### MEMORANDUM

TO: Steam Electric Rulemaking Record

FROM: TJ Finseth, ERG Danielle Lewis, ERG

DATE: April 19, 2013

SUBJECT: Steam Electric Analytical Database

ERG is providing technical support to the U.S. Environmental Protection Agency’s Office of Water, Engineering and Analysis Division (E AD) for development of effluent limitations guidelines and standards (effluent guidelines) for the Steam Elect ric Power Generating Industry. ERG was responsible for compiling all sampling data gathered during the rulemaking into a single database, referred to as the Analytical Database. The Analyti cal Database contains sampling results from EPA’s three- and fou r-day sampling episodes, the CWA 308 monitoring program, data provided by the industry and state en tities, as well as publicly available data from Electric Power Research Institute (EPRI) reports and other technical sour ces. This memorandum describes the data contained in the database, how the data were revised or edited if necessary, and the use of the data in engineering analyses.

1.0 I NTRODUCTION

EPA, together with ERG, conducted a sampling progr am at steam electric power plants to collect
wastewater characterization da ta and treatment performance data associated with FGD wastewater and to collect data for other emergi ng waste streams for which characterization data were not available (i.e., carbon capture and gasifi cation wastewater). As part of this sampling program, EPA obtained wastewater samples from 13 plants. The samples were collected as
follows:

 For seven plants, EPA collected performan ce data for four consecutive days and the plants also subsequently collected f our sets of samples over a four to five month period;

 For four plants, the facility collected pe rformance data for four consecutive days;

 For one plant, EPA collected performan ce data for three consecutive days; and

 For one plant, the facility collect ed performance data for one day.

EPA (or the plant) collected representative sample s at the influent and effluent of the treatment system being evaluated using a combination of 24-hour composite and grab samples, depending on the sample location and the parameter to be analyzed. EPA analyzed the samples for up to 64 parameters, including conventi onal pollutants (e.g., TSS, BOD 5 ), nonconventional pollutants (e.g., TDS, nutrients), and metals. For samples co llected by EPA, EPA quan tified both the total
amount of metal and the dissolv ed portion only. For samples collected by the plants, EPA quantified the total amount of metal. Prior to initiating sampling activities, regardless of whoMemorandum April 19, 2013 Page 2

collected the samples, EPA developed sampling pl ans that detailed the procedures for sample collection, including the pollutants to be sample d, location of the sampling points, and sample collection, preservation, and shipment techniques.

2.0 EPA-C OLLECTED S AMPLES

EPA selected and conducted sampling activities ov er four consecutive days at the following plants in the U.S.:

 Duke Energy Carolina’s Belews Creek Steam Station;

 We Energies’ Pleasant Prairie Power Plant;

 Duke Energy’s Miami Fort Station;

 Duke Energy Carolina’s Allen Steam Station;

 Mirant Mid-Atlantic, LLC’s Di ckerson Generating Station;

 RRI Energy’s Keystone Ge nerating Station; and

 Allegheny Energy’s Hatfield’s Ferry Power Station.

All of the selected plants operate chemical pr ecipitation wastewater trea tment systems to treat their FGD wastewater. The treatment systems at Belews Creek, Allen, and Dickerson also include a biological treatment stage following the chemi cal precipitation.

The pollutants selected for analysis reflect the current understanding of FGD wastewaters, including contributions from the fuel, air po llution control scrubber sorbents, treatment chemicals, and other sources. Table 1 lists the analytical methods in EPA’s sampling program. EPA collected representative samples at the in fluent and effluent of the FGD wastewater treatment systems and, where applicable, the mi d-point of the FGD treatment system (i.e., effluent from chemical precipita tion system prior to biological treatment). All influent samples were collected as grab samples. EPA collected 24-hour composite samples at the mid-point and effluent sampling points for all an alytes except mercury and cyanid e. EPA collected cyanide as a single grab sample and mercury as four indivi dual grab samples over the 24-hour period (i.e., a grab sample collected every six hours) at th e mid-point and efflue nt sampling points.Memorandum March 11, 2013 Page 3

