# Final Sampling Episode Report Tennessee Valley Authority’s
Widows Creek Fossil Plant Stevenson, AL

Episode 6549

Prepared for:



# U.S. Environmental Protection Agency

Engineering and Analysis Division
Office of Water 1200 Pennsylvania Avenue, NW Washington, D.C. 20460

Prepared by:



## Eastern Research Group, Inc. 14555 Avion Parkway
Suite 200 Chantilly, VA 20151

26 August 2008

EPA Contract No. 68-C02-095 Work Assignment 5-22

### i CONTENTS

Page

1. I NTRODUCTION 

### .................................................................................................................1-1 1.1 Background of Detailed Study.............................................................................1-1

1.2 Power Plant Site Selection...................................................................................1-1 1.3 Sampling Episode Overview................................................................................1-2

2. P LANT 

### O VERVIEW 

### .............................................................................................................2-1 2.1 Particulate Control Systems.................................................................................2-2 2.2 Ash Pond System .................................................................................................2-3 2.3 FGD Scrubber System .........................................................................................2-4 2.4 FGD Gypsum Pond System.................................................................................2-5

3. S AMPLE 

### C OLLECTION 

### .......................................................................................................3-1 3.1 Sampling Points, Sample Collection Methods, and Field Measurements ...........3-1 3.1.1 Influent to FGD Pond System..................................................................3-2 3.1.2 Effluent from FGD Pond System.............................................................3-5 3.1.3 Influent to Ash Pond System ...................................................................3-7 3.1.4 Effluent from Ash Pond System ............................................................3-10 3.2 List of Analytes and Sample Preservation.........................................................3-11 3.3 Plant Operational Data.......................................................................................3-12 3.4 Deviations from the Sampling and Analysis Plan .............................................3-13

4. L ABORATORY 

### A NALYTICAL 

### R ESULTS AND 

### D ISCUSSION 

### ...................................................4-1

4.1 Measured and Calculated Results for FGD Pond and Ash Pond Influent Samples................................................................................................................4-1 4.2 FGD Pond System ...............................................................................................4-4 4.3 Ash Pond System .................................................................................................4-4

5. D ATA 

### Q UALITY 

### .................................................................................................................5-1 5.1 Analytical Quality Control...................................................................................5-1 5.2 Field Quality Control ...........................................................................................5-1

5.2.1 Bottle Blanks............................................................................................5-1 5.2.2 Equipment Blanks....................................................................................5-2

5.2.3 Field Blanks .............................................................................................5-3 5.2.4 Field Duplicates .......................................................................................5-4

6. R EFERENCES 

### .....................................................................................................................6-1

Appendix A: A NALYTICAL 

### R ESULTS



### Appendix B: A NALYTICAL 

### D ATA FOR 

### M ETALS



### , FGD P OND AND 

### A SH 

### P OND



### Appendix C: D ATA 

### R EVIEW 

### N ARRATIVES



### Appendix D: P ICTURES 

### F ROM THE 

### S AMPLING 

### E PISODE

### ii LIST OF TABLES

Page

3-1 Sample Collection Information, Widows Creek............................................................ 3-15

3-2 Number of Samples Collected by Sampling Point, Widows Creek............................... 3-16

3-3 Field Measurements, Widows Creek ............................................................................. 3-17

3-4 Analytical Methods and Procedures for Samples Collected at Widows Creek............. 3-18

3-5 Summary of Sample Containe r and Planned Preservation ............................................ 3-19

3-6 Sample Preservation Su mmary, Widows Creek ............................................................ 3-20

3-7 Generating Unit Operating Characteris tics during Sample Collection, Widows

Creek.......................................................................................................................... .... 3-22

3-8 FGD Scrubber System Operating Characteristics, Widows Creek................................ 3-23

3-9 FGD Pond System Operating Char acteristics, Widows Creek...................................... 3-24

3-10 Ash System Operating Characteristics During Sample Collection, Widows Creek...... 3-25

3-11 Ash Pond System Operating Characteristics, Widows Creek ....................................... 3-26

4-1 Biphasic Sample Results for Classica ls and Routine Total Metals Measured Above the Report Limit for the Influent to the FGD Pond System, Widows Creek ....... 4-5

4-2 Biphasic Sample Results for Low-Level Total Metals Measured Above the Report

Limit for the Influent to the F GD Pond System, Widows Creek..................................... 4-6

4-3 Biphasic Sample Results for Classica ls and Routine Total Metals Measured Above the Report Limit for the Influent to the Ash Pond System, Widows Creek......... 4-7

4-4 Classical Pollutants Measured Above the Report Limit for the FGD Pond System,

Widows Creek.................................................................................................................. 4 -8

4-5 Metals Measured Above the Report Limit for the FGD Pond System, Widows

Creek.......................................................................................................................... ...... 4-9

4-6 Classical Pollutants Measured Above the Report Limit for the Ash Pond System,

Widows Creek................................................................................................................ 4-1 1

4-7 Metals Measured Above the Report Limit for the Ash Pond System, Widows

Creek.......................................................................................................................... .... 4-12

5-1 Field Duplicate Resu lts, Widows Creek .......................................................................... 5-5

### LIST OF TABLES (Continued)

Page

iii A-1 FGD Pond Influent Analytic al Data, Wido ws Creek...................................................... A-1

A-2 Ash Pond Influent Analytic al Data, Widows Creek ..................................................... A-11

A-3 ProChem Biphasic Filtration Blank An alytical Results, Widows Creek...................... A-21

A-4 FGD Pond Effluent Analyt ical Data, Widows Creek ................................................... A-22

A-5 Duplicate of FGD Pond Effluent Analytical Data, Widows Creek .............................. A-27

A-6 Ash Pond Effluent Analytic al Data, Widows Creek..................................................... A-32

A-7 Bottle Blank and Equipment Blank Analytical Data, Widows Creek .......................... A-37

A-8 FGD Pond Influent Field Blank Analytical Data, Widows Creek................................ A-43

A-9 FGD Pond Effluent Field Blank Analytical Data, Widows Creek ............................... A-47

A-10 Ash Pond Influent Field Blank An alytical Data, Widows Creek ................................. A-51

A-11 Ash Pond Effluent Fi eld Blank Analytical Da ta, Widows Creek................................. A-52

B-1 Analytical Results for Metals in the FGD Pond System, Widows Creek........................B-1

B-2 Analytical Results for Metals in the Ash Pond System, Widows Creek .........................B-4

### iv LIST OF FIGURES

Page

2-1 Ash Pond System, Widows Creek Fossil Plant ............................................................... 2-7

2-2 FGD Gypsum Pond System, Wi dows Creek Fossil Plant ............................................... 2-8

D-1 Sampler Working Inside a “Cleanbox”........................................................................... D-1

D-2 Composite Set-Up at the In fluent to FGD Pond System ................................................ D-2

D-3 “Shake and Pour” Sample Collection Set-Up................................................................. D-3

D-4 Sample Collection Set-Up at E ffluent from FGD Pond System..................................... D-4

D-5 Composite Set-Up at the In fluent to Ash Pond System.................................................. D-5

D-6 Sample Collection Set-Up at E ffluent from Ash Pond System ...................................... D-6

### 1-1 1. I NTRODUCTION



### The Engineering and Analysis Division (E AD) of the U.S. Environmental Protection Agency (EPA) has been conducting a program that c onsists of site visits and sampling at steam electric power plants. The purpose of this program is to charact erize raw wastewaters generated by coal-fired steam electric power plants, as well as to evaluate treatment technologies and best management practices used to reduce pollutant discharges. This Sampling Episode Report (SER) describes the sampling activities that took place on 10 September 2007 through 13 September 2007, at Tennessee Valley Authority’s Widows Cr eek Fossil Plant (Widows Creek), located in Stevenson, Alabama (Sampling Episode 6549). The focus of Episode 6549 was to characterize

the influents to and effluents from the flue gas desulfurization (FGD) pond system and the ash pond system at Widows Creek.

1.1 Background of Detailed Study

Section 304(m) of the Clean Water Act (C WA) requires EPA to develop and publish a biennial plan that establishes a schedule for th e annual review and revision of national effluent limitations guidelines and standards (ELGs) required by CWA section 304(b). During EPA’s 2005/2006 review of ELGs, EPA determined that the steam electric power generating point source category (40 CFR Part 423) was the seco nd-largest discharger of toxic-weighted pollutants. EPA’s analyses indicated that the toxi c-weighted loadings were predominantly driven by metals present in wastewater discharges, and that the waste streams contributing the majority of the metals are associated with air pollution co ntrols. Other potential sources of metals include coal pile runoff, metal/chemical cleaning wastes , coal washing, and certain low-volume wastes.

In the 2005/2006 study, EPA noted certain data limitations that affected the Agency’s estimate of the potential hazards posed by disc harges from this category. Therefore, EPA

determined that further review of these discharges during the 2007/2008 ELG planning cycle

was warranted. EPA has concentrated its effo rts for the 2007/2008 study on better characterizing the sources generating the pollutant s responsible for the majority of the toxic-weighted pollutant loadings and available pollution control techno logies/practices for steam electric plants.

1.2 Power Plant Site Selection

EPA selected six coal-fired steam electric plants for wastewater sampling. EPA based the plant selection on the process configurations and ch aracteristics of the plants, as well as the site visits conducted for the study. The following charac teristics (not listed in any priority order) were used to select plants for sampling:

• 

### Coal-fired boilers;

• 

### Wet FGD scrubber system, including:

— Type of scrubber,

— Sorbent used,

— Year operation began,

— Chemical additives used,

— Forced oxidation process,

— Water cycling, and

— Solids removal process;

### 1-2 • 

### FGD wastewater treatment system;

• 

### Type of coal;

• 

### NOx controls;

• 

### Ash handling systems;

• 

### Ash treatment system; and

• 

### Mercury air controls.

EPA selected Widows Creek for sampling ba sed on the following site characteristics:

• 

### The plant is a coal-fired power plan t that burns easter n bituminous coal;

• 

### The plant operates two wet FGD system s, which are both limestone forced oxidation systems;

• 

### The plant manages a segregated FGD wastewater treatment system, which is a series of ponds for gypsum dewatering;

• 

### The plant operates selective-catalytic reduction (SCR) systems on both units with wet FGD systems; and

• 

### The plant produces a gypsum by-product.

1.3 Sampling Episode Overview

On December 12, 2006 and June 7, 2007, EPA and its technical contractor, Eastern Research Group, Inc. (ERG), conducted site visi ts at Widows Creek. The purpose of the site

visits was to learn about the FGD and ash pond operations and gather information in order to collect wastewater samples at Widows Creek. Information collected during the December 12 th



### site visit is documented in Engineering Site Visit Report for Tennessee Valley Authority’s

Widows Creek Fossil Plant [1] and the information from both site visits was used to create Sampling Plan, Tennessee Valley Aut hority’s Widows Creek Fossil Plant (Sampling Plan) [2], which describes the sample collection pro cedures used during the sampling episode.

For this sampling episode, EPA arrive d at Widows Creek on Monday, September 10, 2007, to review the sampling points, determine th e set-up for the sample collection, and label sample bottles. EPA then collected the sample s specified in the Sampling Plan on Tuesday, September 11, and Wednesday, September 12, 2007. The following personnel participated in EPA’s sample collection activities:

• 

### Ron Jordan, EPA/EAD;

• 

### Josh Hall, EPA/EAD;

• 

### Karrie-Jo Shell, EPA/Region IV;

• 

### TJ Finseth, ERG;

• 

### Sarah Holman, ERG;

• 

### Jessica Wolford, ERG; and

• 

### Katie Reytar, ERG.

In addition, during the sample collection, EPA colle cted split samples with the Utility Water Act Group (UWAG), acting on be half of the plant.

### 2-1 2. P LANT 

### O VERVIEW



### Widows Creek operates eight coal-fired st eam electric generating units. Units 1 through 6 each have a capacity of approximately 115 mega watts (MW) and came on line in the early 1950s. Units 7 and 8 were added in the early 1960s and have capacities of approximately 480 and 470 MW, respectively. The combined total capacity for Widows Creek is approximately 1,640 MW. The Widows Creek plant is located in Stevenson, Alabam a, beside the Guntersville

Reservoir on the Tennessee River.

Widows Creek uses two different types of co al: a low-sulfur coal in Units 1 through 6

from the 20 Mile and Bowie mines in Colorado and a high-sulfur coal in Units 7 and 8 from the Warrior, Pattiki, and Galatia mines in the Illin ois Basin area. The plant burns approximately 5.5 millions tons of coal per year, which is equal to about 15,000 tons per day. Units 1 through 6 each have a boiler and an electrostatic precipitat or (ESP) as well as boiler optimization controls to reduce nitrogen oxide (NO

x 

### ) emissions. Units 7 and 8 each use an SCR system and have the following configuration:

• 

### Boiler;

• 

### SCR system;

• 

### Air preheater;

• 

### ESP (Unit 7 only); and

• 

### Flue gas desulfurization (FGD) scrubber system.

The SCR systems were retrofit additions to the plant and were inst alled on both Units 7

and 8 in 2003-2004. SCRs are used to control NO

x 

### emissions by injecting ammonia into the flue gas to convert the NO

x 

### to nitrogen and water. The SCR system operation produces no direct industrial wastewater discharges. However, because some ammonia from the SCR operation adheres to the fly ash particulates, which are removed from the flue gas by the ESPs, the SCR operation introduces ammonia into th e fly ash sluicing wastewaters.

During the operation of the SCR systems, some of the sulfur dioxide in the flue gas is

oxidized to sulfur trioxide. Emissi ons of sulfur trioxide contribute to the formation of acid rain in

the environment. To control the formation of sulfur trioxide, Widows Creek injects sodium sulfite into the flue gas, which reacts with the sulfur trioxide and water vapor to produce sodium

bisulfate and sulfur di oxide. Widows Creek injects the s odium sulfite upstream of the air preheaters in Unit 7 and injects lime dow nstream of the air preheaters in Unit 8.

ESPs are particulate control devices that re move the fly ash and other particulates from the flue gas. Widows Creek uses ESPs to remove more than 99 percent of the fly ash from the flue gas emitted from Units 1 through 7. The fly ash and other particulates are collected in hoppers and sluiced to the ash pond system. Secti on 2.1 discusses the particulate control system and Section 2.2 discusses the ash pond system.

The FGD scrubber systems were retrofit additi ons to the plant and were installed on Unit 8 in 1970 and on Unit 7 in 1981. FGD systems ar e used to control sulfur dioxide (SO 2 

### ) emissions. The wastewater generated by the FGD systems is treated on site by a series of gypsum ponds that allow the gypsum and other particul ates to settle out of the wastewater stream

### 2-2 prior to discharge. Section 2.3 discusses the FG D system and Section 2.4 discusses the gypsum pond system.

The FGD system on Unit 8 is not only used to control SO 2 

### emission, but it is also used to control the particulates in the flue gas becau se Widows Creek does not operate an ESP on Unit 8. Plant representatives estimate that the FGD system removes more than 99 percent of the fly ash and other particulates from the flue gas. Widows Creek is also currently operating an agglomerator prior to one of the four FGD modules on Unit 8, which produces positive and negative charges on the flue gas particles that ar e then attracted to each other to form larger particles. The larger particles are more easily removed in the downstream FGD system.

2.1 Particulate Control Systems

As the coal is combusted in the boilers, so lid, noncombustible constituents of the coal, referred to as ash, are generated. The heavier ash particles collect on the bottom of the boiler and are referred to as bottom ash. The finer ash partic les are light enough to be transferred out of the boiler with the flue gas exhaust and are referred to as fly ash. The bottom ash is removed from the bottom of the boiler using a st ream of sluice water that trans ports the particles to the ash pond. The fly ash flows with the flue gas through the SCRs and is removed from the flue gas in the ESP (Units 1 through 7) or the FGD system (Unit 8).

Every four hours, Widows Creek sluices the bottom ash and slag from the bottoms of the Unit 7 and 8 boilers for approximately 30 minutes. The Unit 7 and 8 boilers are typically sluiced around 4:00, 8:00, and 12:00; however, the timing may vary day to day. For Units 1 through 6, Widows Creek sluices the bottom ash and slag of each boiler once duri ng each 12-hour shift for approximately one hour. Widows Creek does not sluice the bottom ash from the Unit 1 through 6 boilers at a predetermined time, but sluices them as needed. The plant transports the bottom ash sluice water to the ash pond.

For Units 1 through 7, Widows Creek uses ESPs to remove the fly ash from the flue gas. The ESP systems use high voltage to generate an el ectric charge on the part icles contained in the flue gas. The charged particles then collect on a metal plate with an oppos ite electric charge. As the particles begin to layer on the metal plates , the plates are tapped/rapped to loosen the particles, which fall into collec tion hoppers. Each unit has multiple hoppers that collect ash from different places in the ESP. The hoppers located cl oser to the inlet of th e ESP collect the larger fly ash particles that are remove d more easily, and the hoppers locate d closer to the outlet of the ESP collect the finer fly ash part icles that are more difficult to remove. The hoppers at the inlet typically collect more fly ash than the hoppers at the outlet of the ESP. For Unit 7, Widows Creek continuously sluices fly ash from the co llection hoppers with inta ke water. The plant automatically cycles through the hoppers in Un it 7 based on which hopper needs to be sluiced. Because they collect more fly ash than the outlet hoppers, the inlet hoppers are sluiced more frequently. Widows Creek cycles through the Unit 7 collection hoppers approximately every 30 minutes. For Units 1 through 6, Widows Creek slui ces the fly ash from the collection hoppers with intake water every two hour s. A complete sluicing cycle fo r each unit takes approximately one hour; therefore, Units 1 th rough 6 alternate between sluici ng and nonsluicing every other hour. As mentioned in Section 2.0, Un it 8 does not have an ESP; theref ore, most of the fly ash is removed in the FGD system. However, Widows Creek does sluice Unit 8 fly ash from the air preheater and economizer hoppers.

### 2-3 2.2 Ash Pond System

The ash pond system at Widows Creek receiv es both the bottom and the fly ash sluice waste streams discussed in Section 2.3, as well as the following other lo w-volume wastewaters:

• 

### Coal pile runoff overflow;

• 

### Boiler blowdown;

• 

### Nonchemical metal cleaning wastewater (includes boiler fire-side wash);

• 

### Condenser backwashing wastewater;

• 

### Roof and switchyard drainage;

• 

### Floor wash water;

• 

### Miscellaneous cooling water; and

• 

### Leachate from the red water pond.

Figure 2-1 presents a flow diagram of the ash pond system at Widows Creek. The ash pond system consists of a diked channel le ading into the main pond, followed by a middle stilling pond, and a final pumping basin. Widows Cr eek transports the ash sluice water from Units 1 through 6 to a different part of the dike d channel than the ash sl uice water from Units 7

and 8. Widows Creek routes the ash sluice from Units 7 and 8 through the bilge and station sump

collection area because the units are located near the sump disc harges to the ash pond. The ash sluice water from Units 1 through 6 is sent to a separate sump collection area. At the time EPA conducted the site visits at Widows Creek, the ash sluice water from Units 1 through 6 was

combined with the ash sluice water from Units 7 and 8 within the diked channel leading to the main ash pond; however, prior to the sampling ep isode, the plant changed the configuration of the diked channels, such that ash sluice water fr om Units 1 through 6 is not combined with the ash sluice water from Units 7 and 8 until reaching the main pond.

The ash sluice water collected in the tw o sump areas flows through long, winding diked

channels created with ash that has been dredged from the pond. As the ash sluice water flows through the diked channels, the larg e bottom ash particles and some of the fly ash particles settle

to the bottom of the channel. Widows Creek c ontinuously removes ash from the diked channels and stacks it in the area surrounding the channels to increase the height of the embankments.

Widows Creek uses a bulldozer to remove the settled ash particles.

As the ash sluice water travel s through the diked channels an d into the pond, some of the ash sluice water leaches through the embankments of the dike and the banks of the pond. This leachate, referred to as “red water” because of its red appearance, is collected by another dike surrounding the ash pond area and is recycled back into the diked channel with the ash sluice water from Units 1 through 6. Widows Creek does not continuously recycle th e “red water” back into the diked channel but rather recycles it ba sed on the water level in the “red water” dike, which is dependent on the amount of rainfall the plant has received.

After the ash sluice water travels thr ough the diked channels, it enters the ash pond, decreasing the flow velocity and allowing the finer fl y ash particles in the wastewater to settle to the bottom of the pond. Within the ash pond, Widows Creek uses a series of booms to collect floating solids, called cenospheres, from the su rface of the wastewater. Cenospheres are small, lightweight, hollow spheres that are formed in th e boilers during the coal combustion process. A

### 2-4 contractor periodically comes to the plant and removes the cenospheres from the pond bank and transports them off site for beneficial use.

From the ash pond, the wastewater flows by gravity to the middle stilling pond, which is separated from the ash pond by a dike. At this po int, Widows Creek injects carbon dioxide into the water to control the pH of the discharge. Carbon dioxide reacts with water to form carbonic acid, which reduces the pH of the water. The pH of the ash pond wastewater is typically in the range of 7.0 to 8.5. Widows Creek has a pH limit of 6.0 to 9.0 for Outfall 001 (discharge to Tennessee River; identified as “emergency overflow” in Figure 2-1); therefore, if the pH of the ash pond water is above 9.0, the plant injects CO 2 

### to reduce the pH to approximately 7.0. If Widows Creek recycles the ash pond water back to the intakes of Units 7 and 8 rather than discharging it through Outfall 001, there is no upper pH limit.

From the middle stilling pond, the ash pond wa stewater enters the pumping basin for final settling and transport. Ba sed on long-term average data, Wido ws Creek has a flow rate of 32.8 million gallons per day (MGD) entering the pumping basin. The plant has two different outfalls for the effluent from the ash pond system, as well as a recycle stream that is used for FGD make-up water (not shown in Figure 2-1). Wi dows Creek recycles mo st of the wastewater entering the pumping basin (27.6 M GD or 84 percent) by pumping it to the intake canal for Units 7 and 8. This recycled ash pond effluent typically accounts for only 3.5 percent of the total intake water for Units 7 and 8. In addition, the plant re cycles approximately 5.2 MGD (16 percent) for use as FGD make-up water. Widows Creek also has a direct discharge permitted via Outfall 001, but this outfall is not used very ofte n, typically only a few days a year.

The influent sampling point for Widows Creek’s ash pond system is located along the diked channel containing the ash sluice water from Units 1 through 6, upstream of where the “red water” is pumped back into the diked channel. EPA decided to collect the ash pond influent sample from the diked channel with Units 1 through 6 ash sluice water because EPA expected

that the ash sluice water from Units 7 and 8 would contain a higher pr oportion of bottom ash, rather than consisting of a ba lanced mix of both fly ash and bottom ash. In addition, using an FGD system for particulate control (as is done in Unit 8) appears to be an uncommon practice in the industry.

The effluent sampling point for Widows Creek’s ash pond system is located at the pumping basin.

2.3 FGD Scrubber System

Widows Creek installed FGD systems on Un its 7 and 8 in 1981 and 1970, respectively. Each FGD system consists of four modules used to scrub the flue gas, for a total of eight FGD modules for the plant. The plant uses a limest one slurry as the sorbent for sulfur dioxide absorption. Widows Creek operates two ball mills where the limestone is ground and mixed with water. The slurry is fed to the absorber at a flow rate of approximately 2,000 gallons per minute. Both of the scrubbers are once-through systems, wherein the gypsum slurry at the bottom of the scrubber system is not recycled within the FGD system, but instead is pumped directly to the gypsum ponds. The limestone controls the pH and the density in the FGD system. The pH in the FGD system is optimized between 5.8 and 6.0. Th e effluent from the scrubber system (i.e., scrubber blowdown) is approximately 15 percent solids.

### 2-5 The Unit 7 FGD system is an open vessel wher e the absorbent liquid (limestone slurry) is pressurized and sprayed downward into the vessel through spray nozzles at various levels. The flue gas flows countercurrently to the spray and dr oplets of the absorbent slurry absorb and react

with the sulfur dioxide in the flue gas to produce calcium sulfat e (i.e., gypsum). The spray tower FGD system on Unit 7 removes 85 to 90 percent of the sulfur dioxide from the flue gas.

The Unit 8 FGD system is an open vessel wher e the absorbent liquid (limestone slurry) is pressurized and sprayed upward like a fountain into the vessel through spray nozzles at the bottom of the FGD system. This fountain spra y tower design extends the amount of time the absorbent droplets are in contact with the flue gas (i.e., while the absorbent liquid is flowing upward and while the absorbent liq uid falls downward, back to the bottom of the FGD system). The Unit 8 FGD system removes 94 to 96 percen t of sulfur dioxide. In addition to removing sulfur dioxide from the flue gas, the Unit 8 scrubb er also removes the fly as h from the flue gas.

Because the FGD systems are operated as once-through systems, Widows Creek has a continuous blowdown from each system. The gypsum slurry is pumped from the FGD systems to the inlet points of the FGD gyps um pond system, where the solid pa rticles in the wastewater are allowed to settle out of the slurry. Section 2.2 discusses the FGD gypsum pond system in more

detail.

As mentioned in Section 2.0, Unit 8 does not ha ve an ESP to remove the fly ash and other particulates from the flue gas prior to the F GD system; therefore, the FGD system removes the fly ash and other particulates from the flue gas as well as sulfur dioxide . These particulates are removed from the FGD system in the gypsum sl urry and are transferred to the FGD gypsum ponds.

2.4 FGD Gypsum Pond System

The FGD gypsum pond system consists of two parallel inlet points and diked channels (the physical configuration of the inlet to the FGD gypsum pond and the number of channels are subject to change), and a series of ponds for se ttling particulates. Figure 2-2 presents a flow diagram for the FGD gypsum pond system. The gypsum slurry from the scrubbers is pumped to the top of the pond system and enters at one of th e inlet points. From the inlet point, the slurry flows along a diked channel to the influent of the first gypsum pond. Because the gypsum accumulates in the channel over time, Widows Creek alternates the inlet point used to allow the plant to remove the solids that have built up in the channel. The gypsum that is removed from each of the channels is placed on the existing gypsum pile and alongside the diked channel to

increase the embankment.

From the diked channel, the wastewater enters the first gypsum pond. Upon entering the first pond, the flow velocity of the slurry slows, wh ich allows the particles in the slurry to settle to the bottom of the pond. The wastewater from the first pond flows by gravity into the second gypsum pond, where the solid particles continue to settle out of the sl urry. These first two gypsum ponds remove most of the gypsum and ot her particulates from the wastewater. Widows Creek regularly removes these solids from the ponds and stacks them along the sides of the ponds to increase the height of the embankment. B ecause the gypsum slurry from Unit 8 contains fly ash, the gypsum removed from the ponds ha d not been marketable gypsum; however,

### 2-6 Widows Creek has begun marketing some of th e ash/gypsum from Unit 8 as well as gypsum

from Unit 7.

The wastewater from the second gypsum pond flows by gravity to the last gypsum pond. The wastewater entering this pond is clear and contains very litt le gypsum. The wastewater from the last pond is discharged to Widows Creek, which flows into the Tennessee River. Widows Creek periodically changes the configurat ion and operation of the gypsum pond system whenever the plant operators thi nk it will facilitate tr eatment, ease operations or aid marketing; therefore, the description of the FGD gypsum pond system in this Sampling Episode Report describes the FGD pond system during the samp ling episode, which is different from the configuration during the tw o previous site visits. Since the ti me of the last site visit and the sampling episode, Widows Creek began to market the gypsum produced from Unit 7.

The influent sampling point for Widows Creek’s FGD gypsum pond system is located along the diked channel upstream of the first gypsum pond. The configura tion of the gypsum pond at the time of sample collection was such that the Unit 7 and Unit 8 influent streams did not enter the diked channel at the same point; theref ore, EPA selected a poin t approximately 100 feet

downstream of where both streams combine. In addition, the sample collection point was immediately downstream of a meta l culvert. EPA decided to collect the sample downstream of

the metal culvert because the waste stream e xhibited a better flow pa ttern on the downstream

side and the bank of the channel was more stable and safer at that point. The effluent sampling point for the FGD gypsum pond system is located at the discharge point to Widows Creek, which is the point that the plant us es for its NPDES monitoring.

### 2-7 Middle Stilling Pond

Pumping

Basin 

### Ash Pond Unit 1-6 Bottom

and Fly Ash

Sluice Water

Unit 7-8 Bottom

Ash Sluice

Water and Unit 7 Fly Ash Sluice

Water Red

Water

SP-3

SP-4 Recycle

to Unit 7-8

Intake

Emergency

Overflow Carbon

Dioxide Diked Channel



### Figure 2-1. Ash Pond System, Widows Creek Fossil Plant

### 2-8 1 st 

### Gypsum Pond

3 rd 

### Gypsum

Pond Gypsum slurry from

Unit 7 FGD scrubber

Discharge to Widows

Creek SP-2 SP-1 Alternate Channel Diked Channel



### 2 nd 

### Gypsum Pond Gypsum slurry from

Unit 8 FGD scrubber



### Figure 2-2. FGD Gypsum Pond Syst em, Widows Creek Fossil Plant

### 3-1 3. S AMPLE 

### C OLLECTION



### During the Widows Creek sampling episode , the sampling team followed the sample collection protocols specified in the Sampling Plan. Section 3.1 describes the sampling points, sample collection methods, and field measurements. Section 3.2 describes the list of analytes and the sample preservation procedures. Section 3.3 di scusses the plant opera tional data collected during the sampling episode. Finally, Section 3.4 discusses any deviations from the planned sampling activities described in the Sampling Plan.

