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NC0039586_Compliance Evaluation Inspection_20190503
�' DUKE Tanya a M.Hamilton Vice President ENERGY Harris Nuclear Plant 5413 Shearon Hams Rd New Hill,NC 27562-9300 MAY 032019 Iticavalmeocoma Serial: RA-19-0161 4141' 0 9 2019 Certified Mail Number: 7006 0100 0006 4208 4774 p aterO ali etmittinta 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. 4 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 (fWER) 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, /74l_ ' 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: 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 Enclosure Harris Nuclear Plant and Harris Energy and Environmental Center NPDES Permit Number NC0039586 Technical Memorandum — NC0039586 Compliance Update (124 pages plus cover) JACOBS® 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 ...***it: '' CA... '.• Date March 18, 2019 4::P0FESS/pN 'iY� Prepared for Duke Energy SE L • Prepared by Bill Kreutzberger—Jacobs Engineering Group, Inc. (Jacobs) 47 Muriel Steele, PhD, PE—Jacobs • FHGINEEQ:' Project Name Shearon Harris Nuclear Plant NPDES Permit Assistance �/ �� ` / Project No. 680115 ,... M.S • 3l 1�I(� 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 Ng/L 10.5 pg/L WER of 1 due to a lack of historical data available Total zinc 126 Ng/L 126 Ng/L for Outfall 006 discharges when the permit was developed. The dissolved criteria were translated J/ACOBS• 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. 0 006 Effluent 006 Effluent Average(43.8 mg/L) 70 o6 60 ra 50 ®0 0®11- ®®®® ®® E 30 20 08 co 10 = 0 6 cP 1 1 1 v0 1j<� , 6/� Ii1-1 ‹)O ‹)0 ck- 1'1� 1d .) 0i1`�i (k) ‹)0 01, �01, j� j� O18 OZ� 01 �01� 0� j9 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.8473(In hardness)+0.884 efforts, as well as NPDES-required Zinc,Chronic = WER x 0.986 x eo.s473On 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 J 150 c 100 • • IV • • 50 • • • i a 1 1� .� i 6, di 1 1 1/�01 �j�0 •;�0 16��0 1/11�1 6/01 )01 %d��0 N0� 1p��0 O/No) 1��i0 _I 1j 1> 1- 06 cP 163 1( 1cs, 01� 1c 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 eo.9422(In hardness)-1.700 characterization efforts, as well as NPDES- Copper,Chronic =WER x 0.960 x e0.8545(I❑hardness)-1.702 required monitoring, were compared against the copper limits in HNP's permit as . well as the calculated limit based on site- 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 µg/L 6.2 µg/L Dissolved Copper Chronic 2.7 µg/L 4.4 µg/L J/ACOBS. 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 0 40 • 35 • 30 0 • o_ 25 •• ® • • • ®•S • • o_ 20 15 ---- -® i®----� ®di 4iD ," 4 -•-� 10 ® ® S ® ® S •sioilb 0 - ' i 9i 1 ?- `)i i 6 10 1 1 1, 1, 8 d' 1� 16. 1,3) 01 '9 8 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 ---n Monthly Ave Limit(at default 25 mg/L hardness) -----Limit,Chr.(at 43.8 mg/L hardness) • 006 Effluent-Monthly Ave 35 30 0 0 • - 25 • • • • 20 0 • • • 0 • 15 • • • • u -0 • •10 •. ._ .._.. ...__. ._. .. . ._._., .._. _ . _ _._ ... _ . ,,.__T _�.... -4- 0 5 0 9p 470~;30 kc) N3O 7v)94. oN30C> O pPcN0)c0 6N30/'c) '.v)0 k10 `>0/��9 �O+p %V)0 N30o�0 c��N3O 1� 1j 1 > 1, 1 1j 1, 1 dd, 1� 4 ,74, 1- 18 8 4 4 1� ,4p 18 l9 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 .!/COBS• 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 m9ic as CaCO corresponding total recoverable zinc WER=5.0 limit for Outfall 006, this time including the determined WER (Table 4). Water Quality Criterion for Acute 30.9 Ng/L Dissolved Copper Chronic 221 µg/L Results from the effluent characterization showed no values Calculated Effluent Limit for Acute 88.8 µg/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. JACOBS• 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 own 60 • n 40 • • • fir • • • •• •® 'b • • .era.s • i `Si -v\\0:\ 1j 01j jcP 018 018 01� �01 30, 19 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) 0 006 Effluent-Monthly Ave 100 80 J • 60 1 a 40 n 0 • • u° 20 • • • ® • • • • • • • ® • ® ® • • 0 i'o 47 ✓(• ✓�%94, soND o °c 4'o °o ✓d,> x�6 2Td '�,o, 470 ��o °i�-94, `�o °c /Lo o(c ✓� 0, ND()1>01? 1� 0,v. 0/ 0� Odd O.? 0,7 01�0J6 0.? �0180j8 16, 01�O`, 0,e o 0'7 0,, 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 JACOBS9 Copper and Zinc Evaluation Attachment 1 Water Effect Ratio Study, Copper — Report ETT Environmental, Inc. — December 2018 3.4 Calculation of hWER Values adjusted) hWERs for total recoverable copper for acute The experimentally derived (hardness PP 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(fWER) 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 fWER 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 3.0 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 gg/L in Round 2. Duke Harris WER Study-Cu ETT Environmental,Inc.; 12/18 Page 5 of 110 2.5 Determination of Final Water Effect Ratio Type I WERsImost accurately simulate design-flow conditions, so these values are used directly in 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%. 1A 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 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 (fWER) 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 defmitive tests (48 Hour) with the secondary species also are conducted as acute tests,with the endpoint being an LC50. 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 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 E !on' Jnc. (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:ro Robert W.Kelley,Ph.D.:QA/QC Farhad Rostampour:Lab Manager n e I ac 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. NCDENR Certification#022 Included results pertain only to provided samples. Page 1 of 110 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 CH2M HILL North Carolina, Inc. Page 7 of 124 JACOBS 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 • 60 n 40 • • ® • u 20 • o* ®®••� ••® •• • ® •®® �f% • 0 Q 'll �'i i 6i cpi 'l0 1j��0 c)0 \ - k:\ � o00ilk/� <"0 `011> 1) 8 1cP 1cP 16' 6:1 .lc 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) 0 006 Effluent-Monthly Ave 100 80 to 60 L . 