored in three surrogate test cups in the incubator daily. Dissolved Oxygen and pH were measured with the use of a Orion 4 Star meter.The meter is calibrated daily. Alkalinity, hardness, total suspended solids (TSS), total organic carbon (TOC), and specific conductance were measured on each laboratory water and effluent sample collected. Total recoverable copper was measured on each test solution at the beginning and end of the test. Dissolved copper also was measured for each test concentration at the beginning and end of the test. Copper analyses were conducted by ETT Environmental of Greer, SC using Standard Methods 18th Edition Method 3111 B (flame atomic absorption), and concentrated to achieve a detection limit of 10 ug/L(or lower with concentration). 2.5 Preparation of Test Solutions Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 88 of 110 2.5.1 Simulated Downstream Water A simulated downstream sample was prepared using 100% effluent. 2.5.2 Copper Spiking Copper was spiked as copper sulfate (CuSO4.5H20) into laboratory water and the simulated downstream water. Prior to spiking the total recoverable copper in each effluent sample was measured. Each day a batch of simulated downstream water was prepared. A 12.72 mg/L stock solution of copper sulfate was prepared by adding 0.05 g of CuSO4.5H20 to one liter of demineralized water. A microliter syringe was used to add the correct volumes of the stock solution to each simulated effluent or control concentration to achieve the desired nominal concentration of copper. 2.6 Test Organisms The test organism used for this study was the fathead minnow Pimephales promelas.Test organisms were fish larvae of less than 24 hours in age which were obtained as eggs from Aquatic Biosytems and then hatched and acclimated to laboratory dilution water for 24 hours. Culture sensitivity is monitored through the use of semi-monthly reference toxicant testing. Voucher specimens from every purchased batch of organisms are set aside and taxonomically verified by a staff taxonomist. Culture organisms are subject to the same light,temperature,and feeding regimes as used for testing. Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 89 of 110 3.0 RESULTS 3.1 Laboratory Water 3.1.1 Acute Toxicity Testing Results The acute definitive test with Pimephales promelas in laboratory water spiked with copper showed a 48 Hour LC50 of 169.265 ug/L Total Recoverable Copper and a 48 Hour LC50 of 157.883 g/L Dissolved Copper. Due to the pattern of the data, the values were calculated using the probit method. The survival data at each concentration are summarized as follows; Nominal Concentration Mean Measured Conc. 48 Hour of Total Recoverable Cu of Total Recoverable Cu Mortality and(Dissolved Cu) 0 ug/L <1.0 ug/L(<1.0) 0% 50.0 ug/L 51.0 ug/L(59.5)2 0% 71.4 ug/L 72.0 ug/L(72.0) 0% 102 ug/L 106.5 ug/L(98.5) 5% 143 ug/L 145 ug/L(131) 20% 204 ug/L 200 ug/L(192) 30% 292 ug/L 271 ug/L(256) 100% 416 ug/L 366 ug/L(359) 100% Survival data for the test may be found in Appendix D2.Results of measured concentrations of total recoverable and dissolved copper are provided in Appendix D3. 3.1.2 Chemical Analyses The pH in the spiked dilution water test ranged from a minimum of 7.4 to a maximum of 7.7. Dissolved oxygen was generally at the saturation point in all treatments throughout the test. 1 The probit method is used when at least two test concentrations show partial mortality. 2 Theoretically the dissolved metal concentration cannot be higher than the total metal concentration,however,the value shown is the value measured. Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 90 of 110 3.2 Simulated Downstream Water 3.2.1 Acute Toxicity Testing Results The acute definitive test with Pimephales promelas in downstream water spiked with copper showed a 48 Hour LC50 of 484.901 ug/L Total Recoverable Copper and a 48 Hour LC50 of 447.288 ug/L of Dissolved Copper. Due to the pattern of the data the value was calculated using the probit method. The survival data at each concentration are summarized as follows; Nominal Concentration Mean Measured Conc. 48 Hour of Total Recoverable Cu of Total Recoverable Cu Mortality and(Dissolved Cu) 0 ug/L <1.0 ug/L (<1.0) 0% 71.4 ug/L 86.5 ug/L(75.0) 0% 102 ug/L 116.5 ug/L(100.5) 0% 143 ug/L 159 ug/L(131) 0% 204 ug/L 211.5 ug/L(189) 0% 292 ug/L 260 ug/L(253) 0% 416 ug/L 401 ug/L (356) 5% 594 ug/L 585 ug/L(537) 45% Measured concentrations were generally higher than nominal concentrations. A significant suppression in survival was noted at a nominal concentration of 594 ug/L of total copper. Survival data for the test may be found in Appendix D2. Results of measured concentrations of total recoverable and dissolved copper are provided in Appendix D3. The probit method is used when at least two test concentrations show partial mortality. Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 91 of 110 3.2.2 Chemical Analyses The pH in the simulated downstream water ranged from a minimum of 7.3 to a maximum of 7.7. Dissolved oxygen was generally near the saturation point in all treatments throughout the test.Other water chemistry parameters are summarized as follows; Parameter Effluent Total Recoverable Copper(ug/L) 22.9 Dissolved Copper(ug/L) 20.2 Alkalinity(mg/L) 50.6 Conductivity(umhos/cm) 347 Hardness(mg/L) 54 Total Organic Carbon(mg/L) 26.0 Total Suspended Solids(mg/L) 13.3 It may be seen that the effluent water was characterized by moderate alkalinity, hardness, TOC and TSS. 3.3 Upstream Waters Not applicable when downstream water is comprised of 100%effluent. Parameter Result Total Recoverable Copper(µg/L) NA Dissolved Copper(µg/L) NA Total Organic Carbon(mg/L) NA Alkalinity(mg/L) NA Hardness(mg/L) NA Conductivity(µmhos/cm) NA Total Suspended Solids(mg/L) NA Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 92 of 110 4.0 CALCULATION OF WATER EFFECT RATIO As noted in the results section,acute testing indicated an LC50 of 169.265 ug/L of total recoverable copper in laboratory dilution water and an LC50 of 484.901 ug/L of total recoverable copper in 100%Duke Harris effluent.The laboratory dilution water LC50 values must be adjusted to downstream water hardness in order to calculate the Water Effect Ratio,using the EPA formula, as follows; LC50 x (downstream hardness/laboratory water hardness)0.9422 T-Cu: 169.265 ug/L x(54/52)9'9422= 181.9948 ug/L Dis-Cu: 157.883 ug/L x(54/52)119422= 169.7568 ug/L The Water Effect Ratio can thus be calculated as follows; Water Effect Ratio(WER) = LC50 in Effluent = 484.901 ug/L = 2.6644 (Total Recoverable Copper) LC50 in Lab Water 181.9948 ug/L Water Effect Ratio(WER) = LCgo in Effluent = 447.288 ug/L = 2.8330 (Dissolved Copper) LCS0 in Lab Water 169.7568 ug/L A final water effect ratio(EWER)will be calculated using the individual WERs only from the three rounds of testing with the primary test organism. Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 93 of 110 ROUND 4-APPENDIX D1 Reference Toxicant Quality Control Chart Pimephales promelas • • Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 94 of 110 ACUTE REFTOX - 2018 cathead Minnow; Toxicant NaCI 10.0 9.0 - J 8.84 8.81 8.63 8.85 8.81 8.84 8.89 8.84 8.85 8.85 8.82 8.52 8.548.528.`5e8.53 :. 03 8.44 8.45 8.42 8.42 r ♦ 8.39 8lJ�� I 8.29 0 8.18 t17 8.0- 1 - V . 77 - - - - 7.-7 7.77 7.77 --I O 7.44 . .4. ' - ' 7.50 7.48 .47 7.47 7.48 7.38 7. 7.39 _ 7 = 7.3f' '.38 - •Y i 8.34 8.33 8.39 8.41 8.32 8.30 8.30 8.29 £.?7,$. 7,e24,R 85E�. a1 P1, . , ,ft ,,3 77,RPTtI,$ 'e.75, . . , , , ,.23, . , le. t, , 80 Misr2118 Apr11"'18 Apr2518 May1518 Jun1318 Ju110'18 Aug718 Aug21"18 S€p1218 Oct218 Oct18'18 1 M&28'18 Apr1T18 Mtay8°18 May22'18 Jun1918 Ju127'18 Aug14"18 Aug29'18 Sep18`1S 01110''18 Date .)ct a Lct ARE_.2 rO D FROM>AN 1 -f MEAN f LC50 ,F UPPER f LOWER Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 95 of 110 ROUND 4 - APPENDIX D2 Toxicity Bench Sheets Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 96 of 110 Page 740(1G, Nominal Initial# Mortality Measured Concentration WER 48 Hour Acute Toxicity Test ...-**** i Cone Rep Organisms 24 hr 48 hr Initial e Facility: YM IA Final Mean , Metal:c_Lk , A lowToi,i Total Sample ID: .� �'` � � +G Time: ' BY: �.S 0% B I0 0 Start Date: ���'I (1 I I � `i C End Date: .A.- - Time: -200 By: _' DIs DIs (Ss D Effluent Log# Upstream Log#: A 0 0 Total Total Total TEST ORGANISMSWI , _i B I 0 0 Test Organism: mu C Dis Dis Dis for Ceriodaphnia dubia Source: Mk D Date Removed; EL; n,t /Time • A \h\ u U Total Total Total Beiwee (Time)and L', MII v 0 for fathead minnows mysids: B / pp ni55 Ae: �0�{ 5 c � � 1 � C DIs DIs DIs Source: ��JcJ R g `,; D Temperature 24-26 C. Light 16 hr It/6 hr kd;50-100 ft candles 1 1 : MIA 1(� I� Total Total Total Laboratory Water DMW/SSF @ 50 mg/L hardnessq•Z3-Ig ® !.; I B I O 0 Downstream Water Preparation 1 En I50I o volume mL Prep.Date C Ols Ds DIs /o effluent l % upstream volume mL Prep.by: I. A 10 0 Total Total Total -l i B I Q D Test Solution Preparation: Metal Salt: SQ/ .i'll I ' C DIs DIs Dis Date: By: Stock.Soln:1Z72 I t/ II I I,pvI i u D Nominal Cone mL Stock Soln. Volume prepared , I loll'I 0 0 )OCO bt L II l+I A 10 I Total Total Total c � l4'I 2_ B 7S/ I�qf,, 0 i� 'I' 10 (o ir: li qq �j C DIs Dis Ds III] D 50 3.6"t 9 ,I 'l A `O .5 Total Total Total '' 1 1-4 5.6 2— i I I Ills DIs -Dis 1,,'1,1 ! rip B I 0 1 ' I 0'2— 4i5,02- 113 I► I D 2-04 OM II III A O Total Total Total A Total Total Total , -l/�f B mmili I !r mil!i I Dls DIs DIs - C DIs DIs DIs Ili 'l;I C �, r11;1 D D , t I II A Total Total Total A Total Total Total 7 I I !I' B l;; B II C Dis Dis DIs l ji C Dis DIs DIs old t D D I is Test Method:per EPA Interim Guidance t I.�•i Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. h 11 ,i1�' 1ti tillll Page 97 of 110 Page 76 a(io Nominal Initial II Mortality Measured Concentration WER 48 Hour Acute Toxicity Test '..3/4'' Conc Rep Organisms 24 hr 48 hr Initial Final Mean Facility: {) t L ) Metal:C A Total total total Sample ID: �� 0% B EMStart Date: io-`fi•IP Time: f,s-30 By:4_41 C DIs DI5 Dis End Date: 1 o-I I-((' Time:h l 5 By: D �® Effluent Loc It: Upstream Log#: A 0 0 Total Total Total TEST ORGANISMS ZqZ B b MI Test Organism: ` C _-� DIs Din Din for Ceriodaphnia dubia Source: D �.� Date Removed; I A I(l 10 Total Total Tr.tai Between fTimm\ and (Timal ` B h c" for fathead minnows or mysids: 483 lid a `/���'J Li IL chit Oit /0 9/4r C DIs DIn DIn Source: 4,65 Age: <Zy'tcs D Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles .r. ' A Total Total Total Laboratory Water DMW!SSF @ 50 mg(L hardness > I i!i; B Downstream Water Preparation i I !li C Din Dis Us %effluent volume mL Prep.Date: 1 I '1 D % upstream volume mL Prep.by: 'L,i A Total Total Total B Test Solution Preparation: Metal Salt: J0 y ill ,i -F.j C Din Dis Din Date;q-U-(g By: SC Stock. Soln: I Z 72 p1f/ _. IL: D Nominal Conc mL Stock Solo. Volume prepared d4; q7 tt'f[ A Total Total Total � /2. I3.7� p 00m e- i B y,.L i c 3 1 .:i, C Din Dis Dis l,i D g4i it 4, 4"ill, A Total Total Totalr". i sl> B i li, Ill i 41.1 C Dis Dis Dis ill l?I t l i ll D , III lii ii. I!. A Total Total Total A Total Total Total -C! i B B l C DIs Din DIs C Dis DIn DIs r i �� 1 D D ,j A Total Total Total A Total Total Total `,, n s 4 B B t: C DIs DIs DIs C Din DIs Din ll tii D D T i Test solution volume:25 mL..Test vessels 1 oz.plastic cups.Transfer volume 0.05 ml. Test Method: per EPA Interim Guidance Page 98 of 110 r 74 ofii, Page 75 of 100 p till- Nominal Initial# Mortality Measured Concentration WER 48 Hour Acute Toxicity Test gonc Rep Organisms 24 hr 48 hr Initial Final Mean Facility: jAA V t. 1-6.i/( 5 Metal://�� A Tnlal 1.0 Total Sample ID: (_.J• 0% B __ 10 _ Start Date:01-2_1-1% Time: )/ Sc, By: S j C DIs DIs DIs End Date:- -I5' Time: .00 By: _.�j D ��� Effluent Log tf: „z��}l� Upstream Log#: A M-11111 Total Tote lot al TEST ORGANISMS B Mill.11 lest Organism: C _.� Dis Din Din for Ceriodaphnia dubia Source: D IIIIII Date Removed; to -:.. , rT_IIT A t ll -iule Total Toth) ��- BC4A:Qer I ,I rote)and (Time) ime` 35 B I D 6 f r fathead minnows or ysids: Q C Din DIs Din Source: Af35 "- 'H e: L g 98 D Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles ti Ig A 10 O Total Total Total Laboratory Water DMW/SSF @ 50 mg/L hardness B 100 Downstream Water Preparation 50 C Din Din Dis %effluent 100% volume mL Prep.Date: D % upstream volume mL Prep,by: 1 A [0 0 Total Total Total i B 10 0 Test Solution Preparation: Metal Salt: ( 30 5 1 1.\ C DIs Dis ols Date: By: Stock.Soln: 12--7�ri1q I L D Nominal Conc mL Stock Soln. Volume prepared \] A 1 O L) Total Total Total 0 0 1 t notL B [n 0 25 I •q(p III O i � C Ds DIs Din . 5- 2., ! D 50 3.11 A 1 O 0 Total Total Total 1 ,.i J.6 2— B 10 0 ICa- . 2.0,2r}- t 13 C DIs Dis Din I13 I I•ZI D 204 1(0.0i \ s I A 10 0 Total Total Total A Total Total Total /�� ►,/yA�► B ID n B .. '. - - 4 C Dis Din DIs C Dis Din Dis t D D A Total Total Total A Total Total Total B B C — DIs Dis Din C Dis DIs DIs D D i Test solution volume:25 mL. Test vassals 1 oz.plastic cups.Transfer volume 0.05 mL. Test Method: per EPA Interim Guidance - 29z1 y/ , s9y Page 99 of 1 10 de 76 of trn Page 77 of 100 f ,,i0m Initial# Mortality eMeasuredConcentration WER 48 Hour Acute Toxicity Test r Rep Organisms 24 hr 413 hr Initial Final Mean Facility: ` IIda tS Cn, ���t �C. F Metal:/��� A �O oted Total Real Sample ID: ut�,_ Th 0% B iiQ, Start Date: !Dim Time: I5,jo BY: A-Mt C DIs Din DIs End Date: I`(r((-IT Time: it,/S By: i i D Effluent Log#: 52.(N Upstream Log#: 0--- 1 A 10 0 Total Total Total TEST ORGANISMS............. \� Test Organism: a2 B C ohs Den Dis for Ceriodaphnia dubia Source: D Date Removed; (Tin 0' I ( I r� +...t, (T:..