During the sampling episode, Unit 8 was shut down, according to plant staff, as a result of a boiler tube leak and slag issues in the boi ler. Widows Creek informed the sampling team of the shut down on Tuesday, September 11, 2007 at approximately 0700, just before the sampling team prepared to sample the influent to the FGD pond system. Unit 8 remained shut down during the entire sampling episode. Additionally, Unit 1 was shut down when EPA arrived at the plant on Monday, September 10, 2007; however, Unit 1 was restarted at approximately 2200 on Tuesday, September 11, 2007.

3.1 Sampling Points, Sample Collectio n Methods, and Field Measurements

This section describes the sampling points, sample collection methods, and the field

measurements obtained for this sa mpling episode. Additional details are available in Section 3 of the Sampling Plan. Figures 2-1 and 2-2 present fl ow diagrams of the pl ant’s two pond systems, including sampling point locations.

Table 3-1 lists the sampling points, samp ling point descriptions, type of sample collection, sample collection date s and times, and the EPA Sample Control Center (SCC) sample

numbers. Table 3-2 lists the sa mpling point numbers and descri ptions, the number of samples collected, and the pollutant parame ters analyzed for this sampling episode. Table 3-3 presents the field measurement data collected from each sampling point.

The sampling points for this episode were:

• 

### SP-1 Influent to FGD Pond System;

• 

### SP-2 Effluent from FGD Pond System;

• 

### SP-3 Influent to Ash Pond;

• 

### SP-4 Effluent from Ash Pond;

• 

### SP-5 Duplicate of Effluent fr om FGD Pond System (SP-2);

• 

### SP-6 Influent to FGD Pond Sy stem (SP-1) Field Blank;

• 

### SP-7 Effluent from FGD Pond System (SP-2) Field Blank;

• 

### SP-8 Influent to Ash Pond (SP-3) Field Blank; and

• 

### SP-9 Effluent from Ash P ond (SP-4) Field Blank.

For all the sampling points, EPA collect ed split samples with Widows Creek’s representative. EPA inserted a “Y ” splitter into the sample tubing configuration at each sampling point (except SP-6 and SP-8) to allow for split sample collection. For this sampling episode, EPA collected all analytes (except for HEM/SGT- HEM and several field blanks collected at SP6 and SP-8) as “true” splits (i.e., samples for th e same analyte were collected simultaneously). The HEM/SGT-HEM samples were collected usi ng a bottle dipper; therefore, EPA and Widows

### 3-2 Creek’s representative collected duplicate samples, with one filling the bo ttle immediately after

the other.

The low-level total metals, low-level total mercury, and routine total metal field blanks collected at SP-6 (influent to FGD pond) and SP-8 (influent to ash pond) were not collected as “true” split samples. The field blanks for th ese samples were collect ed as “multipour” splits because the composite tubing did not have a splitt er in its configuration. The “multipour” splits were collected by the following procedure: one- third of the EPA sample bottle was filled and then one-third of the “split” bottle was filled. Th e EPA sample bottle and the “split” bottle were

each in turn then filled with an additional one-third sample. Finally, the EPA sample bottle was filled completely and then the “split” bottle was filled completely. For a description of the field blank sample collection pr ocedures, see Section 5.2.3.

At each of the nine sampling points, EPA co llected low-level metals sample fractions following EPA Method 1669 collection protocols. To collect low-level metals samples, EPA samplers donned Tyvek® suits and dust masks (dust masks were worn until all low-level mercury samples had been collected). In additi on, EPA set up a “cleanbox,” which consists of a portable plastic rectangular box with a shallow lip and a flip-top lid that secures itself open with clips. The “cleanbox” is double-ba gged, with a clear inner bag en closed in a translucent outer bag. The “cleanbox” is handled with “clean hands/ dirty hands” techniques, whereby the inner bag is handled only by the “clean hands” sampler. When the “cleanbox” is opened, the sampler is able to position his/her hands in the box and pu ll the bag over the opening of the box, but is still able to see the sample bottles and tubing. The “cleanbox” minimizes potential atmospheric contamination during sample collection. Figure D- 1, in Appendix D, is a picture of a sampler working inside a “cleanbox.” To collect samples, EPA placed the sample bottles and the inner bag into the “cleanbox” following the protocols specified in Method 1669, also referred to as “clean hands / dirty hands” protocols. Sampling staff filled the sample container and closed the sample bottle lid and inner bag as quickly as pos sible within the “clea nbox.” The sample bottles were then placed into the outer bag following the “clean hands / dirty hands” protocols.

3.1.1 Influent to FGD Pond System

The influent to the FGD pond system (SP- 1) was collected from the diked channel upstream of the first gypsum pond. As described in Section 2.2, the samples were collected

downstream of the location where the Unit 7 and Unit 8 influent streams combine and immediately downstream of a meta l culvert. Although Unit 8 was shut down just before EPA set up the sample collection at the influent to the FGD pond system, as discussed in Section 3.0,

there was still wastewater enteri ng the diked channel from the Un it 8 influent pipe; however, it appeared to be at a lower flow rate. Accordi ng to plant personnel, the Unit 8 absorber modules continued to purge water to the FGD pond syst em during the sampling episode, even though the unit was shut down; therefore, the influent samp le was likely diluted by this water stream. Based on information provided by Widows Creek, a pproximately 390 gpm of the 1170 gpm total influent flow rate to the FGD pond was from the Unit 8 FGD system. Of the 390 gpm contributed from Unit 8, approximately 35 gpm wa s limestone slurry and the remaining 355 gpm was make-up water. Additionally, Unit 7 was contributing 780 gpm to the FGD pond, which contained a gypsum slurry from the FGD proce ss reactions. Figure 2-2 identifies the sampling location for SP-1. This sample was collected as a 4-hour composite sample because the waste streams at the plant do not undergo equalization prior to flowing to the FGD pond; therefore,

### 3-3 EPA chose to collect a composite to account for so me of the variability in the waste stream. EPA chose a 4-hour composite because it allowed the samplers to set up and break down the sampling point in daylight, which was safer than at nigh t, and because it allowed the samplers enough time to ship the samples and meet all sample hold times. In addition, the dur ation of the composite sampling period was considered sufficient for ca pturing the operational variability of the

scrubber.

As discussed previously, the sampling point was located outside on the gypsum pile. EPA did not set up a tent or tarps to cover the samp lers/samples from rain and/or wind. There were no rain or wind conditions during collection of the field blanks or set-up of the sampling point; however, it did rain during the composite period. The rain did not directly contaminate the samples collected because the sample tubing was enclosed in the composite containers and the containers were located in a closed, clean tras h can; however, the rain could have diluted the samples from the rain falling directly into the diked channel.

Prior to setting up the composite samplers at the influent to the FGD pond system (SP-1), the sampling team collected field blanks (SP-6) for low-level total mercury, low-level total metals, and routine total metals. See Section 5.2. 3 for a description of the field blank sample collection at the influent to the FGD pond system. In addition, the samplers collected one set of HEM/SGT-HEM grab samples by dipping the bottles directly into the diked channel with a bottle dipper. The HEM/SGT-HEM samples were not collected in the compositor because the oil and grease adheres to the sides of the tubing and the composite containers.

EPA collected the wastewater samples fo r the influent to the FGD pond system by compositing 25 individual grab samples over a 4-hour period. The individual grab samples were collected by pumping samples automatically from the diked channel into two composite containers. EPA had one compos ite container for the classica l analytes and one composite container for the metal analytes (see Section 3.2 for the analyte list). The samplers attached one end of a 25-foot length of Teflon® tubing to a piece of PVC pipe and inserted the pipe and tubing into the diked channel. The tubing was a ttached a few feet above the bottom of the PVC pipe because the pipe was pushed into the solids at the bottom of the channel to help keep the tubing in position during the entire com posite period. In this position, the tubing was approximately at mid-depth in the channel. The other end of the Teflon® tubing was attached to a piece of silicone tubing, which was threaded th rough an ISCO peristaltic pump, and attached to a vent cap on the 20-liter composite container. Because there were two composite containers, EPA had two tubing configurations and two ISCO peristaltic pumps. The two ends of the Teflon® tubing were placed side by side on the PVC pipe to ensure that nearly identical samples

were collected. The one difference between the tw o set-ups for the composites was that, due to the difference in preservation requirements for th ese analytes, the composite container for the classicals was placed on ice and the com posite container for the metals was not.

After they placed the PVC pipe and the ends of the Teflon® tubing in the diked channel and secured the PVC pipe so that it would not move during the composite period, the samplers purged the tubing for the metals composite for approximately 3 minutes. The samplers then programmed and calibrated the au tomatic compositor (ISCO perist altic pump) to collect 800 mL of sample every 10 minutes for 4 hours, for a to tal of 20 liters of sample from 25 individual grabs.

### 3-4 After preparing the composite for the metals samples, the samplers followed the same procedures to prepare the composite for the cl assicals samples. The samplers programmed the automatic compositor to collect 800 mL of sample every 10 minutes for 4 hours, calibrated the compositor to collect approximately 800 mL, and a ttached the end of the silicone tubing to the vent cap on a different 20-liter container. They then closed off the inner and outer bags surrounding the composite containe rs and placed each composite c ontainer in a separate trash can. The samplers then surrounded th e classicals container with ice, to keep the grab samples cold, as required for preserva tion. The lid of the trash can wa s then placed on top of the composite containers to protec t the containers from rain; how ever, the lid was not shut down completely because it would kink the tubing. Figu re D-2, in Appendix D, is a picture of the sampling set up for the composite at the influent to the FGD pond system.

The samplers then started both of the automatic compositors at the same time and observed their operation to ensure that the samples were collected in both containers. The samplers then watched the collection of the second individual grab sample s for each compositor. Because both samples were collected successfully, th e samplers left the sampling point to collect the effluent from the FGD pond samp les (SP-2) and did not return to the infl uent sampling point until the compositing time period was complete.

When the samplers returned to the sampli ng point, the compositing period had concluded, and both composite containers were full of sa mple. The samplers immediately collected the second set of HEM/SGT-HEM grab samples by di pping the bottles direc tly into the diked channel with a bottle dipper. The two sets of HEM/SGT-HEM grab sample s were composited by the laboratory for a single sample result. The HEM/SGT-HEM samples were not collected in the compositor because the oil and grease adheres to the sides of the tubing and the composite

containers.

The sampling team then transported the 20-lite r composite containers back to the staging area to pour off and pump off. The samplers us ed a pour-off method, “shake and pour,” to collect the metals samples that did not require filtration and all the classical samples, and then used a pump-off set up to collect all the dissolved metals samples.

For the “shake and pour” method, the sample rs used a funnel with a short length of silicone tubing attached to a “Y” splitter and tw o additional pieces of silicone tubing to pour the samples into the sample bottles. First, two of the samplers (shakers) s hook the 20-liter metals composite container vigorously for several minutes to resuspend all of the solids settled at the

bottom of the container. The shak ers shook the 20-liter container back and forth on its side for approximately 30 seconds, and then quickly placed the container on a table while another sampler removed the cap from the container. Once the cap was removed, the shakers slowly poured the sample into the funnel, which was being held by another sampler, and the sample poured down the tubing, through th e “Y” splitter, and into EP A’s and the Widows Creek’s representative’s sample bottles. Be cause the solids in this sample settled quickly to the bottom of the container, EPA performed the “shake and pour” for each individual bottle so that each bottle would contain approximately the sa me solids content. Figure D-3, in Appendix D, is a picture of the sample collection set-up for “shake and pour” method.

EPA first collected the low-level total metals, low-level total and dissolved mercury, routine total metals, and the arsenic/selenium speciation samples from the 20-liter metals

### 3-5 composite container, using the “shake and pour ” method and filling the bo ttles in a “cleanbox,” as described in Section 3.1. The samplers then placed the metals composite container near the pump-off station and began shaking the 20-liter classicals composite container. After all the solids were resuspended in the classicals composite container, the samplers collected the BOD, Group I, and Group II samples, using the “shake and pour” method and filling the bottles without

a “cleanbox.”

The sampling team then waited approximately 20 minutes to allow the solids in the metals composite container to continue settling for the dissolved metals pump off. After most of

the solids had settled to the bottom of the contai ner, the samplers set up the pump-off station for the collection of dissolved metals samples, which consisted of a length of Teflon® tubing attached to a length of silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team attached a capsule filter to the silicone tubing, which was a short distance downstream of the pump. The sampling team attached another short length of silicone tubing to the capsule filter effluent, which was attached to a “Y” splitter and two lengths of silicone tubing. This set-up allowed EPA to collect “true” split samples with Widows Creek’s representative. Prior to collecting any dissolved metals sa mples of the FGD pond influent, the samplers collected a field blank sample (SP-6) for low-level dissolved metals, routine dissolved metals, and routine hexavalent chromium. See Section 5.2.3 for a description of the dissolved metals field blank sample collection at the influent to the FGD pond system.

After collecting the field blank samples, th e sampling team transferred the end of the Teflon® tubing into the metals 20-liter composite container. The samplers first purged the tubing and filter with sample for 30 seconds (approximate ly 2 liters) and then collected the low-level dissolved metals, routine dissolved metals, a nd routine hexavalent chromium samples.

During the sample collection, the sampling t eam collected two ali quots of sample for field testing, one each at the beginning and end of the composite period. Sample pH and temperature were measured immediately at the sampling point using a pH meter and four-color pH paper. The four-color pH paper was used as an independent check of the pH meter to ensure

that similar results were measured. After return ing to the staging area, the sampling team took

measurements of free and total residual chlorine using a colorimeter. Table 3-3 presents the field

measurement data for the infl uent to the FGD pond system.

3.1.2 Effluent from FGD Pond System

The effluent from the FGD pond system (SP- 2) was collected directly from the waste stream that flows from the final gypsum pond to the Widows Creek, which ultimately is discharged to the Tennessee River. Figure 2-2 identifies the sampling location for SP-2. This sample was collected as a grab sample, because the wastewater is equalized through the long

retention time within the gypsum ponds; therefore, the wast ewater characteristics should be fairly homogeneous.

During the sample collection at the efflue nt from the FGD pond system, the sampling team covered the sample collection area with two tents to cover the samplers and sample bottles

in case of rain. It did rain duri ng the sample collection, but the samplers and sample bottles were protected, thereby minimizing any potential cont amination. However, because the samples were

### 3-6 collected from a flowing waste stream that was not covered, the samples may have been slightly

diluted from the rain.

Prior to collecting samples at the efflue nt from the FGD pond system (SP-2), the sampling team collected field bla nks (SP-7) for low-level total mercury, low-level total metals, routine total metals, low-level dissolved metals, low-level hexavalent chromium, routine dissolved metals, and routine hexavalent chro mium. See Section 5.2.3 for a description of the field blank sample collection at the effluent from the FGD wastewater treatment system.

EPA collected the wastewater samples for the effluent from the FGD pond system by pumping samples from the discharge waste stre am into the sample containers. The sampling team attached one end of a 25-foot length of Te flon® tubing to a piece of PVC pipe and inserted the PVC pipe and tubing into the waste stream. The sampling team positioned the tubing to reach the sampling team at the sampling point set-up ar ea and attached it to a piece of silicone tubing, which was threaded through an ISCO peristal tic pump. The sampling team attached a “Y” splitter to the other e nd of the silicone tubing, with two additional pieces of silicone tubing attached to the “Y” splitter. The length of s ilicone tubing between the pump and the “Y” splitter consisted of two pieces with a small connector , which allowed EPA to attach and detach a capsule filter inline with the tubing configuration. The “Y” splitter allowed EPA to collect “true” split samples with Widows Creek’s representative. Figure D-4, in Appendix D, is a picture of the sampling set-up for the effluent from the FGD pond system.

After configuring the tubing for the sampli ng point, the samplers purged the tubing and filter with sample for approximately one minute. The samplers first collected the low-level

dissolved metals and low-level hexavalent chro mium samples, as well as the QC and duplicate samples, because the capsule filter was alrea dy inline with the tubing configuration from the dissolved metals field blank sample collection. Th e samplers then installed a new capsule filter and purged the filter for approximately one minute. After purging the filter, the samplers

collected the routine dissolved me tals and routine hexavalent chromium samples, as well as the QC and duplicate samples for each analyte. Each of these samples was collected in a “cleanbox,”

as described in Section 3.1.

After collecting all the dissolved metals sa mples, the sampling team removed the capsule filter from the tubing configuration and purged the tubing for 30 seconds. The samplers then collected the low-level total metals, low-level to tal and dissolved mercury, routine total metals, and arsenic/selenium speciation samples, as well as the QC and duplicate samples for each analyte, in a “cleanbox,” as desc ribed in Section 3.1. The sample rs then collected the BOD, Group I, and Group II samples, as well as the QC and duplicate samples for each analyte, by pouring the samples directly from the tubing into the samples bottles without using a “cleanbox.”

The samplers used a bottle dipper to collect the HEM/SGT-HEM and HEM/SGT-HEM QC samples directly from the waste stream to pr event any oil and grease adhering to the sides of the tubing. Therefore, EPA did not collect split sa mples with Widows Creek’s representative for the HEM/SGT-HEM samples, but instead colle cted duplicate samples with Widows Creek’s representative. Two members of the sampling team collected the HEM/SGT-HEM samples from the waste stream at the same time the remainder of the sampling team was collecting the field blank samples. To avoid potentially contam inating the samples by the collection of the HEM/SGT-HEM samples, the samplers collected the HEM/SGT-HEM samples approximately

### 3-7 10 feet downstream from the location where th e tubing was placed for collecting the other samples.

During the sample collection, the sampling team collected an aliquot of sample for field testing. Sample pH and temperature were measur ed immediately at the sampling point using a pH meter and four-color pH paper. The four-color pH paper was us ed as an independent check of the pH meter to ensure that similar results were measured. After returning to the staging area, the sampling team took measurements of free and to tal residual chlorine using a colorimeter. Table 3-3 presents the field measurement data for the effluent fr om the FGD pond system.

3.1.3 Influent to Ash Pond System

The influent to the ash pond system (SP- 3) was collected from the diked channel containing the ash sluice water from Units 1 th rough 6, upstream of where the “red water” is pumped back into the diked channel. As discu ssed in Section 2.4, this sample does not account

for the wastewaters from Units 7 and 8 that en ter the ash pond. Figure 2- 1 identifies the sampling location for SP-3. This sample was collected as a 12-hour composite sample because these waste streams are not equalized prior to entering th e ash pond; therefore, EP A chose to collect a composite to account for some of the variabil ity in the waste stream. EPA chose a 12-hour composite because the bottom ash from Units 1 through 6 is sluiced only once per unit per 12- hour shift; therefore, to accurate ly represent the wastewater en tering the ash pond from Units 1 through 6, the composite needed to be 12 hours to include one bottom ash sluice cycle from each unit, along with the sluicing of the fly ash.

As discussed previously, the sampling point was located outside along the diked channel leading to the ash pond. EPA set up tents to cove r the samplers/samples from rain during the collection of the field blank samples; however, EPA removed the tents from the sampling point

after the field blanks were collected. There were no rain or wind conditio ns during collection of the field blanks or set-up of the sampling poin t; however, it did rain duri ng the composite period. The rain did not affect the samples collected because the sample tubing was enclosed in the composite containers and the containers were located in a closed, clean trash can; however, because it was raining and the samples were collec ted from a flowing waste stream that was not covered, the samples may have been slightly diluted from the rain.

Prior to setting up the composite samplers at the influent to the ash pond system (SP-3), the sampling team collected field blanks (SP-8) for low-level total mercury and low-level total metals. See Section 5.2.3 for a description of the fi eld blank sample collection at the influent to the ash pond system. In addition, the samplers collected one set of the HEM/SGT-HEM grab samples by dipping the bottles di rectly into the diked channe l with a bottle dipper. The HEM/SGT-HEM samples were not collected in the compositor because the oil and grease

adheres to the sides of the tubi ng and the composite containers.

EPA collected the wastewater samples fo r the influent to the ash pond system by compositing 25 individual grab samples over a 12- hour period. The individual grab samples were collected by pumping samples automatically from the diked channel into two composite containers. EPA had one compos ite container for the classica l analytes and one composite container for the metal analytes (see Section 3.2 for the analyte list). EPA attached one end of a 25-foot length of Teflon® tubing to a piece of PVC pipe and inserted the pipe and tubing into the

### 3-8 diked channel. The tubing was attached a few f eet above the bottom of the PVC pipe because the pipe was pushed into the solids at the bottom of the channel to help keep the tubing in position over the entire composite period. In this position, the tubing was approximately at mid-depth in

the channel. The other end of the Teflon® tubi ng was attached to a pi ece of silicone tubing, which was threaded through an ISCO peristaltic pu mp, and attached to a vent cap on the 20-liter composite container. Because there were tw o composite containers, EPA had two tubing configurations and two ISCO peri staltic pumps. The two ends of the Teflon® tubing were placed side by side on the PVC pipe to ensure that ne arly identical samples were collected. The one difference between the two set-ups for the co mposites was that, due to the difference in preservation requirements for these analytes, the composite container for the classicals was placed on ice, whereas the composite container for the metals was not.

After they placed the PVC pipe and the ends of the Teflon® tubing in the diked channel and secured the PVC pipe so that it would not move during the composite period, the samplers purged the tubing for the metals composite for approximately 3 minutes. The samplers then programmed and calibrated the au tomatic compositor (ISCO perist altic pump) to collect 800 mL of sample every 30 minutes for 12 hours, for a total of 20 liters of sample from 25 individual grabs.

After preparing the composite for the metals samples, the samplers followed the same procedures to prepare the composite for the cl assicals samples. The samplers programmed the automatic compositor to collect 800 mL of sample every 30 minut es for 12 hours, calibrated the compositor to collect approximately 800 mL, and a ttached the end of the silicone tubing to the vent cap on a different 20-liter container. They then closed off the inner and outer bags surrounding the composite containers and placed each of the composite containers in a separate trash can. The samplers then surrounded the classicals container with ice, to keep the grab samples cold, as required for preservation. The lid of the trash can was then placed on top of the composite containers to protec t the containers from rain; how ever, the lid was not shut down completely because it would kink the tubing. Figu re D-5, in Appendix D, is a picture of the sampling set up for the composite at th e influent to the ash pond system.

The samplers then started both of the automatic compositors at the same time and observed their operation to ensure that the sample s were collected in both containers. After the first sample was collected, the samplers moved the containers into a position that would be safe overnight. The sampling team stayed at the samp ling point to watch the collection of the second grab sample and determined that sample was onl y collected in one of the 20-liter containers. EPA examined the tubing for the other 20-liter c ontainer and noticed a kink in the line that must have prevented the container from being fille d. When attempting to correct the situation by collecting a manual aliquot via the automatic com positor, the sampling team accidentally added additional sample to the 20-lite r container that already receiv ed the second grab sample. Therefore, the samplers collected two manual grab, via the automatic compositor, samples in the other 20-liter composite container to ensure that the samples co llected in each 20-liter were similar. EPA believes that collecting an addi tional aliquot during one time period will not significantly impact the overall sample. The sample rs then watched the collection of the next two individual grab samples for each compositor. Because the following two samples were collected successfully, the samplers left the sampling point and did not return to the influent sampling point until the compositing time period was complete.

### 3-9 When the samplers returned to the samp ling point, the compositing period was over and both composite containers were full of sample. The samplers immediately collected the second set of HEM/SGT-HEM grab samples by dipping the bottles directly into the diked channel with a bottle dipper. The two sets of HEM/SGT-HEM gr ab samples were composited by the laboratory for a single sample result. The HEM/SGT-HEM samples were not collected in the compositor because the oil and grease adheres to the side s of the tubing and the composite containers.

EPA then retrieved the 20-liter composite c ontainers and transported them back to the staging area to pour off and pump off. The samp lers used a pour-off method, “shake and pour,” which is described in Section 3.1.1, to collect the metals samples that did not require filtration and all of the classical samples. The samplers th en used a pump-off set-up to collect all of the dissolved metals samples.

The sampling team first shook up the 20-liter metals composite container to resuspend the solids. The samplers then purged the funne l, tubing, and “Y” splitter with sample for approximately 45 seconds. After purging the tubing, the samplers collected the low-level total metals, low-level total and dissolved mercury, ro utine total metals, and the arsenic/selenium speciation samples from the 20-liter metals co mposite container, usi ng the “shake and pour” method, and filling the bottles in a “cleanbox,” as described in Section 3.1. The samplers then put the metals composite container near the pum p-off station and began shaking the 20-liter classicals composite container. After all the soli ds were resuspended in the classicals composite container, the samplers collected the BOD, Group I, and Group II samples, using the “shake and pour” method, and filling the bottles without a “c leanbox.” Figure D-3, in Appendix D, is a picture of the sample collection set-up for the “s hake and pour” method at the influent to the ash pond system (SP-3).

At this point, the sampling team could ha ve collected the diss olved metals sample fractions from the metals 20-liter composite cont ainer; however, based on visual observation of the composite container, the samplers determined that the solids had not co mpletely settled in the container. Therefore, to conser ve time, EPA decided to collect the effluent from the ash pond system (SP-4), while waiting for the solids to settle.

After returning from collecting the samples for SP-4, the samplers observed that, after settling in the metals composite container for approximately five hours, nearly all of the solids had settled in the container. The sampling t eam then set up the pump-off station for the collection of dissolved metals samples, which co nsisted of a length of Teflon® tubing attached to a length of silicone tubing, which was th readed through an ISCO peristaltic pump. The samplers attached a capsule filt er to the silicone tubing, which was a short distance downstream of the pump, and attached another short length of silicone tubing to the capsule filter effluent, which was attached to a “Y” spli tter and two lengths of silicone tubing. This set-up allowed EPA to collect “true” split samples with Widows Creek’s representative. Prior to collecting any dissolved metals samples of the ash pond influent , the samplers collected a field blank sample (SP-8) for low-level dissolved metals. See Sectio n 5.2.3 for a description of the dissolved metals field blank sample collection at th e influent to the ash pond system.

After collecting the field blank samples, th e sampling team transferred the end of the Teflon® tubing into the metals 20-liter composite container. The sampling team first purged the

### 3-10 tubing and filter with approximately 1 liter of sa mple and then collected the low-level dissolved metals, routine dissolved metals, and r outine hexavalent ch romium samples.

During the sample collection, the sampling t eam collected two ali quots of sample for field testing, one each at the beginning and end of the composite period. Sample pH and temperature were measured immediately at the sampling point using a pH meter and four-color pH paper (pH paper was not used for the first fiel d test sample due to darkness). The four-color pH paper was used as an independent check of th e pH meter to ensure that similar results were measured. After returning to the staging area, the sampling team took measurements of free and total residual chlorine using a colorimeter. Table 3-3 presents the field measurement data for the influent to the ash pond system.

3.1.4 Effluent from Ash Pond System

The effluent from the ash pond system (SP- 4) was collected directly from the pumping basin, from a metal platform approximately 15 fe et above the water leve l. Figure 2-1 identifies the sampling location for SP-4. This sample wa s collected as a grab sample, because the wastewater is equalized through the long retentio n time within the ash pond and the wastewater characteristics should be fairly homogeneous.

As discussed above, the sampling point was located outside on a platform near the pumping basin. Although the samplers were outside , EPA did not set up a te nt or tarps to cover the samplers/samples from rain because ther e was limited space on the platform. The sampling team did not experience any rain or wind conditions during the sample collection.

Prior to collecting samples at the effluent from the ash pond system (SP-4), the sampling team collected field blanks (SP-9) for low-level total mercury, low-level total metals, low-level dissolved metals, and low-level hexavalent chro mium. See Section 5.2.3 for a description of the field blank sample collection at th e effluent from the ash pond system.

EPA collected the wastewater samples fo r the effluent from the ash pond system by pumping samples from the pumping basin into the sample containers. The sampling team attached one end of a 25-foot length of Teflon® tubing to two pieces of PVC pipe that were attached together to increase the length of the pipe, and inserted the PVC pipes and tubing into the basin. The sampling team attached the PVC pipe to a rail on the platform to secure the pipe and tubing in place during the sample collection. The samplers positioned the tubing to reach them at the sampling point set-up area and attach ed it to a piece of silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team attached a “Y” splitter to the other end of the silicone tubing, w ith two additional pieces of sili cone tubing attached to the “Y” splitter. The length of silicone tubing between the pump a nd the “Y” splitter consisted of two pieces with a small connector, which allowed the sa mplers to attach and de tach a capsule filter inline with the tubing configura tion. The “Y” splitter allowed EPA to collect “true” split samples with Widows Creek’s representative . Figure D-6, in Appendix D, is a picture of the sampling setup for the effluent from the ash pond system.

After configuring the tubing for the sampli ng point, the samplers purged the tubing and filter with sample for approximately 2 minutes. The samplers first collected the low-level dissolved metals and low-level hexavalent chromium samples, as well as the QC samples,

### 3-11 because the capsule filter was al ready inline with the tubing configuration from the dissolved metals field blank sample collection. The samp ling team then collected the routine dissolved metals, routine dissolved metals QC, and routine hexavalent chro mium samples. Each of these samples was collected in a “cleanbox ,” as described in Section 3.1.