40 0 • • • • • • u 20 ® • • • • • • • • • • • • • • • 0 90,,,"od` -)o%'76°,30°o�00�t�'1'0"`40 c,)07���°6,"0'v>01-'so`vo�o%9G`P�p a�00ct��oo��o`4, > dj 1) Ij Ij 1j 16, dp l8 1� l� 1p •d 4 4 1� ,c) 1�p l9 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 Page 6 of 124 CH2M HILL North Carolina,Inc. 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 copper was used to determine the HNP Outfall 006 corresponding total recoverable zinc Hardness=43.8 mg/L as CaCO3 WER=5.0 limit for Outfall 006, this time including Acute 30.9 pg/L the determined WER(Table 4). Water Quality Criterion for Dissolved Copper Chronic 22.1 µg/L Results from the effluent characterization showed no values Calculated Effluent Limit for Acute 88.8 µg/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. CH2M HILL North Carolina, Inc. Page 5 of 124 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 C • • 35 • a 30 • • • n 25 •• O a • %� • • 20 _ io Elbe 5 0 /1i�0 Sir).> ,���� 91 ��1/ 1�6i�0 ��0.j. �c36, `�'�� ��'18�� �O�i �� �0 dj 01, O?j 01) �01, dd 18 O�6 01� 04 �016 016 19 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 • • • 25 • • • • L 20 • • • • 0 15 • • • • • 10 • • • 5 0 9p~')dyN)v)0`)0 6°N";4�Oc� o`)cv0`).01 v)o lb'•cbd`v) �v)0 6c��POD c� 20`v)cN30 dj 1 1 `t> 1 p 16 1 , 5, ,16 ' 018 018 Odd' icp 16 O<9 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 Page 4 of 124 CH2M HILL North Carolina, Inc. 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 J 150 100 • • • 50 • ;•• o •: sI •• lie.osis °Gem • — ss> -> `9i 1,j 1i `''i Qi 6.. ci 10 1- Vi 1�v30 1j��0 �0 1• �0 i11/� 6/�01 �',01d, 1��0 1���0 1��`�O 1<i� i��,0 N01 1, 01, d' d 1� 1� 1� 01 1� 0 8 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(In hardness)-1.700 characterization efforts, as well as NPDES- Copper,Chronic =WER x 0.960 x eo.ss4s(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- hardness-dependent water quality standards calculation for copper 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 µg/L 6.2 µg/L Dissolved Copper Chronic 2.7 µg/L 4.4 µg/L CH2M HILL North Carolina. Inc Page 3 of 124 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 60 • •_ •• •• u 50 • • • rra �� • •elm • •••• •• ! • 40 • ? •••. • bp E 30 • 20 • 10 = 0 i `ri �i 9, 11 1i `�'i i 6j c? 1<30 �j<1 .-1¶ 16<> <111 6<0 <COI �c3�0 1<. I�F.O /'1i�07 1> 1j 1j 01) cP •8 1� 1cP � 01,33 c 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 e 0.8473(In hardness)+0.884 efforts, as well as NPDES-required Zinc,Chronic = WER x 0.986 x e0.8473(In hardness)+0.884 monitoring, were compared against the zinc limits in HNP's permit as well as the Equations 1 and 2 calculated limit based on site-specific Hardness-dependent water quality standards calculation for zinc hardness (Figure 2). Page 2 of 124 CH2M HILL North Carolina, Inc. JACOBSTechnical 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 O��N' c,�Q�� Date March 18, 2019 :Q%�FESS/pN Prepared for Duke Energy SE L Prepared by Bill Kreutzberger—Jacobs Engineering Group, Inc. (Jacobs) 47 Muriel Steele, PhD, PE—Jacobs �! ''FINE0 40 Project Name Shearon Harris Nuclear Plant NPDES Permit Assistance �/ !yG...... ' �� ` Project No. 680115 •�F� 3 M,S 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 for Outfall 006 discharges when the permit was Total Zinc 126 pg/L 126 pg/L developed. The dissolved criteria were translated CH2M HILL North Carolina, Inc. Page 1 of 124 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]—(0.0 cx 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 fWER) 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 110 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 fWER as follows; Site Specific CMC =[(cmc)x(fWER)x(downstream flow)] -(upstr. Cu conc x upstr.flow) (Effluent flow) [7.7822A x 5.9789B x 7.9 mgd] (0.0c x 0.0) (7.9 mgd) A:recalculated CMCI(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]c(0.0 x 0.0) (7.9 mgd) A:recalculated CMC at 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 8of110 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 fWER 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)]-1.700)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 ER Lab Water Site Water SMAV Hard.Adj. CMC© CCC @ Upstream Effluent Upstream Effluent WER# ype 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 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 W ER 4.9996 7.7822 5.4564 Limits per Interim Guidance IWER 4.9996 nCCC= 5.4564 IWC= 1.0000 CCC Eft Criterion= 27.2797 fWER 4.9996 nCMC= 7.7822 IWC= 1.0000 CMC Eff Criterion= 38.9079 Page 10 of 110 environments,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 Duke Harris-WER 1 Cu ETT Environmental;07/18 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 ChemistryMeasurements for Acute Definitive Tests PP 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 QH 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 18`h 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 (CuSO4.5H20) 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 1 Cu ETT Environmental;07/18 Page 16 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 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. 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 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 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. 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 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) 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)09422= 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) = LC50 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 Cl. Duke Harris-WER 1 Cu ETT Environmental;07/18 Page 21 of 110 ROUND l - APPENDIX A2 Survival Data for Acute Definitive Tests Duke Harris-WER Round 1 Cu ETT Environmental,Inc.;07/18 Page 22 of 110 Page 60 0f tQ1 I Nominal Initial# Mortality Measured Concentration WER 48 Hour Acute Toxicity Test `''-N ��� _�-�cvi Metals Conc Rep Organisms 24 hr 48 hr Initial Pina. Mean Facllily KQ . ) — - U l f LO .