Table 1. Analytical Methods Used for EPA’s Sampling Program

Parameter Method Number

Classicals
Biochemical oxygen demand (BOD 5 ) 1 SM 5210 B
Chemical oxygen demand (COD) EPA 410.4
Total suspended solids (TSS) SM 2540 D

Total dissolved solids (TDS) SM 2540 C

Sulfate EPA 300.0

Chloride EPA 300.0
Ammonia as nitrogen EPA 350.1

Nitrate/nitrate as nitrogen EPA 353.2
Total Kjeldahl nitrogen (TKN) EPA 351.2
Total phosphorus EPA 365.1
Total cyanide 1 SM 4500 CN E

Total and Dissolved Metals
Mercury EPA 1631E 4

Hexavalent chromium (dissolved only) 1 EPA 218.6
Antimony, arsenic, cadmium, chromium, copper, lead, manganese 2

, nickel, selenium, silver, thallium, and vanadium EPA 200.8 with collision
cell 5

Aluminum, barium, beryllium, boron, calcium, cobalt, iron, magnesium, molybdenum, sodium, tin, titanium, and zinc 3 EPA 200.7 6

1 Only sites in the United States we re analyzed for this parameter.

2 At sites in the United States, manganese was analyzed us ing method EPA 200.8 with collis ion cell. At sites not in the United States, manganese was analyzed using method EPA 200.7.

3 Zinc was analyzed using EPA Method 200.8 with collision cell for the Belews Creek, Pleasant Prairie, Miami Fort, and Allen sampling episodes, but was analyzed by EPA Method 200.7 for the Dickerson, Keystone, Hatfield’s Ferry, Brindisi, and Monfalcone sampling episodes.

4 For samples requiring biphasic separation because the so lids content was greater than one percent, the solid samples were analyzed using Method FGS-069.

5 For samples requiring biphasic separation because the so lids content was greater than one percent, the solid samples were analyzed using Method 6020.

6 For samples requiring biphasic separation because the so lids content was greater than one percent, the solid samples were analyzed using Method 6010B.

EPA also conducted a three-day sa mpling episode at Enel’s Federi co II Power Plant (Brindisi), located in Brindisi, Italy to characterize untre ated FGD scrubber purge wastewater and treated
FGD wastewater from an FGD wa stewater treatment system cons isting of chemical precipitation followed by vapor-compression evaporation. EPA colle cted samples for the same list of analytes listed in Table 1, except for excluding the follo wing analytes either because of holding time
considerations or time constr aints for the sampling event:

 BOD 5 ;

 Total cyanide; and

 Dissolved metals (all analytes).Memorandum April 19, 2013 Page 4

EPA collected representative samples of the infl uent to the FGD wastewater treatment system, the distillate from the brine concentrator, and th e condensate from the crystallizer. EPA collected all analytes at the influent to the FGD wastewater treatment system as one-day grab samples. EPA collected six-hour composite samples at the brine concentrator and crystallizer sampling points for all analytes except mercury. EPA collect ed mercury as three individual grab samples over the six-hour period (i.e., a grab sample co llected every two hours) at these points.

EPA also requested that a second plant in Ital y, A2A’s Centrale di Monfalcone (Monfalcone), collect one-day grab samples. Monfalcone opera tes a chemical precipitation followed by vaporcompression evaporation system to treat FGD wastewater. Monfalcone personnel collected samples of the FGD influent to wastewater treatm ent, the distillate from the brine concentrator, and the condensate from the crystallizer.

3.0 CWA 308 M ONITORING P ROGRAM

In addition to the sampling activities conduc ted by EPA, the CWA 308 monitoring program required a subset of steam electric power plants to collect samples. Each of the seven U.S. plants selected for the EPA sampling program were re quired to participate in the CWA 308 monitoring program. For those seven plants, EPA required the collection of four sets of samples over a fouror five-month period.