After collecting all the dissolved metals sa mples, the sampling team removed the capsule filter from the tubing configuration and purged the tubing for 1 minute. The samplers then collected the low-level total metals, low-level to tal and dissolved mercury, routine total metals, and arsenic/selenium speciation samples, as we ll as the QC samples, for each analyte in a “cleanbox,” as described in Section 3.1. The samp ling team then collected the BOD, Group I, and Group II samples, by pouring the samples direct ly from the tubing into the samples bottles without using a “cleanbox.”

The samplers used a bottle dipper to colle ct the HEM/SGT-HEM samples directly from the pumping basin to prevent any oil and grease a dhering to the sides of the tubing. Therefore, EPA did not collect split samp les with Widows Creek’s repres entative for the HEM/SGT-HEM samples, but instead collected duplicate samp les with Widows Creek’s representative. Two members of the sampling team collected the HEM/SGT-HEM samples at the same time the Group I samples were being collected from the pumping basin. The HEM/SGT-HEM samples were not collected from the same point within the basin as the other samples because the samplers could not reach that po int with the bottle dipper; however, the samplers attempted to

collect it as close to th e same point as possible.

During the sample collection, the sampling team collected an aliquot of sample for field testing. Sample pH and temperature were measur ed immediately at the sampling point using a pH meter and four-color pH paper. The four-color pH paper was us ed as an independent check of the pH meter to ensure that similar results were measured. After returning to the staging area, the sampling team took measurements of free and tota l residual chlorine using a colorimeter. Table 3-3 presents the field measurement data for the effluent from the ash pond system.

3.2 List of Analytes and Sample Preservation

Analytes in EPA’s Widows Creek sampli ng episode included those in the following classes of pollutants:

• 

### Classicals:

— Biochemical oxygen demand, 5-day (BOD 5 

### ),

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus,

— Hexane extractable material (HEM), and

— Silica-gel treated hexane extractable material (SGT-HEM); and

### 3-12 • 

### Metals:

— Routine total metals (27 metals: aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium, ch romium, cobalt, copper, iron, lead, magnesium, manganese, mercury, molybdenum, nickel, selenium, silver, sodium, thallium, tin, titanium, vanadium, yttrium, and zinc),

— Routine dissolved metals (27 metals),

— Routine hexavalent chromium,

— Low-level total mercury,

— Low-level dissolved mercury,

— Low-level hexavalent chromium,

— Low-level total metals (11 metals: antimony, arsenic, cadmium, chromium, copper, lead, nickel, sele nium, silver, thallium, zinc), and

— Low-level dissolved metals (11 metals).

The analytes selected reflect the curren t understanding of coal-fired power plant air pollution control wastewaters, in cluding contributions from coal , scrubber sorb ents, treatment chemicals, and other sources. Table 3-4 lists the analytical methods used to determine pollutant

concentrations.

Table 3-5 lists the containe rs used for sample collection as well as the preservation requirements for each sample, and Table 3-6 summa rizes the chemical preservation for each of the samples that were preserved on site. The sampling team preserved samples in accordance with procedures described in S ection 3.4 of the Sampling Plan. A ll samples except routine total and dissolved metals, low-level total and dissolved metals, low-level total and dissolved mercury, and low-level hexavalent chromium sa mples were placed on ice and cooled to <6°C immediately following collection. All dissolved metals samples, except low-level dissolved mercury, were filtered in the fi eld. The routine and low-level hexavalent chromium samples were preserved in the field, but all other metals samples were acid-preserved at the laboratory, prior to extraction. The routine hexavalent chromium samp les were supposed to be preserved to a pH between 9.3 and 9.7 using an ammonium sulfate buffer solution; however, the sampling team discontinued preservation for some samples becau se 10 percent of the sample volume was added before the required pH was achieved (the pH of these preserved samples was approximately 9.0). The low-level hexavalent chromium sample bottles were prepreserved with 2 mL of 50-percent NaOH. The Group II and HEM/SGT-HEM samples were preserved with sulfuric acid to a pH of <2 immediately after collection in the staging area, and the pH wa s confirmed with four-color pH strips.

3.3 Plant Operational Data

During the sampling episode at Widows Cree k, plant personnel pr ovided the sampling team with operational data for each of the gene rating units and the FGD scrubber systems, as well as operational and flow data for the FGD pond and ash pond systems. Table 3-7 presents the unit operating characteristics, Table 3-8 presents the FGD scrubber system operating characteristics, Table 3-9 presents the FGD pond system operating characteristics, Table 3-10 presents the ash system operating characteristi cs, and Table 3-11 presents the ash pond system operating characteristics dur ing the sampling episode.

### 3-13 As noted in Section 3.0, Unit 8 was shut down during the sampling episode due to a boiler tube leak and slag issu es in the boiler. Unit 8 was shut down on Tuesday, September 11, 2007 at 0600 and remained down during the enti re sampling episode. In addition, when EPA arrived at Widows Creek on Monday, September 10, 2007, Unit 1 was already shut down. According to plant personnel, the unit was shut down because of a feedwater heater drain line

failure. Widows Creek restarted Unit 1 at approximately 2200 on Tuesday, September 11, 2007.

3.4 Deviations from the Sampling and Analysis Plan

The sampling episode proceeded as specified in the Sampling Plan with the exceptions

described below:

• 

### Sample Collection Point for Influent to FGD Pond System (SP-1). As described in Section 2.2, Widows Creek cha nged the configuration of the inlet to the FGD pond system from what EPA had seen during the site visits. EPA planned to collect the composite sample of the influent to the FGD pond system

as close to the inlet of th e diked channel as possible after some solids removal. However, because the Unit 8 influent point was further downstream than the Unit 7 influent and because of safety concerns , EPA collected the samples from a point

well downstream of the Unit 7 influent a nd approximately 100 feet downstream of

the Unit 8 influent.

• 

### Sample Collection Point for Influent to Ash Pond System (SP-3). As described in Section 2.4, Widows Creek changed the c onfiguration of the influent to the ash pond system from what EPA had seen dur ing the site visits. EPA planned to collect the composite sample of the infl uent to the ash pond system after the ash sluice from Units 1 through 6 was commingl ed with the ash sluice from Units 7 and 8. However, the new configuration of the influent no longer commingled the two ash sluice streams prior to entering the ash pond. Therefore, EPA chose to

collect the ash sluice from Units 1 th rough 6 to represent the ash pond influent because EPA expected the ash sluice water from Units 7 and 8 would be over influenced by the bottom ash.

• 

### Composite Program for Influent to the FGD Pond System (SP-1) and Influent to the Ash Pond System (SP-3). For the influent to the FGD pond system and the ash pond system, EPA pla nned to collect composite samples by collecting 24 individual grab samp les of 833 mL over the compositing time period. However, EPA decided to collect 25 individual grab samples over the time period because the sample period starts a nd ends with a grab sample; therefore, EPA collected 800 mL of samples for each individual grab.

• 

### Pour Off of Influent to the FGD Pond Sy stem (SP-1) and Influent to the Ash Pond System (SP-3) Composite Samples. EPA planned to pump off each of the samples from the composite containers into the individual sample containers. However, based on further considera tion, EPA determined it would be too difficult to shake the composite containe rs with the tubing (needed for the pump off) attached to the cap of the contai ner; therefore, EPA changed the planned methodology. EPA developed the “shake and pour” method for the sample

### 3-14 collection to allow the sample to be vigorously shaken prior to being poured into

individual containers. Section 3.1.1 de scribes the “shake and pour” methodology

in detail.

• 

### Total Metal Field Blank Sample Collectio n at the Influent to the FGD Pond System (SP-6) and Influent to the Ash Pond System (SP-8) . EPA planned to collect the total metals field blank samples at SP-6 and SP-8 as duplicate samples with Widows Creek’s representative becau se the composite tubing does not have a “Y” splitter inline with the tubing configuration; however, EPA collected the samples as “multipour” splits, by partially filling the EPA bottle, then filling the split bottle, and then repeating the partia l filling of both bottles two more times until both bottles were completely full.

• 

### Preservation of Routine Hexavalent Chromium. The routine hexavalent chromium samples were supposed to be preserved to a pH between 9.3 and 9.7 using an ammonium sulfate buffer solution; however, for some of the samples, preservation was discontinued because 10 percent of the sample volume was added before the required pH was achieve d (the pH of these preserved samples was approximately 9.0).

### 3-15 Table 3-1. Sample Collection Information, Widows Creek

Sampling

Point

Number Sampling Point Description Type of Sample Sample Collection

Date and Time SCC Number

SP-1 Influent to FGD Pond System 4-Hour Composite 09/11/2007 0824 to 1224; 1445 a 70520

SP-2 Effluent from FGD Pond System Grab 09/11/2007

1035 70521

SP-3 Influent to Ash Pond System 12-Hour Composite 09/11/2007 1920 until

09/12/2007 0635

09/12/2007 0811 b

09/12/2007 1330 c 70522

SP-4 Effluent from Ash Pond System Grab 09/12/2007

1109 70523

SP-5 Duplicate of Effluent from FGD Pond System Grab 09/11/2007

1035 70524

SP-6 Influent to FGD Pond System Field

Blank Grab 09/11/2007

0719 d and 1539 e 70525

SP-7 Effluent from FGD Pond System Field

Blank Grab 09/11/2007

0959 70526

SP-8 Influent to Ash Pond System Field Blank Grab 09/11/2007 1818 d

09/12/2007 1323 e 70527

SP-9 Effluent from Ash Pond System Field

Blank Grab 09/12/2007

1035 70528

a – Collection of the pour-offs for total metals and classi cals, as well as the pump-offs for the dissolved metals samples from the composite collection containers. b – Collection of the pour-offs for total metals and classicals samples from the composite collection containers. c – Collection of the pump-offs for the dissolved metals samples from the composite collection containers.

d – Collection of field blanks for total metals.

e – Collection of field blanks for dissolved metals.

### 3-16Table 3-2. Number of Samples Collected by Sampling Point, Widows CreekSamplingPointNumberSampling Point Description Low-Level Total Metals (11 analytes) Low-Level Dissolved Metals (11 analytes) Low-Level Total Mercury Low-Level Dissolved Mercury Low-Level Hexavalent Chromium Routine Total Metals (27 analytes) Routine Dissolved Metals (27 analytes) BOD 5 Group I

a Group II b HEM / SGT-HEM Routine Hexavalent Chromium Selenium/Arsenic Speciation

cSP-1 Influent to FGD Pond System 1 1 1 1 1 1 1 1 1 1 1 1+dupSP-2 Effluent from FGD PondSystem1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+dupSP-3 Influent to Ash Pond System 1 1 1 1 1 1 1 1 1 1 1 1+dupSP-4 Effluent from Ash PondSystem1+QC 1+QC 1+QC 1+QC 1+QC1+QC 1+QC 1 1 1 1 1 1+dupSP-5 Duplicate of Effluent fromFGD Pond System1 1 1 1 1 1 1 1 1 1 1SP-6 Influent to FGD Pond SystemField Blank1 1 1 1 1 1SP-7 Effluent from FGD PondSystem Field Blank1 1 1 1 1 1 1SP-8 Influent to Ash Pond SystemField Blank1 1 1SP-9 Effluent from Ash PondSystem Field Blank1 1 1 1Total Number of Samples 9+2QC 9+2QC 9+2QC 5+2QC 4+2QC 7+2QC 7+2QC5+1QC 5+1QC 5+1QC 4+1QC 7+1QC 4+4dupa–Group I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate and chloride.b–Group II includes ammonia as nitrogen, nitrate/nitrite as nitrogen,total Kjeldahl nitrogen (TKN), and total phosphorus.c – The selenium/arsenic speciation results from the sampling episode were not available at thetime this report was finalizedand therefore are not included in this report.

### 3-17Table 3-3. Field Measurements, Widows CreekTempoCpH (S.U.)SamplingPointNumberSampling PointDescriptionTimeMeterThermometerMeteraStripsFreeChlorine(mg/L)TotalChlorine(mg/L)ManganeseInterferenceReading(mg/L)WasteStream FlowRate (MGD)Influent to FGD Pond(beginning of composite)0804 35.6 38.5 7.83 7 0.13 0.28 0.22SP-1Influent to FGD Pond(end of composite)1328 32.6 34.5 7.15 7 0.00 0.00 0.001.68SP-2 Effluent from FGD Pond 1121 28.5 28 8.14 8 0.36 0.13 0.04 1.68Influent to Ash Pond(beginning of composite)1907 33.1 34 8.82 NA 0.12 0.06 0.06SP-3Influent to Ash Pond(end of composite)0705 33.8 35 8.35 7 0.00 0.06 0.0012.10SP-4 Effluent from Ash Pond 1147 29.3 30 7.82 7 0.00 0.03 0.02 29.92a – The pH meter was calibrated on the morning of September 11 and 12, 2007 using pre-packaged buffer solutions at pHs 4.0, 7.0, and 10.0.Note – At SP-1, the sampling team noted a high solids content in the sample.Note – At SP-2, the field test jar was clear and colorless; there were no visible solids. During the sampling collection period, the sampling team noted a moderatebreeze, as well as occasional wind gusts.NA – Not Analyzed.

### 3-18 Table 3-4. Analytical Methods and Procedures for Samples Collected at Widows Creek

Method Number Parameter Method Type

Classicals

SM 5210 B Biochemical Oxygen Demand (BOD 5 ) Probe

SM 2540 D Total Suspended Solids (TSS) Gravimetric

SM 2540 C Total Dissolved Solids (TDS) Gravimetric

ASTM D516-90 Sulf ate Turbidimetric

SM 4500–Cl–C Chloride Titrimetric, mercuric

nitrate

SM 4500—NH3 F (18th ed.) Ammonia as Nitrogen Distillation, potentiometric

SM 4500-NO3 H Nitrate/Nitrat e as Nitrogen Autoanalyzer

SM 4500—N, C Total Kjeldahl Nitrog en (TKN) Digestion, distillation, potentiometric

EPA 365.3 (Rev 1978) Total Phosphorus Digestion, spectrophotometric

EPA 1664A Hexane Extractable Material (HEM) Gravimetric

EPA 1664A Silica Gel Treated Hexane Extractable Material (SGT-HEM) Gravimetric

Metals

EPA 1631E Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry Oxidation, Purge and Trap, and CVAFS

EPA 1636 Determination of Hexavalent Chromium by Ion Chromatography Ion Chromatography

EPA 1638 Determination of Trace Elements in Ambient Waters by Inductively Coupled Plasma – Mass Spectroscopy (includes antimony, arsenic, cadmium, chromium, copper, lead, nickel, selenium, silver, thallium, and zinc) ICP/MS

EPA 200.7, 245.1 Metals by Inductively Coupled Plasma Atomic Emission Spectrometry and Cold Vapor Atomic Absorption Spectroscopy ICP and CVAA

ASTM D1687-92 Hexavalent Chromium Colorimetric

CVAFS – Cold vapor atomic fluorescence spectrometry. ICP/MS – Inductively coupled plasma with mass spectrometry. ICP – Inductively coupled plasma. CVAA – Cold vapor atomic adsorption.

### 3-19 Table 3-5. Summary of Sample Co ntainer and Planned Preservation

Parameter Sample Container and Volume On-Site Preservation

Classicals

BOD 5 One 1-L plastic bottle ≤ 6 o C

Group I a Two 1-L plastic bottles ≤ 6 E C

Group II b Two 1-L plastic bottles H 2 SO 4 to pH <2, ≤ 6 E C

HEM/SGT-HEM Two 1-L wide mouth glass jars H 2 SO 4 to pH <2, ≤ 6 o C

Metals

Routine total metals, 27 element quantitation (Method 200.7, 200.8, 200.9, 245.1) One 500-mL plastic bottle None
(acid preserve at laboratory)

Routine dissolved metals, 27 element quantitation (Method 200.7, 200.8, 200.9, 245.1) One 500-mL plastic bottle 0.45 μm filter (performed in field)

(acid preserve at laboratory)

Low-level total mercury (Method 1631) One 250-mL glass (ultraclean), fluoropolymer lined caps None
(acid preserve at laboratory)

Routine hexavalent chromium One 250-mL plastic bottle 0.45 μm filter (performed in field)

Ammonium sulfate buffer to pH 9.3 – 9.7, ≤ 6 E C

Low-level dissolved mercury (Method 1631) Two 250-mL glasses (ultraclean), fluoropolymer lined caps None
(acid preserve and filter at laboratory)

Low-level total elements by ICP/MS (11 elements, Method 1638) One 250-mL LDPE (ultraclean), fluoropolymer lined caps None
(acid preserve at laboratory)

Low-level dissolved elements by ICP/MS (11 elements, Method 1638) Two 250-mL LDPE (ultraclean), fluoropolymer lined caps 0.45 μm filter (performed in field)

(acid preserve at laboratory)

Low-level hexavalent chromium (Method 1636) One 250-mL LDPE (ultraclean), fluoropolymer lined caps 0.45 μm filter (performed in field)

2 mL 50% NaOH per 250 mL sample (performed in field) c

Selenium/arsenic speciation Two 125-mL amber glasses (ultraclean) None for original sample, ≤ 6 E C

Duplicate: HCl to pH <2, ≤ 6 E C

a – Group I includes TSS, TDS, sulfate, and chloride. b – Group II includes ammonia as nitrogen, nitrate/nitrite as nitrogen, TKN, and total phosphorus. c – Method 1636 has a preservation requirement that the low-level hexavalent chromium sample be cooled to ≤ 6 E C; however, EPA did not cool the low-level hexavalent chromium samples due to contamination concerns.a – Preservation of this sample was stopped due to excessive buffering of the sample. The pH of the sample was not changing with the addition of the ammonium sulfate buff er solution; therefore, the preservation was stopped to prevent the sample from being diluted by the preservative.



### 3-20 Table 3-6. Sample Preservation Summary, Widows Creek

Sampling

Point

Number Analysis Date and Time Chemical Initial pH Final pH Amount Added

70520 Group II V1 9/11/07 H 2 SO 4 7 2 255 drops

70520 Group II V2 9/11/07 H 2 SO 4 7 2 255 drops

70520 HEM/SGT-HEM G1 V1 9/11/07 0735 H 2 SO 4 7 2 225 drops

70520 HEM/SGT-HEM G1 V2 9/11/07 0735 H 2 SO 4 7 2 225 drops

70520 HEM/SGT-HEM G2 V1 9/11/07 1330 H 2 SO 4 7 2 130 drops

70520 HEM/SGT-HEM G2 V2 9/11/07 1330 H 2 SO 4 7 2 130 drops

70520 Routine Hexavalent

Chromium 9/11/07 Ammonium

Sulfate Buffer 7 9.5 80 drops

70520 Arsenic/Selenium Speciation (Duplicate) 9/11/07 1500 HCl 7 2 70 drops

70521 Group II V1 9/11/07 1130 H 2 SO 4 8 2 25 drops

70521 Group II V2 9/11/07 1130 H 2 SO 4 8 2 25 drops

70521 Group II MS/MSD V1 9/11/07 H 2 SO 4 8 2 25 drops

70521 Group II MS/MSD V2 9/11/07 H 2 SO 4 8 2 25 drops

70521 HEM/SGT-HEM V1 9/11/07 1015 H 2 SO 4 8 2 25 drops

70521 HEM/SGT-HEM V2 9/11/07 1015 H 2 SO 4 8 2 25 drops

70521 HEM/SGT-HEM MS/MSD

V1 9/11/07 1015 H 2 SO 4 8 2 25 drops

70521 HEM/SGT-HEM MS/MSD

V2 9/11/07 1015 H 2 SO 4 8 2 25 drops

70521 Routine Hexavalent

Chromium 9/11/07 1030 Ammonium

Sulfate Buffer 7.4 9 250 drops a

70521 Routine Hexavalent

Chromium MS/MSD 9/11/07 1050 Ammonium

Sulfate Buffer 7.4 9 250 drops a

70521 Arsenic/Selenium Speciation (Duplicate) 9/11/07 1120 HCl 7.5 2 25 drops

70522 Group II V1 9/12/07 0900 H 2 SO 4 8 2 20 drops

70522 Group II V2 9/12/07 0900 H 2 SO 4 8 2 20 drops

70522 HEM/SGT-HEM G1 V1 9/11/07 2000 H 2 SO 4 8 2 20 drops

70522 HEM/SGT-HEM G1 V2 9/11/07 2000 H 2 SO 4 8 2 20 drops

70522 HEM/SGT-HEM G2 V1 9/12/07 0730 H 2 SO 4 8 2 15 drops

70522 HEM/SGT-HEM G2 V2 9/12/07 0730 H 2 SO 4 8 2 15 drops

70522 Routine Hexavalent

Chromium 9/12/07 1330 Ammonium

Sulfate Buffer 7.2 9 250 drops a

70522 Arsenic/Selenium Speciation V1 9/12/07 0800 HCl 8 <2 20 drops

70522 Arsenic/Selenium Speciation V2 9/12/07 0800 HCl 8 <2 20 drops

70523 Group II V1 9/12/07 1100 H 2 SO 4 7 2 20 dropsa – Preservation of this sample was stopped due to excessive buffering of the sample. The pH of the sample was not changing with the addition of the ammonium sulfate buff er solution; therefore, the preservation was stopped to prevent the sample from being diluted by the preservative.



### 3-21 Table 3-6. Sample Preservation Summary, Widows Creek

Sampling

Point

Number Analysis Date and Time Chemical Initial pH Final pH Amount Added

70523 Group II V2 9/12/07 1100 H 2 SO 4 7 2 20 drops

70523 HEM/SGT-HEM V1 9/12/07 1100 H 2 SO 4 7 2 25 drops

70523 HEM/SGT-HEM V2 9/12/07 1100 H 2 SO 4 7 2 25 drops

70523 Routine Hexavalent

Chromium 9/12/07 1120 Ammonium

Sulfate Buffer 6.5 9 250 drops a

70523 Arsenic/Selenium Speciation 9/12/07 1100 HCl 7 2 10 drops

70524 Group II V1 9/11/07 H 2 SO 4 8 2 25 drops

70524 Group II V2 9/11/07 H 2 SO 4 8 2 25 drops

70524 Routine Hexavalent

Chromium 9/11/07 1050 Ammonium

Sulfate Buffer 7.4 9 250 drops a

70525 Routine Hexavalent

Chromium 9/11/07 Ammonium

Sulfate Buffer 7 9 80 drops

70526 Routine Hexavalent

Chromium 9/11/07 1030 Ammonium

Sulfate Buffer 6 9.5 250 drops

### 3-22a – Coal usage was calculated as the average amount of the coalused each day from September 10,2007 through September 12, 2007.b – Electricity production was calculated as the average MW generated each day from September 10, 2007 through September 12, 2007.c – Unit 1 was derated when EPA arrived at the plant as a result of a feedwater heater drain line failure, but was brought backup on 9/11/07 at 10:00 PM.d – Unit 8 was generating approximately 450 MW before it was shut down. Unit 8 was shut down at approximately 6:00 AM on 9/11/07 and remained down forthe rest of the sampling episode.HS ESP – Hot-side electrostatic precipitator.CS ESP – Cold-side electrostatic precipitator.BH – Baghouse.Table 3-7. Generating Unit Operating Characteristics during Sample Collection, Widows CreekUnitIDBoiler TypeCoal TypeCoalUsagea(tpd)Source of Coal (CoalRegion and/or State)Capacity(MW)ElectricityProduction (orPercentCapacity)bSCR (No,On, Off)ParticulateControl System(HS/CS ESP, orBH)Wet FGDSystem(Yes/No)1cWall-fired Low-SulfurEasternBituminous379 20 Mile & Bowie minesin CO115 65.5 (57%)cNo ESP No2 Wall-fired Low-SulfurEasternBituminous1,467 20 Mile & Bowie minesin CO115 96 (83%) No ESP No3 Wall-fired Low-SulfurEasternBituminous1,253 20 Mile & Bowie minesin CO115 81 (70%) No ESP No4 Wall-fired Low-SulfurEasternBituminous1,437 20 Mile & Bowie minesin CO115 111 (97%) No ESP No5 Wall-fired Low-SulfurEasternBituminous982 20 Mile & Bowie minesin CO115 92 (80%) No ESP No6 Wall-fired Low-SulfurEasternBituminous1,308 20 Mile & Bowie minesin CO115 106 (92%) No ESP No7 TangentiallyFiredHigh-SulfurEasternBituminous4,439 Warrior, Pattiki, &Galitin mines in theIllinois Basin480 439 (91%) On ESP & FGD Yes8dTangentiallyFiredHigh-SulfurEasternBituminous2,044 Warrior, Pattiki, &Galitin mines in theIllinois Basin470 450d(96%) On FGD Yes

### 3-23Table 3-8. FGD Scrubber System Operating Characteristics, Widows CreekUnit IDType ofScrubberSorbentAdditives (DBA,Formic Acid, etc.)FGD Make-upWater SourceSO2RemovalPercentageForced Oxidation(Yes/No)Percent Solidsin SlurryType of SolidsSeparation7 Spray Limestone NA Intake 85-90% Yes 15 % Settling ponds8aSpray/FountainLimestone NA Intake 94-96% Yes 15 % Settling pondsa – Unit 8 was shut down at 6AM on 9/11/07 and remained down while samples were collected. As a result, the FGD influent that was collected was likely adilute sample, as Unit 8’s absorber tanks continued to be purged to the FGD pond during sampling.NA – Not applicable.

### 3-24 Table 3-9. FGD Pond System Operatin g Characteristics, Widows Creek

FGD Blowdown Information

Scrubber slurry flow rate 1,170 gpm a

Scrubber slurry duration Continuous

Scrubber slurry percent solids 15%

Dewatering cycle frequency NA

Time since last cycle NA

Percent filtrate recycled back to scrubber NA

Scrubber purge flow rate Same as scrubber slurry flow rate

Scrubber purge duration Same as scrubber slurry duration

Amount of solids generated 130 tph b

FGD Pond Information

pH control system NA

Chemicals added to pond system NA

Pond size 146 acres

Pond size 32,200,000 gallons

Pond retention time 6.9 days

Frequency of pond dredging As needed

Sections of pond Two upper ponds and one lower pond

Final discharge structure type Curtain

Effluent flow rate 3.705 MGD

Frequency of effluent discharge Continuous

a – Estimated flow rate based on information provided by Widows Creek. Under normal conditions, the flow rate is roughly 1,150 gpm per unit (2,300 gpm total). Because Unit 8 was derated, th e plant had reduced flow to the FGD pond system. b – Unit 7 produces 60 tons/hour and Unit 8 produces 70 tons/hour. NA – Not applicable.

### 3-25Table 3-10. Ash System Operating Characteristics During Sample Collection, Widows CreekUnitIDFly AshGeneration(tph)Fly AshSluice WaterFlow Rate(gph)Source ofFly AshSluiceWaterSluice CycleDuration andFrequencyContinuousSluicing(Yes/No)Bottom AshGeneration(tph)Bottom AshSluice WaterFlow Rate(gph)Source ofBottomAsh SluiceWaterSluice CycleDuration andFrequencyContinuousSluicing(Yes/No)1 1.39≈28,000 Intake Approx. 1 hr1x every 2 hrsNo 0.35≈56,000 Intake Approx. 1 hr1x every 12-hrshiftNo2 5.38≈28,000 Intake Approx. 1 hr1x every 2 hrsNo 1.34≈56,000 Intake Approx. 1 hr1x every 12-hrshiftNo3 4.59≈28,000 Intake Approx. 1 hr1x every 2 hrsNo 1.15≈56,000 Intake Approx. 1 hr1x every 12-hrshiftNo4 5.27≈28,000 Intake Approx. 1 hr1x every 2 hrsNo 1.32≈56,000 Intake Approx. 1 hr1x every 12-hrshiftNo5 3.60≈28,000 Intake Approx. 1 hr1x every 2 hrsNo 0.90≈56,000 Intake Approx. 1 hr1x every 12-hrshiftNo6 4.80≈28,000 Intake Approx. 1 h1x every 2 hrsNo 1.20≈56,000 Intake Approx. 1 hr1x every 12-hrshiftNo7 16.65≈180,000 Intake Approx. 30min/cycle,continuouslyYes 5.55≈180,000 Intake Approx. 30min 1x every 4hrsNo8 7.67 N/A N/A N/A N/A 2.56≈180,000 Intake Approx. 30min 1x every 4hrsNoN/A – Not applicable.

### 3-26 Table 3-11. Ash Pond System Operatin g Characteristics, Widows Creek

Ash Sluice Information

Total influent flow rate Unknown; the plant does not measure the influent flow rate to ash pond.

Influent duration Continuous

Influent percent solids Specific values for the combined influent are unavailable; typically fly ash sluice is approximately 7-10 percent solids and typical bottom ash sluice is approximately 2-3 percent solids.

Amount of solids generated Approximately 450,000 tons of fly ash is generated each year, but only 285,000 tons are sluiced to the ash pond (Unit 8 fly is removed in scrubber and transferred to the FGD pond system). Approximately 110,000 tons of bottom ash is generated each year and sluiced to the ash pond.