- A road To WI Total Sample ID: ija,y b !-�n1 0% B _ `j U Start Date /-/z,I{> Time: ,--2j -) By. --. ;. C 0 DIs DI:; Dis End Date: Time: By: i . t"fl ,1 D Effluent Lo< if: J -_1j� i) _Upstream Log If: A G� Vt roil Toiwi lot;,, TEST ORGANISMS B S C) Kest Organism: �x, y� ` 2� ��" C Ds o,s Dis for Ceriodaphnia dubia So e� �? S D �0 Date Removed; 7- i1—f% 6� -7-- r - —I I /T;mc\ .,d, ?777) (Tir.,,_, A 0 Total Total Total DelWGeii / t tom)_ \I iiiic/ u" - \_ niic1 B S 0 for fathead minnows or mysids: 1-3 C 5 a Din Dis Dis Source: Age: ( D V Temperature 24-26 C. Light 16 hr It l8 hr kd;50-100 ft candles I.—. A 5 0 Total Total Total Laboratory Water DMW /SSF© 50 mg/L hardness r 55 B 5 0 Downstream Water Preparation �j e C 5 0 ols Dis Dis % effluent volume nlL Prep.Date: D S 6 % upstream volume mL Prep.by: A !!!'mil 0 Total Total Total 5oB U Test Solution Preparation: Metal Salt: C11)01 C S. O Dis Dis as Date: By: Stock.Soln:IZ-7 I L D 5 D Nominal Conc mL Stock Soln. Volume prepared A Q Total Total Total ( 0 500 rn!, f B 5 0 1_ 1' 9 1 1. 1 C 5 6 Dis Dls Din 2-/ •9 D S 0 I3� L {-A Total Total Total ✓O I• ll i. B 2 "71/�•�v� �1 C 5 0 Dis Dls Dis I v /'`'n I 1. D S. 0 19,� 5 62-- • A 5 3 Total Total Total A Total Total Total , A B 5 I B 10!/j�/ C 5 ' Dis Dis Dis C Dis DIs Dls '- �` D 5 3 D ` A 5 A Total Total Total A Total Total Total 7)aq •'4 (,, C Din Dis Dis Dis Dis Dis D D F.�• mot: II: Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. Test Method: per EPA Interim Guidance iii,; Z o 8 ,^o 244- 5D D"Y 1, H Page 23 of 110 1 e60of'l Page 61 of 100 Nominal Initial If Mortality Measured Concentration WER 48 Hour Acute Toxicity Test Conc Rep Organisms 24 hr 48 fir Initi Final Mean Facility: J/ T 1 Metal:-} f%� A l (1 1UIC total toll Sample ID: �� G 0°i B �'� -- Start Dale: /�/2_I -). Time: f 5 J By: �) — C _.J 0 Dis Dis Di:, End Dale: Time: B : D 6J > Ilnill U 7slream Loq It: A MIN. lot l„,, lou: TEST ORGANISMS B Test Organism: 5-X I.-ZGl �-2- C 5 f �_�- Din Dis D�5 for Ceriodaphnia dubia Source: AA_K_-7 D =III 0 Dale Removed; -7_ I `_l �Cl-L -7- rime) n lit 7-, �i r_ �• � A ! t ! -,mai Imal tour Beivveeri I l J (Time)and �L-0 1 (Time) ime) J B �/-'� 0 for fathead minnows or mysids: `^ C 0 Din Ds Din Source: Age: D 5 0 Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles A S O Total Total Total Laboratory Water DMW/SSF @ 50 mg/L hardness 7 5-1 _` B 5 0 Downstream Water Preparation 6C y 0 Dis Dls Din % effluent volume mL Prep.Date: D 5 0 % upstream volume rnL Prep.by: A 0 Total Total Total Ii, B 0 Test Solution Preparation: Metal Salt: (',L)st01 C 5 0 Dis Din Din Date: By: Stock.Soln:12--7Z f1ic I Li D 50 Nominal Conc mL Stockc �J Soln. _Volume prepared J A 0 Total Total Total 0 /f t rn f'I S B 5 / Z . �I� C S.. vl Din Din Ds CP .2 D 5 0 a, 6, •3'4 A 5 5 Total Total Total I Z-3 •`"1 1 Z . B S s _ ri.5 , 6�� C �j Dis Dts Din r 9 U D cJ s .55 I - .5 d A 5 Total Total Total A Total Total Total B 5 5 B C S Dis Ds Dis C Din Dis Din D . . s D A Total Total Total A Total Total Total B B C DIs Din Din C Dis Din DIs D D Test solution volume:25mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. Test Method: per EPA Interim Guidance Page 24 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 0 Ill - ,. ACUTE TOXICIT1' TEST - CHrMISTRY i 4d Hour ---- 24 Hour Readings 14 Hour Readings 'r Readings Readi ---,thin'Rendingsr Did old no. "r� ' old old nr... nr�• Condo( [h3solv.cQ :: Dics(lvrd Dissolvrd D.Slb lord (Prt�hnsrrm)0, Urssol,cd II O'yl:rn Ifl r rn f It Orygrn PII O yC mg/l. (-Irygrr, pH or!.>hmtr Qri'grn P ml./L Effluent nt met. tppn rng/t. C----- ratio r, rngll. ---1 , cry_ii,2,_____i___cl • - A _ I�f 7 14-1`S Date: G� '3LI L Time: ✓, �� Initials: j 71 Hour Readings 72 Hour Readings 96 Hour Readings old old new new' old old Dissolved Dissolved Dissolved Elilucnt Oxygen pH ()lyre!) PH Osyre4 pH L l m Concentration nlg/L P mg/L . YP y41 :., v'� si ,I ji:;! M l�1 tr& r 111 1 t ii Il' J� • • t I4 • Date: _ x , P Time: 11 Initials:11 V." 11[ Lab ID#: 'iF . .. ._ cal: 5 t VIA 6C '1"kg-P3 — C)k, • :,.,1,,-::- 3 1 . .>< 0 0 1. 1 S gl _ Page 28 of 110 ROUND 1 -APPENDIX A5 Chain of Custody Documentation Duke Harris-WER Round 1 Cu ETT Environmental,Inc.;07/18 Page 29 of 110 Erre 41 i ....... I. CI .IN OF CUSTODY RECORD } Page _ —of «.,, 11biI7i7ilr . PO Box 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.ETTENV IRONMENTAL.COM Client: 17\ 1' /. - - Wi�P.t (r01}�(�j��d 1►D Ct f aM Hill NOr 4 �aIt Aro, Program Containers Preservative Parameters Facility: cI 1 1 y� l Ohe_ar A i-Iarn5 NucI eat -Ra " hie Whole Effluent Toxicity State: Nj C NPDES it: N GQO31s%6 . Acute Chronic Test Organisms C] m • U. O -S d O O Q V (Composite only) (Grab or Comoosbe)) < �' — U. v .g _ - z S n — I. - 6 _ V 1-H?504 = m g - y rn Sign,and Print below ; ti c c 2-HCt F o' �, m 4 to U the dotted line o € .E U •� H B 4 3,4.11.403 yOH� u F. o ? 7. ti P. N E'- _ : C o p VI G O c� -" O i=Zm4G u o. _ �_ 7 a — _" ,. — -- _ r. 8 SAMPLE ID E Composite Smrt Date Time Sample Collection Onte Time Collected by Urn rn Z c- C7 > 6-Other < < lJ 0 U 0 if i in = ii _ 5 f 'Chemical Analysis&Other Cu Fail=O�la C ,.7-10 a o?oa 7-ii-; 0 5 � ..P J 41✓ q @. %i $ 52J(3 N G d Special Instructions: " • lefort ie51Ai- -tD Mari e, .S- ea.1 e a& .t �(e} .,CJIrn * �+FGgS a mved lock. -EA) 711 I(g C;t 5 0.rn vEG( 7 i. 18 �' (31 of 1 -80, 0.q°C. -Bp Sample Custody Transfer Record Secure Receipt Sample Date Time Relinquished By/Organization Received By/Organization Area Temp°C Preserved? t nn ':�-if—#' :�; n.?i,.�L7ti_/C-i9 I I�i1, ig ii-Hts UPS d c E*r` : 1- 7 COMPOSITE SAMPLING PROCEDURES TEilIPERATURE 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: 1 sample each hour'tor 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 1 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 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 1 10 PROFIT 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 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 33 of 110 i E !o'iJinc. (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 B 1. 