EPA required four additional pl ants (not sampled by EPA) to participate in its CWA 308 monitoring program. The four plants are listed below along with the reason for their selection:

 Tampa Electric Company’s Polk Stati on - One of two currently operating integrated gasification combined cycle (IGCC) plants;

 Wabash Valley Power Association’s Wabash River Station - On e of two currently operating IGCC plants;

 Appalachian Power Company’s Mountaineer Plant - Only plant in United States operating a carbon capture system; and

 Kansas City Power & Light’s Iatan Station - Only plant in United States operating a one-stage vapor-compression evaporat ion system for treatment of FGD

wastewater. 1

For these four plants, EPA required the plants to collect four consecutive days of samples at two to four locations specifically identified for each plant. EPA se lected the sample locations to characterize gasification wastew ater, carbon capture wastewater , and the treatment of FGD wastewater and gasifica tion wastewater by vapor-compression evaporation systems. EPA used the same sampling approach that was used fo r EPA’s on-site sampling program as described above. The CWA 308 monitoring samples were colle cted directly by the plants and shipped to EPA-contracted laboratories for analysis.

1 At the time of the sampling episode, the Iatan Station was the only plant in the United that EPA had identified as operating a vapor-compression evaporation system. Since th at time, two additional plants are in the process of installing or operating a vapor-compression evapora tion system for the treatment of FGD wastewater.Memorandum April 19, 2013 Page 5

4.0 A NALYSIS OF EPA-C OLLECTED AND CWA 308 M ONITORING P ROGRAM S AMPLES

Two contracted laboratories, Fr ontier Global Services (Frontier) and TestAmerica Laboratories – Denver (TestAmerica), analyzed both the EPA collected samples and the CWA 308 monitoring samples. Frontier analyzed all total and dissolv ed mercury samples and TestAmerica analyzed the remaining classicals and total and dissolved me tals samples. Both laboratories followed the requirements of the analytical methods listed in Table 1. ERG verified that the performance of the laboratories was acceptable by conducting QC checks of the analyt ical data as outlined in the Quality Assurance Project Plan for the Steam Electric Rulemaking (QAPP). ERG chemists reviewed all data and documented any qualificati ons of the analytical data from each sampling

event.

ERG compiled a database to hold all sampling re sults, known as the Steam Electric Analytical Database. This database contains sampling result s for each sampling point for all analytes at the EPA sampling sites and the CWA 308 monitored sites. This database also includes the results of the field blank and field duplic ate analyses. ERG modified the results to reflect any qualifications identified by laboratories and ERG chem ists as part of the data review process.
These modifications are detailed in the data review narratives that accompany each of the Sampling Episode Reports (SERs) for the EP A sampled plants and the CWA 308 monitoring program memorandum 2

.

5.0 A DDITIONAL S OURCES OF S AMPLING D ATA

In addition to the EPA sampling program a nd the CWA 308 monitoring program, EPA obtained sampling results from states, operating companies, and other public sources. These data were added to the Analytical Databa se, and include the following:

 Long-term monitoring data for Progress Ener gy Carolinas’ Roxboro Steam Electric Plant provided by the North Carolina Department of Environment and Natural Resources;

 Long-term monitoring data for the Belews Cr eek Steam Station and Allen Steam Station provided by Duke Energy Carolinas;

 Ash impoundment sampling data collected dur ing the EPA’s detailed study sampling

program;

 Ash impoundment sampling data included in El ectric Power Research Institute (EPRI) Power Plant Integrated Systems-Chemi cal Emissions Study (PISCES) Reports;

 Permit application data provided by member companies of the Utility Water Act Group (UWAG); and

 Data included in the Development Document for Final Effluent Limitations Guidelines, New Source Performance Standards, and Pret reatment Standards for the Steam Electric Point Source Category, EP A 440-1-82-029, November 1982.