- 1 r d (T:me) c A 1V Total --Trial -rota GCLvV�:bli uil�;/G�iu t nilc) . B' i (D 0 for fathead minnows or mysids: rtc 0 a_S-eysl -{o C Din Din DIS Source: _ Age:4''hv-5 `ems D Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles A IC 9 Total Total Total Laboratory Water DMW /SSF a@ 50 mg/L.hardness B it ,6/ Downstream Water Preparation 5q`1 C Dis Des Ols % effluent tool- volume kftiO mL Prep.Date: /O-4•(p I D % upstream volume mL Prep.by: ] A Total Total Total t B Test Solution Preparation: Metal Salt: Cu S 0y C . Din Din Dis Date:q-21•� By: Stock.Soin: 12,,72-015/(-- D Nominal Conc mL Stock Soln. VolumeLI prepared A Total Total Total Z9z 13.71) bo 1 L IC Din DIs Dis l L( Ze.03 11 D I A Total Total Total B C DIs Din Dis D otal A Total Total Total A Total Total Total B B Ns C Dis DIs Din C Dis DIs Dls D D dal A Total Total Total A Total Total Total B B .s C Des Dis Dis C Din Dis Din D D Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 ml. Test Method: per EPA Interim Guidance Page 100 of 110 ROUND 4 -APPENDIX D3 Measured Concentrations of Total Recoverable Copper in Test Solutions Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 101 of 1 10 Measured Total Recoverable and Dissolved Copper Duke Harris Plant-Secondary Species Site Specific Study September 2018 `S.ample:Spiked Dilution Water(Diluted DMR Initial Date:09/27/18 Nominal Measured Total Recoverable Copper(µg/L) %of Measured Dis.Cu(µg/L) % Total Cu Initial Day l Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Mean Nominal Initial Day 2 Mean Dissolved 0 <1.0 <1.0 <1.0 I I <1.0 50.0 47.0 55.0 51.0 102% 56.0 63.0 59.5 117% 71.4 70.0 74.0 72.0 101% 64.0 80.0 72.0 100% 102.0 106.0 107.0 106.5 104% 95.0 102.0 98.5 92% 143.0 138.0 151.0 145.0 101% 132.0 129.0 131.0 90% 204.0 192.0 207.0 200.0 98% 190.0 194.0 192.0 96% 292.0 271.0 271.0 93% 256.0 256.0 94% 416.0 366.0 366.0 88% 359.0 359.0 98% Sample:Simulated Downstream-Duke Harris Initial Date:9/27/18 Nominal Measured Total Recoverable Copper(µg/L) %of Measured Dis.Cu(µg/L) % Total Cu Initial Day I Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Mean Nominal Initial Day 2 Mean Dissolved 0.0' 23.4 _ 22.4 22.9 20.2 20.2 _ 71.4 82.0 93.0 86.5 121% 70.0 80.0 75.0 87% 102.0 109.0 124.0 116.5 114% 99.0 102.0 100.5 86% 143.0, 148.0, 170.0 159.0 111% 133.0 129.0 131.0 82%_ 204.0_203.0 230.0 211.5 104% 184.0 194.0_ 189.0 89% 292.0 260.0 260.0 89% 253.0 253.0 97% 416.0_401.0 401.0 96% 356.0 356.0 89%_ 594.0 585.0 585.0 98% 537.0 ' 537.0 92% Page 102 of 110 ROUND 4-APPENDIX D4 Water Chemistry Measurements for Acute Definitive Tests Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 103 of 110 . . ACUTE TOX 1 c ri- y TEST - C1-1E-M ISTI- ' ------- --_. -------- ----------- o, Initial Readingl: )4 Hour Readings 24 Hour Readings 48 Hour Readings 48 Hour Readings Co•ii.(1,,i, old old nrw old old OCW 1,11 D‘ssolvrd (poll‘mirro,)Of D.s‘ol,rtl fht;olvcd Drtsol,rd Olsoly:.4. LITIocM C) yErn p li or Sxlind C) 1,.,1 III I 01 ytcri MI Or yrn pl I Ox yEco pl I Calico,'r•Ito il mEil. (PP,I mr/L /1 mt. . mr/L mr/L --- _____:____________ _ _____ __, ...,, ___ ____p_.____________ II --=------, Date -- — Time. 0 . - Initials. e.../ . .. 96 HourRings 72 Hour Readings 72 Hour Readings ead . old old nov nov old old Dissolved Dissolved Dissolved Eillucnt Oxygen PH Osygen pH Oxygen. pH Concentration roga. cog/L tariL . 1. • 1 • , . .. . Datc: . Timc: Initials: • —Client: PiKtf)-1Pti-e5 ?Rom t_6.5 Lab ID#: 1 - -TAte • airip- CR c=4 1 . . . . , o 0 1 2 2 Page 104 of 1 10 ROUND 4 -APPENDIX D5 Chain of Custody Documentation Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 105 of 110 enn otith entail aaae -_ PO Box 16414,Greenville,SC 29606-7414 (864)877-5942, (800)991-2325 Fax:(864)877 6938 Shipping Address:4 Craftsman Ct,Greer,SC 29550 W W W.ETTEN VIRO N NO NTAL.CON: lient: t4 ) ': ° l A Program Containers Preservative; �TT FFacility: _ Parameters t -• t s-, __ Whole Effluent Toxicity State: k�4 (1 ' NPDES 3 -icntc Chronic Test Organisms — I I i ° I .J . /` 7:3J v (Composite only) (Grab or Composite) j- I o: = u c . _ 4 5 = Sign,and Print below <' ?i Sn T 2=11r. s = a s _ ' E. - € rc _ J = so _ . F. t o :=Hno- = .& _ _ •_ _ a the dotted line :_ _ _ it H • s=a,oH ° ' ' E •_ - - ' - - . SAMPLE ID �? o C O o c _ E a . o` ' r - _ - = — -Composite Sort Dote Time Sample Collection Due Time Collected by U ✓+ rr Z C i — .. r I ^ ` - - --.. . - v: ,� J t^_ — r _ J — r <t Chemical 0natyntsã Other 7 0 0 4,-). `L'L `a r c tit d l N' j I WAR Cat t Z n 5a4�3 CD O t Special Instructions: a Sample Custody Transfer Record Secure Receipt Sample rm)Date Time Relinquished By/Organization , Received B 1'„erzanization Area Temp°C Preserved? 9—as—�8► 3o f �, z�'t-/P.. - I I �iii i iillN` I �,�/ Oh , cam ' 2 I lE ‘151/1271141X°:)-°-'0, ..,_.-1-c- 0.,,2 , COMPOSITE SAMPLING PROCEDURES TEMPERATURE MONITORING PROCEDURES HOLD TIME PROCEDURES Composite samples must be collected over a 24 hour period. Sample temperature during collection and transport must be between For toxicity testing the sample must first be used within 36 hours Time Proportional: I sample each hour for 24 hours.Equal volut 0.0 and 6.0°C.Samples must not be frozen.Use water ice in sealed bags. of sample collection(completion of composite sample). or at minimum I sample every 4 hours over 24 hours. Sample may not be used after 72 hours from sample collection. Flow Proportional:As aer instructions in NPDES permit. I APPENDIX D6: Statistical Analysis PROB T RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 189 0 20 2.2765 0.5 253 5 20 2.4031 3.36 356 5 20 2.5514 3.36 537 45 20 2.7300 4.87 767 100 20 2.8848 8.09 1. Enter data in yellow boxes Test Type: WER Species: C dubia Sample ID Harris DisCu Fish LC50 Date: 9/27/18 447.288 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value. Page 107 of 110 PROEM" RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit _ 0.'1 0 20 -1.0000 0.5 72 0 20 '1.8573 0.5 106.5 5 20 2.0273 3.36 145 20 20 2.1614 4.16 200 30 20 2.3010 4.48 271 100 20 2.4330 8.09 1. Enter data in yellow boxes • Test Type: WER Species: C dubia Sample ID DMW TCu Fish LC50 = Date: 9/27/18 169.265 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value. Page 108 of 110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 72 0 20 1.8573 0.5 98.5 5 20 1.9934 3.36 131 20 20 2.1173 4.16 192 30 20 2.2833 4.48 256 100 20 2.4082 8.09 1. Enter data in yellow boxes Test Type: WER Species: C dubia Sample ID DMW DisCu Fish LC50 = Date: 9/27/18 157.883 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value. Page 109 of 110 PROBIT RAW DATA Test Percent Number of Log of Conc. Mortality Organisms Test Conc Probit 0.1 0 20 -1.0000 0.5 211.5 0 20 2.3253 0.5 260 5 20 2.4150 3.36 401 5 20 2.6031 3.36 585 45 20 2.7672 4.87 836 100 20 2.9222 