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; 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 107 µmhos/cm 42.9 mg/L 7.8 Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 37 of 110 L 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 I 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 2 Cu ETT Environmental;08/18 Page 38 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 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 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 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; 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% . J 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 1 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(mhos/cm) NA Total Suspended Solids(mg/L) NA Duke Harris-WER 2 Cu ETT Environmental;08/18 Page 42 of 110 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 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: 10.236 ug/L x(58/50)0 9422= 11.7723 ug/L Dis-Cu: 9.402 ug/L x(58/50) 0. 422= 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) LCS0 in Lab Water 11.7723 ug/L Water Effect Ratio(WER) = LCco 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. 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.;08/18 Page 45 of 110 Page 64 0f fl I WER 48 Hour Acute Toxicity Test Nominal Initial# MortalityMeasured Concentration I Conc Rep,,Organisms 24 hr 48 hr, Initial Final Mean Facility: 1)Mt,0 Metal: cuc...........: A 5- 0 Total Total Total Sample ID: B 5 0 Start Date: $ \5 ig Time: 30D By: ieVA C 0 Dls Dis Din End Date: cf )7/[1 Time: j3Z5 By:_,1 m D 5- Q Effluent Log#: Upstream Log#: Total Total Total TEST ORGANISMS anism: A'F 8•►0 G-L f B 6- 0 Test Org Z C b d DIs Dls DIs for Ceriodaphnia dubia Source: I v r� I g 11v.s.ro I D c f? Date Removed; 8, it-HY I /l Rpt-........, (—{nfl (Tim& and 71.9� ) (Time( . 1 o B 5 0 for fathead minnows or mysids: C 0 DIs DIs Dls Source: Age: NI III D i. ! Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles l A C Total Total Total Laboratory Water MW/SSF@ 50 mg/L hardness 2- 1I 1 B 5 ,3 Downstream Water Preparation i,l ill C 6' 2 DIs DIs Ells % effluent volume mL Prep.Date: :'1,,, D 3 % upstream _volume mL Prep.by: tiiiii KC A t Total Total Total l,i l;,k B 5 Test Solution Preparation: Metal Salt: 5b1'si4o :Ii `25 C S 5 ( 2•72 L DIs Dls Dls Date: ills (� BYkr Stock. Soln: 1 S ijl 'll', ' 5 p J7 Nominal Conc mL Stock Soin. Volume prepared i , ICE! A 'r Total Total Total L\.2 •)7 ,c)-1)0 i; ll B 5 5 L zy 'I,I ` �,� C1 C "✓ tc' Dls Dls Dts 8 AO _ .3y . . I i t , A Total Total Total I/.7 .1)1 ..i 6 _6" 2s ,?d IA H jl'. C DIs Din DIs 5 .v [-3i 7 lc IIi � D 6 ,: i, A 5 S Total Total Total A Total Total Total j: l ! I 3 B 5,. B li ,I" t ,', C ,6-- Dls Din DIs C Dls Dls DIs ] !C1 D D lii';:.,II A Total Total Total A Total Total Total .l B Nf i B li C DIs DIs DIs C DIs Din DIs i', D D - Test Method: per EPA Interim Guidance Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. s'�l ft Page 46 of 110 age 64 of 1p Page 65 of 100 t '�� >t Non'om/tfnaI Initial# Mortality Measured Concentration WER 48 Hour Acute Toxicity Test Rep Organisms 24 hr 48 hr Initial Final Mean Facility: Wit . ilo-rl'3 Metal: conc A 5 O Total Total Total Sample ID: ()(A*-eI OO( 0%_ B ,c 0 Start Date: S-is•1 Time: 1300 By: AM_ C 5 D Din Din Dls End Date: S It Ill 1 Time: /32.5— By: ‘t/V\ D 73 , Effluent Log#: 5-21-2 3 Upstream Log#: , ,` �� A $- p Total Total Total TEST ORGANISMS �t B .S O Test Organism: A•P ti94o, 6-Li( fd I(J C2 b M 0 �' 9, S-kc/'ib , 6 0 Ds Din Din for Ceriodaphnia dubia Source: D l Date Removed; X./y(a) —=L1 — • u.. • Tula bieiWCCII t /ulJ (Time)and L ctro (Time) ime) F ,35- B - _5- 0. for fathead minnows or mysids: _. C 5` D Din Din DIn Source: Age: D 5 0 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 mm /L hardness B - / Downstream Water Preparation C 5 0 Dls Din Din % effluent Jog° volume -/OoO mL Prep.Date: /sv �..�,, D 0 % upstream volume mL Prep.hy: 1 A 5- . Z Total Total Total B 5- I . Test Solution Preparation: Metal Salt: Cu S O y.s//,� O Din Dis Dis Date: $_15-7 t r By: R141 Stock. Soln: 17,7 Z ere w D / Nominal Conc mL Stock Soln. Volume prepared A S Z Total Total Total ZS r cis 10 wi `--- (dZ B 5 . 1 35 1.38 _ 5— 3 Dis Dls DIG 51) i,qi D 5- .5 "?I•4 7. 8i A 5- r Total Total Total 1(a Z y, 0 I tl13 B S 1 L13 S.t)2, C 3. Din Dis Dls vD I a :o'L D ; 3 al A S Total Total Total A Total Total Total 3 --2)3ti B 5- B . S C 9 Dis , Din Din C -Dfs Dis Din D 51 D A Total Total Total A Total Total Total t B B C Dis Dis Din C Din DIs Dls D t D Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. Test Method: per EPA Interim Guidance I i Page 47 of 110 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 Measured Total Recoverable and Dissolved Copper Duke Harris Plant-Primary Species Site Specific Study August 2018 Sample:Spiked Dilution Water(Diluted DMV1 Initial Date:08/15/18 %Nominal Measured Total Recoverable Copper(µg/L) %of Measured Dis.Cu(µg/L) % Total Cu eInitial Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Mean Nominal itial Day 2 Mean Dissolved 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% 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% 35.0 39.0 29.0 34.0 97% 23.0 28.0 23.5 69% Sample:Simulated Downstream-Duke Harris Initial Date:8/15/18 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 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% 35.0 55.0 no data 55.0 157% 43.0 37.0 40.0 73% 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% 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% 204.0 218.0 215.0 216.5 106% 185.0 187.0 186.0 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 ii ACUTI TOXICITY TEST C'TILi'I IST'itl' �I�� � 48 Flour Rca 46{loin Reading lnilial Readings 1•1/lour ffeariings 14 Hour fi'radings nr�• r(x old -Dill ^tw I,s+ nr�•. nr� alA nitl i:.� CnnJur uvns Dg1a IvK.