2 See DCNs SE01304, SE01305, SE01306, SE01307, SE 01308, SE01309, SE01310, SE01295, and SE01295A1 through SE01295A11.Memorandum April 19, 2013 Page 6

6.0 U SES OF S AMPLING D ATA

EPA used the data contained in the Steam Electri c Analytical Database to conduct analyses for the proposed steam electric e ffluent guidelines. EPA used the Steam Electric Analytical
Database to:

 Evaluate wastewater discharges from steam electric power plants;

 Evaluate technology options for handling and treating steam electric wastewater;

 Calculate concentrations of pollutants after implementation of selected treatment technologies;

 Calculate industry baseline loadings and associated pollutants removals after implementation of selected treatment technologies; and

 Develop the proposed effluent limitations.

All data obtained by EPA during the rulemaking process is contained in the Steam Electric Analytical Database (DCN SE02120.A1).

After calculating the pollutant loadings presented in the proposed rule, ERG determined that some of the analytical data were not entered into the database correctly. The data entry errors were associated only with the long-term self -monitoring data submitted directly from Duke Energy for its Belews Creek Steam Station. Additi onally, the affected results are associated only with samples from the effluent of the biological treatment system. The following is a summary of
the errors:

 Forty-five arsenic results were treated as de tected values at the reporting limit (RL) but
should have been non-detect results. This ch ange means these results should have been treated as 1/2 the RL value (e.g., 10 x 0.5 = 5) instead of being trea ted as the RL value (e.g., 10) in the calculation of the average co ncentration used to represent the arsenic biological treatment effluent in the pollutant loadings.

 Two mercury results were treate d as detected values at the RL of 1 ng/L but should have been non-detect results. This change means th ese results should have been treated as 1/2 the RL value (i.e., 0.5 ng/L) instead of being tr eated as the RL value (i.e., 1 ng/L) in the calculation of the average concentration us ed to represent th e mercury biological
treatment effluent in th e pollutant loadings.

 One mercury result was entered as 0.432 ug/ L when it should have been 0.423 ug/L.

Table 2 provides a detailed listing of the results that were affect ed by these data entry errors. The table includes information on the plant name, analyte, and date of each sample, along with the actual non-detect indicator, amount, and RL which are the valu es presented in the analytical database and the non-detect indicator, amount , and RL used in calculation of average concentrations for pollutant loadings.

ERG has corrected these data entry errors in the Steam Electric Analytical Database (DCN SE02120.A1). The results included in the database reflect the information in the “Actual Result” columns contained in Table 2; however, ERG was una ble to recalculate the pollutant loadings to account for these changes prior to proposal. All changes listed in Table 2 would result in a biological treatment post-complianc e concentration that is lower than the value used in theMemorandum April 19, 2013 Page 7

version of the pollutant loadi ngs presented for the proposed rule, which would increase the calculated pollutant removals from baseline. EPA plans to use the corrected values to revise the pollutant loadings calcul ations for the final rule 3

.

Table 2. List of Samples Affe cted by Data Entry Errors

Plant Name Sample Date Analyte Actual Result a Data Used in Calculation of Average Concentrations for Pollutant Loadings b