8.09 1. Enter data in yellow boxes Test Type: WER Species: C dubia Sample ID Harris TCu Fish LC50 Date: 9/27/18 484.901 A value of>0 must be entered for the control concentration,thus a nominal value of 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value. Page 1 I 0 of 1 10 Shearon Harris Nuclear Plant-Permit NC0039586 JACOBS Copper and Zinc Evaluation Attachment 2 Reasonable Potential Analysis — Spreadsheet Calculations February 25, 2019 Freshwater RPA- 95% Probability/95%Confidence Using Metal Translators MAXIMUM DATA POINTS=58 REQUIRED DATA ENTRY CHECK WQS Table 1. Project Information Table 2. Parameters of Concern 0 CHECK IF HQW OR ORW WQS Name WOS Type Chronic wolf. Acute PQL Units Facility Name Shearon Harris Par01 Arsenic Aquactic Life C 150 FW 340 ug/L WWTP/WTP Class Class II Facility Pare2 Arsenic Human Health Water Supply C 10 HH/WS N/A ug/L NPDES Permit NC0039586 Par03 Beryllium Aquatic Life NC 6.5 FW 65 ug/L Outfall 006 Par04 Cadmium Trout NC 0.8987 TR 3.2753 ug/L Flow,Qw(MOD) 7.900 ParO5 Chlorides Water Supply NC 250 WS ni p/f Receiving Stream Harris Reservoir Paros* Chlorinated Phenolic Compounds Water Supply NC 1 A ug/L HUC Number Par07 ♦ Total Phenolic Compounds Aquatic Life NC 300 A ug/L Stream Class Paros Chromium Ill Aquatic Life NC 185.7637 FW 1428.0791 ug/L WS-V ❑Apply WS Hardness WQC Par09 Chromium VI Aquatic Life NC 11 FW 16 pg/L 7Q10s(cfs) 0.00 Par10 Chromium,Total Aquatic Life NC N/A FW N/A pg/L 7Q10w(cfs) 0.00 Peril Copper Aquatic Life NC 63.4083 FW 88.4756 ug/L 30Q2(cfs) 0.00 Par12 Cyanide Aquatic Life NC 5 FW 22 10 ug/L QA(cfs) 0.00 Par13 Fluoride Aquatic Life NC 1,800 FW .ug/L 1Q10s(cfs) 0.00 Par14 Lead Aquatic Life NC 5.4881 FW 140.8349 ug/L Effluent Hardness(Median) 43.6291666666667 mg/L Par15 Mercury Aquatic Life NC 12 FW 0.5 ng/L Upstream Hardness fault 25 mg/L(Hard Aveage=20.8819858421678 mg/L) Part6 Molybdenum Human Health NC 2000 HH ug/L Combined Hardness Chronic 43.63 mg/L ' Par17 Nickel Aquatic Life NC 59.6352 FW 536.9197 pg/L Combined Hardness Acute 43.63 mg/L Par18 Nickel Water Supply NC 25.0000 WS N/A pg/L Data Source(s) Part9 Selenium Aquatic Life NC 5 FW 56 ug/L ❑CHECK TO APPLY MODEL Par20 Silver Aquatic Life NC 0.06 FW 0.7724 ug/L Par21 Zinc Aquatic Life NC 203.1420 FW 201.4938 ug/L Par22 Zinc Aquatic Life NC 8 3 FW 8.3 Ib/d Par23 Par24 Follow directions for data entry.In some cases a Par25 comment menu list the available choices or a dropdown menu will provide a list you may select from.Error message occur if data entry does not meet input criteria. RPA Harris 006.xlsm,input 1/24/2019 REASONABLE POTENTIAL ANALYSIS H1 Use"PASTE SPECIAL Effluent Hardness(monthly average) ValuMaxes"ithenmum data"COPY" points=58 Date Data BDL=1/2DL Results 1 1/1/2016 45.5 45.5 Std Dev. 7.3196 2 2/1/2016 50.5 50.5 Mean 43.1766 3 3/1/2016 45.8 45.8 C.V. 0.1695 4 4/1/2016 41.0 41 n 36 5 5/1/2016 50.0 50 10th Per value 35.05 mg/L 6 6/1/2016 48.4 48.4 Median Value 43.63 mg/L 7 7/1/2016 35.5 35.5 Max.Value 57.40 mg/L 8 8/1/2016 41.2 41.2 9 9/1/2016 43.5 43.5 10 10/1/2016 27.7 27.6666667 11 11/1/2016 30.0 30 12 12/1/2016 38.5 38.5 13 1/1/2017 34.6 34.6 14 2/1/2017 40.5 40.5 15 4/1/2017 41.6 41.625 16 5/1/2017 44.5 44.475 17 6/1/2017 47.3 47.325 18 7/1/2017 43.7 43.7333333 19 8/1/2017 45.0 45.025 20 9/1/2017 44.4 44.425 21 10/1/2017 48.7 48.7333333 22 11/1/2017 46.4 46.375 23 12/1/2017 45.5 45.45 24 1/1/2018 43.5 43.525 25 2/1/2018 43.0 42.975 26 3/1/2018 41.7 41.675 27 4/1/2018 22.4 22.4 28 5/1/2018 38.1 38.1 29 6/1/2018 57.4 57.4 30 7/1/2018 54.0 53.95 31 8/1/2018 52.6 52.6 32 9/1/2018 53.0 52.975 33 10/1/2018 51.1 51.1 34 11/1/2018 41.38 41.375 35 12/1/2018 38.2 38.2 36 1/1/2019 38.25 38.25 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 RPA Harris 006.xlsm,data -1 - 1/24/2019 REASONABLE POTENTIAL ANALYSIS Par11 Par21 Use"PASTE SPECIAL Use"PASTE SPECIAL Copper Values"then"COPY" Zinc Values"then"COPY" .Maximum data .Maximum data points=58 points=58 Date Data BDL=1/2DL Results Date Data BDL=1/2DL Results 1 4/18/2017 7,47 7.47 Std Dev. 9 0552 1 4/25/2017 18.95 18.95 Std Dev. 21 6028 2 4/25/2017 10.4 10.4 Mean 17.9473 2 5/3/2017 19.2 19.2 Mean 22.9560 3 5/9/2017 t4_4 14.4 C.V. 0.5045 3 5/9/2017 25.2 25.2 C.V. 0.9411 4 5/16/2017 14.6 14.6 n 58 4 5/16/2017 22.2 22.2 n 58 5 5/23/2017 15 15 5 5/23/2017 21.85 21.85 6 5/30/2017 12.3 12.3 Mull Factor= 1.00 6 5/30/2017 11.9 11.9 Mult Factor= 1.00 7 6/6/2017 22.9 22.9 Max.Value 47.30 ug/L 7 6/6/2017 16 16 Max.Value 107.0 ug/L 8 6/13/2017 34.4 34.4 Max.Pred Cw 47.30 ug/L 8 6/13/2017 40.65 40.65 Max.Pred Cw 107.0 ug/L 9 6/20/2017 22 22 9 6/20/2017 22 22 10 6/27/2017 18.2 18.2 10 6/27/2017 13.9 13.9 11 7/5/2017 14.4 14.4 11 7/5/2017 9.54 9.54 12 7/11/2017 24 24 12 7/11/2017 26.9 26.9 13 7/25/2017 18.4 18.4 13 7/25/2017 28.9 28.9 14 8/1/2017 11.5 11.5 14 8/1/2017 9.28 9.28 15 8/8/2017 18.9 18.9 15 8/8/2017 28.3 28.3 16 8/22/2017 15.6 15.6 16 8/22/2017 12.49 12.49 17 9/5/2017 15.85 15.85 17 9/5/2017 11.5 11.5 18 9/12/2017 14.3 14.3 18 9/12/2017 16.9 16.9 19 10/3/2017 8.95 8.95 19 10/3/2017 9.37 9.37 20 10/17/2017 34.1 34.1 20 10/17/2017 65.9 65.9 21 10/31/2017 22.7 22.7 21 10/31/2017 26.8 26.8 22 11/6/2017 37.1 37.1 22 11/6/2017 76.3 76.3 23 11/14/2017 19.65 19.65 23 11/14/2017 26.85 26.85 24 11/28/2017 9.62 9.62 24 11/28/2017 10.1 10.1 25 12/5/2017 11.8 11.8 25 12/5/2017 12 12 26 12/12/2017 14.4 14.4 26 12/12/2017 23.8 23.8 27 1/9/2018 9.405 9.405 27 1/9/2018 16.05 16.05 28 1/23/2018 13.6 13.6 28 1/23/2018 99.9 99.9 29 2/13/2018 11.2 11.2 29 2/13/2018 14.3 14.3 30 2/15/2018 10.4 10.4 30 2/15/2018 17.2 17.2 31 2/27/2018 12.7 12.7 31 2/27/2018 29 29 32 3/6/2018 12.4 12.4 32 3/6/2018 23.1 23.1 33 3/13/2018 36.15 36.15 33 3/13/2018 83.85 83.85 34 3/20/2018 43.4 43.4 34 3/20/2018 107 107 35 4/4/2018 15.4 15.4 35 4/4/2018 20.4 20.4 36 4/10/2018 9.845 9.845 36 4/10/2018 16.1 16.1 37 4/24/2018 28.6 28.6 37 4/24/2018 21.6 21.6 38 5/1/2018 47.3 47.3 38 5/1/2018 11.3 11.3 39 5/7/2018 17.85 17.85 39 5/7/2018 14 14 40 5/22/2018 24.3 24.3 40 5/22/2018 12 12 41 6/26/2018 26.9 26.9 41 6/26/2018 14.8 14.8 42 7/2/2018 24.4 24.4 42 7/2/2018 14.8 14.8 43 7/12/2018 20.8 20.8 43 7/12/2018 16.45 16.45 44 8/21/2018 20.9 20.9 44 8/21/2018 13.8 13.8 45 8/28/2018 17.4 17.4 45 8/28/2018 6.26 6.26 46 9/4/2018 19.4 19.4 46 9/4/2018 11.3 11.3 47 9/11/2018 14 14 47 9/11/2018 12.6 12.6 48 9/26/2018 17.4 17.4 48 9/26/2018 7.9 7.9 49 10/3/2018 22.3 22.3 49 10/3/2018 19.6 19.6 50 10/24/2018 18.1 18.1 50 10/24/2018 15.6 15.6 51 11/6/2018 23.8 23.8 51 11/6/2018 41.2 41.2 52 11/13/2018 12.2 12.2 52 11/13/2018 17.4 17.4 53 11/27/2018 8.41 8.41 53 11/27/2018 9.02 9.02 54 12/5/2018 8.89 8.89 54 12/5/2018 7.31 7.31 55 12/11/2018 7.325 7.325 55 12/11/2018 7.16 7.16 56 12/26/2018 8.4 8.4 56 12/26/2018 7.05 7.05 57 1/2/2019 7.95 7.95 57 1/2/2019 8.47 8.47 58 1/8/2019 6.88 6.88 58 1/8/2019 8.15 