�. ` Drssolvrd Drssnlvrd it DNSolvcd (wmhDlnmi(r Uu1ol.cdII Ol)'Crn pll it Orygru pII O'Yl:cn P jt' Ury�rr, pll or SAbmri Oryern P ml•!1_ - Lfftucnr mil_ (lrptl mg/L rtrp.rl- - — -, 1' Con[cntnlion mg/L l- , ;. —_. -- Li Date. g'1 'd' —g---J 11-- .1! Time: lr'-5t:sO )376 ,,I Initials: I Am °1 .1 i 71 Hour Readings 71 Hour Readings 96 Hour Readings !I, old old li, old old an'' new j; Dissolved DiissoIvEA Dissolved Os cn PH OxYecct PH ! I+' OxygcD pH E(llucnl YS ii! CooccmntioD mg/L 1 g& caTIL 1 ' _ ,Isii .111 li n ;Ili r: h — " I .1 • I i jl _ Date: 1 Time: 01 Initials: I<il iI 'II . ... Lab ID#; rent: :. /\-)\Akt' \C\O'C 'S,5 I i , 00117 • i i Page 51 of 11 0 ROUND 2 -APPENDIX B5 Chain of Custody Documentation Duke Harris-WER Round 2 Cu ETT Environmental,Inc.;08/18 Page 52 of 110 t` i ( .H H AIN OF CUSTODY RECORD envil?onmenLal. Page o_ PO Box la.-'4,Greenville,SC 29606-7414 (864)877-6942, (800)891-2325 Faz(864)877 6938 Shipping Address:4 Craftsman Ct,Greer,SC 29650 W W W.ETTENVIRONMENTAL.COM Client: L3t.t �-., L r) e,y-C2t U Program Containers Preservative Parameters Facility: :_,/ /. - frl7 7 rGr - _ i Whole Effluent Toxicity n State: Ai C_, NPDES#: — Acute Chronic Test Organisms ; ,,., 1 :.i — p _U 5.4 n 66 a (Composite only) (Grab or Composite) Q p j = u o . z U o = i I-H2SO4 ot _ „' c - •'_ IS u 7 Sign,and Print below - E c o 2=HCL .E o _ • • 3, _ _ E = I the dotted line = U _ =linos _ - r -, _ SAMPLE ID �? Composite Stan Date Time Sample Collection Dote Time Collected by U r i Z c- U > - 6.pc,- < < U iU U IE t_ 2 _ U = 2 Chemical Analysis&Other 6at.71-<-4./ 18—/ —/, (8-1 - V° A.A �l _ _ 7 ✓ 4� _ Cu f Z 5aaarl oc, Dec© C7✓�tx,.°3 0�.3� uanr).,.; to . M t 1 > Special Instructions: Sample Custody Transfer Record Secure Receipt Sample Date Time Relinquished By/Organizati n Received By/Organization Area Temp'C Preserved? -, ' * --- . ( rinfIL ft:, (44,1, 4,1.) ?II,1 6( I 0 O� 6 t i 1 1 O.t 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«itltin 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 1 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 2.2122 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 0.1 is used.This does not impact the result. Lower test concentrations with no mortality are not necessary to determine the Probit LC50 value Page 58 of 110 EloJ1nc. (864) 877-6942 . FAX(864)877-6938 P.O. Box 16414, Greenville, SC 29606 Craftsman Court, Greer, SC 29650 APPENDIX C 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 CS. 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 (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 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 �H 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 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 3 Cu ETT Environmental;09/18 Page 63 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 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 data1 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) I 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 u 113 u 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. 1 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)0.9422 T-Cu: 20.358 ug/L x(54/50)0.9422= 21.8891 ug/L Dis-Cu: 19.748 ug/L x(54/50)0.9422= 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) = LC40 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- - - - - - -- - • - - - - -- -- -- -- - � T 2. , F 2. 2. 2.' 2. 2. r 2. 2. c 2. 2. 2. 2- 2. 2. 2. t 2. 3 03 2.2:: H1 - - -- - -- -- - -- -- - - - - Lt -- -I 2.00-- -- WAIF. - 1. 5 1. 1. 1. 4 1. 5 1. 1. + 1- 1.50 Dec1917 Jan30.18 Feb2T18 Ma20.18 A a24 i8 May30.18 .t1n2618 Jut:1018 Aug2918 Sep2418 Ja,3'18 Feb1218 1410118 Ap?18 May818 .dae518 .1u13'18 Au8018 Sep1018 OctZ18 Upper Lower tLC 50 u-Mean --Control *Control Limit Limit 'UCL&LCL are+l-2 standard deviations from mean(respectively) Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 69 of 110 ROUND 3 -APPENDIX C2 Survival Data for Acute Definitive Tests Duke Harris-WER 3 Cu ETT Environmental;09/18 Page 70 of 110 Page 70 of 100 ~� Nominal Initial It Mortality Measured Concentration WER 48 Hour Acute Toxicity Test ..---- Nor Conc Rep Organisms 24 hr 48 hr Initial Final Mean Facility: 171\kbD _ Metal: A '�l io,,,, n . Iolan Sample ID t .L 0% B 5 (,) Slant Date:(4 f( 0 Time: \!j(x) By: � ...\-- C 0 Dis DIs Dis End Date: 1-2 -f ' Time: 0I() By: J- _ D `) 0 Effluent Log 1. Upstream Log N: A O ist,,: to Iorr TEST ORGANISMS i 2 B `� Test Organiser: - - ....,!L'---t � iv.-l�q-(3 , 5'�,q l� '--► C r5 oh Dis Dis f r Ceriodaphnia dubia,, Source: D —Date Removed; 1_5-- ( " 1 A t) lntoi 1 alai Too - Between Z(,% Y) (Time)and ? o (Tirnel LQ B 0 for fathead minnows or mysids: C 5 0 Dis DIs Dis Source: Age: 3 D 5 Q Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles A 0 Total Total Total Laboratory Water DMW/ SSF Q 50 mg/L hardness q[23- g 0 Downstream Water Preparation C 5- 0 DIs Ols DIs % effluent volume mL Prep.Date: _ G t D 5' 0 % upstream volume mL Prep.by: i A r 0 Total Total Total 12 3 B 5 0 Test Solution Preparation: Metal Salt: (,/) 01-542 D C 5 O DIs Dis Dis Date: By: Stock.Sole: /2.72-tvl t— 1. /I D S i) Nominal Conc mL Stock Soln. Volume prepared A 5 i Total Total Total 0 0 5t0 AIL B 0 , l1 C15. i IC C 5 0 DIs DIs Ols C., 1241 D 5 0 F4 ,31 1 A 5 Total Total Total f z.3 .1 n Z -... B 5 1-1.5 ,Koh li C 5 i Dis Dis Dis Z5 , 8" D 5 3 l- II II,MIIMMON A 5 Total Total Total A Total Total Total 05 B 5j 5 B C ✓ 5 Ds DIs DIs C Dis Dis Dis D 5 5 D A Total Total Total A Total Total Total B B C DIs Ole Dis C Dis DIs Ole 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 sot Page 71 of 110 le 70°t iG Page 71 of 100 Nominal Initial# Mortality Measured Concentration 1NEFZ 48 Hour Acute Toxicity Test GDpc Refl `Organisms 24 hr 48 hr Initial Final Mean Facllll : ! (At. .cat/11-) Metal: It.t;.! Tal.a tot& Sample ID: 0% B 1 O Start Date: V I•-',2_,Z(-j`p Time: IAA By: _ Yr C O DIs Dh: rill: End Date: q•-2 of' Time: [O By: , \0.- D (7 (^) Effluent Log t/: ✓7.