NonDetect
Indicator Amount RL NonDetect
Indicator Amount RL

Belews Creek 8/4/2008 Arsenic ND 10 D 10

Belews Creek 8/11/2008 Arsenic ND 10 D 10

Belews Creek 8/18/2008 Arsenic ND 10 D 10

Belews Creek 8/25/2008 Arsenic ND 10 D 10

Belews Creek 9/2/2008 Arsenic ND 10 D 10

Belews Creek 9/8/2008 Arsenic ND 10 D 10

Belews Creek 9/15/2008 Arsenic ND 10 D 10

Belews Creek 9/22/2008 Arsenic ND 10 D 10

Belews Creek 9/29/2008 Arsenic ND 10 D 10

Belews Creek 10/6/2008 Arsenic ND 10 D 10

Belews Creek 10/12/2008 Arsenic ND 10 D 10

Belews Creek 10/20/2008 Arsenic ND 10 D 10

Belews Creek 10/26/2008 Arsenic ND 10 D 10

Belews Creek 11/3/2008 Arsenic ND 10 D 10

Belews Creek 11/9/2008 Arsenic ND 10 D 10

Belews Creek 11/16/2008 Arsenic ND 10 D 10

Belews Creek 11/24/2008 Arsenic ND 10 D 10

Belews Creek 1/21/2010 Arsenic ND 2 D 2

Belews Creek 1/27/2010 Arsenic ND 2 D 2

Belews Creek 3/10/2010 Arsenic ND 2 D 2

Belews Creek 3/24/2010 Arsenic ND 2 D 2

Belews Creek 4/7/2010 Arsenic ND 2 D 2

Belews Creek 4/28/2010 Arsenic ND 2 D 2

Belews Creek 5/12/2010 Arsenic ND 2 D 2

Belews Creek 5/26/2010 Arsenic ND 2 D 2

Belews Creek 6/9/2010 Arsenic ND 2 D 2

Belews Creek 6/23/2010 Arsenic ND 2 D 2

3 EPA will also revise the pollutant loadings calculations as a result of the difference between the data set used to
calculate effluent limitations and the data set used to calcula te pollutant loadings. There are a total of 14 data points, which affect both chemical precipitation and chemical precipitation with biological treatment effluent concentrations, included in loadings calculations that are not included in the data set used for limitations development. EPA plans to remove these points for the final rule. These changes are described in Analysis of Differences Between the Data Set Used for Limitations Development and the Data Set Used for Loadings (DCN SE02122).Memorandum April 19, 2013 Page 8

Table 2. List of Samples Affe cted by Data Entry Errors

Plant Name Sample Date Analyte Actual Result a Data Used in Calculation of Average Concentrations for Pollutant Loadings b

NonDetect
Indicator Amount RL NonDetect
Indicator Amount RL

Belews Creek 7/28/2010 Arsenic ND 5 D 5

Belews Creek 8/11/2010 Arsenic ND 2 D 2

Belews Creek 8/25/2010 Arsenic ND 2 D 2

Belews Creek 9/8/2010 Arsenic ND 2 D 2

Belews Creek 10/7/2010 Arsenic ND 5 D 5

Belews Creek 10/27/2010 Arsenic ND 5 D 5

Belews Creek 11/4/2010 Arsenic ND 2 D 2

Belews Creek 11/23/2010 Arsenic ND 2 D 2

Belews Creek 12/8/2010 Arsenic ND 5 D 5

Belews Creek 1/26/2011 Arsenic ND 5 D 5

Belews Creek 2/16/2011 Arsenic ND 5 D 5

Belews Creek 2/23/2011 Arsenic ND 5 D 5

Belews Creek 3/9/2011 Arsenic ND 5 D 5

Belews Creek 3/23/2011 Arsenic ND 5 D 5

Belews Creek 4/13/2011 Arsenic ND 5 D 5

Belews Creek 4/27/2011 Arsenic ND 5 D 5

Belews Creek 5/11/2011 Arsenic ND 5 D 5

Belews Creek 5/25/2011 Arsenic ND 5 D 5 Belews Creek 9/15/2008 Mercury ND 0.001 D 0.001 Belews Creek 9/22/2008 Mercury ND 0.001 D 0.001 Belews Creek 8/11/2010 Mercury D 0.423 D 0.432 a – Actual result indicates the non-detect indicator, amount, and RL as reported by the plant providing the long-term monitoring data. b – Data used in concentration calculations indicates the non-detect indicator, amount, and RL as it was used in calculations associated with developing pollutant loadings for the proposed rule. EPA will update the pollutant loadings calculations to use the “Actual Results” for the final rule.