8.15 RPA Harris 006.xlsm,data -2- 1/24/2019 Date: 1/24/2019 FACILITY:Shearon Harris NPDES PERMIT:NC0039586 Dissolved to Total Metal Calculator In accordance with Federal Regulations,permit limitations must be written as Total Metals per 40 CFR 122.45(c) Receiving Receiving Rec.Stream NPDES Total Suspended Combined Combined Instream Instream Effluent Stream Stream 1Q10 Flow Limit Solids Hardness Hardness Wastewater Wastewater Upstream Hardness summer summer 7Q10 -Fixed Value- chronic Acute Concentration Concentration Hardness(mg/L) Median 7010(CFS) (MOD) [MGD] MGD (mg/L) (mg/L) (mg/L) (Chronic) (Acute) (mg/L) 0.0000 0.0000 0.0000 7.9000 10 [ 43.629 II 43.629 II 100.0000 I 100.0000 25 43.62917 Upstream Hard Average(mg/L)= 20.88199 Cu WER I ,1'u ,6 I EFF Hard Med(mg/L)= 43.62917 US EPA Maximum Allowable Effluent Concentration COMMENTS(identify parameters to PERCS Branch to maintain in facility's LTMP/STMP): Dissolved Metals Translators-using (MAEC)as a Total Metal 'Note-Updated dissolved copper criteria to include WER in calculation(Muriel Steele,2019-01-24) PARAMETER Default Partition .Dissolved Metal_Translator Chronic Acute Coefficients Chronic Acute [ug/I] [ug/I] (streams) lug/I) [ug/1) Cadmium(d) 0.23 1.33 0.252 0.90 5.27 Cd-Trout streams 0.23 0.83 0.252 0.90 3.28 Chromium III(d)(h) 38 289 0.202 185.76 1428.08 Chromium VI(d) 11 16 1.000 11.00 16.00 Chromium,Total(t) N/A N/A Copper(d)(h)* 22.0 30.8 0.348 63.41 88.48 Lead(d)(h) 1.01 26 0.184 5.49 140.83 Nickel(d)(h) 26 232 0.432 59.64 536.92 Ni-WS streams(t) 25 Silver(d)(h,acute) 0.06 0.77 1.000 0.06L 0.77 Zinc(d)(h) 59 58 0.288 203.14 201.49 Beryllium 6.5 65 1.000 6.5 65 Arsenic(d) 150 340 1.000 150 340 (d)=dissolved metal standard.See 15A NCAC 028.0211 for more information. (h)=hardness-dependent dissolved metal standard.See 15A NCAC 02B.0211 for more information. (t)=based upon measurement of total recoveable metal.See 15A NCAC 02B.0211 for more information. The Human Health standard for Nickel in Water Supply Streams is 25 mg/L which is Total Recoverable metal standard. The Human Health standard for Arsenic is 10 µg/L which is Total Recoverable metal standard. Shearon Harris Outfall 006 NC0039586 Freshwater RPA- 95% Probability/95% Confidence Using Metal Translators Qw = 7.9 MGD MAXIMUM DATA POINTS = 58 Qw(MGD)= 7.90 WWTP/WTP Class:Class II Facility COMBINED HARDNESS(me/L) IQIOS(cfs)= 0.00 IWC% @1Q1OS = 100 Acute=43.63 mg/L 7Q1OS(cfs)= 0.00 IWC% @ 7Q1OS= 100 Chromic=43.63 mg/L 7Q1OW(cfs)= 0.00 IWC%@ 7Q1OW= 100 YOU HAVE DESIGNATED THIS RECEIVING 30Q2(cfs)= 0.00 IWC%@ 30Q2= 100 STREAM AS WATER SUPPLY Avg.Stream Flow,QA(cfs)= 0.00 IW%C @ QA= 100 Effluent Hard:0 val>100 mg/L 1 val<25 mg/L Receiving Stream:NO HUC NUMBER Stream Class:WS-V Effluent Hard Med=43.6291666666667 mg/L PARAMETER TYPE STANDARDS&CRITERIA(2) cr) REASONABLE POTENTIAL RESULTS RECOMMENDED ACTION (1) NC WQS/ Applied Y2 FAV/ a E n #Det. Max Pred Cw Allowable Cw Chronic Standard Acute Acute: 88.48 Copper NC 63.4083 FW 88.4756 ug/1. 58 58 47.30 Chronic-----63.41 --•-------------------•--------- No value>Allowable Cw Acute: 201.5 Zinc NC 203.1420 FW 201.4938 ug/L 58 58 107.0 Chronic: ----203.1 --•----------------------------- No value>Allowable Cw Acute: 0 0 N/A — — — — — — — — — — — — — — — — — — — Chronic: Acute: 0 0 N/A ---Chronic: ----------•----------------------------- Acute: 0 0 N/A Chronic: ---------------------------------- RPA Harris 006.xlsm,rpa Page 1 of 1 1/24/2019 Attachment 3 Meeting Summary and Slides for June 5,2019 Meeting DWR Response,July 10,2019 CORRECTIVE ACTION PLAN FOR COPPER AND ZINC FOR HARRIS NUCLEAR PLANT NPDES PERMIT-YEAR 3 ACTIVITIES REPORT This page is intentionally left blank. CH2M HILL NORTH CAROLINA,INC. JACOBS Meeting Minutes 111 Corning Road,Suite 200 Cary, North Carolina 27518 United States T+1.919.859.5000 F+1.919.859.5151 www.jacobs.com Subject Presentation to DWR Regarding Water Effect Ratio Studies Project Shearon Harris Nuclear Plant-Permit NC0039586 Copper&Zinc Study Project No. BL0115CH File Prepared by Jacobs Phone No. 919-859-5768 Location Archdale Buildling 1106Z South Date/Time June 5,2019 @13:30 Participants see below Attendees: Bill Kreutzberger, CH2M/Jacobs Julie Grzyb, NCDEQ William Bromby, CH2M/Jacobs Connie Brower, NCDEQ Don Safrit, Duke Energy Chris Ventalaro, NCDEQ Bob Wilson, Duke Energy Nick Coco, NCDEQ Della Allen, Duke Energy Carol Hollenkamp, NCDEQ, via conference call Jim Eayres, Duke Energy Cindy Moore, NCDEQ, via conference call Bob Kelley, ETT David Hill, NCDEQ, via conference call Overview A PowerPoint presentation was used to facilitate the discussion at the meeting. A copy of the slides used is included as an attachment to these minutes. - Don Safrit opened meeting with a safety moment, introductions, and background on the Harris Nuclear Plant(HNP) NPDES permit - Bill Kreutzberger presented majority of content in ppt slides - The majority of the discussion was about how the WER was performed; focus was on dilution percent for testing, instream vs effluent, and ultimate application of WER to established formulae - Bob Kelley was able to address many DEQ comments by pointing to precedent or EPA's Interim Guidance details - Since DWR has never incorporated the use of a WER in a permit, there were several key points/policy considerations were left for further review Detailed Summary The first half of the presentation went without comment from DEQ: Intro, Permit Overview, Schedule of Compliance, and Effluent Characterization. 1-12M HILL. Inc. is wnolly-owred subsidiary of Jacobs) JACOBS Meeting Minutes June 5,2019 @13:30 Majority of comments came during WER Studies slides and did not necessary follow with slide deck order. Below, the topics discussed are highlighted and specific comments detailed. Order is roughly chronological but primary organized by topic. Hardness - Julie stated that they typically applied hardness to permits limits development based on a mass-balance approach. o Bill K and Bob K both indicated that our studies and analysis based it on effluent hardness since permit limits were based on 100% effluent with no dilution Dilution (in-stream vs 100% effluent) - Connie asked why we were not using in-stream water for at least one of the tests (implying that one of the WER tests would then be a Type 2 test) o Bill K indicated that we conducted only Type 1 tests (at 100% effluent)—similarly to how we approached the situation for similar facilities in SC. - Julie stated that they had wanted us to use dilution for the lab tests, saying this was what they expected. - Carol (or Cindy) pointed to a 4/16/18 email sent from DEQ to Don Safrit in which they suggest lab tests performed with 90% dilution o Bill asked to clarify what exactly was meant by 90% dilution (diluted with stream water or lab water) o Bob K pointed out that our