-1 I_1 Upstream Log 11: G A 5 (,) loud ioii lot& TEST ORGANISMS B 5 0 fest Organism:- Al �_ � •_ J. z5 � ��1 S r-R-i1 C to Die; Di;: Dis for eriodaphnia dui, Source: D 0 Date Removed; G'_ ilb' Inlet A , ret,, Tct t Between I-li n /Time\and 2zUO /\ t a tlt - n (Time) B 5 (l) for fathead minnows or mysids: 35 C 5 D Ds ols Dis . , Source; Age: D 0 Temperature 24-26 C. Light 16 hr II/8 hr Id;50-100 it candles A 5 C) Total Total Total Laboratory Water DMW/SSF @ 50 mg/L hardness j 1 B 5 0 Downstream Water Preparation i ✓O C S 0 DIs Dis Dto %effluent 100o volum COO mL Prep.Date: D , S. 0 % upstream volume mL Prep.by: A S 0 Total Total Total B S 0 Test Solution Preparation: Metal Salt: 11`‘A C S 0 DIs DIs Ells Date: By: Stock.Soln: D 5 0 Nominal Conc mL Stock SDIn. Volume prepared A 5 1 Total Total Total l�1 1 0 500 rj,t!j to - B 5 0 25 ,615 C 5 ( ) DIs DIs Dis 35 I-3 g' D 5 O 50 1 -611 A g Total Total Total 1 I,. i -1 ln 1�3 B 5 Ion _OI • C 5 Q DIs DIs DIs 1 iI 3 .6 2— • .D I 1 ‘3",0� `� A 3 Total Total Total A Total Total Total B 5 B 1 - C 5 3 DIs Dis DIs C DIs DIs DIs 3 D A Total Total Total A Total Total Total B B C Dis DIs 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(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 <1.0 <1.0 <1.0 1.6 <1.0 <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 33.5 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% 35.0 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 P !' ACUTE. TOX►CITY TEST- - CHE-fvf 1S•T'r{Y �8/Jnur Rcndinl;s 4A Hour Readings •al 24 NCrur Rradings I 1�Hour/(endings old nc� lnifial Readings nt„ old ^ old °Id nr��� Lh3solva.(J, t; Condwurm Drssoivxd Dusolvcd H : (Vn'rhu�cml or ()mot.rd O,yrcn D pil Urualvrd. II Oxygen rll or Saluurl 01yrrn nil Oiyrcn P mg1L rn• IL WI mgI1 Morro mt/L mill. �\ mglL lPPtl q� ctnlhUon _C-- El Cn n r --- -------, El 11111.01111 T Date: - 1 Time: Ai 3 a initials: 71 Hour Readings 72 Hour Readings 96 Hour Readings old old °C`''' nc>•' old old Dissolved Dissolved Dissolved piygco PH Oxygen. pH E(ilucnl Oxygen pH mgn- COO cc°rnli°a mg/1. mg/1 Datc: — Time: Initials: Lab ID#: Client: y��43 1201 } iris- D 1 00120 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 rso in I CHAINOF CUSTODY RECORD e1 vir',onayal 1F ,Pass of PO Box 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.ETTENV I R❑NM ENTA L.COM Client: ppi / w- �� ...-_ .-....__ L 4 T fr ) Program Containers Preservative Parameters Facility: 1 \\'hole Effluent Toxicin State: („1(7 NPDES 4: i Acute 'Chronic Test Organisms '— - (Composite only) (Gran or Composite) < — l_ ".ci L. v c _ - J C =? `i - I=H2SO4 � = = _ :_ .^_ — -- - - _ Sign,and Print below 3 - = o 2-HCL — = - ''' _ -' _ _ _ > _ g _ - s the dotted line ' =' U _ 3=HNO3 0 ? _ _ s o = ` -- :) p U E •- O c %,-3 J=ZnAc ' J c) L I _ .. SAMPLE ID e Composite Start Date Time Sample Collection Dnic Time Collected by U ;n Z, ^_ U > 6=olin: < <,U v U c _ 2 T v3 - U = 3 z Chemical Analysis a.other ' 00,),:l 0,,,..2), we-R ami 2 n 51-1-4-13 CD 00 . 1 _A r x Special Instructions: Sample Custody Transfer Record Secure Receipt Sample Date Time Relinquished By/Organization Received B rsanization I. rea Temp'C Preserved? �ij �18 . 3° 114111r �. FTr Qe2 '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 taithin 36 hours Time Proportional: I sample each hour for 24 hours.Equal volts 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 ETV 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 2CL 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 80 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 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 PROBIT 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 Eenvironments,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 D I. 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 J 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 half gallon plastic jugs and preserved in coolers at 0-6°C. 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 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 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 (CuSO4.5H2O) 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. A 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 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. 1 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)°.9422 T-Cu: 169.265 ug/L x(54/52)°.9422= 181.9948 ug/L Dis-Cu: 157.883 ug/L x(54/52)°-9422= 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) = LC50 in Effluent = 447.288 ug/L = 2.8330 (Dissolved Copper) LC50 in Lab Water 169.7568 ug/L A final water effect ratio(FWER)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 DI Reference Toxicant Quality Control Chart Pimephales promelas Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 94 of 110 ACUTE REFTOX - 2018 Fathead Minnow; Toxicant NaCI 10.0 9.0 8.52 8.548.52 8.` 8.53 8.64 8.61 8.63 8.65 8.61 8.64 8.69 8.64 8.65 8.65 8.62 CA 8.44 8.4E. 8.42 8.42 8.39 8. 8.18 8.29 O V8.0 - - - 7.77 7.77 7.77 J Ak. A 7 ?.3e 7.3eoe 7.38 ? 739 7 7.44 4 7.50 7.4e .47 7.47 7.4e 03 7.0 'ice • , g.• 8.33 e.39 e.41 ._ e?7 e.f7,e.24.a.71. ZS.g.F�.ft on,a 77 7t118.23 e 34 e.;F', . . . . e.332.e..f, e._'"-J "a e..c29 6.0 M1ar21'18 Apr1118 Apr2518 M1ay15"18 Jun1318 Ju110'18 AugT18 Aug21'18 Sep1Z18 OctZ18 Od1648 MIar2818 Apr1718 May818 May22"18 Jun19'18 Ju127"18 Aug1418 Aug2918 Sep18'18 Od1018 !)ate UC.a.c.ARE 2 SID 0 FROM MEw 1 f MEAN f LC50 - UPPER LOWER Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 95 of 110 r ROUND 4-APPENDIX D2 Toxicity Bench Sheets Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 96 of 110 ti Page 74oil I. Nominal Initial# Mortality Measured Concentration WER 48 Hour Acute Toxicity Test , \ Conc Rep Organisms 24 hr 48 hr...Initial Final Mean Facility: V 1'l IA') Metal:C� I, A 10 tob 1 ToOd Died Sample ID: 0 0% B [0 0 Start Date: c�-7-ic Time: 11 ) By: - Time: ILO() By: -' C Ols DIs DI:. End Date: ��t , �., D Effluent Log.