Ash Pond Information

pH control system CO 2 injection in middle stilling pond

Chemicals added to pond system CO 2 Drainage area routed to pond system 253 acres

Pond size 340 acres

Pond size 191,000,000 gallons

Pond retention time 6.6 days

Frequency of pond dredging Varies; as needed to maintain pond capacity.

Sections of pond Main pond, middle stilling pond, pumping basin

Final discharge structure type Either pumped to Units 7&8 intake, FGD makeup or sometimes discharged directly through a corrugated pipe to a channel that flows to the Tennessee River (which is very infrequent).

Effluent flow rate 29.9 MGD

Frequency of effluent discharge Continuous

### 4-1 4. L ABORATORY 

### A NALYTICAL 

### R ESULTS AND 

### D ISCUSSION



### This section summarizes and di scusses the analytical data co llected during this sampling episode. Section 4.1 discusses the methods used by the laboratories for th e biphasic analysis of SP-1 and SP-3, and presents the results of the analyses. Section 4.2 presents the laboratory analytical data for the influent to and effluent from the FGD pond system. Section 4.3 presents the laboratory analytical data for the influent to and effluent from the ash pond system.

Appendix A provides all analytical results for all samples collected at Widows Creek, including all qualified results a nd all results that were measur ed above the method detection limit, but below the reporting limit (i.e., J-values). Appendix B presents the analytical results in a

format similar to that used for Sections 4.2 and 4.3, but with the J-values shown (J-values are not included in the tables presen ted in Sections 4.2 and 4.3).

4.1 Measured and Calculated Results for FGD Pond and Ash Pond Influent Samples

The samples of the influent to the FGD wast ewater treatment system were expected to contain significant amounts of r eadily settleable solids, to a large degree consisting of gypsum, unreacted limestone, and fly ash. Because of th is, EPA was concerned that there could be analytical interferences for the metals analyses, since the acid digestion procedures used may not be sufficiently rigorous for samples with high solid s loads. Therefore, EPA directed its contract laboratories to separate the aque ous and solid phases of the samp le prior to conducting certain analyses, where allowed by the analytical method and if necessary to obtain acceptable analytical results. This biphasic approach provides EPA with both measured and calculated pollutant

concentrations for the follo wing phases of the sample:

• 

### Aqueous phase;

• 

### Solid phase; and

• 

### Total sample.

The routine metals laboratory, ProChem Analytic al (ProChem), and the low-level laboratory, Battelle Marine Sciences Laboratory (Battelle), used two different appr oaches for the biphasic analysis because of the different methods used fo r routine versus low-level metals analyses. This section describes the approaches used by each labor atory and presents the results of the analyses.

Routine Metals and Selected Classicals Analyses for FGD Influent

ProChem used EPA Method 200.7 to analyze th e wastewater samples for routine metals, and EPA Method 245.1 to analyze for routine mercury. EPA Method 200.7 states, “Aqueous samples containing total suspended solids ≥ 1% (w/v) should be extracted as a solid type sample.” [4] Because EPA expected the solids c ontent to be greater than one percent, ProChem developed an approach for the analysis of the FGD influent samples that consisted of filtering the solids from the sample and analyzing the solid and aqueous phases separately. To calculate the total sample concentration from the solid and aq ueous phase results, the laboratory also needed to measure the original sample volume, solid phase weight, and filtrate volume. EPA developed the following equation to calcula te the individual metal total concentrations for the sample.

### 4-2 Sample Solid Solid Filtrate Filtrate 

### V ) Wt (C ) V (C ion Concentrat Sample Total × + ×

= (4-1)

where:

C Filtrate 

### = concentration of the analyte in the aqueous phase of the sample;

V Filtrate 

### = volume of the filtrate;

C Solid 

### = concentration of the analyte in the solid phase of the sample;

Wt Solid 

### = weight of the solids in the sample; and

V Sample 

### = volume of the original sample.

ProChem used the same approach for the six cla ssical pollutants that were analyzed as biphasic samples: ammonia as nitrogen, chloride, sulfate, nitrate/nitrite, total Kjeldahl nitrogen (TKN), and total phosphorus.

Table 4-1 presents the results of the bipha sic analysis for the routine total metals, ammonia as nitrogen, nitrate/nitr ite, chloride, sulfate, TKN, and total phosphorus. Only those analytes that were detected at the influent to the FGD pond syst em (at levels above the reporting limits) are included in the table. Results are r ounded to three significan t figures. Appendix Table A-1 presents all the analytical results from the influent to th e FGD pond system (SP-1) sample analysis, including J-values.

Low-Level Metals Analyses for FGD Influent

Battelle used EPA Method 1638 to analyze the wastewater samples for low-level metals, and EPA Method 1631E to analyze for low-le vel mercury. EPA Method 1638 does not contain any language stating how wastewater samples with high solid concentrations should be analyzed; therefore, Battelle developed an approach for th e analysis of the FGD influent samples that minimized potential contamination to the samples. Battelle’s approach consisted of analyzing the

total metals concentration and dissolved metals concentration for each analyte directly from the sample bottles, and calculating the solid phase concentration. By usi ng this approach, the laboratory did not have to perfor m an extra filtration step to determine the individual metals concentrations for the various phases in the samp le. Battelle did not have any problems with the digestion of the solids during the total sample analyses for the Widows Creek FGD influent samples.

To calculate the solid phase concentration from the total and dissolved phase results, Battelle also needed to measure the TSS level in the total metals sample bottle. EPA used the following equation to calculate th e individual metal solid phase c oncentrations for the sample:

TSS Diss Total

Solid 

### C C

- C C = 

### (4-2)

where:

C Solid 

### = concentration of the metal in the solid phase of the sample;

C Total 

### = total concentration of the metal in the sample;

C Diss 

### = concentration of the metal in th e dissolved phase of the sample; and

C TSS 

### = TSS concentration of the sample.

### 4-3 Table 4-2 presents the results of the biphasi c analysis for low-level total metals. Only those analytes that were detect ed at the influent to the FGD pond system (at levels above the reporting limits) are included in the table. Resu lts are rounded to three significant figures. Appendix Table A-1 presents all th e analytical results from the influent to the FGD pond system (SP-1) sample analysis, includi ng results where analytes were measured above the detection level, but below the repor ting limit (i.e., J-values).

Analytical Deviations

During the analysis of the Widows Creek FGD pond influent samples, ProChem did not

measure the filtrate volume for the routine tota l metals samples, which was needed for the calculation of the total sample concentration (see Equation 4-1). To determine the total sample results for the routine metals, EPA calculated the filtrate volume using the original sample volume, solid-phase weight, and the density of th e original sample, which were all measured by the laboratory. Therefore, the routine metals tota l concentrations were ca lculated using Equation 4-1 without making any assumptions.

For the FGD pond influent biphasic classical analyses, ProChem did not measure the original sample volume and the filtrate volume, which were needed for the calculation of the total sample concentration (see Equation 4-1). To determine the total sample results for the routine metals, EPA calculated the original sa mple volume and the filtrate volume using the original sample weight, solid-pha se weight, filtrate weight, a nd the density of the original sample, which were all measured by the laborato ry. Therefore, the classical analytes total concentrations were calculated using E quation 4-1 without making any assumptions.

Ash Pond Influent

Prior to analyzing the ash pond influent samp les, ProChem determined that the sample contained a solids content greater than one per cent solids; therefore, ProChem performed the phase separation prior to the anal ysis of the ash pond influent samples. ProChem used the same procedures as described previously for the FGD influent samples. In addition, the same analytical deviations experienced during the analysis of the FGD pond influent samples, described above, were experien ced during the analysis of th e ash pond influent samples for routine total metals and classical analytes. Table 4-3 presents the results of the biphasic analysis for the routine total metals, ammonia as nitrogen, ch loride, sulfate, nitrate/nitrite, TKN, and total phosphorus for the influent to the ash pond system ( SP-3) samples. Only those analytes that were detected at SP-3 (at levels above the reporting limits) are included in the table. Results are rounded to three significant figures . Appendix Table A-2 presents a ll the analytical results from the influent to the ash pond system (SP- 3) sample analysis, including J-values.

ProChem performed a filtration blank associ ated with the biphasic sample separation process for the FGD influent (SP-1) and the as h pond influent (SP-3) sample analyses. For the blank, ProChem poured blank wate r through the filter used for th e separation and analyzed the filtered blank water for the routine metal analytes . No metals were measured in the filtration blank sample above the report limit, indicati ng that there was no contamination from the filtration process. Appendix Table A-3 presents al l the analytical results from the filtration blank. The filtration blank results apply to both the F GD influent and the ash pond influent samples.

### 4-4 4.2 FGD Pond System

Table 4-4 presents the analytical results of the classical pollutants at the influent to the FGD pond system (SP-1) and the effluent from the FGD pond system (average of SP-2 and SP-5 results). Table 4-5 presents the analytical results of the routine and low-level metals for these same sampling points. Only those analytes that we re detected in one or more samples (at levels above the reporting limits) for th e sampling episode are included in the table. Results are rounded to three significan t digits. If an analyte was measur ed above the method detection limit, but below the report limit, “NQ” is reported followed by the sample-specific report limit in parentheses. If an analyte was not detected in a sample above the method detection limit, “ND” is reported followed by the sample-specific report limit in parentheses. Note that the results presented in Tables 4-4 and 4-5 are not paired results, meaning th at sample collection across the treatment system was not timed to reflect the am ount of time it takes the wastewater to pass from the influent to the effluent point.

Appendix Tables A-1, A-4, and A-5 present all th e analytical results from the influent to the FGD pond system (SP-1), the effluent from the FGD pond system (SP-2), and the duplicate of the effluent from the FGD pond system (SP-5) sample analyses, including J-values. Appendix Table B-1 presents the analytical results for the me tal analytes in a format similar to Table 4-5; however, Table B-1 also includes results where analytes were measured above the detection level, but below the reporting limit (i.e., J-values).

4.3 Ash Pond System

Table 4-6 presents the analytical results of the classical pollutants at the influent to the ash pond system (SP-3) and effluent from the ash pond system (SP-4). Table 4-7 presents the analytical results of the routin e and low-level metals for these same sampling points. Only those analytes that were detected in one or more sa mples (at levels above th e reporting limits) for the sampling episode are included in the table. Result s are rounded to three si gnificant digits. If an analyte was measured above the method detectio n limit, but below the report limit, “NQ” is reported followed by the sample-specific report limit in parentheses. If an analyte was notdetected in a sample above the method detection limit, “ND” is reported followed by the samplespecific report limit in parentheses. Note that th e results presented in Tables 4-6 and 4-7 are not paired results, meaning that sample collection across the treatment system was not timed to

reflect the amount of time it takes the wastewater to pass from the influent to the effluent point.

Appendix Tables A-2 and A-6 present all the an alytical results from the influent to the ash pond system (SP-3) and the effluent from the ash pond system (SP-4) sample analyses, including J-values. Appendix Table B-2 presents the analytical results for the metal analytes in a format similar to Table 4-7; however, Table B- 2 also includes results where analytes were measured above the detection level, but below the reporting limit (i.e., J-values).

### 4-5 Table 4-1. Biphasic Sample Results for Clas sicals and Routine Total Metals Measured Above the Report Limit for the Influent to the FGD Pond Syst em, Widows Creek

Analyte Aqueous Phase Result (mg/L) Solid Phase Result (mg/kg) Calculated Total Sample Result (mg/L)

Classical Pollutants

Ammonia As Nitrogen (NH 3 -N) 0.530 25.2 2.26

Nitrate/Nitrite (NO 3 -N + NO 2 -N) 0.610 6.10 1.00

Total Kjeldahl Nitrogen (TKN) 3.85 267 22.3

Chloride 840 709 832

Sulfate 1,750 149,000 11,900

Total Phosphorus 2.30 E 119 E 10.5

Analyte Aqueous Phase Result (ug/L) Solid Phase Result (mg/kg) Calculated Total Sample Result (ug/L)

Routine Total Metals

Aluminum 12,600 5,110 O 234,000

Antimony NQ (20.0) NQ (2.00) NJ (86.9)

Arsenic 51.9 10.9 523

Barium 168 162 7,200

Beryllium 6.76 0.870 44.3

Boron 27,500 58.9 28,900

Cadmium 14.7 1.73 89.2

Calcium 1,580,000 103,000 5,990,000

Chromium 62.1 30.0 1,360

Copper 60.5 13.7 653

Iron 21,400 6,410 299,000

Lead NQ (50.0) 9.85 436

Magnesium 223,000 2,490 321,000

Manganese 1,710 26.3 2,780

Mercury ND (2.00) 0.610 26.5

Molybdenum 862 11.9 1,340

Nickel 116 8.71 489

Selenium 502 3.96 L 652

Sodium 84,000 538 104,000

Thallium 16.9 ND (1.00) NJ (43.4)

Titanium 103 186 8,180

Vanadium 118 33.8 1,580

Yttrium 11.4 4.74 217

Zinc 395 63.6 3,140

E – Sample analyzed outside holding time. L – Sample result between 5x and 10x blank result. O – OPR %Recovery below contract-specified criteria. ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filtered aqueous and/or the filtered solid analytical results, includin g Jvalues, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculated result is presented in Appendix A with a CJ flag designation. NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appendix A with a J flag designation.

### 4-6 Table 4-2. Biphasic Sample Results for Lo w-Level Total Metals Measured Above the Report Limit for the Influent to the FGD Pond System, Widows Creek

Analyte Dissolved Sample Result (ug/L) Calculated Solid Phase Result (mg/kg) Total Sample Result (ug/L)

Low-level Total Metals

Antimony 8.90 1.25 51.8

Arsenic 18.0 17.4 617

Cadmium 3.16 2.41 86.0

Chromium ND (16.0) 40.2 1,380

Copper NQ (4.00) 24.0 826

Lead ND (1.00) 15.9 545

Mercury 0.0761 0.640 24.7

Nickel 29.6 17.6 634

Selenium 325 9.50 651

Thallium 22.5 2.08 93.8

Zinc ND (10.0) 78.6 2,720

ND – Not detected (number in parenthesis is the report limit). NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appendix A with a J flag designation.

### 4-7 Table 4-3. Biphasic Sample Results for Clas sicals and Routine Total Metals Measured Above the Report Limit for the Influent to the Ash Pond System, Widows Creek

Analyte Aqueous Phase Result (mg/L) Solid Phase Result (mg/kg) Calculated Total Sample Result (mg/L)

Classical Pollutants

Ammonia As Nitrogen (NH 3 -N) 0.180 14.3 0.400

Nitrate/Nitrite (NO 3 -N + NO 2 -N) 0.140 13.8 0.360

Total Kjeldahl Nitrogen (TKN) 2.91 286 7.41

Chloride 16.0 354 21.4

Sulfate 49.0 621 58.1

Total Phosphorus 3.12 E 854 E 16.6

Analyte Aqueous Phase Result (ug/L) Solid Phase Result (mg/kg) Calculated Total Sample Result (ug/L)

Routine Total Metals

Aluminum 44,300 2,700 O 94,800

Antimony NQ (20.0) ND (2.00) NJ (38.0)

Arsenic 89.5 2.29 131

Barium 967 270 6,080

Beryllium 8.64 NQ (0.500) 11.3

Boron 3,560 44.0 4,330

Cadmium NQ (5.00) NQ (0.500) 9.93

Calcium 89,800 807 103,000

Chromium 29.5 4.09 107

Copper 96.5 4.89 188

Iron 11,000 3,680 80,700

Lead 57.9 7.95 208

Magnesium 17,500 451 25,700

Manganese 144 10.3 337

Mercury ND (0.200) 0.140 2.66

Molybdenum 41.0 1.33 65.5

Nickel NQ (50.0) NQ (5.00) NJ (95.0)

Selenium 28.0 ND (0.500) L 27.5

Sodium 19,300 645 31,200

Thallium ND (10.0) ND (1.00) ND (19.0)

Titanium 608 345 7,150

Vanadium 222 6.77 346

Yttrium 83.2 2.70 133

Zinc 157 33.2 785

E – Sample analyzed outside holding time. L – Sample result between 5x and 10x blank result. O – OPR %Recovery below contract-specified criteria. ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filtered aqueous and/or the filtered solid analytical results, includin g Jvalues, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculated result is presented in Appendix A with a CJ flag designation. NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appendix A with a J flag designation.

### 4-8 Table 4-4. Classical Pollutants Measured Above the Report Limit for the FGD Pond System, Widows Creek

Analyte Method Unit FGD Pond Influent (SP-1) FGD Pond Effluent (SP-2/SP-5) a

Classical Pollutants

Ammonia As Nitrogen (NH 3 -N) 4500-NH 3 F MG/L 2.26 0.220

Nitrate/Nitrite (NO 3 -N + NO 2 -N) 4500NO 3 H MG/L 1.00 0.0945

Total Kjeldahl Nitrogen (T KN) 4500-N,C MG/L 22.3 2.51

Biochemical Oxygen Demand (BOD) 5210B MG/L 172 <10.0

Chloride 4500-CL-C MG/L 832 1,120

Hexane Extractable Material (HEM) 1664A MG/L 22.0 ND (5.00)

Silica Gel Treated HEM (SGTHEM) 1664A MG/L 6.00 E NA

Sulfate D516-90 MG/L 11,900 2,060

Total Dissolved Solids (TDS) 2540 C MG/L 4,740 5,830

Total Phosphorus 365.3 MG/L 10.5 0.0115 E

Total Suspended Solids (TSS) 2540 D MG/L 25,300 E 8.00 E

a – The FGD effluent results represent the average of the FGD effluent and the duplicate of the FGD effluent analytical measurements. < – Average result includes at least one non-detect value. (Calculation uses detection limit for non-detected results). E – Sample analyzed outside holding time. NA – Not analyzed. ND – Not detected (number in parenthesis is the report limit). Note: Results shown are not pair ed samples. See Section 4.2.a – The FGD effluent results represent the average of the FGD effluent and the duplicate of the FGD effluent analytical measurements. R – MS/MSD % Recovery outsid e method acceptance criteria. L – Sample result between 5x and 10x blank result. NA – Not analyzed. ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filt ered aqueous and/or the filtered solid analytical results, including J-values, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculate d result is presented in Appendix A with a CJ flag designation. NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appe ndix A with a J flag designation. A “NQ” for the average

FGD effluent indicates that the original FGD effluent and/or the dup licate of the FGD effluent is a J-value. The analytical result for the original FGD effluent and/or the duplicate of the FGD effluent is presented in Appendix A with a J flag designation. Note: Results shown are not pair ed samples. See Section 4.2.



### 4-9 Table 4-5. Metals Measured Above the Report Limit for the FGD Pond System, Widows

Creek

FGD Pond Influent (SP-1) FGD Pond Effluent (SP-2/SP-5) a Analyte Method Unit Total Dissolved Total Dissolved

Routine Metals

Aluminum 200.7 UG/L 234,000 86.6 111 NQ (50.0)

Antimony 200.7 UG/L NJ (86.9) NQ (20.0) NQ (20.0) NQ (20.0)

Arsenic 200.7 UG/L 523 13.9 49.5 46.7

Barium 200.7 UG/L 7,200 257 179 191

Beryllium 200.7 UG/L 44.3 NQ (5.00) NQ (5.00) NQ (5.00)

Boron 200.7 UG/L 28,900 24,100 31,500 29,200

Cadmium 200.7 UG/L 89.2 NQ (5.00) NQ (5.00) NQ (5.00)

Calcium 200.7 UG/L 5,990,000 849,000 987,000 932,000

Chromium 200.7 UG/L 1,360 18.7 NQ (10.0) NQ (10.0)

Hexavalent Chromium D1687-92 UG/L NA ND (2.00) NA ND (2.00)

Copper 200.7 UG/L 653 NQ (10.0) NQ (10.0) NQ (10.0)

Iron 200.7 UG/L 299,000 NQ (100) NQ (100) NQ (100)

Lead 200.7 UG/L 436 ND (50.0) ND (50.0) ND (50.0)

Magnesium 200.7 UG/L 321,000 176,000 189,000 184,000

Manganese 200.7 UG/L 2,780 583 623 543 R

Mercury 245.1 UG/L 26.5 ND (2.00) ND (2.00) ND (2.00)

Molybdenum 200.7 UG/L 1,340 876 1,500 1,470

Nickel 200.7 UG/L 489 NQ (50.0) NQ (50.0) NQ (50.0)

Selenium 200.7 UG/L 652 366 236 226

Sodium 200.7 UG/L 104,000 76,700 69,500 66,200

Thallium 200.7 UG/L NJ (43.4) 14.3 NQ (10.0) NQ (10.0)

Titanium 200.7 UG/L 8,180 ND (10.0) NQ (10.0) ND (10.0)

Vanadium 200.7 UG/L 1,580 NQ (20.0) 42.1 40.0

Yttrium 200.7 UG/L 217 ND (5.00) ND (5.00) ND (5.00)

Zinc 200.7 UG/L 3,140 ND (10.0) NQ (10.0) ND (10.0)a – The FGD effluent results represent the average of the FGD effluent and the duplicate of the FGD effluent analytical measurements. R – MS/MSD % Recovery outsid e method acceptance criteria. L – Sample result between 5x and 10x blank result. NA – Not analyzed. ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filt ered aqueous and/or the filtered solid analytical results, including J-values, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculate d result is presented in Appendix A with a CJ flag designation. NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appe ndix A with a J flag designation. A “NQ” for the average

FGD effluent indicates that the original FGD effluent and/or the dup licate of the FGD effluent is a J-value. The analytical result for the original FGD effluent and/or the duplicate of the FGD effluent is presented in Appendix A with a J flag designation. Note: Results shown are not pair ed samples. See Section 4.2.



### 4-10 Table 4-5. Metals Measured Above the Report Limit for the FGD Pond System, Widows

Creek

FGD Pond Influent (SP-1) FGD Pond Effluent (SP-2/SP-5) a Analyte Method Unit Total Dissolved Total Dissolved

Low-Level Metals

Antimony 1638 UG/L 51.8 8.90 11.8 11.9

Arsenic 1638 UG/L 617 18.0 47.6 46.5

Cadmium 1638 UG/L 86.0 3.16 3.73 3.74

Chromium 1638 UG/L 1,380 ND (16.0) NQ (16.0) NQ (16.0)

Hexavalent Chromium 1636 UG/L NA NA NA 3.20

Copper 1638 UG/L 826 NQ (4.00) NQ (4.00) NQ (4.00)

Lead 1638 UG/L 545 ND (1.00) NQ (1.00) ND (1.00)

Mercury 1631E UG/L 24.7 0.0761 0.0438 0.0107

Nickel 1638 UG/L 634 29.6 36.2 33.3 L

Selenium 1638 UG/L 651 325 208 293

Thallium 1638 UG/L 93.8 22.5 11.1 11.0

Zinc 1638 UG/L 2,720 ND (10.0) ND (10.0) ND (10.0)

### 4-11 Table 4-6. Classical Pollutants Measured Above the Report Limit for the Ash Pond System, Widows Creek

Analyte Method Unit Ash Pond Influent (SP-3) Ash Pond Effluent (SP-4)

Classical Pollutants

Ammonia As Nitrogen (NH3-N) 4500-NH 3 F MG/L 0.400 0.160

Nitrate/Nitrite (NO3 -N + NO2-N) 4500NO 3 H MG/L 0.360 0.230

Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 7.41 3.39

Biochemical Oxygen Demand (BOD) 5210B MG/L 53.0 4.00

Chloride 4500-CL-C MG/L 21.4 20.0

Hexane Extractable Material (HEM) 1664A MG/L ND (5.00) 6.00

Silica Gel Treated HEM (SGT-HEM) 1664A MG/L NA ND (5.00)

Sulfate D516-90 MG/L 58.1 80.7

Total Dissolved Solids (TDS) 2540 C MG/L 224 281

Total Phosphorus 365.3 MG/L 16.6 0.250 E

Total Suspended Solids (TSS) 2540 D MG/L 9,190 E 12.0 E

E – Sample analyzed outside holding time. NA – Not analyzed. ND – Not detected (number in parenthesis is the report limit). Note: Results shown are not pair ed samples. See Section 4.3.R – MS/MSD % Recovery outsid e method acceptance criteria. L – Sample result between 5x and 10x blank result. NA – Not analyzed. ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filt ered aqueous and/or the filtered solid analytical results, including J-values, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculate d result is presented in Appendix A with a CJ flag designation. NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appendix A with a J flag designation. Note: Results shown are not pair ed samples. See Section 4.3.



### 4-12 Table 4-7. Metals Measured Above the Report Limit for the Ash Pond System, Widows

Creek

Ash Pond Influent (SP-3) Ash Pond Effluent (SP-4) Analyte Method Unit Total Dissolved Total Dissolved

Routine Metals

Aluminum 200.7 UG/L 94,800 663 1,070 357

Antimony 200.7 UG/L NJ (38.0) NQ (20.0) NQ (20.0) NQ (20.0)

Arsenic 200.7 UG/L 131 46.0 38.2 30.1

Barium 200.7 UG/L 6,080 178 227 206

Beryllium 200.7 UG/L 11.3 ND (5.00) ND (5.00) ND (5.00)

Boron 200.7 UG/L 4,330 2,150 2,210 2,200

Cadmium 200.7 UG/L 9.93 ND (5.00) ND (5.00) ND (5.00)

Calcium 200.7 UG/L 103,000 40,300 58,500 55,400

Chromium 200.7 UG/L 107 NQ (10.0) 13.5 11.9

Hexavalent

Chromium D1687-92 UG/L NA ND (2.00) NA 12.0

Copper 200.7 UG/L 188 NQ (10.0) NQ (10.0) NQ (10.0)

Iron 200.7 UG/L 80,700 ND (100) 144 ND (100)

Lead 200.7 UG/L 208 ND (50.0) ND (50.0) ND (50.0)

Magnesium 200.7 UG/L 25,700 7,110 6,680 6,430

Manganese 200.7 UG/L 337 NQ (15.0) NQ (15.0) NQ (15.0)

Mercury 245.1 UG/L 2.66 ND (0.200) ND (0.200) ND (0.200)

Molybdenum 200.7 UG/L 65.5 50.1 143 136

Nickel 200.7 UG/L NJ (95.0) ND (50.0) ND (50.0) ND (50.0)

Selenium 200.7 UG/L 27.5 26.8 16.2 15.3

Sodium 200.7 UG/L 31,200 13,400 21,300 20,000

Thallium 200.7 UG/L ND (19.0) ND (10.0) NQ (10.0) ND (10.0)

Titanium 200.7 UG/L 7,150 ND (10.0) 14.5 ND (10.0)

Vanadium 200.7 UG/L 346 66.8 68.5 64.7

Yttrium 200.7 UG/L 133 ND (5.00) ND (5.00) ND (5.00)

Zinc 200.7 UG/L 785 ND (10.0) NQ (10.0) ND (10.0)

Low-Level Metals

Antimony 1638 UG/L 13.1 L 8.54 4.39 4.45R – MS/MSD % Recovery outsid e method acceptance criteria. L – Sample result between 5x and 10x blank result. NA – Not analyzed. ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filt ered aqueous and/or the filtered solid analytical results, including J-values, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculate d result is presented in Appendix A with a CJ flag designation. NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appendix A with a J flag designation. Note: Results shown are not pair ed samples. See Section 4.3.



### 4-13 Table 4-7. Metals Measured Above the Report Limit for the Ash Pond System, Widows

Creek

Ash Pond Influent (SP-3) Ash Pond Effluent (SP-4) Analyte Method Unit Total Dissolved Total Dissolved

Arsenic 1638 UG/L 88.9 49.5 34.9 29.0

Cadmium 1638 UG/L NQ (20.0) NQ (2.00) NQ (0.500) NQ (0.500)

Chromium 1638 UG/L ND (160) ND (16.0) 13.5 L 12.6 L

Hexavalent

Chromium 1636 UG/L NA NA NA 14.7

Copper 1638 UG/L 114 NQ (4.00) 1.49 NQ (1.00)

Lead 1638 UG/L 104 ND (1.00) 0.490 ND (0.250)

Mercury 1631E UG/L 1.02 NQ (0.000500) 0.00157 NQ (0.000500)

Nickel 1638 UG/L NQ (200) ND (20.0) NQ (5.00) NQ (5.00)

Selenium 1638 UG/L ND (200) ND (100) 17.1 15.6

Thallium 1638 UG/L NQ (4.00) ND (0.400) 1.46 1.49

Zinc 1638 UG/L 198 ND (10.0) NQ (2.50) ND (2.50)

### 5-1 5. D ATA 

### Q UALITY



### QA/QC procedures applicable to the Widows Creek sampling episode are outlined in the Quality Assurance Project Plan for the Steam Electric Detailed Study (QAPP) [3]. This section describes the QC procedures used to assess th e precision and accuracy of the analytical data presented in Section 4 and Appendices A and B. QC practices used for this sampling episode include the analysis of matrix spikes, blanks , duplicate samples, and QC standard checks.

5.1 Analytical Quality Control

EPA contracted directly with analytical labor atories for the analysis of samples collected during this episode. EPA’s Sample Control Center (SCC) verified that the performances of the laboratories selected by EPA wa s acceptable by conducting QC checks of the analytical data as specified by the SCC’s Quality Assurance Project Plan dated 15 February 2008. SCC data review chemists prepared written data review narratives describing any qualifications of the analytical data from this episode. The data review narratives are included in Appendix C.