method already represents a 'worst case scenario'. Because we performed Type I tests (no or low dilution), the resulting final WER is the lowest WER calculated from the three tests. If we would have conducted one WER using dilution as a Type II test, our resulting final WER is calculated as a geometric mean of three WER results. He was confident that if included dilution through a Type 2 test the resulting WER would likely be higher than what we currently have calculated. Type I versus Type II - The Type I versus Type II is based on in-stream flow conditions. - Nick suggested that if sampling were done during drought period then dilution could be incorporated without moving into Type II regime. o Bill responded with a few points • This would mean we would still do 2 Type l's and 1 Type II in accordance with the EPA Interim Guidance • One of the reasons that the permit limits are based on 100% effluent is that while there is a lot of water in Harris Lake, the 7Q10 flow of the watershed is near 0.0 cfs JACOBS Meeting Minutes June 5,2019 @13:30 • And, regardless of stream flow rate, the near-field dilution would be basically the same Application of WER and hardness results to metals criteria calculation Example formula: Copper,Acute = WER *0.960*e[0.9422*(Inhardness)-1.700] - Connie and Chris were concerned that applying both the increased WER and the increased hardness into the equation would be `double dipping'. They assumed if a higher WER were granted, then the hardness input would still be 25 (mg/L as CaCO3) o Bob K indicated that in his opinion it would not be `double dipping', and furthermore would be inconsistent from the Interim Guidance o Bill K indicated that in his experience, effluent hardness was used when the water quality criteria were being applied directly to the effluent with no consideration of effluent hardness - Julie indicated that some type of mixing zone analysis may be necessary to determine conditions to calculate permit limits-dilution and thus appropriate hardness Secondary Species Test - When looking at slide 24 Carol (or Cindy)asked why it indicated that the Secondary Species test confirmed the Primary Species test if the WER values were within a factor of of five. She indicted that her ] review of the Interim guidance indicated that it needed to be within a factor of three. o Bob K said he thought it was five but would look into it. He also indicated that the Interim Guidance was not completely clear as to whether this was all WER tests of the final WER. Zinc There was little or no discussion concerning Zinc. When asked by Bill whether they had any questions regarding zinc criteria, Julie stated "zinc will work out". Wrap Up/Action Items The meeting concluded with DWR indicating that the discussion was very useful, and they had several policy questions to consider as they moved forward to consider their comments on our submitted reports. Julie indicated they would be getting back to us soon with comments or requests for more information. Don and Bill thanked DWR for the meeting. The meeting concluded approximately 2:30 PM. I I JACOBS Meeting Minutes June 5,2019©13:30 Attachment Meeting PowerPoint Slides HNP NPDES Permit Copper & Zinc Study 6/5/2019 Shearon Harris Nuclear Plant— Permit NC0039586 Copper & Zinc Study { June 5,2019 I � JACOBS wwwjacobs.com I worldwide HNP Meeting Agenda • Safety Moment • Introductions • Overview of Permit Obligations & Compliance Strategy • Effluent Characterization • Water Effect Ratio Studies • Discussion • Path Forward with NCDEQ-DWR JACOBS 2 JACOBS Engineering Group 1 HNP NPDES Permit Copper& Zinc Study 6/5/2019 Introductions — Permittee Representatives Duke Energy Consultants • Bob Wilson • Bill Kreutzberger Environmental Coordinator— Senior Technical Consultant- Harris Nuclear Plant Jacobs • James Eayres • William Bromby Supervising Scientist—Harris Project Engineer—Jacobs Nuclear Plant • Bob Kelly • Don Safrit Vice President-ETT Senior Environmental Specialist —Duke Energy • JACOBS 3 NPDES Permit Overview • Permit issued August 29,2016:effective September 1,2016 and expires August 31,2021 pi • Permit limits include for five internal y.` outfalls and 2 outfalls to surface waters as follows: Internal Outfalls 001 -cooling tower blowdown 002-wastewater treatment plant 003-metal cleaning waste treatment system 004-low volume waste treatment system ow, 005-radwaste treatment system Outfalls to Surface Waters 006—combined discharge from 001 to 005 007—wastewater system for environmental center JACOBS 4 JACOBS Engineering Group 2 HNP NPDES Permit Copper& Zinc Study 6/5/2019 HNP Copper & Zinc - Permit Obligations & Compliance • HNP Discharge Point into Harris Reservoir (Class WS-V) • Surface Water Standards for Copper&Zinc • New NPDES Permit Limits in Outfall 006 (September 2021 compliance deadline) - Limited monitoring data at time of permit issuance - Copper and Zinc Limits based upon • No dilution(100%effluent) • Hardness of 25 mg/L(as CaCO3) • Water Effect Ratio(WER)of 1.0 • EPA default chemical translator(0.348) Daily Max Monthly Average (Acute) (Chronic) Copper 10.5 pg/L 7.9 pg/L Zinc 126 pg/L 126 pg/L 5 Schedule of Compliance - HNP Approach September 1,2016 September 1,2017 September 1,2018 September 1,2019 September 1,2020 September 1,2021 t t NPDES Corrective Year 2 Report Year 3 Year 4 Deadline to Permit Issued - Action Plan - •Further Effluent - Report Report - Achieve Gmds on copper and zmc Effluent characterization charaderaation _ _ Compliance based on default values A.Proposed approaches •Prelvninary WER Results pg •Plan for completing WER Effluent Characterization f ` •Effluent hardness s25 mg/L "` - '' •zinc-no compliance issues •Copper addnonat stud.reo d WER Study WER Report •angonq eoluem characrenzation ® Submitted •Fnal WER report to •Final WER report to be subndled 1 Mixing Zone 1 Analysis I Add'1 Water Chemistry .. t Management i Only Proceed el I Add'I Physical i if Necessary % Management, 44, 1 t Treatment i i Request for i Variance t Process i 6 JACOBS Engineering Group 3 HNP NPDES Permit Copper& Zinc Study 6/5/2019 Schedule of Compliance - HNP Approach September 1,2016 September 1,2017 September 1,2018 p September 1,2019 September 1,2020 September 1,2021 NPDES Corrective Year 2 Report Year 3 Year 4 Deadline to Permit Issued WI Action Plan - •Further Effluent Report - Report - Achieve Limes on copper and zinc Effluent Characterzation characterization Compliance based on default values &Proposed approaches 'Prelrninary WER Results •Plan for competing WER Effluent Characterization •Effluent hardness>25 mg/L •Zinc—no compliance issues•Copper—addaional studies read WER Study WER Report •Ongoing emuent Fharaaerization ® Submitted •Annual report submitted •Final WER report to be submitted _ 1 Mixing Zone ` • t Add'1 Water i ...._.