#. Upstream Log#: A I� roll Total Total TEST ORGANISMS B (� /1 Test Organism: C l� Ols DIs DIs for Ceriodaphnia dubia Source: � D Date Removed; A 10 / (Time)and (Tuna V f Total Total Total / Between �t t�r�e) 15-5 fathead minnows qr mysids: B 10 0 C N5S R 212( . z �gF 5 C DIs Dts DIs Source. Age: I Ii D Temperature 24-26 C. Light 16 hr It 18 hr kdi 50-100 ft candles Total Total Total Laboratory Water DMW/SSF @ 50 mg/L hardnessqZ3 I? Il;IA i B )0 0 Downstream Water Preparation I C Ols DIs is To effluent volume mL Prep.Date: Il lI l D e/e upstream volume mL Prep.by: IIIr;': A 10 n Total Total Total �I, 1 B I O Test Solution Preparation: Metal Salt: DIs DIs Date: BY Stock.Soln:1Z7z�I 1---'� C DIs P 1,k, Ij D Nominal Conc mL Stock Soln. Volume prepared • ` 61 0 0 )000M� li 1,l A 10 1 Total Total Total L��� B 10 0 Z5 ii t. 1 L;I 14 I O" C Die DIs DIs Ir 'I : D I ¶0 1•4 5.62 A Total Total Total.' u B , 1 p2 %.QZ. ( 113 I l 2-1 i, C DIs DIs -DIs ' I Z.O1' 1G•Q1 � I ' D �) ilk.. ill A I 0 .1 Total Total Total A Total Total Total II '; B ID �_ B , , 1{' C� C DIs DIs DIs DIs DIs . DIs II11I Ij D D tIIIIII II il' A Total Total Total l A Total Total Total I:. ' I{ii I B l B ;1 t'.�I'i, C DIs DIs DIs I ii! I C DIs DIs DIs II D �lit ii` D .1i Lill Test Method: per EPA Interim Guidance IIi Test solution volume:25 mL.Test vessels 1 oz.plastic cups.Transfer volume0.05 11,1111 + lti I iii l': Page 97 of 110 Page 76 of 1 00 Nominal Initial It Mortality Measured Concentration WER 48 Hour Acute Toxicity Test ---- Non "`\ rvletai. Conc Rep Organisms 24 hr 48 hr Initial Final Mean Facility: p/nt,V _ � GC A 1.1,0 Total Total Sample ID: (A 0% B Start Date: lo-/ IP Time: hS 3O BY A/1'1 C as a5 Dis End Date: 10-1 t•(k Time: 6l By: iir D Effluent Log#: Upstream Log II: A to 10 Toms Total Total TEST ORGANISMS 1 ZqZ B (b (b Test Organism: C Dis DIs ols for Ceriodaphnia dubia Source: D Date Removed; A '10- InTtaI Total .ot:: Between (Time) and (Time\ U B ID (0 for fathead minnows or mysids: /185 4-45 ,71-1- t C Die DIs Dib Source: A41 Age: <2YIto I 1 D Temperature 24-26 C. Light 16 hi It/8 hr kd;50-100 ft candles I A Total Total " Total Laboratory Water DMW I SSF p, 50 mg/L hardness f B Downstream Water Preparation I if C Dis as as % effluent volume mL Prep.Date: ' D % upstream volume mL Prep.by: I A Total Total Total B Test Solution Preparation: Metal Salt: CuJOy C Die Die Dis Date:CI-2W By: LIC-- Stock.Soln: I Z 72 nj/<. ': iI. Il D Nominal Conc mL Stock Soln. l Volume prepared �I`. A Total Total Total L- (gZ 13• /Q O 0Qm C" l B 'Ilk 17,43 / ,li I, C Die Die Die I I:. D `_ l! A Total Total Total ll B !S C Ds Dis Dis 41 11, Ii A Total Total Total A Total Total Total INS, B B {, C1 C Die Dis Die C DIs Die Dis 1 I D D ICI A Total Total Total A _ Total Total Total I B B 1 a Ci Die Die Dis C Ms Ole Dls 1 D a Test a Test solution volume:25 mL. Test vessels 1 oz.plastic cups.Transfer volume 0.05 mL. Test Method: per EPA Interim Guidance d il64 Page 98 of 110 -. ge 74 pf j, Page 75 of 100 t..` „a, Initial# Mortality Measured Concentration WER 48 Hour Acute Toxicity Test' �.r` Rep Organisms 24 hr 48 hr� eltia! Final Mean Facility: �Vt' ���t r, Metal: Con' A Q 0lulu: Intel total Sample ID: • CIA 0% B 10 t J Start Date: -ZT1-1% Time: )I S(' By: .---- -" ---------i C Dis Dis Dis End Date:-22-1- Time: 0 By: . ' _- D Effluent Log#: 5-2'10 Upstream Log#: A I /0 Total Total Total TEST ORGANISMS 25 B I° /0 Test Organism: C DIs DIs Din for Ceriodaphnia dubia Source: D Date Removed; (li V Total Tula! lots: - vt t tier I I ill Id/arid I It 1Cf B 10 6 f r fathead minnows or iysids: AF35 C1-24-1 C . DIs DIs Ds Source: g 4 93 e: D Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles �_ A 10 O Total Total Total Laboratory Water DMW/SSF @ 50 mg/L hardness B 10 f 1 Downstream Water Preparation S0C Dts DIs Dis % effluent 100°to volume mL Prep.Date: D % upstream volume mL Prep.by: A [Q V Total Total Total B 10 0 Test Solution Preparation: Metal Salt: ( t50 1 - 5(-� 1 I'• C Dis DIs Dla Date: By: Stock.Soh: +Z•7 ft/ D Nominal Conc mL Stock Soln. Volume prepared A (0 . 0 . Total Total Total D 0 1 r UX B 10 0 Q . 25 I • gCa 111 y 02' (/e C DIs DIs DIs 35 2• ! D 50 3(.ctil A 4 O 0 Total Total Total 11.i ,/62-- B 10 0 (02- 1`3.(V--- ` (1 1S C DIs DIs Din 113 11'Z' D Z ICP•04 tI j, A ID 0 Total Total Total A Total Total Total B I0 n B t C Dls Dis Din C DIs Dis DIs D D f A Total Total Total A Total Total Total B B . C _ DIs pis 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 2 9 Z, V/61 sly Page 99 of 110 76 of I, Page 77 of 100 NotI"final Initial# Mortality Measured Concentration WER 48 Hour Acute Toxicity Test Rep Organisms 24 hr 48 hr Initial Final Mean Facility: hut ik t-ia(r-S Metal: r^ .en� A --1-0 Matra loll TOtel Sample ID: C.___ 0% B Start Date: IDq-($ Time: I5J() By: AAA C _ Din Din Dis End Date: Itt((-(ci) Time: /I. 15 By: i D Effluent Lod it: 5-Zc/l(� Upstream Log tt: 'A IC) 0 Total Total Total TEST ORGANISMS 2t2 B 1 Test Organism: C Din Din Din for Ceriodaphnia dubia Source: D Date Removed; r in...„, A i v Tutul Thiel Ton Latvucct ;Tien e)ariu \Titilc% — —L t � .. ..g (D 0 for fathead minnows or mysids: r.c d 41;1-eyst / coif C Din Din Din Source: - - Age:4 J'I r4 D Temperature 24-26 C. Light 16 hr It/8 hr kd;50-100 ft candles 1 la A 1 D 91 Total Total Total Laboratory Water DMW./SSF a@50.mg/Lhardness 5C19 B b .' Downstream Water Preparation C Dis Din Dis % effluent jpp I- volume JRba mL Prep,Date: /O-/o'IOp r D % upstream volume mL Prep.by: I 1 A Total Total Total --1 B Test Solution Preparation: Metal Salt: Cu ay • C . Din Din DIs Date:q.21,-lY By: Stock. Soln: (2••72- st(-- D Nominal Conc mL Stock Sp voln. Volumee prepared A •Total Total Total Z 7— I3• /d 1 L C DIs Din Din 511 a V 3 D A Total Total Total I B Ci Din Dis Din D al A Total Total Total A Total Total Total B B C Din Din Din C DIs Din DIs D D 1 A Total Total Total A Total Total Total B B C Din DIs Din C Din Din Dis D D Test solution volume:25 mL. Tent vassals 1-oz.plastic cups.Transfer volume 0.05 ml. Test Method: per EPA Interim Guidance Page l00 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 110 Measured Total Recoverable and Dissolved Copper Duke Harris Plant-Secondary Species Site Specific Study September 2018 Sample:S iked Dilution Water(Diluted DMV,Initial Date:09/27/18 Nominal Measured Total Recoverable