5.2 Field Quality Control

This section discusses the bottle blanks, equipment bla nks, field blanks, and field duplicate sample results. Section 3.8 of the Sa mpling Plan discusses field QC specifications. Tables presented in this section include results for only certain analytes (e.g., only those detected in the respective field QC sample or those de tected during the sampling episode). Appendix A contains the results for all analyt es, both detected and nondetected.

5.2.1 Bottle Blanks

EPA collects bottle blanks to evaluate possi ble contamination from the sample collection bottles. Bottle blanks were collected and analyzedfor low-level metals by the supplier of the precleaned bottles, Albion Environmental.

Albion Environmental collected the bottle blanks for the low-level metals and low-level hexavalent chromium samples bottles (250 mL LDPE), and the speciation sample bottles (125 mL amber glass bottles) by filling the pre-cleaned bottle to the neck with ASTM Type 1 water, preserving the sample with nitric acid to a pH <2, and allowing the sample to sit for at least 24

hours. Albion Environmental then anal yzed the samples using EPA Method 1638.

Albion Environmental collected the bottle blan ks for the 4-liter blank water bottles by filling the pre-cleaned bottle with ASTM Type 1 water and allowing it to soak for approximately 24 hours. Albion Environmental then poured a repr esentative aliquot into a pre-cleaned LDPE sample bottle, preserved the sample with nitric ac id to a pH <2, and allowed the sample to sit for

at least 24 hours. Albion E nvironmental then analyzed th e samples using EPA Method 1638.

Albion Environmental collected the bottle blanks for the low-level mercury sample bottles (250 flint glass bottles a nd 1-L borosilicate glass bottles) by filling the pre-cleaned bottle to the neck with ASTM Type 1 water, preservi ng the sample with bromine monochloride, and allowing the sample to sit for at least 24 hours. Albion Environmental then analyzed the samples using EPA Method 1631E.

### 5-2 Albion Environmental collected the bottle bl ank for the 10-liter and 20-liter composite containers by filling the containers with appr oximately two liters of ASTM Type 1 water and allowing it to soak for approximately 24 hours. During this period, Albion Environmental shook the container periodically and changed its orienta tion to expose all surfa ces of the container to the ASTM Type 1 water. Albion Environmental then shook the 10-liter an d 20-liter containers and poured a representative sample into a pre-cl eaned sample bottle (a LDPE bottle for low-level metals and a glass bottle for low-level mercury) . The blank samples were then preserved and analyzed according to the an alytical methods (i.e., EPA Me thod 1638 or 1631E), as described above for the other bottle blank samples.

No metals were detected in the bottle blank, indicating th at there was no contamination from the sample containers. Appendix Table A-7 pr esents all of the analy tical results from the bottle blank and equipment blank analyses for al l of the equipment used for the collection of low-level samples.

5.2.2 Equipment Blanks

EPA collects equipment blanks to evaluate possible contamination from the equipment used for sample collection. EPA did not collect specific equipment blanks for this sampling program; however, the field blanks as collected (as described in Section 5.2.3) include the sampling equipment. In addition, Albion Enviro nmental collected and analyzed equipment blanks for low-level metals for each type of pre-cleaned equipment supplied for the episode.

Albion Environmental collected the equipm ent blanks for the capsule filters and fabricated tubing sets by pumping approximate ly 500 mL of ASTM T ype 1 water through the pre-cleaned filter or tubing set and discarding th e water. Albion Environmental then pumped additional water through the pre-cl eaned filter or tubing set into a pre-cleaned bottle (a LDPE bottle for low-level metals and a glass bottle fo r low-level mercury). The blank samples were then preserved and analyzed according to the analytical methods (EPA Method 1638 or 1631E),

as described in Section 5.2.1 for the bottle blank samples. For the fabricated tubing sets, Albion Environmental collected and analyzed equipmen t blanks for the individual components of the tubing sets, the assembled tubing sets, or both.

During the analysis of the equipment blanks , Albion Environmental detected barium at 0.490 ug/L and 0.476 ug/L in 2 of the 14 pieces of #73 silicone tubing that were analyzed from the various cleaning batches used to assemble th e tubing sets. Barium was not detected above the report limit in the equipment blanks for the ot her 12 analyses. In addition, barium was not detected in any of the field blank samples (a bove the report limit), as described in Section 5.2.3. Finally, barium was measured at a concentra tion greater than 300 times the equipment blank result at all of the sampling points for both th e total and dissolved phases. Therefore, the potential contamination from the sampling equi pment did not significantly affect the sampling

results.

No other metals were detected in the equi pment blanks, indicating that there was no other contamination from the sample equipment. Appe ndix Table A-7 presents all of the analytical results from the bottle blank and equipment blank analyses for all of the equipment used for the collection of low-level samples. EPA assumed th e barium equipment blank concentration to be

### 5-3 0.490 ug/L for all tubing sets containing #73 silic one tubing because the tubing set may have been fabricated using #73 silicone from the cleani ng batch that had a detec tion for barium at that

concentration.

5.2.3 Field Blanks

The sampling team collected field blanks (SP-6, SP-7, SP-8, and SP-9) to evaluate possible contamination caused by sampling equi pment, sampling equipment decontamination procedures, sample collection procedures, or at mospheric contamination. EPA analyzed the field blank samples for the low-level and routine meta ls analyses, including both total and dissolved

metals 1



### .

The low-level and routine total metals field blank samples for the influent to the FGD pond system (SP-6) and the influent to the ash pond system (SP-8) were collected by pumping ASTM Type 1 water through the composite tubi ng consisting of 25 fe et of Teflon® tubing attached to a length of silicone tubing. Th e container holding the ASTM Type 1 water was placed in a large plastic bag and the end of th e Teflon® tubing was placed directly into the container. The large plastic bag was closed o ff as quickly as possible to minimize potential atmospheric deposition. The sample bottles were placed in a “cleanbox” and the ASTM Type 1 water was pumped through the tubing and poured in to the sample bottles. EPA collected the total metals field blank samples as “multipour” split samples with Widows Creek’s representative, using the same procedure discussed in the sample collection desc ription (Section 3.1).

The low-level and routine dissolved metals field blank samples for the influent to the FGD pond system (SP-6) and the influent from the ash pond system (SP-8) were collected by pumping ASTM Type 1 water through the pump-off tubing used for the dissolved metals sample collection and a capsule filter. The container holding the ASTM Type 1 water was placed in a large plastic bag and the tubing was placed directly into the container. The large plastic bag was closed off as quickly as possible to minimi ze potential atmospheric deposition. The sample bottles were placed in a “cleanbox” and the ASTM Type 1 water was pumped through the tubing, capsule filter, and a “Y” splitter, and pou red into the sample bottles. EPA collected the dissolved metals field blank samples as “true” split samples with Widow Creek’s representative, using the same procedure discussed in the sa mple collection descri ption (Section 3.1).

The low-level and routine total metals field blank samples for the effluent from the FGD pond system (SP-7) and the effluent from the as h pond system (SP-9) were collected by pumping ASTM Type 1 water through the tubing used for the sample collection. The container holding the ASTM Type 1 water was placed in a large plastic bag and the tubing was placed directly into the container. The large plastic bag was closed o ff as quickly as possible to minimize potential atmospheric deposition. The sample bottles were placed in a “cleanbox” and the ASTM Type 1

1 EPA did not collect a low-level dissolved mercury field blan k sample in the field because the sample filtration was performed at the laboratory to minimize potential mercury contamination. The laboratory performed a filtration blank prior to filtering the sample, which is assessed as th e field blank for the low-level dissolved mercury sample. Mercury was detected at a concentration of 0.000245 ug/L in the filtration blank performed for the first day of samples, which includes the influent to the FGD pond system, the effluent from the FGD pond system, and the duplicate of the effluent from the FGD pond system; however, this concentration is below the report limit of 0.0005 ug/L. Therefore, this sample result is flagged as a J-value. Mercury was not detected above the method detection limit (0.000188 ug/L) in the filtration blank performed for th e second day of samples, which includes the influent to the ash pond system and the effluent from the ash pond system.

### 5-4 water was pumped through the tubing and “Y” split ter, and poured into the sample bottles. The

low-level and routine dissolved metals field bl ank samples for the effluent from the FGD pond system (SP-7) and the effluent from the ash pond system (SP-9) were collected by attaching a capsule filter inline with the sample tubing configuration and pumpi ng ASTM Type 1 water through the tubing, capsule filter, a nd “Y” splitter, and into the sa mple bottles. EPA collected all analytes for the effluent samp le field blanks as “true” spl it samples with Widows Creek’s representative, using the same procedure disc ussed in the sample collection description (Section 3.1).

No metals were detected in the field bl ank samples above the reporting limit, indicating that there was no contamination from the samp le collection procedures. Appendix Tables A-8 through A-11 present all the analytical results for the field blanks from the influent to the FGD pond system (SP-6), effluent from the FGD pond system (SP-7), in fluent to the ash pond system (SP-8), and effluent from the ash pond system (SP-9) sample analyses, including all qualified

results and all results that were measured a bove the method detection limit, but below the reporting limit (i.e., J-values).

5.2.4 Field Duplicates

The sampling team collected field duplicat e samples to assess the sampling measurement precision for the episode. Field dupl icate samples are separate samp les collected from the same location as the original sample. The duplicate is filled immediately after the original sample, and is stored and analyzed independently. The re lative percent difference (RPD) between the two sample results is examined to determine the precision of the data. EPA used the following equation to calculate the RPD for the duplicate sample results.

100

2 D S D S (%) RPD × ⎟ ⎠ ⎞ ⎜ ⎝ ⎛ + −

= 

### (5-1)

where: S = concentration of the analyte from original sample analysis; D = concentration of the analyte from the duplicate sample analysis; and RPD = relative percent difference between the original and duplicate sample

result.

During this sampling episode, duplicate sa mples (SP-5) for all analytes (except HEM/SGT-HEM) were collected from the efflue nt from the FGD pond syst em (SP-2). Table 5-1 presents analytical results and the RPD for SP-2 and SP-5 and includes anal ytical results for only those analytes that were detected in one or more samples for the sampling episode. Results are rounded to three significant dig its. Appendix Tables A-4 and A- 5 present all the analytical results for the effluent from the FGD pond system (SP-2) and the duplicate of the effluent from the FGD pond system (SP-5) sample analyses, incl uding all qualified results and all results that were measured above the method detection limit, but below the reporting limit (i.e., J-values).

### 5-5< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.R – MS/MSD % Recovery outside method acceptance criteria.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, Widows CreekAnalyteOriginal FGD EffluentConcentration (SP-2)Duplicate FGD EffluentConcentration (SP-5)Average ResultRelative PercentDifference (%)UnitsClassical PollutantsAmmonia As Nitrogen (NH3-N) 0.210 0.230 0.220 9.1 MG/LNitrate/Nitrite (NO3-N + NO2-N) 0.100 0.0890 0.0945 12 MG/LTotal Kjeldahl Nitrogen (TKN) 2.472.542.51 2.8 MG/LBiochemical Oxygen Demand(BOD)ND (9.00) 11.0 < 10.0 NC MG/LChloride 1,120 1,110 1,120 0.90 MG/LHexane Extractable Material(HEM)ND (5.00) NA ND (5.00) NC MG/LSulfate 1,840 2,270 2,060 21 MG/LTotal Dissolved Solids (TDS) 6,040 5,620 5,830 7.2 MG/LTotal Phosphorus 0.0100 E 0.0130 E 0.0115 26 MG/LTotal Suspended Solids (TSS) 8.00 8.00 E 8.000.0 MG/LRoutine Total MetalsAluminum 117 105 111 11 UG/LAntimony NQ (20.0) NQ (20.0) ND (20.0) NC UG/LArsenic 50.2 48.8 49.5 2.8 UG/LBarium 186 171 179 8.4 UG/LBeryllium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LBoron 31,700 31,200 31,500 1.6 UG/LCadmium NQ (5.00) NQ (5.00) ND (5.00) NC UG/L

### 5-6< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.R – MS/MSD % Recovery outside method acceptance criteria.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, Widows CreekAnalyteOriginal FGD EffluentConcentration (SP-2)Duplicate FGD EffluentConcentration (SP-5)Average ResultRelative PercentDifference (%)UnitsCalcium 987,000 986,000 987,000 0.10 UG/LChromium NQ (10.0) NQ (10.0) ND (10.0) NC UG/LCopper NQ (10.0) NQ (10.0) ND (10.0) NC UG/LIron NQ (100) NQ (100) ND (100) NC UG/LLead ND (50.0) ND (50.0) ND (50.0) NC UG/LMagnesium 193,000 185,000 189,000 4.2 UG/LManganese 636 609 623 4.3 UG/LMercury ND (2.00) ND (2.00) ND (2.00) NC UG/LMolybdenum 1,530 1,470 1,500 4.0 UG/LNickel NQ (50.0) NQ (50.0) ND (50.0) NC UG/LSelenium 241 230 236 4.7 UG/LSodium 69,200 69,700 69,500 0.72 UG/LThallium NQ (10.0) NQ (10.0) ND (10.0) NC UG/LTitanium NQ (10.0) NQ (10.0) ND (10.0) NC UG/LVanadium 42.7 41.4 42.1 3.1 UG/LYttrium ND (5.00)ND (5.00)ND (5.00) NC UG/LZinc NQ (10.0) NQ (10.0) ND (10.0) NC UG/LRoutine Dissolved MetalsAluminum NQ (50.0) NQ (50.0) ND (50.0) NC UG/LAntimony NQ (20.0) NQ (20.0) ND (20.0) NC UG/LArsenic 47.2 46.1 46.7 2.4 UG/L

### 5-7< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.R – MS/MSD % Recovery outside method acceptance criteria.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, Widows CreekAnalyteOriginal FGD EffluentConcentration (SP-2)Duplicate FGD EffluentConcentration (SP-5)Average ResultRelative PercentDifference (%)UnitsBarium 191 191 191 0.0 UG/LBeryllium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LBoron 28,700 29,700 29,200 3.4 UG/LCadmium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LCalcium 934,000 929,000 932,000 0.54 UG/LChromium NQ (10.0) NQ (10.0) ND (10.0) NC UG/LHexavalent Chromium ND (2.00) ND (2.00) ND (2.00) NC UG/LCopper NQ (10.0) NQ (10.0) ND (10.0) NC UG/LIron NQ (100) NQ (100) ND (100) NC UG/LLead ND (50.0) ND (50.0) ND (50.0) NC UG/LMagnesium 182,000 186,000 184,000 2.2 UG/LManganese 543 R 542 543 0.18 UG/LMercury ND (2.00) ND (2.00) ND (2.00) NC UG/LMolybdenum 1,480 1,450 1,470 2.0 UG/LNickel NQ (50.0) NQ (50.0) ND (50.0) NC UG/LSelenium 231 221 226 4.4 UG/LSodium 66,900 65,500 66,200 2.1 UG/LThallium NQ (10.0) NQ (10.0) ND (10.0) NC UG/LTitanium ND (10.0) ND (10.0) ND (10.0) NC UG/LVanadium 39.7 40.2 40.0 1.3 UG/LYttrium ND (5.00)ND (5.00)ND (5.00) NC UG/L

### 5-8< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.R – MS/MSD % Recovery outside method acceptance criteria.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, Widows CreekAnalyteOriginal FGD EffluentConcentration (SP-2)Duplicate FGD EffluentConcentration (SP-5)Average ResultRelative PercentDifference (%)UnitsZinc ND (10.0) ND (10.0) ND (10.0) NC UG/LLow-Level Total MetalsAntimony 11.8 11.8 11.80.0 UG/LArsenic 47.3 47.9 47.6 1.3 UG/LCadmium 3.66 3.80 3.73 3.8 UG/LChromium NQ (16.0) NQ (16.0) ND (16.0) NC UG/LCopper NQ (4.00) NQ (4.00) ND (4.00) NC UG/LLead NQ (1.00) NQ (1.00) ND (1.00) NC UG/LMercury 0.0428 0.0448 0.0438 4.6 UG/LNickel 35.6 36.7 36.2 3.0 UG/LSelenium 205 211 208 2.9 UG/LThallium 11.111.111.1 0.0 UG/LZinc ND (10.0) ND (10.0) ND (10.0) NC UG/LLow-Level Dissolved MetalsAntimony 11.8 11.9 11.9 0.84 UG/LArsenic 47.0 46.0 46.52.2 UG/LCadmium 3.76 3.71 3.74 1.3 UG/LChromium NQ (16.0) NQ (16.0) ND (16.0) NC UG/LHexavalent Chromium 3.29 3.10 3.20 5.9 UG/LCopper NQ (4.00) NQ (4.00) ND (4.00) NC UG/LLead ND (1.00) ND (1.00) ND (1.00) NC UG/L

### 5-9< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.R – MS/MSD % Recovery outside method acceptance criteria.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, Widows CreekAnalyteOriginal FGD EffluentConcentration (SP-2)Duplicate FGD EffluentConcentration (SP-5)Average ResultRelative PercentDifference (%)UnitsMercury 0.0106 0.0107 0.0107 0.94 UG/LNickel 32.8 L 33.8 L 33.3 3.0 UG/LSelenium 213 373 293 55 UG/LThallium 11.0 10.9 11.0 0.91 UG/LZinc ND (10.0) ND (10.0) ND (10.0) NC UG/L

### 6-1 6. R EFERENCES



### 1. Eastern Research Group, Inc., 2007. Engineer ing Site Visit Report for Tennessee Valley Authority’s Widows Creek Fossil Plan t. July 18. DCN 04714. EPA-HQ-OW-2006-0071-

0399.

2. Eastern Research Group, Inc., 2007. Samp ling Plan, Tennessee Valley Authority’s Widows Creek Fossil Plant. Sept ember 4. DCN 04840A1. EPA-HQ-OW-2006-0071-

0691.1.

3. Eastern Research Group, Inc., 2007. Quality Assurance Project Plan for the Steam Electric Detailed Study. September 25. DCN 05079. EPA-HQ-OW-2006-0071-0724.

4. U.S. EPA. 2001. Method 200.7: Trace Elements in Water, Solids, and Biosolids, by Inductively Coupled Plasma-Atomic Emi ssion Spectrometry. Revision 5.0. EPA-821-R01-010. January.

### Appendix A

ANALYTICAL RESULTS

### A-1CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L NA NP NP 2.26Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L NA NP NP 1.00Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L NA NP NP 22.3Biochemical Oxygen Demand (BOD) 5210B MG/L 30 NP NP 172Chloride 4500-CL-C MG/L NA NP NP 832Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP 22.0Silica Gel Treated HEM (SGT-HEM) 1664A MG/L 1 NP NP 6.00 ESulfate D516-90 MG/L NA NP NP 11,900Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 4,740Total Phosphorus 365.3 MG/L NA NP NP 10.5Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 25,300 EClassical Pollutants – Solid (wet weight)Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/KG 1 NP NP 25.2Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/KG 1 NP NP 6.10Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/KG 1 NP NP 267Chloride 4500-CL-C MG/KG 1 NP NP 709Sulfate D516-90 MG/KG 50 NP NP 149,000

### A-2CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationTotal Phosphorus 365.3 MG/KG 20 NP NP 119 EClassical Pollutants – Filtered AqueousAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 0.530Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1 NP NP 0.610Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 3.85Chloride 4500-CL-C MG/L 1 NP NP 840Sulfate D516-90 MG/L 50 NP NP 1,750Total Phosphorus 365.3 MG/L 5 NP NP 2.30 ERoutine Metals – TotalAluminum 200.7 UG/L NA NC 217 234,000Antimony 200.7 UG/L NA NC 86.9 76.2 CJArsenic 200.7 UG/L NA NC 43.4 523Barium 200.7 UG/L NA NC 8.69 7,200Beryllium 200.7 UG/L NA NC 21.7 44.3Boron 200.7 UG/L NA NC 1,000 28,900Cadmium 200.7 UG/L NA NC 21.7 89.2Calcium 200.7 UG/L NA NC 2,170 5,990,000Chromium 200.7 UG/L NA NC 43.4 1,360

### A-3CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCobalt 200.7 UG/L NA NC 217 138 CJCopper 200.7 UG/L NA NC 43.4 653Iron 200.7 UG/L NA NC 434 299,000Lead 200.7 UG/L NA NC 217 436Magnesium 200.7 UG/L NA NC 869 321,000Manganese 200.7 UG/L NA NC 65.2 2,780Mercury 245.1 UG/L NA NC 2.00 26.5Molybdenum 200.7 UG/L NA NC 43.4 1,340Nickel 200.7 UG/L NA NC 217 489Selenium 200.7 UG/L NA NC 21.7 652Silver 200.7 UG/L NA NC 86.9 9.82 CJSodium 200.7 UG/L NA NC 2,170 104,000Thallium 200.7 UG/L NA NC 43.4 16.2 CJTin 200.7 UG/L NA NC 130 21.2 CJTitanium 200.7 UG/L NA NC 43.4 8,180Vanadium 200.7 UG/L NA NC 86.9 1,580Yttrium 200.7 UG/L NA NC 21.7 217Zinc 200.7 UG/L NA NC 43.4 3,140

### A-4CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationRoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 86.6Antimony 200.7 UG/L 1 0.700 20.0 12.3 JArsenic 200.7 UG/L 1 0.500 10.0 13.9Barium 200.7 UG/L 1 0.100 2.00 257Beryllium 200.7 UG/L 1 0.500 5.00 1.58 JBoron 200.7 UG/L 10 27.0 1,000 24,100Cadmium 200.7 UG/L 1 0.100 5.00 0.991 JCalcium 200.7 UG/L 10 51.0 500 849,000Chromium 200.7 UG/L 1 0.200 10.0 18.7Hexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 1.61 JCopper 200.7 UG/L 1 0.200 10.0 3.79 JIron 200.7 UG/L 1 5.40 100 17.9 JLead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 176,000Manganese 200.7 UG/L 1 0.200 15.0 583Mercury 245.1 UG/L 10 0.500 2.00 ND (2.00) U

### A-5CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationMolybdenum 200.7 UG/L 1 0.200 10.0 876Nickel 200.7 UG/L 1 1.10 50.0 25.0 JSelenium 200.7 UG/L 1 0.600 5.00 366Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 76,700Thallium 200.7 UG/L 1 0.500 10.0 14.3Tin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 15.8 JYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) URoutine Metals – Filtered AqueousAluminum 200.7 UG/L 1 10.6 50.0 12,600Antimony 200.7 UG/L 1 0.700 20.0 16.9 JArsenic 200.7 UG/L 1 0.500 10.0 51.9Barium 200.7 UG/L 1 0.100 2.00 168Beryllium 200.7 UG/L 1 0.500 5.00 6.76Boron 200.7 UG/L 10 27.0 1,000 27,500

### A-6CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCadmium 200.7 UG/L 1 0.100 5.00 14.7Calcium 200.7 UG/L 20 102 1,000 1,580,000Chromium 200.7 UG/L 1 0.200 10.0 62.1Cobalt 200.7 UG/L 1 0.600 50.0 26.6 JCopper 200.7 UG/L 1 0.200 10.0 60.5Iron 200.7 UG/L 1 5.40 100 21,400Lead 200.7 UG/L 1 0.700 50.0 8.70 JMagnesium 200.7 UG/L 1 8.90 200 223,000Manganese 200.7 UG/L 1 0.200 15.0 1,710Mercury 245.1 UG/L 10 0.500 2.00 ND (2.00) UMolybdenum 200.7 UG/L 1 0.200 10.0 862Nickel 200.7 UG/L 1 1.10 50.0 116Selenium 200.7 UG/L 1 0.600 5.00 502Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 84,000Thallium 200.7 UG/L 1 0.500 10.0 16.9Tin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 103

### A-7CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationVanadium 200.7 UG/L 1 0.600 20.0 118Yttrium 200.7 UG/L 1 0.200 5.00 11.4Zinc 200.7 UG/L 1 0.200 10.0 395Routine Metals – Solid (wet weight)Aluminum 200.7 MG/KG 1 1.75 5.00 5,110 OAntimony 200.7 MG/KG 1 0.110 2.00 1.38 JArsenic 200.7 MG/KG 1 0.110 1.00 10.9Barium 200.7 MG/KG 1 0.0200 0.200 162Beryllium 200.7 MG/KG 1 0.0100 0.500 0.870Boron 200.7 MG/KG 1 0.200 10.0 58.9Cadmium 200.7 MG/KG 1 0.0200 0.500 1.73Calcium 200.7 MG/KG 10 4.00 50.0 103,000Chromium 200.7 MG/KG 1 0.0200 1.00 30.0Cobalt 200.7 MG/KG 1 0.360 5.00 2.60 JCopper 200.7 MG/KG 1 0.0300 1.00 13.7Iron 200.7 MG/KG 1 1.06 10.0 6,410Lead 200.7 MG/KG 1 0.100 5.00 9.85Magnesium 200.7 MG/KG 1 2.18 20.0 2,490

### A-8CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationManganese 200.7 MG/KG 1 0.0200 1.50 26.3Mercury 245.5 MG/KG 1 0.00600 0.0250 0.610Molybdenum 200.7 MG/KG 1 0.0600 1.00 11.9Nickel 200.7 MG/KG 1 0.0800 5.00 8.71Selenium 200.7 MG/KG 1 0.170 0.500 3.96 LSilver 200.7 MG/KG 1 0.100 2.00 0.226 JSodium 200.7 MG/KG 1 6.23 50.0 538Thallium 200.7 MG/KG 1 0.110 1.00 ND (1.00) UTin 200.7 MG/KG 1 0.100 3.00 0.488 JTitanium 200.7 MG/KG 1 0.120 1.00 186Vanadium 200.7 MG/KG 1 0.0800 2.00 33.8Yttrium 200.7 MG/KG 1 0.0300 0.500 4.74Zinc 200.7 MG/KG 1 0.200 1.00 63.6Low-Level Metals – TotalAntimony 1638 UG/L 200 1.40 4.00 51.8Arsenic 1638 UG/L 200 3.04 30.0 617Cadmium 1638 UG/L 200 0.200 20.0 86.0Chromium 1638 UG/L 200 16.6 160 1,380

### A-9CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCopper 1638 UG/L 200 0.800 40.0 826Lead 1638 UG/L 200 0.200 10.0 545Mercury 1631E UG/L 1,000 0.188 0.500 24.7Nickel 1638 UG/L 200 2.60 200 634Selenium 1638 UG/L 200 3.20 200 651Silver 1638 UG/L 200 0.400 20.0 5.10 JThallium 1638 UG/L 200 0.0800 4.00 93.8Zinc 1638 UG/L 200 41.8 100 2,720Low-Level Metals - DissolvedAntimony 1638 UG/L 20 0.140 0.400 8.90Arsenic 1638 UG/L 20 0.304 3.00 18.0Cadmium 1638 UG/L 20 0.0200 2.00 3.16Chromium 1638 UG/L 20 1.66 16.0 ND (16.0) UCopper 1638 UG/L 20 0.0800 4.00 2.83 JLead 1638 UG/L 20 0.0200 1.00 ND (1.00) UMercury 1631E UG/L 1 0.000188 0.000500 0.0761Nickel 1638 UG/L 20 0.260 20.0 29.6Selenium 1638 UG/L 100 1.60 100 325

### A-10CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. FGD Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationSilver 1638 UG/L 20 0.0400 2.00 ND (2.00) UThallium 1638 UG/L 20 0.00800 0.400 22.5Zinc 1638 UG/L 20 4.18 10.0 ND (10.0) ULow-Level Metals – Solid (dry weight)Antimony 1638 MG/KG NA 0.0408 0.117 1.25Arsenic 1638 MG/KG NA 0.0885 0.874 17.4Cadmium 1638 MG/KG NA 0.00640 0.583 2.41Chromium 1638 MG/KG NA 0.484 4.66 40.2Copper 1638 MG/KG NA 0.0233 1.17 24.0Lead 1638 MG/KG NA 0.00580 0.291 15.9Mercury 1631E MG/KG NA 0.00490 0.0129 0.640Nickel 1638 MG/KG NA 0.0757 5.83 17.6Selenium 1638 MG/KG NA 0.0932 5.83 9.50Silver 1638 MG/KG NA 0.0116 0.583 0.149 JThallium 1638 MG/KG NA 0.00230 0.117 2.08Zinc 1638 MG/KG NA 1.22 2.91 78.6

### A-11CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L NA NP NP 0.400Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L NA NP NP 0.360Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L NA NP NP 7.41Biochemical Oxygen Demand (BOD) 5210B MG/L 30 NP NP 53.0Chloride 4500-CL-C MG/L NA NP NP 21.4Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP ND (5.00) USulfate D516-90 MG/L NA NP NP 58.1Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 224Total Phosphorus 365.3 MG/L NA NP NP 16.6Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 9,190 EClassical Pollutants – Solid (wet weight)Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/KG 1 NP NP 14.3Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/KG 1 NP NP 13.8Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/KG 1 NP NP 286Chloride 4500-CL-C MG/KG 1 NP NP 354Sulfate D516-90 MG/KG 1 NP NP 621Total Phosphorus 365.3 MG/KG 50 NP NP 854 E