� Chemistry ! r ,sr..,.:-•,� Management Only Proceed i t Add'l Physical i if Necessary iuNV .*,`q Management, I...,.,...::. �.,„„, t Treatment • 1 Request for I jVariance t t Process i 7 Calculating Water Quality Criteria with Site-Specific Information Acute WER*[0.960•e^{0.9422[In Hardness]-1.700}] Copper Chronic WER*[0.960•e^{0.8545[In Hardness1-1.7021] Acute WER*[0.978•e^{0.8473[In Hardness]+0.884}] Zinc Chronic WER*[0.986•e^{0.8473[In Hardness1+0.884}1 • Basis of NPDES Permit Limits - Hardness-25 mg/L - Water Effect Ratio(WER)-1.0 -- EPA default translator of 0.348 for dissolved to total recoverable metal JACOBS 8 JACOBS Engineering Group 4 HNP NPDES Permit Copper & Zinc Study 6/5/2019 Effluent Characterization NPDES Permit NC0039586 Copper&Zinc Study ¢! JACOBS www Jacobs corn worldwide 9 Schedule of Compliance - HNP Approach September 1,2016 September 1,2017 September 1,2018 September 1.2019 September 1,2020 September 1,2021 t t NPDES Corrective Year 2 Report Year 3 Year 4 Deadline to Action Plan Eunher Effwenl Report Report Achieve Permit copper and Effluent charaaenzahon charaaerzabon Compliance Limits on capper an0 iinc. •Preliminary WER Results based on default values &Proposed approaches yy,Plan for completing WER T r Effluent Characterization •Effluent M1ardness>25 mg/L �'^" ••""""•""""'—" Zinc compla s u •` •Copper�atldihonalai studies reqd WER Study WER Report •ongoing effluent characterization . Submitted •Annual repo,sub rated •Final WER report to be submitted _ I Mixing Zone r .. Analysis r Add'I Water i ,tittAry Chemistry IL Management I Only Proceed I t Add'I Physical i if Necessary pp`•, . , j Management, i.�_"'"" e„,..._... t Treatment Request for i Variance t Process i 10 JACOBS Engineering Group 5 HNP NPDES Permit Copper& Zinc Study 6/5/2019 Hardness Characterization • Limits hardness dependent • Default(25 mg/L)used in calculating HNP original limits • Actual hardness >25 mg/L - Effluent average was 43.8 mg/L as calcium carbonate(CaCO3) • 006 Effluent -006 Effluent Average(43.8 mg/L) 70 O 60 • ® • • • "50 s•r°••••• • •••• I. • • • ° • • • • 40 �••I • ` • • •••• • rn E 30 a OD 4—Scheduled shutdown of HNP m 20 `h 10 S 0 , ', %oi� 7.� ' ice ��� '6 e �76, �i6 �%i6. Q 7e ie 'Low hardness in April 2018 due to scheduled outage JACOBS 11 Zinc Characterization — Maximum Daily Values • Zinc values substantially lower after change of corrosion inhibitors • In compliance without permit modification 250 200 150 126 µg/L Hardness=25.0 mg/L c 100 • (default value) N • • • 50 • • • ° 0 • •b • S� a• • 8 I809• ®® RA a ° •e••o • , `ri i .9 7 v' . 6 6 6, l 1 d T6 'tij �iJ 2i6 i, �O 2 C is ji �O �O ? 2 �? ,Tj Oj) Oj) Or) 2 !8 't6 p.78 p't6 O'TB 20� pJ8 r'y 8 JACOBS 12 JACOBS Engineering Group 6 HNP NPDES Permit Copper& Zinc Study 6/5/2019 Zinc Characterization — Maximum Daily Values • No reasonable potential to exceed hardness modified limit 250 202 µg/L 200 Hardness=43.8 mg/L 150 00 126 µg/L Hardness=25.0 mg/L 100 • s (default value) • • • 50 • • • s •s• 780 ••l • e• •=•d• •,*s so: • °snow • 0 i TT Ji „'i 4/ 6 8i JO Tl 2j JO � T � i/ 61;0 ''54, <a jam? 4 ir/ - 0 �0 0 Jl<' ?J T J �O O O 3� 0 ?J OJ) d 8 J8 J8 l� OT8 J8 JACOBS 13 Copper Characterization — Maximum Daily Values 100 90 80 70 60 a0 ? 50 O~Scheduled shutdown of HNP • 40 • • • • 30 • • • • •• • • • • • • 20 • • 30 •—Ili ✓ �• �•° • _ • 10.5µel ' _ '�°♦ •Hardness=25.0 mg/L 0 (default value) 3� 18 J,D 'r �l i0 Ti jaTB �Ol8 ' Tj Tj Tj OJ) 4 TO Ty OT8 l0 9 JACOBS 14 I I I JACOBS Engineering Group 7 HNP NPDES Permit Copper& Zinc Study 6/5/2019 Copper Characterization — Maximum Daily Values 100 90 80 70 60 nn 50 04—Scheduled shutdown of HNP • ° 40 • • • • 30 • • • • •• • • • • • a 17.8 µg/L 20 • •• • _ • _r._•__..____._. Hardness 43.8 mg/L • 10 �•� • • 3 ' •• • • _ •� 10.5µg/L • Hardness=25.0 mg/L 0 (default value) i S i rrir a' S 9 r r 2 rs - -- ? - fir i� i2 �o � l� o �a 1 2 r� ors ors ors lore r8 r8 ore ore orb 2or ora ry JACOBS 15 Copper Characterization — Monthly Average 70 60 50 m 40 a v 30 • • a a • u° • • • 20 • • • • • • • • • a • • a 10 • • • 7.9 µg/L Hardness=25.0 mg/L 0 (default value) JACOBS 16 JACOBS Engineering Group 8 HNP NPDES Permit Copper& Zinc Study 6/5/2019 1 Copper Characterization — 1 Monthly Average 70 60 50 4a 30 • • • • I V • • • 20 • • • • • 12.8 µg/L • • • Hardness=43.8 mg/L • • • 10 • • 7.9 µg/L Hardness=25.0 mg/L 0 (default value) 9q 2O14 '0117 jOq) ?,44. jo1'6�0;�je j18`v,%jOf jO�4�j �O �oti�j4p2Oje jor9 I JACOBS 17 Characterization Results • Hardness - Effluent hardness is 43.8 mg/L versus the 25 mg/L used as the basis of permitting • Zinc levels - In compliance with current permit limits and less than half recalculated values based on effluent hardness - No Reasonable Potential to exceed Zinc criteria • Copper levels - Exceed both monthly average and daily maximum current permit limits - Recalculating based on actual hardness not sufficient to achieve compliance • EPA and State rules allow adjustment of criteria based on site specific conditions - NC rules include WER as part of calculation of dissolved criterion - WER = Toxicity End Point(effluent+natural water) Toxicity End Point(lab water) • WER studies appropriate for copper JACOBS 18 I JACOBS Engineering Group 9 1 HNP NPDES Permit Copper & Zinc Study 6/5/2019 Harris Outfall 006 — Compliance Plan Described in CAP (8/2017) and Year 2 Report (8/2018) • Characterization plan—Hardness and metals (copper and zinc) - Weekly for 3 months - Twice per month after 3 months - QA/QC samples • Options for permit modifications - Mixing zone analysis - Biotic ligand model - Water effect ratio(WER)-Selected • WER Study-Ongoing - Plans and procedure - Preliminary results • Potential future studies JACOBS 19 Water Effect Ratio Studies NPDES Permit NC0039586 Copper&Zinc Study JACOBS www.jacobs com I worldwide 20 JACOBS Engineering Group 10 HNP NPDES Permit Copper& Zinc Study 6/5/2019 Schedule of Compliance — HNP Approach September 1,2016 September 1,2017 September 1,2018 September 1,2019 September 1,2020 September 1,2021 I t f NPDES Corrective Year 2 Report Year 3 Year 4 Deadline to Permit Issued Action Plan •Further Effluent Report Report I. IM Achieve Limits on copper and zinc. Effluent Characterization Characterization -_ Compliance based on defaut values &Proposed approaches ••Preliminary WER Results •Plan for completing WER a Effluent Characterization •Emuent hardness c25 yL ;s}. v . .._. «..;,- „e+.,.. ...w. ;. •Zinc-no compliance issues yy •copper-addthenal studies rood WER Study WER Report •Ongoing effluent characterization 22 Submitted 1 •Annual report submmed •Final WER report to be submitted • _ Mixing Zone u, Analysis f """" ' ✓ • Add'!Water k Chemistry 1' �t Management Only Proceed i 1 Add'I Physical i if Necessary % =„ysa4 Management, Treatment I Request for i ��{ 1 Variance i Process 21 WER Study Details • WER studies conducted between July and September 2018 • WER procedures based on EPA Interim Guidance (1994) - All WER tests conducted based on 100% effluent(Type 1) using 24-hour composite samples - Three tests with a primary species- Ceriodaphnia dubia - One test with a secondary species-Pimephales promelas • Measured concentration of dissolved and total recoverable copper plus other required parameters 1 JACOBS 22 jl JACOBS Engineering Group 11 HNP NPDES Permit Copper& Zinc Study 6/5/2019 WER Results WER Results for HNP Samples for Outfall 006 Total Cu Dia.Cu Date Species \VER WER Round 1. 