Copper(µg/L) %of Measured Dis.Cu(µg/L) % Total Cu nitial Day 1 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 <1.0 <1.0 <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 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_ 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 IF 1 . -!, • .. _ . • . ACUTE TOXICITY TEST - CI-IENI 1 si.R v r1 ---,_„ _ _ Initial Readings 24 Hour Readings 24 Hour Readings 48 Hour Readings 18 Hour Readings Condo(livm old old nrw or. old old Orw Of w Pic D.ssolvrd (pmkosicrol of Dissol,rd Dossolvcd Dissols•cd 0 issolz4. Eirlocoi 0 x yErn p11 or Slim Olyvcr, r i I Osygcn ph I Oxygcn pl I 0,nut pl I --------, Conlon mE/I.. WO/ mg/L mr/I. mg/L mg/L ----, --- 41 ____ Time' i ) SO 2-00 . .,, 72 Hour Readings 72 Hour Readings 96 Hour Readings old old ocsv new old old Dissolved Dissolved Dissolved Efflucol Oxygen pH °Inca pH Otygco pH ' .1 Cooccotration mgIL mg/L WA- ii i • ,I II. q . 11 ), I' . !I 4 I 1.• . • r, 1 Date: Timc: 1! F Initials: II I! . Pi VIaPti ft LES ?RD:J.16ms 'r, Client: i Lab ID#: .... 'Wee ftan(cD- cu c74 5Z1161 . . 1. . ., C 0 1 2 2 .. ;. Page 104 of 110 'I! is ROUND 4 -APPENDIX D5 Chain of Custody Documentation Duke Harris-WER 4 Fish Cu ETT Environmental;9/18 Page 105 of 110 . CHAIN OF CUSTODY RECORD F Pale e` i PO Box 16-. G;eenville,SC 29606-7414 (864)877-6942, (800)891-2325 Fax:(864)877 6938 Shipping Address:4 Craftsman CI,Greer,SC 29550 W WW.ETTENVIRONMENTAL.COM o. Client: - I ,� g I l �"1 0 f rir. 1`f Program : Containers Preservatives Parameters ameters Facility: l �{ _ Whole Effluent Toxicity State: d`, . ! , NPDES a. i Acute Chronic Test Organisms ij _ r• (Composite only) (Grab or Composite) 4 - c' F. 'i Z Sign,and Print below > 5 2=1�Ct. : = n — _ m c 2 _ - N the dotted line _ _ U n = J=NaOH i _ ❑ °� 'r J _ ` = - SAMPLE ID U Composite Start Datc I Time Sample Collection Date Time Collected by U :n an z = t. > 6.D�,�r i< < U u cu C _ M s = ) = 3 c Chemical Analysis&Other 1(N.,1-+1.0-1( I-,%Li-Vij CI' '-R.5.)-1 1 _n'_2-1C49-J,./L2-__*- ') ')(0 / 5e. / CD ON C _ _ _ Special Instructions: Sample Custody Transfer Record Secure Receipt Sample Date Time Relinquished By/Organization Received B�•d rganization Area Temp°C Preserved? 1-15-18 1130 'P,2 / g /2 Oh en-,,s . W/ { " r z /9 f ' 9/)E i 8' /53° , '` ii,7 X 0-0.,-.. F_-rt" O. 0 COMPOSITE SAMPLING PROCEDURES TEdfPER 1TURE 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: 1 sample each hour for 24 hours.Equal volul 0.0 and 6.0°C.Samples must not be frozen.lise water ice in sealed bags. of sample collection(completion of composite sample). or at minimum 1 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. APPENDIX D6: Statistical Analysis PROBIT 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 1 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 0.5 106.5 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 PROFIT 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 110 of 110 Shearon Harris Nuclear Plant-Permit NC0039586 JACOBS Copper and Zinc Evaluation Attachment 2 Reasonable Potential Analysis — Spreadsheet Calculations February 25, 2019 CH2b1 HILL North Carolina. Inc. 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 ❑CHECK IF HQW OR ORW WQS Name was Type Chronic Mow. Acute PQL Units Facility Name Shearon Harris Par01 Arsenic Aquactic Life C 150 FW 340 ug/L WWTP/WTP Class Class II Facility Par02 Arsenic Human Heaitn C 10 HH/WS N/A ug/L Water Supply 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(MGD) 7.900 1 Par05 Chlorides Water Supply NC 250 WS nip.i Receiving Stream Harris Reservoir Pars* Chlorinated Phenolic Compounds Water Supply NC 1 A ug/L HUC Number Par07 y Total Phenolic Compounds Aquatic Life NC 300 A ug/L Stream Class Paroa 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 Part 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 nglL Upstream Hardness fault 25 mg/L(Hard Aveage=20.8819858421678 mg/L) Par16 Molybdenum Human Health NC 2000 HH ug/L Combined Hardness Chronic 43.63 mg/L I Par17 Nickel Aquatic Life NC 59.6352 FIN 536.9197 pg/L Combined Hardness Acute 43.63 mg/L Parl8 Nickel Water Supply NC 25.0000 WS N/A pg/L Data Source(s) Par19 Selenium Aquatic Life NC 5 FW 56 ug/L 0 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 1 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) Values"xi thenmum"CdataOPY" Ma points=58 Date Data BDL=II2DL 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 _Use"PASTE SPECIAL Par21 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 14.4 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 Mult 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 12/2019 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 l 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(mglL) Median 7010(CFS) (MGD) [MGD] MGD] (mg/L) (mg/L) (mg/L) (Chronic) (Acute) (mglL) 0.0000 , 0.0000 I 0 0000 7 9000 10 [ 43 629 II 43 629 II 100.0000 II 100.0000 1 25 143.629171 Upstream Hard Average(mg/L)= 20.88199 Cu WEIR"' 4 9996 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 =DissolvedMetal-Translator Chronic Acute Coefficients Chronic Acute tug/I) [ug/I] (streams) [ug/I) [ug/I] Cadmium(d) 0.23 1 33 0.252 0.90 5.27 Cd-Troutreams 0.23 0.83 0.90 3.28 Chromium Ill(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 EMS .: streams(t) .,, -2, ..' 14 Silver(d)(h,acute) 0.06 0.77 1.000 0.06 0.77 Zinc(d)(h) 59 58 0.288 203.14 .,01 49 Beryllium 1 65 . 1.000 65 Arsenic(d) 340 1.000 1501 340 (d)=dissolved metal standard.See 15A NCAC 02B.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(ma/L) 1Q1OS(cfs)= 0.00 IWC% @1Q1OS = 100 Acute=43.63 mg/L 7Q1 OS(cfs)= 0.00 IWC% @ 7Q1 OS= 100 Chromic=43.63 mg/L 7Q10W(cfs)= 0.00 IWC%@ 7Q10W= 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 STANDARDS&CRITERIA(2) cn REASONABLE POTENTIAL RESULTS RECOMMENDED ACTION TYPE f (1) NC WQS/ Applied %z FAV/ as Chronic Standard Acute n #Det. Max Pred Cw Allowable Cw Acute: 88.48 Copper NC 63.4083 FW 88.4756 ug/L 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.xism,rpa Page 1 of 1 1/24/2019