### A-12CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical Pollutants – Filtered AqueousAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 0.180Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1 NP NP 0.140Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 2.91Chloride 4500-CL-C MG/L 1 NP NP 16.0Sulfate D516-90 MG/L 2 NP NP 49.0Total Phosphorus 365.3 MG/L 10 NP NP 3.12 ERoutine Metals – TotalAluminum 200.7 UG/L NA NC 95.0 94,800Antimony 200.7 UG/L NA NC 38.0 6.15 CJArsenic 200.7 UG/L NA NC 19.0 131Barium 200.7 UG/L NA NC 3.80 6,080Beryllium 200.7 UG/L NA NC 9.50 11.3Boron 200.7 UG/L NA NC 190 4,330Cadmium 200.7 UG/L NA NC 9.50 9.93Calcium 200.7 UG/L NA NC 95.0 103,000Chromium 200.7 UG/L NA NC 19.0 107Cobalt 200.7 UG/L NA NC 95.0 48.6 CJ

### A-13CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCopper 200.7 UG/L NA NC 19.0 188Iron 200.7 UG/L NA NC 190 80,700Lead 200.7 UG/L NA NC 95.0 208Magnesium 200.7 UG/L NA NC 380 25,700Manganese 200.7 UG/L NA NC 28.5 337Mercury 245.1 UG/L NA NC 0.475 2.66Molybdenum 200.7 UG/L NA NC 19.0 65.5Nickel 200.7 UG/L NA NC 95.0 66.8 CJSelenium 200.7 UG/L NA NC 9.50 27.5Silver 200.7 UG/L NA NC 38.0 3.99 CJSodium 200.7 UG/L NA NC 950 31,200Thallium 200.7 UG/L NA NC 19.0 ND (19.0) UTin 200.7 UG/L NA NC 57.0 12.4 CJTitanium 200.7 UG/L NA NC 19.0 7,150Vanadium 200.7 UG/L NA NC 38.0 346Yttrium 200.7 UG/L NA NC 9.50 133Zinc 200.7 UG/L NA NC 19.0 785

### A-14CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationRoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 663Antimony 200.7 UG/L 1 0.700 20.0 7.45 JArsenic 200.7 UG/L 1 0.500 10.0 46.0Barium 200.7 UG/L 1 0.100 2.00 178Beryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 2,150Cadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 40,300Chromium 200.7 UG/L 1 0.200 10.0 3.09 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 0.233 JIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 7,110Manganese 200.7 UG/L 1 0.200 15.0 2.07 JMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) U

### A-15CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationMolybdenum 200.7 UG/L 1 0.200 10.0 50.1Nickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 26.8Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 13,400Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 66.8Yttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) URoutine Metals – Filtered AqueousAluminum 200.7 UG/L 1 10.6 50.0 44,300Antimony 200.7 UG/L 1 0.700 20.0 6.27 JArsenic 200.7 UG/L 1 0.500 10.0 89.5Barium 200.7 UG/L 1 0.100 2.00 967Beryllium 200.7 UG/L 1 0.500 5.00 8.64Boron 200.7 UG/L 1 2.70 100 3,560

### A-16CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCadmium 200.7 UG/L 1 0.100 5.00 3.62 JCalcium 200.7 UG/L 1 5.10 50.0 89,800Chromium 200.7 UG/L 1 0.200 10.0 29.5Cobalt 200.7 UG/L 1 0.600 50.0 14.3 JCopper 200.7 UG/L 1 0.200 10.0 96.5Iron 200.7 UG/L 1 5.40 100 11,000Lead 200.7 UG/L 1 0.700 50.0 57.9Magnesium 200.7 UG/L 1 8.90 200 17,500Manganese 200.7 UG/L 1 0.200 15.0 144Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 41.0Nickel 200.7 UG/L 1 1.10 50.0 23.6 JSelenium 200.7 UG/L 1 0.600 5.00 28.0Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 19,300Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 608

### A-17CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationVanadium 200.7 UG/L 1 0.600 20.0 222Yttrium 200.7 UG/L 1 0.200 5.00 83.2Zinc 200.7 UG/L 1 0.200 10.0 157Routine Metals – Solid (wet weight)Aluminum 200.7 MG/KG 1 1.75 5.00 2,700 OAntimony 200.7 MG/KG 1 0.110 2.00 ND (2.00) UArsenic 200.7 MG/KG 1 0.110 1.00 2.29Barium 200.7 MG/KG 1 0.0200 0.200 270Beryllium 200.7 MG/KG 1 0.0100 0.500 0.146 JBoron 200.7 MG/KG 1 0.200 10.0 44.0Cadmium 200.7 MG/KG 1 0.0200 0.500 0.336 JCalcium 200.7 MG/KG 1 0.400 5.00 807Chromium 200.7 MG/KG 1 0.0200 1.00 4.09Cobalt 200.7 MG/KG 1 0.360 5.00 1.82 JCopper 200.7 MG/KG 1 0.0300 1.00 4.89Iron 200.7 MG/KG 1 1.06 10.0 3,680Lead 200.7 MG/KG 1 0.100 5.00 7.95Magnesium 200.7 MG/KG 1 2.18 20.0 451

### A-18CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationManganese 200.7 MG/KG 1 0.0200 1.50 10.3Mercury 245.5 MG/KG 1 0.00600 0.0250 0.140Molybdenum 200.7 MG/KG 1 0.0600 1.00 1.33Nickel 200.7 MG/KG 1 0.0800 5.00 2.30 JSelenium 200.7 MG/KG 1 0.170 0.500 ND (0.500) USilver 200.7 MG/KG 1 0.100 2.00 0.210 JSodium 200.7 MG/KG 1 6.23 50.0 645Thallium 200.7 MG/KG 1 0.110 1.00 ND (1.00) UTin 200.7 MG/KG 1 0.100 3.00 0.651 JTitanium 200.7 MG/KG 1 0.120 1.00 345Vanadium 200.7 MG/KG 1 0.0800 2.00 6.77Yttrium 200.7 MG/KG 1 0.0300 0.500 2.70Zinc 200.7 MG/KG 1 0.200 1.00 33.2Low-Level Metals – TotalAntimony 1638 UG/L 200 1.40 4.00 13.1 LArsenic 1638 UG/L 200 3.04 30.0 88.9Cadmium 1638 UG/L 200 0.200 20.0 3.19 JChromium 1638 UG/L 200 16.6 160 ND (160) U

### A-19CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCopper 1638 UG/L 200 0.800 40.0 114Lead 1638 UG/L 200 0.200 10.0 104Mercury 1631E UG/L 52 0.00978 0.0260 1.02Nickel 1638 UG/L 200 2.60 200 25.6 JSelenium 1638 UG/L 200 3.20 200 ND (200) USilver 1638 UG/L 200 0.400 20.0 ND (20.0) UThallium 1638 UG/L 200 0.0800 4.00 2.60 JZinc 1638 UG/L 200 41.8 100 198Low-Level Metals - DissolvedAntimony 1638 UG/L 20 0.140 0.400 8.54Arsenic 1638 UG/L 20 0.304 3.00 49.5Cadmium 1638 UG/L 20 0.0200 2.00 0.136 JChromium 1638 UG/L 20 1.66 16.0 ND (16.0) UCopper 1638 UG/L 20 0.0800 4.00 0.623 JLead 1638 UG/L 20 0.0200 1.00 ND (1.00) UMercury 1631E UG/L 1 0.000188 0.000500 0.000368 JNickel 1638 UG/L 20 0.260 20.0 ND (20.0) USelenium 1638 UG/L 100 1.60 100 ND (100) U

### A-20CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.U – Result below the MDL. (Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.O – OPR %Recovery below contract-specified criteria.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-2. Ash Pond Influent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationSilver 1638 UG/L 20 0.0400 2.00 ND (2.00) UThallium 1638 UG/L 20 0.00800 0.400 ND (0.400) UZinc 1638 UG/L 20 4.18 10.0 ND (10.0) U

### A-21 Table A-3. ProChem Biphasic Filtration Bl ank Analytical Results, Widows Creek

Analyte Method Unit Dilution

Factor Sample-Specific

MDL Sample-Specific

RL Concentration

Aluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) U

Antimony 200.7 UG/L 1 0.700 20.0 ND (20.0) U

Arsenic 200.7 UG/L 1 0.500 10.0 ND (10.0) U

Barium 200.7 UG/L 1 0.100 2.00 ND (2.00) U

Beryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) U

Boron 200.7 UG/L 1 2.70 100 ND (100) U

Cadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) U

Calcium 200.7 UG/L 1 5.10 50.0 ND (50.0) U

Chromium 200.7 UG/L 1 0.200 10.0 ND (10.0) U

Cobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) U

Copper 200.7 UG/L 1 0.200 10.0 ND (10.0) U

Iron 200.7 UG/L 1 5.40 100 ND (100) U

Lead 200.7 UG/L 1 0.700 50.0 ND (50.0) U

Magnesium 200.7 UG/L 1 8.90 200 ND (200) U

Manganese 200.7 UG/L 1 0.200 15.0 ND (15.0) U

Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) U

Molybdenum 200.7 UG/L 1 0.200 10.0 ND (10.0) U

Nickel 200.7 UG/L 1 1.10 50.0 ND (50.0) U

Selenium 200.7 UG/L 1 0.600 5.00 ND (5.00) U

Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) U

Sodium 200.7 UG/L 1 40.5 500 ND (500) U

Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) U

Tin 200.7 UG/L 1 0.400 30.0 ND (30.0) U

Titanium 200.7 UG/L 1 0.200 10.0 ND (10.0) U

Vanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) U

Yttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) U

Zinc 200.7 UG/L 1 0.200 10.0 ND (10.0) U

ND – Not detected (number in parenthesis is the report limit). U – Result below the MDL. (Number shown in parentheses is the reporting limit).

### A-22U – Result below the MDL. (Number shown in parentheses is the reporting limit).E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % recovery outside method acceptance criteria.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationClassical PollutantsAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 0.210Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1 NP NP 0.100Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 2.47Biochemical Oxygen Demand (BOD) 5210B MG/L 6 NP NP ND (9.00) UChloride 4500-CL-C MG/L 1 NP NP 1,120Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP ND (5.00) USulfate D516-90 MG/L 50 NP NP 1,840Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 6,040Total Phosphorus 365.3 MG/L 1 NP NP 0.0100 ETotal Suspended Solids (TSS) 2540 D MG/L 1 NP NP 8.00Routine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 117Antimony 200.7 UG/L 1 0.700 20.0 15.8 JArsenic 200.7 UG/L 1 0.500 10.0 50.2Barium 200.7 UG/L 1 0.100 2.00 186Beryllium 200.7 UG/L 1 0.500 5.00 1.95 JBoron 200.7 UG/L 10 27.0 1,000 31,700Cadmium 200.7 UG/L 1 0.100 5.00 0.525 JCalcium 200.7 UG/L 10 51.0 500 987,000Chromium 200.7 UG/L 1 0.200 10.0 1.65 J

### A-23U – Result below the MDL. (Number shown in parentheses is the reporting limit).E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % recovery outside method acceptance criteria.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationCobalt 200.7 UG/L 1 0.600 50.0 2.22 JCopper 200.7 UG/L 1 0.200 10.0 2.98 JIron 200.7 UG/L 1 5.40 100 64.8 JLead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 193,000Manganese 200.7 UG/L 1 0.200 15.0 636Mercury 245.1 UG/L 10 0.500 2.00 ND (2.00) UMolybdenum 200.7 UG/L 1 0.200 10.0 1,530Nickel 200.7 UG/L 1 1.10 50.0 32.0 JSelenium 200.7 UG/L 1 0.600 5.00 241Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 69,200Thallium 200.7 UG/L 1 0.500 10.0 1.45 JTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 1.48 JVanadium 200.7 UG/L 1 0.600 20.0 42.7Yttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 0.335 JRoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 46.8 JAntimony 200.7 UG/L 1 0.700 20.0 14.8 J

### A-24U – Result below the MDL. (Number shown in parentheses is the reporting limit).E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % recovery outside method acceptance criteria.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationArsenic 200.7 UG/L 1 0.500 10.0 47.2Barium 200.7 UG/L 1 0.100 2.00 191Beryllium 200.7 UG/L 1 0.500 5.00 1.79 JBoron 200.7 UG/L 10 27.0 1,000 28,700Cadmium 200.7 UG/L 1 0.100 5.00 0.272 JCalcium 200.7 UG/L 10 51.0 500 934,000Chromium 200.7 UG/L 1 0.200 10.0 1.10 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 1.77 JCopper 200.7 UG/L 1 0.200 10.0 2.43 JIron 200.7 UG/L 1 5.40 100 21.1 JLead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 182,000Manganese 200.7 UG/L 1 0.200 15.0 543 RMercury 245.1 UG/L 10 0.500 2.00 ND (2.00) UMolybdenum 200.7 UG/L 1 0.200 10.0 1,480Nickel 200.7 UG/L 1 1.10 50.0 29.7 JSelenium 200.7 UG/L 1 0.600 5.00 231Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 66,900Thallium 200.7 UG/L 1 0.500 10.0 1.61 J

### A-25U – Result below the MDL. (Number shown in parentheses is the reporting limit).E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % recovery outside method acceptance criteria.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 39.7Yttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) ULow-Level Metals – TotalAntimony 1638 UG/L 20 0.140 0.400 11.8Arsenic 1638 UG/L 20 0.304 3.00 47.3Cadmium 1638 UG/L 20 0.0200 2.00 3.66Chromium 1638 UG/L 20 1.66 16.0 14.6 JCopper 1638 UG/L 20 0.0800 4.00 1.46 JLead 1638 UG/L 20 0.0200 1.00 0.0828 JMercury 1631E UG/L 1 0.000188 0.000500 0.0428Nickel 1638 UG/L 20 0.260 20.0 35.6Selenium 1638 UG/L 100 1.60 100 205Silver 1638 UG/L 20 0.0400 2.00 0.0449 JThallium 1638 UG/L 20 0.00800 0.400 11.1Zinc 1638 UG/L 20 4.18 10.0 ND (10.0) ULow-Level Metals - DissolvedAntimony 1638 UG/L 20 0.140 0.400 11.8Arsenic 1638 UG/L 20 0.304 3.00 47.0

### A-26U – Result below the MDL. (Number shown in parentheses is the reporting limit).E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % recovery outside method acceptance criteria.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationCadmium 1638 UG/L 20 0.0200 2.00 3.76Chromium 1638 UG/L 20 1.66 16.0 14.4 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 3.29Copper 1638 UG/L 20 0.0800 4.00 0.842 JLead 1638 UG/L 20 0.0200 1.00 ND (1.00) UMercury 1631E UG/L 1 0.000188 0.000500 0.0106Nickel 1638 UG/L 20 0.260 20.0 32.8 LSelenium 1638 UG/L 100 1.60 100 213Silver 1638 UG/L 20 0.0400 2.00 ND (2.00) UThallium 1638 UG/L 20 0.00800 0.400 11.0Zinc 1638 UG/L 20 4.18 10.0 ND (10.0) U

### A-27E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationClassical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 0.230Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1 NP NP 0.0890Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 2.54Biochemical Oxygen Demand (BOD) 5210B MG/L 6 NP NP 11.0Chloride 4500-CL-C MG/L 1 NP NP 1,110Sulfate D516-90 MG/L 100 NP NP 2,270Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 5,620Total Phosphorus 365.3 MG/L 1 NP NP 0.0130 ETotal Suspended Solids (TSS) 2540 D MG/L 1 NP NP 8.00 ERoutine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 105Antimony 200.7 UG/L 1 0.700 20.0 15.2 JArsenic 200.7 UG/L 1 0.500 10.0 48.8Barium 200.7 UG/L 1 0.100 2.00 171Beryllium 200.7 UG/L 1 0.500 5.00 1.85 JBoron 200.7 UG/L 10 27.0 1,000 31,200Cadmium 200.7 UG/L 1 0.100 5.00 0.479 JCalcium 200.7 UG/L 10 51.0 500 986,000Chromium 200.7 UG/L 1 0.200 10.0 1.54 JCobalt 200.7 UG/L 1 0.600 50.0 2.15 J

### A-28E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationCopper 200.7 UG/L 1 0.200 10.0 2.82 JIron 200.7 UG/L 1 5.40 100 55.3 JLead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 185,000Manganese 200.7 UG/L 1 0.200 15.0 609Mercury 245.1 UG/L 10 0.500 2.00 ND (2.00) UMolybdenum 200.7 UG/L 1 0.200 10.0 1,470Nickel 200.7 UG/L 1 1.10 50.0 30.8 JSelenium 200.7 UG/L 1 0.600 5.00 230Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 69,700Thallium 200.7 UG/L 1 0.500 10.0 1.67 JTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 1.21 JVanadium 200.7 UG/L 1 0.600 20.0 41.4Yttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 0.702 JRoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 47.4 JAntimony 200.7 UG/L 1 0.700 20.0 14.4 JArsenic 200.7 UG/L 1 0.500 10.0 46.1Barium 200.7 UG/L 1 0.100 2.00 191

### A-29E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationBeryllium 200.7 UG/L 1 0.500 5.00 1.76 JBoron 200.7 UG/L 10 27.0 1,000 29,700Cadmium 200.7 UG/L 1 0.100 5.00 0.292 JCalcium 200.7 UG/L 10 51.0 500 929,000Chromium 200.7 UG/L 1 0.200 10.0 1.01 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 1.80 JCopper 200.7 UG/L 1 0.200 10.0 2.12 JIron 200.7 UG/L 1 5.40 100 19.7 JLead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 186,000Manganese 200.7 UG/L 1 0.200 15.0 542Mercury 245.1 UG/L 10 0.500 2.00 ND (2.00) UMolybdenum 200.7 UG/L 1 0.200 10.0 1,450Nickel 200.7 UG/L 1 1.10 50.0 29.3 JSelenium 200.7 UG/L 1 0.600 5.00 221Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 65,500Thallium 200.7 UG/L 1 0.500 10.0 1.61 JTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 40.2

### A-30E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) ULow-Level Metals – TotalAntimony 1638 UG/L 20 0.140 0.400 11.8Arsenic 1638 UG/L 20 0.304 3.00 47.9Cadmium 1638 UG/L 20 0.0200 2.00 3.80Chromium 1638 UG/L 20 1.66 16.0 14.7 JCopper 1638 UG/L 20 0.0800 4.00 1.27 JLead 1638 UG/L 20 0.0200 1.00 0.129 JMercury 1631E UG/L 1 0.000188 0.000500 0.0448Nickel 1638 UG/L 20 0.260 20.0 36.7Selenium 1638 UG/L 100 1.60 100 211Silver 1638 UG/L 20 0.0400 2.00 ND (2.00) UThallium 1638 UG/L 20 0.00800 0.400 11.1Zinc 1638 UG/L 20 4.18 10.0 ND (10.0) ULow-Level Metals - DissolvedAntimony 1638 UG/L 20 0.140 0.400 11.9Arsenic 1638 UG/L 20 0.304 3.00 46.0Cadmium 1638 UG/L 20 0.0200 2.00 3.71Chromium 1638 UG/L 20 1.66 16.0 13.6 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 3.10Copper 1638 UG/L 20 0.0800 4.00 1.05 J

### A-31E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilutionFactorSample-Specific MDLSample-Specific RLConcentrationLead 1638 UG/L 20 0.0200 1.00 ND (1.00) UMercury 1631E UG/L 1 0.000188 0.000500 0.0107Nickel 1638 UG/L 20 0.260 20.0 33.8 LSelenium 1638 UG/L 100 1.60 100 373Silver 1638 UG/L 20 0.0400 2.00 ND (2.00) UThallium 1638 UG/L 20 0.00800 0.400 10.9Zinc 1638 UG/L 20 4.18 10.0 ND (10.0) U

### A-32E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-6. Ash Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical Pollutants – TotalAmmonia As Nitrogen (NH3-N)4500-NH3FMG/L1 NP NP 0.160Nitrate/Nitrite (NO3-N + NO2-N)4500NO3HMG/L1 NP NP 0.230Total Kjeldahl Nitrogen (TKN)4500-N,CMG/L1 NP NP 3.39Biochemical Oxygen Demand (BOD)5210BMG/L1.2 NP NP 4.00Chloride4500-CL-CMG/L1 NP NP 20.0Hexane Extractable Material (HEM)1664AMG/L1 NP NP 6.00Silica Gel Treated HEM (SGT-HEM)1664AMG/L1 NP NP ND (5.00)USulfateD516-90MG/L5 NP NP 80.7Total Dissolved Solids (TDS)2540 CMG/L1 NP NP 281Total Phosphorus365.3MG/L1 NP NP 0.250ETotal Suspended Solids (TSS)2540 DMG/L1 NP NP 12.0ERoutine Metals – TotalAluminum200.7UG/L1 10.6 50.0 1,070Antimony200.7UG/L1 0.700 20.0 3.40JArsenic200.7UG/L1 0.500 10.0 38.2Barium200.7UG/L1 0.100 2.00 227Beryllium200.7UG/L1 0.500 5.00 ND (5.00)UBoron200.7UG/L1 2.70 100 2,210Cadmium200.7UG/L1 0.100 5.00 ND (5.00)UCalcium200.7UG/L1 5.10 50.0 58,500Chromium200.7UG/L1 0.200 10.0 13.5Cobalt200.7UG/L1 0.600 50.0 ND (50.0)U

### A-33E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-6. Ash Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCopper200.7UG/L1 0.200 10.0 1.58JIron200.7UG/L1 5.40 100 144Lead200.7UG/L1 0.700 50.0 ND (50.0)UMagnesium200.7UG/L1 8.90 200 6,680Manganese200.7UG/L1 0.200 15.0 7.91JMercury245.1UG/L1 0.0500 0.200 ND (0.200)UMolybdenum200.7UG/L1 0.200 10.0 143Nickel200.7UG/L1 1.10 50.0 ND (50.0)USelenium200.7UG/L1 0.600 5.00 16.2Silver200.7UG/L1 0.400 20.0 ND (20.0)USodium200.7UG/L1 40.5 500 21,300Thallium200.7UG/L1 0.500 10.0 0.806JTin200.7UG/L1 0.400 30.0 ND (30.0)UTitanium200.7UG/L1 0.200 10.0 14.5Vanadium200.7UG/L1 0.600 20.0 68.5Yttrium200.7UG/L1 0.200 5.00 ND (5.00)UZinc200.7UG/L1 0.200 10.0 1.20JRoutine Metals – DissolvedAluminum200.7UG/L1 10.6 50.0 357Antimony200.7UG/L1 0.700 20.0 3.30JArsenic200.7UG/L1 0.500 10.0 30.1Barium200.7UG/L1 0.100 2.00 206Beryllium200.7UG/L1 0.500 5.00 ND (5.00)U

### A-34E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-6. Ash Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationBoron200.7UG/L1 2.70 100 2,200Cadmium200.7UG/L1 0.100 5.00 ND (5.00)UCalcium200.7UG/L1 5.10 50.0 55,400Chromium200.7UG/L1 0.200 10.0 11.9Hexavalent ChromiumD1687-92UG/L1 1.00 2.00 12.0Cobalt200.7UG/L1 0.600 50.0 ND (50.0)UCopper200.7UG/L1 0.200 10.0 0.795JIron200.7UG/L1 5.40 100 ND (100)ULead200.7UG/L1 0.700 50.0 ND (50.0)UMagnesium200.7UG/L1 8.90 200 6,430Manganese200.7UG/L1 0.200 15.0 2.84JMercury245.1UG/L1 0.0500 0.200 ND (0.200)UMolybdenum200.7UG/L1 0.200 10.0 136Nickel200.7UG/L1 1.10 50.0 ND (50.0)USelenium200.7UG/L1 0.600 5.00 15.3Silver200.7UG/L1 0.400 20.0 ND (20.0)USodium200.7UG/L1 40.5 500 20,000Thallium200.7UG/L1 0.500 10.0 ND (10.0)UTin200.7UG/L1 0.400 30.0 ND (30.0)UTitanium200.7UG/L1 0.200 10.0 ND (10.0)UVanadium200.7UG/L1 0.600 20.0 64.7Yttrium200.7UG/L1 0.200 5.00 ND (5.00)UZinc200.7UG/L1 0.200 10.0 ND (10.0)U

### A-35E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-6. Ash Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLow-Level Metals – TotalAntimony1638UG/L5 0.0350 0.100 4.39Arsenic1638UG/L5 0.0760 0.750 34.9Cadmium1638UG/L5 0.00500 0.500 0.356JChromium1638UG/L5 0.415 4.00 13.5LCopper1638UG/L5 0.0200 1.00 1.49Lead1638UG/L5 0.00500 0.250 0.490Mercury1631EUG/L1 0.000188 0.000500 0.00157Nickel1638UG/L5 0.0650 5.00 1.94JSelenium1638UG/L5 0.0800 5.00 17.1Silver1638UG/L5 0.0100 0.500 0.0252JThallium1638UG/L5 0.00200 0.100 1.46Zinc1638UG/L5 1.05 2.50 1.73JLow-Level Metals - DissolvedAntimony1638UG/L5 0.0350 0.100 4.45Arsenic1638UG/L5 0.0760 0.750 29.0Cadmium1638UG/L5 0.00500 0.500 0.331JChromium1638UG/L5 0.415 4.00 12.6LHexavalent Chromium1636UG/L5 1.75 2.50 14.7Copper1638UG/L5 0.0200 1.00 0.895JLead1638UG/L5 0.00500 0.250 ND (0.250)UMercury1631EUG/L1 0.000188 0.000500 0.000369JNickel1638UG/L5 0.0650 5.00 1.60J

### A-36E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-6. Ash Pond Effluent Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationSelenium1638UG/L5 0.0800 5.00 15.6Silver1638UG/L5 0.0100 0.500 0.0132JThallium1638UG/L5 0.00200 0.100 1.49Zinc1638UG/L5 1.05 2.50 ND (2.50)Ua – Barium was detected in two equipment blanks for #73 silicone tubing at 0.490 ug/L and 0. 476 ug/L. Because #73 silicone tubing was used in this fabricated tubing set, the barium concentration is assumed to be 0.490 ug/L. ND – Not detected (number in parenthesis is the report limit).



### A-37 Table A-7. Bottle Blank and Equipment Bl ank Analytical Data, Widows Creek

Analyte Method Process Units Concentration

LDPE 250 ml Plastic Bottles – Bottle Blank (for low-level metals and low-level hexavalent chromium samples)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Flint 125 ml Amber Glass Bottles – Bottle Blank (for speciation samples)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)a – Barium was detected in two equipment blanks for #73 silicone tubing at 0.490 ug/L and 0. 476 ug/L. Because #73 silicone tubing was used in this fabricated tubing set, the barium concentration is assumed to be 0.490 ug/L. ND – Not detected (number in parenthesis is the report limit).



### A-38 Table A-7. Bottle Blank and Equipment Bl ank Analytical Data, Widows Creek

Analyte Method Process Units Concentration

Flint 250 ml Glass Bottles – Bottle Blank (for low-level mercury samples)

Mercury EPA 1631E Total Recoverable UG/L ND (0.00020)

Capsule Filter – Equipment Blank (for di ssolved low-level metals sample collection)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Mercury EPA 1631E Dissolved UG/L ND (0.00020)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

LDPE 4000 ml Plastic Bottles – Bottle Bl ank (for low-level metals field blank water)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)a – Barium was detected in two equipment blanks for #73 silicone tubing at 0.490 ug/L and 0. 476 ug/L. Because #73 silicone tubing was used in this fabricated tubing set, the barium concentration is assumed to be 0.490 ug/L. ND – Not detected (number in parenthesis is the report limit).



### A-39 Table A-7. Bottle Blank and Equipment Bl ank Analytical Data, Widows Creek

Analyte Method Process Units Concentration

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Borosilicate 1000 ml Glass Bo ttles – Bottle Blank (for low- level mercury field blank water)

Mercury EPA 1631E Total Recoverable UG/L ND (0.00020)

LDPE 10 L Composite Bottles – Bottle Blank (alternat ive sample composite bott le for composite sample collection for the FGD pond influent and ash pond influent)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Mercury EPA 1631E Total Recoverable UG/L ND (0.00020)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

LDPE 20 L Composite Bottles – Bottle Blank (sample composite bottle for compos ite sample collection for the FGD pond influent and ash pond influent)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)a – Barium was detected in two equipment blanks for #73 silicone tubing at 0.490 ug/L and 0. 476 ug/L. Because #73 silicone tubing was used in this fabricated tubing set, the barium concentration is assumed to be 0.490 ug/L. ND – Not detected (number in parenthesis is the report limit).



### A-40 Table A-7. Bottle Blank and Equipment Bl ank Analytical Data, Widows Creek

Analyte Method Process Units Concentration

Mercury EPA 1631E Total Recoverable UG/L ND (0.00020)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Pump-Off Tubing Set – Equipment Bl ank (Teflon® and #73 silicone tubing for dissolved sample collection for low-level metals)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium a EPA 1638 Dissolved UG/L 0.490

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Mercury EPA 1631E Total Recoverable UG/L ND (0.00020)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Tubing Set – Equipment Blank (25 feet of Teflon® t ubing attached to 10 feet #73 silicone tubing for composite sample collection for low-level mercury and metals from FGD pond influent and ash pond influent)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium a EPA 1638 Dissolved UG/L 0.490

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)a – Barium was detected in two equipment blanks for #73 silicone tubing at 0.490 ug/L and 0. 476 ug/L. Because #73 silicone tubing was used in this fabricated tubing set, the barium concentration is assumed to be 0.490 ug/L. ND – Not detected (number in parenthesis is the report limit).