7/12/18 primary 5.9789 4.9996 Round 2 8/15 18 primary 10.8966 10.3127 Round 3 9/26/18 primary 8.2006 7.4639 Round 4 9/27/18 secondary 2.6644 2.8330 • All WER Values were Type 1 since effluent limits are based on 100%effluent • Final WER is calculated as lowest value since all were Type 1 WER JACOBS 23 WER Study — Copper Results • Total Copper WER of 6 • Dissolved Copper WER of 5 1a° • Tests with secondary 160 species confirmed WER 140 from primary species 120 - Values are within a factor of ) 100 5 of those with the primary -- species 0 so —1 60 40 20 I 11111 , Round 1 Round 2 Round 3 ■006 Effluent •Lab Water JACOBS 24 JACOBS Engineering Group 12 1 HNP NPDES Permit Copper& Zinc Study 6/5/2019 4 1 1 1 Recalculated Criteria and Effluent Limits 1 1 1 HNP Outfall 006 (Average hardness 43.8 mg/L as CaCO3, 1 WER of 5.0) Water Quality Acute 30.9 pg/L Criterion for 1 Dissolved Copper Chronic 22.1 pg/L Calculated Effluent Limit for Total Acute 88.8 pg/L 1 Recoverable Chronic 63.6 pg/L 1 Copper 1 1 JACOBS 25 1 1 1 1 I Copper Characterization — 1 Maximum Daily Values 1 ioo 1 88.8 µg/L 90 Hardness=43.8 mg/L 1 80 WER=5.0 1 70 1 60 Y 50 Ow—Scheduled shutdown of HNP 1 `m s 0 Et 40 ° 0 1 30 0 0 0 0 0 0 0 a 0 0 17.8 µg/L 1 20 0 0 00.. 8 8 ®0 ® o Hardness=43.8 mg/L c% o •® • • ° • io 9 1 . • • 10.5 µg/L 1 • • Hardness=25.0 mg/L 0 (default value) 1 i i i `9i 'r7 'ti i i 6 B 49 72 i �i 1 �1 �s �� s�2 <'" �6 �"'� �8 �'t�'i ,Tj OJ) Oj) O�j 1pr, .rR 78 Oj8 Oj8 Oj� 20r8 Oj8 7y 1 1 JACOBS 26 1 1 1 1 JACOBS Engineering Group 13 1 1 HNP NPDES Permit Copper& Zinc Study 6/5/2019 Copper Characterization — Monthly Average 70 .63.6 µg/L 60 Hardness=43.8 mg/L WER=5.0 50 40 cu 1 a 30 • • • v • ® • 20 • • • • • • • 12.8 µg/L • • ® ® • Hardness=43.8 mg/L 10 • s • 7.9 Rg/L Hardness=25.0 mg/L 0 (default value) le, 24`j�l��l j� 0,��o� .41)j�r j8 170,jj8�kektl 0 �BG?•�8����y8`V0.4 j0r9 JACOBS 27 Conclusions based on WER Study Results • Copper limits for out fall 006 should be based on site specific information related to hardness and WER • The Acute and Chronic water quality criteria for copper are based on the following formulas in the 15A NCAC 2B .0211(11)(c): Copper,Acute = WER x 0.960 x e0.9422()n hardness)-1..700 Copper,Chronic = WER x 0.960 x e0.8545(tn hardness)-1.702 • Acute and Chronic dissolved criteria for copper based on average effluent hardness and the WER results are: Copper, Acute =30.9 ug/L Copper, Chronic =22.1 ug/L • Using EPA's default metal translator of 0.348 for dissolved to total recoverable copper, calculated effluents limits in 100% effluent are: Copper, Acute =88.8 ug/L Copper, Chronic =63.6 ug/L JACOBS 4 28 I I JACOBS Engineering Group 14 1 1 1 HNP NPDES Permit Copper & Zinc Study 6/5/2019 1 1 I 1 Proposed Modified Limits 1 Total Recoverable Metals Limits for Outfall 006 Original Permit Modified for Modified by WER Limits Hardness and Hardness Daily Max 10.5 pg/L 17.8 pg/L 89.1 pg/L Copper Monthly Avg 7.9 pg/L 12.8 pglL 63.8 pg/L Zinc 126 pg/L 202 pg/L - 1 1 JACOBS 29 1 i Discussion NPDES Permit NC0039586 Copper&Zinc Study • JACOBS' www,acobs coActo 30 �// t�..IIJJ 1 JACOBS Engineering Group 15 HNP NPDES Permit Copper & Zinc Study 6/5/2019 Path Forward NPDES Permit NC0039586 Copper&Zinc Study `. JACOBS www.Jacobs.corn I worldwide 31 Next Steps with NCDEQ-DWR • Get feedback on study results from DWR • Revise submittals as appropriate • Determine whether other investigations are necessary • Incorporate path forward in Year 3 Compliance Report • Submit a request to modify the NPDES permit when appropriate JACOBS 32 JACOBS Engineering Group 16 1 ,16 StArE J'� 4 y Received by PRH ROY COOPER 41 JUL 1 6 2019 Governor MICHAEL S.REGAN ` ,14:74 vsoo• Secretory LINDA CULPEPPER NORTH CAROLINA Director Enviratunenfal Quality July 10,2019 Bentley K.Jones Shearon Harris Nuclear Plant 5412 Shearon Harris Road New Hill,North Carolina 27562-9300 Response: DWR Review of Duke Energy Progress, LLC Shearon Harris Nuclear Plant (NPDES Permit NC0039586): 2018 Water Effects Ratio Study Dear Mr.Jones: On May 9, 2019, the Division received the results of a Water Effects Ratio study for the Shearon Harris Nuclear Plant from Duke Energy Progress, LLC. On June 5t11, a meeting was held with Duke and its 1 consultants to discuss the results. Based on the discussions and the Division's review of the study methods and results,the Division provides the following comments: • The Division requests the WER study be conducted in accordance with Appendix F of EPA's 1994 Interim Guidance on Determination and Use of Water-Effect Ratios for Metals which specifies utilizing either a dye dispersion study or dilution model to incorporate the near-field effects of a facility's 1 discharge when developing a WER for Special Flowing-Water Situations. • The Division requests that, as it is the more conservative species in the stream when determining WERs, the primary organism used in the WER study be the fathead minnow to insure adequate protection of the receiving stream. Additionally, the Division wishes to inform the Permittee that,per Appendix A Part B of EPA's 1994 1 Interim Guidance on Determination and Use of Water-Effect Ratios for Metals,dilution will be taken into consideration when determining the WER but will not be included again in calculation of the dissolved standard. 1 The process associated with the WER will be continually developed,as the process is fairly new to the Division. In this case,the more protective WER of the two Shearon Harris Nuclear Plant WER studies shall be applied to copper limits in NPDES permit NC0039586. Future WER verifications shall be 1 conducted using the most updated Division-approved procedure. I If you have questions concerning these comments, please call me at(919)707-3609 or by email at ncdenr.nick.coco@ g ov. Sincerely, 777";._ Nick Coco, Engineer NPDES Complex Permitting Unit 1 CC: Julie Grzyb, DWR NPDES Complex Permitting Unit Cyndi Karoly, DWR Water Sciences Section Connie Brower, DWR Classifications and Standards Branch 1 D North512North Carolina Department olf Env Q I rc ISalisbury Street 11617 Mali Serviceironmental Center I Raleigh.Division Northof CarolinaWaterResou 27699es -1617 w•�V/e`' 919.707.9000