### A-41 Table A-7. Bottle Blank and Equipment Bl ank Analytical Data, Widows Creek

Analyte Method Process Units Concentration

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Mercury EPA 1631E Total Recoverable UG/L ND (0.00020)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Tubing Set – Equipment Blank (25 feet of Teflon® tubi ng, 5 feet #73 silicone tubi ng, Y-splitter, two pieces of 5 feet #24 silicone tubing for sample collection fo r low-level mercury and metals from FGD pond effluent and ash pond effluent)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium a EPA 1638 Dissolved UG/L 0.490

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Mercury EPA 1631E Total Recoverable UG/L ND (0.00020)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Funnel Assembly Set – Equipment Blank (Plastic funnel attached to #73 silicone tubing, Y-splitter, and 2 pieces of 5 feet of #24 silicone t ubing for sample collection for low- level total and dissolved mercury and

total metals at the FGD influe nt and ash pond influent)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)a – Barium was detected in two equipment blanks for #73 silicone tubing at 0.490 ug/L and 0. 476 ug/L. Because #73 silicone tubing was used in this fabricated tubing set, the barium concentration is assumed to be 0.490 ug/L. ND – Not detected (number in parenthesis is the report limit).



### A-42 Table A-7. Bottle Blank and Equipment Bl ank Analytical Data, Widows Creek

Analyte Method Process Units Concentration

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium a EPA 1638 Dissolved UG/L 0.490

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Mercury EPA 1631E Total Recoverable UG/L ND (0.00020)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

### A-43J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-8. FGD Pond Influent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationRoutine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 ND (20.0) UArsenic 200.7 UG/L 1 0.500 10.0 ND (10.0) UBarium 200.7 UG/L 1 0.100 2.00 ND (2.00) UBeryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 14.1 JCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 9.62 JChromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND (10.0) UIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 ND (200) UManganese 200.7 UG/L 1 0.200 15.0 ND (15.0) UMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 0.457 JNickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND (5.00) USilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 ND (500) UThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) U

### A-44J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-8. FGD Pond Influent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) URoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 ND (20.0) UArsenic 200.7 UG/L 1 0.500 10.0 ND (10.0) UBarium 200.7 UG/L 1 0.100 2.00 ND (2.00) UBeryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 14.3 JCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 44.5 JChromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND (10.0) UIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 ND (200) UManganese 200.7 UG/L 1 0.200 15.0 ND (15.0) UMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 0.312 JNickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND (5.00) USilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 ND (500) UThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) U

### A-45J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-8. FGD Pond Influent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) UYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) ULow-Level Metals – TotalAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND (0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.276 JCopper 1638 UG/L 1 0.00400 0.200 0.00550 JLead 1638 UG/L 1 0.00100 0.0500 0.00220 JMercury 1631E UG/L 1 0.000188 0.000500 ND (0.000500) UNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 ND (0.100) UThallium 1638 UG/L 1 0.000400 0.0200 ND (0.0200) UZinc 1638 UG/L 1 0.209 0.500 ND (0.500) ULow-Level Metals - DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 0.00120 JChromium 1638 UG/L 1 0.0830 0.800 0.315 JCopper 1638 UG/L 1 0.00400 0.200 ND (0.200) ULead 1638 UG/L 1 0.00100 0.0500 0.00130 JNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) U

### A-46J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-8. FGD Pond Influent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationSelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 0.00270 JThallium 1638 UG/L 1 0.000400 0.0200 0.000600 JZinc 1638 UG/L 1 0.209 0.500 ND (0.500) U

### A-47J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-9. FGD Pond Effluent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationRoutine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND(50.0) UAntimony 200.7 UG/L 1 0.700 20.0 ND(20.0) UArsenic 200.7 UG/L 1 0.500 10.0 ND(10.0) UBarium 200.7 UG/L 1 0.100 2.00 ND(2.00) UBeryllium 200.7 UG/L 1 0.500 5.00 ND(5.00) UBoron 200.7 UG/L 1 2.70 100 9.01 JCadmium 200.7 UG/L 1 0.100 5.00 ND(5.00) UCalcium 200.7 UG/L 1 5.10 50.0 ND(50.0) UChromium 200.7 UG/L 1 0.200 10.0 ND(10.0) UCobalt 200.7 UG/L 1 0.600 50.0 ND(50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND(10.0) UIron 200.7 UG/L 1 5.40 100 ND(100) ULead 200.7 UG/L 1 0.700 50.0 ND(50.0) UMagnesium 200.7 UG/L 1 8.90 200 ND(200) UManganese 200.7 UG/L 1 0.200 15.0 ND(15.0) UMercury 245.1 UG/L 1 0.0500 0.200 ND(0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 ND(10.0) UNickel 200.7 UG/L 1 1.10 50.0 ND(50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND(5.00) USilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 ND(500) UThallium 200.7 UG/L 1 0.500 10.0 ND(10.0) UTin 200.7 UG/L 1 0.400 30.0 ND(30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND(10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND(20.0) U

### A-48J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-9. FGD Pond Effluent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationYttrium 200.7 UG/L 1 0.200 5.00 ND(5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND(10.0) URoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 ND(50.0) UAntimony 200.7 UG/L 1 0.700 20.0 ND(20.0) UArsenic 200.7 UG/L 1 0.500 10.0 ND(10.0) UBarium 200.7 UG/L 1 0.100 2.00 ND(2.00) UBeryllium 200.7 UG/L 1 0.500 5.00 ND(5.00) UBoron 200.7 UG/L 1 2.70 100 9.23 JCadmium 200.7 UG/L 1 0.100 5.00 ND(5.00) UCalcium 200.7 UG/L 1 5.10 50.0 ND(50.0) UChromium 200.7 UG/L 1 0.200 10.0 ND(10.0) UHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND(2.00) UCobalt 200.7 UG/L 1 0.600 50.0 ND(50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND(10.0) UIron 200.7 UG/L 1 5.40 100 ND(100) ULead 200.7 UG/L 1 0.700 50.0 ND(50.0) UMagnesium 200.7 UG/L 1 8.90 200 ND(200) UManganese 200.7 UG/L 1 0.200 15.0 ND(15.0) UMercury 245.1 UG/L 1 0.0500 0.200 ND(0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 ND(10.0) UNickel 200.7 UG/L 1 1.10 50.0 ND(50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND(5.00) USilver 200.7 UG/L 1 0.400 20.0 ND(20.0) USodium 200.7 UG/L 1 40.5 500 ND(500) UThallium 200.7 UG/L 1 0.500 10.0 ND(10.0) U

### A-49J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-9. FGD Pond Effluent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationTin 200.7 UG/L 1 0.400 30.0 ND(30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND(10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND(20.0) UYttrium 200.7 UG/L 1 0.200 5.00 ND(5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND(10.0) ULow-Level Metals – TotalAntimony 1638 UG/L 1 0.00700 0.0200 ND(0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND(0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND(0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.237 JCopper 1638 UG/L 1 0.00400 0.200 ND(0.200) ULead 1638 UG/L 1 0.00100 0.0500 0.00540 JMercury 1631E UG/L 1 0.000188 0.000500 ND(0.000500) UNickel 1638 UG/L 1 0.0130 1.00 ND(1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND(1.00) USilver 1638 UG/L 1 0.00200 0.100 0.00290 JThallium 1638 UG/L 1 0.000400 0.0200 0.000400 JZinc 1638 UG/L 1 0.209 0.500 0.442 JLow-Level Metals - DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND(0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND(0.150) UCadmium 1638 UG/L 1 0.00100 0.100 0.00230 JChromium 1638 UG/L 1 0.0830 0.800 0.258 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 1.81 JCopper 1638 UG/L 1 0.00400 0.200 ND(0.200) ULead 1638 UG/L 1 0.00100 0.0500 0.0432 J

### A-50J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-9. FGD Pond Effluent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationNickel 1638 UG/L 1 0.0130 1.00 ND(1.00) USelenium 1638 UG/L 1 0.0160 1.00 0.0358 JSilver 1638 UG/L 1 0.00200 0.100 0.00250 JThallium 1638 UG/L 1 0.000400 0.0200 0.000600 JZinc 1638 UG/L 1 0.209 0.500 ND(0.500) U

### A-51Table A-10. Ash Pond Influent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLow-Level Metals – TotalAntimony 1638 UG/L 1 0.00700 0.0200 ND(0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND(0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND(0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.297 JCopper 1638 UG/L 1 0.00400 0.200 0.00670 JLead 1638 UG/L 1 0.00100 0.0500 ND(0.0500) UMercury 1631E UG/L 1 0.000188 0.000500 ND(0.000500) UNickel 1638 UG/L 1 0.0130 1.00 ND(1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND(1.00) USilver 1638 UG/L 1 0.00200 0.100 ND(0.100) UThallium 1638 UG/L 1 0.000400 0.0200 0.000400 JZinc 1638 UG/L 1 0.209 0.500 ND(0.500) ULow-Level Metals – DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND(0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND(0.150) UCadmium 1638 UG/L 1 0.00100 0.100 0.00110 JChromium 1638 UG/L 1 0.0830 0.800 0.290 JCopper 1638 UG/L 1 0.00400 0.200 0.0619 JLead 1638 UG/L 1 0.00100 0.0500 0.00150 JNickel 1638 UG/L 1 0.0130 1.00 ND(1.00) USelenium 1638 UG/L 1 0.0160 1.00 0.0271 JSilver 1638 UG/L 1 0.00200 0.100 0.00280 JThallium 1638 UG/L 1 0.000400 0.0200 ND(0.0200) UZinc 1638 UG/L 1 0.209 0.500 ND(0.500) UJ – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).

### A-52Table A-11. Ash Pond Effluent Field Blank Analytical Data, Widows CreekAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLow-Level Metals – TotalAntimony 1638 UG/L 1 0.00700 0.0200 ND(0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND(0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND(0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.276 JCopper 1638 UG/L 1 0.00400 0.200 0.0301 JLead 1638 UG/L 1 0.00100 0.0500 0.0191 JMercury 1631E UG/L 1 0.000188 0.000500 0.000330 JNickel 1638 UG/L 1 0.0130 1.00 ND(1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND(1.00) USilver 1638 UG/L 1 0.00200 0.100 0.00240 JThallium 1638 UG/L 1 0.000400 0.0200 0.000700 JZinc 1638 UG/L 1 0.209 0.500 ND(0.500) ULow-Level Metals – DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND(0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND(0.150) UCadmium 1638 UG/L 1 0.00100 0.100 0.00210 JChromium 1638 UG/L 1 0.0830 0.800 0.278 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 2.50 JCopper 1638 UG/L 1 0.00400 0.200 0.0234 JLead 1638 UG/L 1 0.00100 0.0500 0.0210 JNickel 1638 UG/L 1 0.0130 1.00 ND(1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND(1.00) USilver 1638 UG/L 1 0.00200 0.100 0.00230 JThallium 1638 UG/L 1 0.000400 0.0200 0.000500 JZinc 1638 UG/L 1 0.209 0.500 ND(0.500) UJ – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. (Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit)

### Appendix B

ANALYTICAL DATA FOR METALS , FGD POND AND ASH POND

### B-1CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.L – Sample result between 5x and 10x blank result.J - Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U - Result below the MDL. Number shownin parentheses is the reporting limit).NA – Not analyzed.ND – Not detected (number in parenthesis is the report limit).Note: Results shown are not paired samples. See Section 4.2.Table B-1. Analytical Results for Metals in the FGDPond System, Widows CreekFGD Pond Influent (SP-1)Original FGD Pond Effluent (SP-2)Duplicate FGD Pond Effluent (SP-5)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedRoutine MetalsAluminum 200.7 UG/L 234,000 86.6 117 46.8 J 105 47.4 JAntimony 200.7 UG/L 76.2 CJ 12.3 J 15.8 J 14.8 J 15.2 J 14.4 JArsenic 200.7 UG/L 523 13.9 50.2 47.2 48.8 46.1Barium 200.7 UG/L 7,200 257 186 191 171 191Beryllium 200.7 UG/L 44.3 1.58 J 1.95 J 1.79 J 1.85 1.76 JBoron 200.7 UG/L 28,900 24,100 31,700 28,700 31,200 29,700Cadmium 200.7 UG/L 89.2 0.991 J 0.525 J 0.272 J 0.479 J 0.292 JCalcium 200.7 UG/L 5,990,000 849,000 987,000 934,000 986,000 929,000Chromium 200.7 UG/L 1,360 18.7 1.65 J 1.10 J 1.54 J 1.01 JHexavalentChromiumD1687-92 UG/L NA ND (2.00) U NA ND (2.00) U NA ND (2.00) UCobalt 200.7 UG/L 138 CJ 1.61 J 2.22 J 1.77 J 2.15 J 1.80 JCopper 200.7 UG/L 653 3.79 J 2.98 J 2.43 J 2.82 J 2.12 JIron 200.7 UG/L 299,000 17.9 J 64.8 J 21.1 J 55.3 J 19.7 JLead 200.7 UG/L 436 ND (50.0) U ND (50.0) U ND (50.0) U ND (50.0) U ND (50.0) UMagnesium 200.7 UG/L 321,000 176,000 193,000 182,000 185,000 186,000Manganese 200.7 UG/L 2,780 583 636 543 R 609 542Mercury 245.1 UG/L 26.5 ND (2.00) U ND (2.00) U ND (2.00) U ND (2.00) U ND (2.00) UMolybdenum 200.7 UG/L 1,340 876 1,530 1,480 1,470 1,450

### B-2CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.L – Sample result between 5x and 10x blank result.J - Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U - Result below the MDL. Number shownin parentheses is the reporting limit).NA – Not analyzed.ND – Not detected (number in parenthesis is the report limit).Note: Results shown are not paired samples. See Section 4.2.Table B-1. Analytical Results for Metals in the FGDPond System, Widows CreekFGD Pond Influent (SP-1)Original FGD Pond Effluent (SP-2)Duplicate FGD Pond Effluent (SP-5)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedNickel 200.7 UG/L 489 25.0 J 32.0 J 29.7 J 30.8 J 29.3 JSelenium 200.7 UG/L 652 366 241 231 230 221Silver 200.7 UG/L 9.82 CJ ND (20.0) U ND (20.0) U ND (20.0) U ND (20.0) U ND (20.0) USodium 200.7 UG/L 104,000 76,700 69,200 66,900 69,700 65,500Thallium 200.7 UG/L 16.2 CJ 14.3 1.45 J 1.61 J 1.67 J 1.61 JTin 200.7 UG/L 21.2 CJ ND (30.0) U ND (30.0) U ND (30.0) U ND (30.0) U ND (30.0) UTitanium 200.7 UG/L 8,180 ND (10.0) U 1.48 J ND (10.0) U 1.21 J ND (10.0) UVanadium 200.7 UG/L 1,580 15.8 J 42.7 39.7 41.4 40.2Yttrium 200.7 UG/L 217 ND (5.00) U ND (5.00) U ND (5.00) U ND (5.00) U ND (5.00) UZinc 200.7 UG/L 3,140 ND (10.0) U 0.335 J ND (10.0) U 0.702 J ND (10.0) ULow-Level MetalsAntimony 1638 UG/L 51.8 8.90 11.8 11.8 11.8 11.9Arsenic 1638 UG/L 617 18.0 47.3 47.0 47.9 46.0Cadmium 1638 UG/L 86.0 3.16 3.66 3.76 3.80 3.71Chromium 1638 UG/L 1,380 ND (16.0) U 14.6 J 14.4 J 14.7 J 13.6 JHexavalentChromium1636 UG/L NA NA NA 3.29 NA 3.10Copper 1638 UG/L 826 2.83 J 1.46 J 0.842 J 1.27 J 1.05 JLead 1638 UG/L 545 ND (1.00) U 0.0828 J ND (1.00) U 0.129 J ND (1.00) UMercury 1631E UG/L 24.7 0.0761 0.0428 0.0106 0.0448 0.0107

### B-3CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.L – Sample result between 5x and 10x blank result.J - Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U - Result below the MDL. Number shownin parentheses is the reporting limit).NA – Not analyzed.ND – Not detected (number in parenthesis is the report limit).Note: Results shown are not paired samples. See Section 4.2.Table B-1. Analytical Results for Metals in the FGDPond System, Widows CreekFGD Pond Influent (SP-1)Original FGD Pond Effluent (SP-2)Duplicate FGD Pond Effluent (SP-5)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedNickel 1638 UG/L 634 29.6 35.6 32.8 L 36.7 33.8 LSelenium 1638 UG/L 651 325 205 213 211 373Silver 1638 UG/L 5.10 J ND (2.00) U 0.0449 J ND (2.00) U ND (2.00) U ND (2.00) UThallium 1638 UG/L 93.8 22.5 11.1 11.0 11.1 10.9Zinc 1638 UG/L 2,720 ND (10.0) U ND (10.0) U ND (10.0) U ND (10.0) U ND (10.0) UCJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At least one of th e sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above th e method detection limit, and the calculated total sample concentration is less than the calculated sample-specific report limit. L – Sample result between 5x and 10x blank result. J - Result measured above the MDL, but less than the reporting limit.

U - Result below the MDL. Number shown in parentheses is the reporting limit). NA – Not analyzed. ND – Not detected (number in parenthesis is the report limit). Note: Results shown are not pair ed samples. See Section 4.3.



### B-4 Table B-2. Analytical Results for Metals in the Ash Pond System, Widows Creek

Ash Pond Influent (SP-3) Ash Pond Effluent (SP-4) Analyte Method Unit Total Dissolved Total Dissolved

Routine Metals

Aluminum 200.7 UG/L 94,800 663 1,070 357

Antimony 200.7 UG/L 6.15 CJ 7.45 J 3.40 J 3.30 J

Arsenic 200.7 UG/L 131 46.0 38.2 30.1

Barium 200.7 UG/L 6,080 178 227 206

Beryllium 200.7 UG/L 11.3 ND (5.00) U ND (5.00) U ND (5.00) U

Boron 200.7 UG/L 4,330 2,150 2,210 2,200

Cadmium 200.7 UG/L 9.93 ND (5.00) U ND (5.00) U ND (5.00) U

Calcium 200.7 UG/L 103,000 40,300 58,500 55,400

Chromium 200.7 UG/L 107 3.09 J 13.5 11.9

Hexavalent Chromium D1687-92 UG/ L NA ND (2.00) U NA 12.0

Cobalt 200.7 UG/L 48.6 CJ ND (50.0) U ND (50.0) U ND (50.0) U

Copper 200.7 UG/L 188 0.233 J 1.58 J 0.795 J

Iron 200.7 UG/L 80,700 ND (100) U 144 ND (100) U

Lead 200.7 UG/L 208 ND (50.0) U ND (50.0) U ND (50.0) U

Magnesium 200.7 UG/L 25,700 7,110 6,680 6,430

Manganese 200.7 UG/ L 337 2.07 J 7.91 J 2.84 J

Mercury 245.1 UG/L 2.66 ND (0.200) U ND (0.200) U ND (0.200) U

Molybdenum 200.7 UG/L 65.5 50.1 143 136

Nickel 200.7 UG/L 66.8 CJ ND (50.0) U ND (50.0) U ND (50.0) U

Selenium 200.7 UG/L 27.5 26.8 16.2 15.3

Silver 200.7 UG/L 3.99 CJ ND (20.0) U ND (20.0) U ND (20.0) U

Sodium 200.7 UG/L 31,200 13,400 21,300 20,000

Thallium 200.7 UG/L ND (19. 0) U ND (10.0) U 0.806 J ND (10.0) U

Tin 200.7 UG/L 12.4 CJ ND (30.0) U ND (30.0) U ND (30.0) U

Titanium 200.7 UG/L 7,150 ND (10.0) U 14.5 ND (10.0) U

Vanadium 200.7 UG/L 346 66.8 68.5 64.7

Yttrium 200.7 UG/L 133 ND (5.00) U ND (5.00) U ND (5.00) U

Zinc 200.7 UG/L 785 ND (10.0) U 1.20 J ND (10.0) U

Low-Level Metals

Antimony 1638 UG/L 13.1 L 8.54 4.39 4.45

Arsenic 1638 UG/L 88.9 49.5 34.9 29.0

Cadmium 1638 UG/L 3.19 J 0.136 J 0.356 J 0.331 J

Chromium 1638 UG/L ND (160) U ND (16.0) U 13.5 L 12.6 L

Hexavalent Chromium 1636 UG/L NA NA NA 14.7CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At least one of th e sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above th e method detection limit, and the calculated total sample concentration is less than the calculated sample-specific report limit. L – Sample result between 5x and 10x blank result. J - Result measured above the MDL, but less than the reporting limit.

U - Result below the MDL. Number shown in parentheses is the reporting limit). NA – Not analyzed. ND – Not detected (number in parenthesis is the report limit). Note: Results shown are not pair ed samples. See Section 4.3.



### B-5 Table B-2. Analytical Results for Metals in the Ash Pond System, Widows Creek

Ash Pond Influent (SP-3) Ash Pond Effluent (SP-4) Analyte Method Unit Total Dissolved Total Dissolved

Copper 1638 UG/L 114 0.623 J 1.49 0.895 J

Lead 1638 UG/L 104 ND (1.00) U 0.490 ND (0.250) U

Mercury 1631E UG/L 1.02 0.000368 J 0.00157 0.000369 J

Nickel 1638 UG/L 25.6 J ND (20.0) U 1.94 J 1.60 J

Selenium 1638 UG/L ND (200) U ND (100) U 17.1 15.6

Silver 1638 UG/L ND (20.0) U ND (2.00) U 0.0252 J 0.0132 J

Thallium 1638 UG/L 2.60 J ND (0.400) U 1.46 1.49

Zinc 1638 UG/L 198 ND (10.0) U 1.73 J ND (2.50) U

### Appendix C

DATA REVIEW NARRATIVESC o m put er Sci e nces C o r p orat i on

ww w.csc

. com



### MEMORANDUM

DATE: December 14, 200 7

TO: Ron Jordan, Project Offic e r EPA EAD

FROM: Sara Clark, Q u ality Assurance Che m ist

Co m puter Sciences Corporation

SUBJECT: Data Review Narrative for Classi cal Anal y ses for the Steam Electri c Power Study, Episode 65 49

OVE RVI E W

Under EPA Contract Num b er 68-C-03-058, ProChem Analy tical, Inc. subm itted classical wet chem istry

data for seven sam p les in Episode 65 49 . Sam p les 70520 and 70 52 2, identified a s FGD Influent and Ash

Pond I n fluent respectively

, were expected to contain a significant and variable p a rticulate concentration. EPA and industry represe ntatives were concerned that the variable nature of the sam p les would 1)

co m p licate th e collection of a representa tive sa m p le f o r both EPA and industry analy ses and 2) lead to analy tical interferenc es. Therefore, for so m e cla ssi c a l analy ses (those with a listed phase in Table 1), the

laborator y was directed by EPA to separate the FGD influent and A s h Pond I n flu e nt sam p les into an aqueous-phase and a solid-phase and analy ze each. The two sets of results (aqueous and solid phases) are provided in the analy tical database, as a r e calculat e d total results (derived by com b ining aqueous and solid phases results).

Table 1 provides a co m p let e listing of sam pl es, matric es, descriptions, sa m p ling dates, phases, and the required analy t es.

Table 1 - Sam p le Identifiers , Des cri ptions, Sam p ling Dates an d An alytes

EPA Sa mple # Ma trix Sample Descri ption Sa mpling

Da te P h a s e A n al yt es

70 5 20 Aq ue ous SP- 1 – F G D In fl ue nt 9/ 1 1 / 0 7 N A BO D ( S M 52 10 B)

, HEM ( 166 4A ), SG T-H E M (1 6 6 4 A )

, Hexa val e nt
C h r o m i u m (ASTM D 1 68 7-

92 ), TSS (SM 25 4 0 D )

, an d

TD S ( S M 25 40 C)

70 5 20 Aq ue ous SP- 1 – F G D In fl ue nt 9/ 1 1 / 0 7 Filtered Aq ue ous Chlori de (SM 45 0 0 -Cl

- C), Sulfate (AST M D516-90),

TK N (SM 4500 -N C),

A m m o n i a ( S M 45 00- NH 3 F), Tot a l P h os ph o r us (365 .3 ), and Ni trate/Nitrite ( S M 4 500 -N O3 H )

61 0 1 St e v en so n Ave n ue Alexa n d r ia, Vi rgi n ia 22 3 04

7 0 3

. 46 1.200 0 Fax 703 .4 61 .20 2 0Table 1 - Sam p le Identifiers , Des cri ptions, Sam p ling Dates an d An alytes

EPA Sa mple # Ma trix Sample Descri ption Sa mpling

Da te P h a s e A n al yt es

70 5 20 Aq ue ous SP- 1 – F G D In fl ue nt 9/ 1 1 / 0 7 Filtered

So lid Chlori de (SM 45 0 0 -Cl - C), Sulfate (AST M D516-90),

TK N (SM 4500 -N C),

A m m o n i a ( S M 45 00- NH 3 F), Tot a l P h os ph o r us (365 .3 ), Nitrat e/Nitrite (SM

4 500 -N O3 H) , an d To tal

So lid s (2 540 B)

70 5 20 Aq ue ous SP- 1 – F G D In fl ue nt NA Calculated

To tal Chlori de (SM 45 0 0 -Cl

- C), Sulfate (AST M D516-90),

TK N (SM 4500 -N C),

A m m o n i a ( S M 45 00- NH 3 F), Tot a l P h os ph o r us (365 .3 ), and Ni trate/Nitrite ( S M 4 500 -N O3 H )

70 5 21 Aq ue ous SP- 2 – F G D

Effl uent 9/ 1 1 / 0 7 N A BO D ( S M 52 10 B)

, HEM ( 166 4A ), SG T-H E M (1 6 6 4 A )

, Hexa val e nt
C h r o m i u m (ASTM D 1 68 7-

92 ), TSS (SM 25 4 0 D )

,

TD S ( S M 25 40 C)

, Chlori de (SM 45 0 0 -Cl

- C), Sulfate (AST M D516-90),

To tal Ph o s ph oru s ( 365 .3 )

,

TK N (SM 4500 -N C), Nitrate/Nitrite (SM 4 500

-

NO 3 H)

, a n d Am m onia ( S M 4 500 -N H3 F)

70 5 22 Aq ue ous SP- 3 – As h P o nd

In flue nt 9/ 1 2 / 0 7 N A BO D ( S M 52 10 B)

, HEM ( 166 4A ), SG T-H E M (1 6 6 4 A )

, Hexa val e nt
C h r o m i u m (ASTM D 1 68 7-

92 ), TSS (SM 25 4 0 D )

, an d

TD S ( S M 25 40 C)

70 5 22 Aq ue ous SP- 3 – As h P o nd

In flue nt 9/ 1 2 / 0 7 Filtered Aq ue ous Chlori de (SM 45 0 0 -Cl

- C), Sulfate (AST M D516-90),

TK N (SM 4500 -N C),

A m m o n i a ( S M 45 00- NH 3 F), Tot a l P h os ph o r us (365 .3 ), and Ni trate/Nitrite ( S M 4 500 -N O3 H )

2Table 1 - Sam p le Identifiers , Des cri ptions, Sam p ling Dates an d An alytes

EPA Sa mple # Ma trix Sample Descri ption Sa mpling

Da te P h a s e A n al yt es

70 5 22 Aq ue ous SP- 3 – As h P o nd

In flue nt 9/ 1 2 / 0 7 Filtered

So lid Chlori de (SM 45 0 0 -Cl

- C), Sulfate (AST M D516-90),

TK N (SM 4500 -N C),

A m m o n i a ( S M 45 00- NH 3 F), Tot a l P h os ph o r us (365 .3 ), To tal So lid s (2 5 40B ), a n d Nitrate/Nitrite (SM 4 500

- NO 3 H)

70 5 22 Aq ue ous SP- 3 – As h P o nd

In flue nt NA Calculated

To tal Chlori de (SM 45 0 0 -Cl

- C), Sulfate (AST M D516-90),

TK N (SM 4500 -N C),

A m m o n i a ( S M 45 00- NH 3 F), Tot a l P h os ph o r us (365 .3 ), and Ni trate/Nitrite ( S M 4 500 -N O3 H )

70 5 23 Aq ue ous SP- 4 – As h P o nd

Effl uent 9/ 1 2 / 0 7 N A BO D ( S M 52 10 B)

, TSS (SM 25 4 0 D ) , TDS (SM

2 540 C), Ch l o ri d e (SM

4 500

- C l

- C), To tal

Pho s pho ru s (36 5

. 3 )

, TKN ( S M 4 500 -N C )

, Nitrate/Nitrite (SM 4 500

- NO 3 H) , Am monia (SM

4500-NH3 F), Sulfate ( A STM D51 6 -9 0) , H E M

( 166 4A ), SG T-H E M ( 166 4A ), an d H e x a v a len t
C h r o m i u m (ASTM D 1 68 7-

92 )

9/ 1 1 / 0 7 N A BO D ( S M 52 10 B)

, Hexa val e nt C h rom i u m ( A STM D16 87- 92 )

70 5 24 Aq ue ous SP- 5 – F G D

Effl uent D upl i cat e

9/ 1 2 / 0 7 N A TSS ( S M 2 540D )

, TD S (SM 25 4 0 C), Chlori de (SM

4 500

- C l

- C), To tal

Pho s pho ru s (36 5

. 3 )

, TKN ( S M 4 500 -N C )

, Nitrate/Nitrite (SM 4 500

- NO 3 H) , Am monia (SM

4 500 -N H3 F), and Sulfate (AS T M D 5 16

- 9 0 )

70 5 25 Aq ue ous SP- 6 - F G D I n fl ue nt
Field Blank 9/ 1 1 / 0 7 N A Hexa val e nt C h rom i u m ( A STM D16 87- 92 )

70 5 26 Aq ue ous SP- 7 – F G D

Effl uent Fi el d B l ank 9/ 1 1 / 0 7 N A Hexa val e nt C h rom i u m ( A STM D16 87- 92 )

NA= No t ap p licab le

3

### These data ha ve been reviewed in accor d ance with CSC’ s Data Re view Guidelines for Classic a l Wet

Chemistr y Analyses (DR-02 Revision 2, Septem ber 1, 2007) an d wit h the specifications listed in the contract. A summary of the results of the data re view process is provided below, followed by detailed descriptions of data issues i d entified with these sa m p l e s. Based on this review, al l data in this episode are considered to be of accepta ble qualit y with the qualific ations described below and detailed in the attached data review summary table (Table 2).

SUMMARY

All sa m p le s were analy z e d within the contract-sp ecif i ed holding times for all cl assic a l wet ch e m istry

param e ters sp ecified in the sam p ling and analy s is plan , except for th e total phosp horus, SGT- HEM, and TSS analy ses as described below. The calibration an d continuing c a libration standards were successfully analy zed. La boratory blanks were perfo r m ed for each analy s is, and there was no conta m ination detected

above the m i nim u m level (ML). Effluent and infl ue n t field blanks were analy z ed for hexaval e nt
chrom i u m . The analy t e was not detected above the M L in either bl ank. The QC sam p les, including the ongoi ng precision and reco very sam ple (OPR) and m a trix spike/m a trix spike du pl icate (MS/MSD)

sa m p le s, de monstrated that laboratory pe rformance fo r these analy ses was a c c e pta b le with the exceptions

described below.

DATA ISSU ES

Nitrate and Nitrite

The MS and MSD recoveries (60% and 27% , respectiv ely ) f o r sample 705 21 were below the contractspecified acceptance criter i a of 75-125%. The RP D (77%) was above the criteria of 20%. Because

nitrate/nitrite was not detec t ed in the sample, CSC recommends that the result be included in the database without q u alification.

Total Phosphorus

The following sa m p les w e re analy zed for total phosp horus less than one da y (4-6 hours) past holding time: samples 70521, 70523, and 7 0524; filtered solid and filtered aqueous sam p les 70520 and 70522.

CSC considers these results to be estimat ed values.

HEM

The RPD between the MS and MSD for sam p le 70521 was 34% , which is above the contract specified

acceptanc e cr iteria of 20%. The MS/MSD percent rec overies were within contra ct specified a cceptance
criteria. Because HEM was not det ected in the sam ple, CSC considers the result to be acceptable without qualification.

SGT-HEM

The analy s is of SGT-HEM for sam p le 70520 was perf ormed one d a y o u t of hol d i ng tim e. CSC considers

the SGT-HE M result for this sa m p le to be an esti m at ed value.

TSS

The followin g sam p les an aly zed for TS S were analy zed one da y p ast holding ti me: 70520, 7 0522 , 70 523

, and 70524. CSC considers the TSS results fo r these sam p les to be esti m at ed values.

4

### BOD

FGD Effluent sam p le 70521 did not m e et the contract-specified m i n i m u m dissolved ox y g en de pletion of

2.0 m g /L, indicating that a less dilute sam p l e aliquot should have been analy zed. Therefore, the BOD

result for sa mple 70521 is reported in the database as n o t detected at an elevated ML of 9 m g /L.

TECHNICAL NOT E S:

SGT-HEM

Although HEM/SGT-HE M analy ses were requested fo r sam p les 7 0521 and 70522, SGT-HEM analy s is was not required because HEM was not detected in these sa mples.

Phase Separation and Calculations

As described in the phase separation document, EPA’s contract laboratory was a s ked to m e as ure and record the following data as part of the phase separ ati on process:

• Original sample weight

• Original sample volume

• Net weight of solid phase on the filter

• Filtrate weig ht

• Filtrate volume

These data were required elem ents of the for m ula used to calculate a total result; there should be one set

of these recor d s for each of Group I and Group II analy ses. The laborator y failed to provide those item s listed in bold above.

CSC calculat e d the total results for the F GD Influent and Ash Pon d Influent sam p l es using the f o llowing

form ula:

L Vol. kg) Wt. mg/kg (Conc. L) Vol. x mg/L (Conc. mg/L ion Concentrat Sample Total

sample original phase solid phase solid Filtrate Filtrate × +

=



### Several varia b les were not recorded by the labor atory as requested

— m ost i m po rtantly, the original

sam p le volume and filtrat e volum e. In discussion with the lab, CS C was able to calculate the missing

variables based on ot her in formation that the laborato r y was able to provide including the original sa m p le density, original sam p le weight, solid phase weight, a nd the filtrate weight. This series of cal culations follows and is detailed in the phase sepa r ation data ele m ents table (Table 3):

• Original sample weight = (Original sa mple volum e) x (Original sam ple density )

• Filtrate weight = (Original sam p le weight) - (Solid-phase weight)

• Filtrate volume = (Filtrat e weight) / (Original sam p le densit y )

In generating the classicals “Calculat e d Total” resu lts f o r the Steam Electric Study, CSC used all values greater than the ML

. 

### How e ver, if any concentration was aff ected by contam ina tion in an associated blank

at less than 5 times the a s s o ciated blank result, it was changed to a zero before going through the calculation, per CSC' s data review protocols. Ne gative values submitted by the laborator y were not used

in the calculations.

5

### Please note that the results for the various phases will be labeled in the PROCEDUR field of the EPA database as “FILTERED AQUE OUS”, “FILTERED SOLID (WE T WEIGHT)”, and “CALCULATED

TOTAL”.

Minimum L e v e ls

When two results are m a th em ati cally com b ined to obt ain a Calculat ed Total result, CSC will report the larger of the two MLs asso ciated with ea ch result as the Calculated Total ML.

Percent Soli ds

The percent solid results in Table 3 are provided if needed by EPA t o convert soli d phase wet weight

basis values t o dry weight results. Perce n t solids were not used t o generate the “Calculated T o tal” results.

If you have any questions regarding the analy ses of these sam p les or the review of these data, please contact Barbara Beard by t e lephone at (703) 461-2154 , by facsi m i l e at (703) 461-8056, or by em ail at

bbeard2@csc.com

.

cc: Brian D’Am ico, EPA Beverly Rand olph, EPA

Marla Sm ith, EPA Nelson Andrews, EPA Brian Englert, EPA Deb Bartram, ERG TJ Finseth, ERG Lynn Walters, CSC

Barbara B ear d, CSC

6

### Table 2

Data Review Summary T a ble

Episode: 6549 Analysis: Classi cals

Industry: Steam Electric Power Study Reviewe r : Sara Clark

Sample An al yt e Acti on Reas on CS C Q u al Lev e l

70 5 20 2 5 ,300 m g /L

70 5 22 9, 19 0 m g / L

70 5 23 12 m g / L

70 5 24 TSS

8 m g / L

7 052 0 Filtered

So lid 11 9 m g / kg

7 052 0 Filtered Aq ue ous 2. 3 m g / L

70 5 21 0. 01 m g / L

7 052 2 Filtered

So lid 85 4 m g / kg

7 052 2 Filtered Aq ue ous 3. 12 m g / L

70 5 23 0. 25 2 m g / L

70 5 24 To tal

Pho s pho ru s

0. 01 3 m g / L

70 5 2 0 S G T

- HEM Sam p les analyzed

out si de hol di n g t i m e NA

20 m g / L

7 052 0

Calculated

To tal N A 1 0 .5 m g / L

7 052 2

Calculated

To tal To tal

Pho s pho ru s Esti m a ted v a lue

Ass o ciated pha seseparat e d resul t
esti m a ted N A 1 6 .6 m g / L

NA= N o t Ap pl icable

ND= N o n det ect

7

### Table 3

Phase Separation Data Element s

Episode: 6549 Analysis: Classi cals

Industry: Steam Electri c Study Reviewe r : Sara Clark

Grou p n u mbe r I I I I I I

Sample num b er 70 5 2 0 7 0 5 2 0 7 0 5 2 2 7 0 5 2 2

Orig ina l sa mple v o l (mL) 91 6. 0 a 94 8. 2 a 93 7. 9 a 91 9. 7 a

Net weig ht of so lid pha s e on the filter (g) 63 .4 0 6 6 .4 3 1 4 .9 3 1 4 .6 1

Density (g /mL ) 1. 01 2 5 1

. 01 2 5 1

. 00 3 0 1. 00 3 0

Orig ina l sa mple weig ht (g) 92 7. 5 9 6 0. 1 9 4 0. 8 9 2 2. 5

Filtra te weig ht (g) 86 4. 1 a 89 3. 7 a 92 5. 9 a 90 7. 9 a

Filtra te vo lume (mL) 85 3. 4 a 88 2. 6 a 92 3. 1 a 90 5. 2 a

Percent Solid (of s o lid phase ) (% ) 71

. 9 6 5

. 9 7 1

. 9 70

. 2

a 

### Derived value. Calculate d using lab measured result s

8Computer Sciences Corporation

www.csc.com

6101 Stevenson Avenue Alexandria, Virginia 22304

703.461.2000 Fax 703.461.2020 

### MEMORANDUM

DATE: December 19, 2007

TO: Ron Jordan, Work Assignment Manager

EPA EAD

FROM: Maria A. Vargas, Quality Assurance Chemist Computer Sciences Corporation

SUBJECT: Data Review Narrative for Total and Dissolv ed Metals Analyses for the Steam Electric Study, Episode 6549

Under EPA contract number 68-C-03-0 44, ProChem Analytical submitted da ta for the analysis of metals by EPA Method 200.7 and mercury by Method 245.1. Seven aqueous samples in this episode were analyzed for total and dissolved metals. Sample 70520 identified as SP – 1 FGD Influent and sample 70522 identified as the Ash Pond Influent, were expected to contain a significant and variable particulate concentration. EPA and industry re presentatives were concerned that the variable nature of the sample would 1) complicate the collection of a representative sample for both EPA and industry analyses and 2) lead to analytical interferences. Therefore the laboratory was directed by EPA to separate the FGD Influent and Ash Pond Influent samples into an aqueous-phase and a solid-phase, and analyze each for metals and mercury. The two sets of results (filte red aqueous and filtered so lid phases) are provided in the analytical database, including the calculated tota l result (derived by combining filtered aqueous and filtered solid phase results).

Table 1 provides a list of samples, matrices, desc riptions, sampling dates, phases, and the required analytical methods.

Table 1 - Sample Identifiers, Descriptions , Sampling Dates, and Analysis Methods

EPA Sample # Matrix Sample Description Sampling

Date Phase Methods

9/11/2007 Dissolved

9/11/2007 Filtered Solid 9/11/2007 Filtered Aqueous 70520 Aqueous SP – 1 FGD Influent

NA Calculated Total 200.7, 245.1

Dissolved 70521 Aqueous SP – 2 FGD Effluent 9/11/2007 Total 200.7, 245.1

9/12/2007 Dissolved

9/12/2007 Filtered Solid 9/12/2007 Filtered Aqueous 70522 Aqueous Ash Pond Influent

NA Calculated Total 200.7, 245.1

Dissolved 70523 Aqueous Ash Pond Effluent 9/12/2007 Total 200.7, 245.1

Dissolved 70524 Aqueous SP – 5 FGD Effluent Duplicate 9/11/2007 Total 200.7, 245.1

Dissolved 70525 Aqueous SP – 6 FGD Influent Field

Blank 9/11/2007 Total 200.7, 245.1

Dissolved 70526 Aqueous SP – 7 FGD Effluent Field

Blank 9/11/2007 Total 200.7, 245.12 NA= Not applicable



### These data have been reviewed in accordance with CSC's Data Review Guidelines for Metals Analyses (November 2004), the EAD contract, and with the speci fications listed in EPA Methods 200.7 (Rev. 5.0), and 245.1 (03/83). All data are of acceptable quality with the qualifiers described below and detailed in the data review summary table (Table 2).

SUMMARY

All seven samples were successfully analyzed within the contract-specified holding times. The method detection limit (MDL) study was performed and was within the contract-specified criteria. Both aqueous and solid phase initial precision and recovery (IPR) anal yses were performed and were within the contract

criteria.

Calibration curves, calibration standards, and calibra tion blanks were successfully analyzed, with the exceptions noted below. Preparati on blanks performed for each analysis detected no contamination above the laboratory’s reporting limits. QC samples, in cluding ongoing precision and recovery (OPR) samples, matrix spike (MS) samples, matrix spike duplicate (MSD) samples, and laboratory serial dilution samples demonstrated that laboratory performance for these an alyses was acceptable, with the exception of the

issues described below and summarized in Table 2. Th e field filter blanks and the laboratory filter blank detected no analytes above the contract-specified MLs. The MS/MSD analyses were performed on the total and dissolved fractions of samples 70521 and 70523.

DATA ISSUES

Method and Analytical Blanks

Several analytes were detected in the preparation blanks (PB), initial calib ration blanks (ICBs), and continuing calibration blanks (CCBs) associated with the samples in this Episode at concentrations greater than the respective MDLs, but less than the me thod-specified MLs. The data quality is affected as

follows:

• Sample Results Less than Five Times Blank Results : When the sample result is less than five times the blank result, there are no means by which to ascertain whether or not the presence of the analyte may be attributed to contamination. Therefore, CSC recommends that the data be reported in the database as a non-detect at the ML, adjusted for sample size, dilution, and

matrices. These instances are detailed below and in the attached data review summary table. a) filtered solid selenium in sample 70522

• Sample Results Greater than Five Times but Less than Ten Times Blank Results : CSC considers these results to be of acceptable quality, but th ey may be maximum values. These instances are detailed below and in the attached data review summary table. a) filtered solid selenium in sample 70520

• Sample Results Greater than Ten Times Blank Results or Analyte Not Detected in Sample : CSC does not consider the presence of the analyte in th e blank to adversely affect the data in cases where the sample results are greater than ten times the associated blank results or where the analyte is not detected in associated samples. Several samples fall into this category, but because CSC considers such data to be acceptable without qualification, these cases do not merit further

detail.3 

### Ongoing Precision and Recovery (OPR)

The solid OPR recoveries for aluminum (73%) and silver (79%) were below the contract acceptance criteria (80%). Silver was not detected in th e filtered solid phase samples 70520 and 70522; therefore, their results are not affected by this low OPR. Beca use aluminum was detected in both the filtered solid phase samples 70520 and 70522, CSC considers the r esults of acceptable quality but they may be

minimum values.

Matrix Performance

The MS recovery of dissolved manganese (72%) in sample 70521 was below the contract-specified acceptance criteria of 75%. The related MSD recovery (88%) and the relative percent difference (RPD) (4%) were within their acceptance criteria. CSC r ecommends that the result fo r dissolved manganese in sample 70521 be considered a minimum value.

The MS recovery of total antimony (125%) in sample 70521 was within the contract-specified criteria of 75-125%. The related MSD recovery (126%) was margin ally above the contract-specified criteria of 125%. The RPD (1%) between the MS and MSD was within the acceptance criteria of 20%. Because total antimony was not detected, CSC recommends that the result in sample 70521 be included in the database without qualification.

Serial Dilutions

The serial dilution percent differences for total a nd dissolved samples 70521 and 70523 were above the contract-specified criteria of 10% for the following analytes:

• 70521 dissolved arsenic (18%) and selenium (15%)

• 70521 total arsenic (13%) and selenium (17%)

• 70523 dissolved aluminum (34%), selenium (22%), and sodium (18%)

• 70523 total iron (16%), selenium (25%), and sodium (14%)

However, the MS/MSD recoveries were within the criteria for all analytes. CSC does not qualify sample

data based on serial dilution results alone a nd believes that no further action is required

.



### TECHNICAL NOTE

Phase Separation and Calculations

As described in the phase separation document, EPA’s contract laboratory was asked to measure and record the following data as part of the phase separation process:

• Original sample weight

• Original sample volume

• Net weight of solid phase on the filter

• Filtrate weight

• Filtrate volume

• Original sample density

The laboratory failed to provide those items listed in bold above.

CSC calculated the total result for the FGD In fluent sample using the following formula:4 

### The filtrate volume was calculated using the original volume, solid-phase weight, and the density of the original sample measured by the laboratory. This ser ies of calculations are as follows and detailed in the phase separation data elements table (Table 3):

• Original sample weight = (Original sa mple volume) x (Original sample density)

• Filtrate weight = (Original sample weight) - (Solid weight)

• Filtrate volume = (Filtrate weight) / (Original sample density)

In the generation of the routine metals “Calcula ted Total” results, at EPA's request, CSC included concentrations that were greater th an the MDL but less than the ML unless both factors in the calculations were less than the ML. However, if any concentra tion was affected by contamination in an associated blank at less than 5 times the associated blank result, it was changed to a zero before going through the calculation, per CSC's data review protocols. Ne gative values submitted by the laboratory were not used

in the calculations.

Please note that the results for the various phases will be labeled in the PROCEDUR field of the EPA database as “FILTERED AQUEOUS”, “FILTERED SOLID (WET WEIGHT)”, and “CALCULATED

TOTAL”.

Minimum Levels

When two results are mathematically combined to obtain a Calculated Total result, CSC will report the larger of the two MLs associated with each result as the Calculated Total ML.

Due to severe matrix interferences, the laboratory an alyzed several samples at 10-fold dilutions for mercury. The affected samples are as follows: dissolved and filtere d aqueous mercury for sample 70520; total and dissolved mercury for sample 70521; and total and dissolved mercury for sample 70524. Reporting limits for these results ha ve been adjusted for dilution.

Percent Solids

Percent solids evaluations were performed for samp les 70520 and 70522 and are summarized in Table 3. The percent solids results is provided to convert if desired, solid phase wet weight basis values to dry weight results; percent solids results were not used to generate the “Calculated Total” results.

If you have any questions regarding the analyses of these samples or the review of these data, please contact Barbara Beard by telephone at (703) 461-2154 , by facsimile at (703) 461-8056, or by email at

bbeard2@csc.com.

cc: Brian D’Amico, EPA Deb Bartram, ERG Beverly Randolph, EPA TJ Finseth, ERG Marla Smith, EPA Lynn Walters, CSC Nelson Andrews, EPA Barbara Beard, CSC Brian Englert, EPA 

### L Vol. kg) Wt. x μg/mg 1000 mg/kg (Conc. L) Vol. x μg/L (Conc. μg/L ion Concentrat Sample Total

sample original solid solid Filtrate Filtrate 

### × +

=5 

### Table 2 Data Review Summary Table

Episode: 

### 6549 Analysis: 

### Metals

Industry: 

### Steam Electric Study Reviewer: 

### Maria A. Vargas

Sample Analyte Action Reason CSC Qual Level

70520 solid phase Sample result between 5x

and 10x blank result 3.96 mg/kg

70520

calculated total Se Maximum value Associated solid phase

result is a maximum NA

652 ug/L

70520 solid phase OPR %R below contractspecified criteria 5110 mg/kg

70520

calculated total Al Minimum value Associated solid phase

result is a minimum. NA

234000 ug/L

70521 dissolved Mn Minimum value MS %R below contractspecified criteria NA 543 ug/L

70522 solid phase Se Report in database

as not detected Sample result < 5x blank

result NA ND

70522 solid phase OPR %R below contractspecified criteria 2700 mg/kg

70522

calculated total Al Minimum value Associated solid phase

result is a minimum NA

94800 ug/L

NA= Not Applicable

ND= Not detected6 

### Table 3 Phase Separation Data Elements

Episode: 

### 6549 Analysis: 

### Metals

Industry: 

### Steam Electric Study Reviewer: 

### Maria A. Vargas

Sample number 70520 70522

Original sample vol (mL) 460 500

Net weight of solid phase on the filter (g) 19.98 9.5

Density (g/mL) 0.9984 0.9958

Original sample weight (g) 459.26 a 497.90 a

Filtrate weight (g) 439.28 a 488.4 a

Filtrate volume (mL) 439.98 a 490.46 a

Percent Solid (of solid phase) (%) 60.5 65.1

a 

### Derived value. Calculated using lab measured results (if available), or otherwise estimatedComputer Sciences Corporation

www.csc.com

6101 Stevenson Avenue Alexandria, Virginia 22304

703.461.2000 Fax 703.461.2020 

### MEMORANDUM

DATE: November 28, 2007

TO: Ron Jordan, Work Assignment Manager

EPA EAD

FROM: Cris Robinson, Quality Assurance Chemist Computer Sciences Corporation

SUBJECT: Data Review Narrative for Trace Metals Analyses for the Steam Electric Study, Episode

6549

Under EPA contract number 68-C-03- 046, Battelle Marine Sciences submitted data for the analyses of trace metals for nine aqueous samples in Epidsode 6549. All nine samples were analyzed for total mercury (Hg) by Method 1631E; and total and dissolv ed metals including antimony (Sb), arsenic (As), cadmium (Cd), copper (Cu), chromium (Cr), lead (Pb) , nickel (Ni), selenium (Se), silver (Ag), thallium (Tl), and zinc (Zn) by Method 1638 (ICP-MS). Fi ve of the nine (FGD and Ash Pond effluents, FGD effluent duplicate, and FGD and Ash Pond effluent fiel d blanks) were analyzed for hexavalent chromium by Method 1636. Five samples were analyzed for di ssolved mercury. Because influent samples for this study were expected to be highly variable in solid s content, EPA chose to obt ain results for the solid phase as well. The solid phase results for sample 70520 were not directly analyzed, but rather calculated from total, dissolved, and TSS results.

Table 1 - Sample Identifiers, Descriptions , Sampling Dates, and Analysis Methods

EPA Sample # Matrix Sample Description Sampling Date Phase Methods

Total 1631E, 1638 9/11/07 Dissolved 1631E, 1638 70520 Aqueous FGD influent

NA Calculated Solid 1631E, 1638

Total 1631E, 1638

Dissolved 1631E, 1638 70521 Aqueous FGD effluent 9/11/07

NA 1636

Total 1631E, 1638 70522 Aqueous Ash Pond influent 9/12/07 Dissolved 1631E, 1638

Total 1631E, 1638

Dissolved 1631E, 1638 70523 Aqueous Ash Pond effluent 9/12/07

NA 1636

Total 1631E, 1638

Dissolved 1631E, 1638 70524 Aqueous FGD effluent duplicate 9/11/07

NA 1636

Total 1631E, 1638 70525 Aqueous FGD influent field blank 9/11/07 Dissolved 16382 Table 1 - Sample Identifiers, Descriptions , Sampling Dates, and Analysis Methods

EPA Sample # Matrix Sample Description Sampling Date Phase Methods

Total 1631E, 1638

Dissolved 1638 70526 Aqueous FGD effluent field blank 9/11/07

NA 1636

Total 1631E, 1638 70527 Aqueous Ash Pond influent field blank 9/11/07 Dissolved 1638

Total 1631E, 1638

Dissolved 1638 70528 Aqueous Ash Pond effluent field blank 9/12/07

NA 1636

NA = Not applicable



### These data have been reviewed in accordance with CSC's Data Review Guidelines for Metals Analyses (November 2004), with the EAD contract, and with the specifications listed in EPA Methods 1631E (Aug 2002), 1636 (Jan 1996), and 1638 (Jan 1996). All data are of acceptable quality with the qualifiers

described below and detailed in the da ta review summary table (Table 2).

SUMMARY

All nine samples were successfully analyzed with in the method-specified holding times, and initial precision and recovery (IPR) analyses and met hod detection limit (MDL) studies were acceptably performed. All QC samples, including ongoing precisi on and recovery samples (OPR), matrix spike and matrix spike duplicate (MS/MSD) samples, and qua lity control samples (QCS) were within method specified criteria. The MS/MSD analyses were performed on samples 70521 and 70523. Calibration

curves and calibration verification standa rds were successfully analyzed.

All calibration and preparation blanks were free of contamination above the report limit (minimum level or ML). No analytes were detected at levels above the reporting limit in the field blanks. These blanks

are discussed in detail below.

DATA ISSUES

Method and Analytical Blanks

Several analytes were detected in the preparation bl anks (PBs), initial calibration blanks (ICBs), and continuing calibration blanks (CCBs) asso ciated with the samples in this episode at concentrations greater than the respective MDLs, but less than the method- specified MLs. The data quality is affected as

follows:

• Sample Results Less than Five Times Blank Results : When the sample result is less than five times the blank result, there are no means by which to ascertain whether or not the presence of the analyte may be attributed to contamination. Therefore, CSC recommends that the data be reported in the database as a non-detect at the ML, adjusted for sample size, dilution, and matrices. The affected samples and analytes are as follows: 70520 dissolved Cr, Zn; 70521 dissolved Zn; 70521 total Zn; 70524 dissolved Zn; 70524 total Zn.3 

### • Sample Results Greater than Five Times but Less than Ten Times Blank Results : CSC considers these results to be of acceptable quality, but they may be maximum values. The affected samples and analytes are as follows: 70521 dissolved Ni; 70522 total Sb; 70523 dissolved Cr; 70523 total Cr; 70524 dissolved Ni.

• Sample Results Greater than Ten Times Blank Results or Analyte Not Detected in Sample : CSC does not consider the presence of the analyte in th e blank to adversely affect the data in cases where the sample results are greater than ten times the associated blank results or where the analyte is not detected in associated samples. Because CSC considers such data to be acceptable without qualification, these cases do not merit further detail.

Laboratory Duplicate

The RPD for two analytes in laboratory duplicates were above the internal laboratory limit of 25%. These include sample 70522 dissolved Cd (38%) and samp le 70523 total Ag (48%). However, because the MS/MSD for these analytes produced an acceptable RP D, and Method 1638 does not specify limits for laboratory duplicates, CSC considers the associat ed results acceptable without qualification.

Field Duplicate

Field duplicate RPD values were above the method- specified limit (20%) fo r the following duplicate pairs:

• 70521 and 70524 (FGD effluent and FGD effluent fi eld duplicate) total metals results for Ag (25%) and Pb (43%).

• 70521 and 70524 (FGD effluent and FGD effluent fiel d duplicate) dissolved metals results for Cu (22%) and Se (54%).

CSC does not routinely qualify results based on field duplicate RPD failure.

TECHNICAL NOTES

Sample Temperature

Trace metals samples were not chille d during shipment for this study.

Additional Analytes

Two additional analytes, arsenic and chromium, were included for evaluation by Method 1638. Since they are not specified in the method, the MLs for th ese (0.15 μg/L and 0.80 μg/L, respectively) were set to ten times the laboratory MDL.

Minimum Levels

In order to alleviate interference caused by high leve ls of dissolved solids, the laboratory performed various dilutions on several samples on which Method 1636 and 1638 were performed. MLs are adjusted appropriately.4 

### Solid-Phase Calculations

CSC calculated the solid-phase results for mercury using the following formula:

The results for the various phases will be labeled in the PROCEDUR field of the EPA database as “DISSOLVED”, “TOTAL”, and “CALCULATED SOLID (DRY WEIGHT)”.

When two results are mathematically combined to obtain a Calculated Solid result, CSC will report the larger of the two MLs associated with each result as the Calculated Solid ML.

In the generation of the Calculated Solid result, at EPA's request, CSC included Total and Dissolved concentrations that were greater than the MDL but l ess than the ML. However, if any concentration was affected by contamination in an associated blank at less than 5 times the associated blank result, it was changed to a zero before going through the calculation, per CSC's data review protocols. Negative values submitted by the laboratory were not used in the calculations.

The TSS result for the sample 70520 bottle analyzed for mercury is 38767 mg/L. The TSS result for the sample 70520 bottle analyzed for Me thod 1638 metals is 34333 mg/L.

If you have any questions regarding the analyses of these samples or the review of these data, please contact Barbara Beard by telephone at (703) 461-21 54, facsimile at (703) 461-8056, or via email at

bbeard2@csc.com.

cc: Brian Damico, EPA Beverly Randolph, EPA Marla Smith, EPA Nelson Andrews, EPA Brian Englert, EPA Deb Bartram, ERG TJ Finseth, ERG Lynn Walters, CSC Barbara Beard, CSC sample original Dissolved Total


### L mg TSS L ng Conc L ng Conc

/ ) /

. /

. ( μg/g) or (ng/mg ion concentrat phase Solid −

=5 

### Table 2 Data Review Summary Table

Episode: 6549 Analysis: Trace Metals

Industry: STELEC Study Reviewer: Cris Robinson

Sample Analyte Action Reason SCC Qual Level

Cr 70520

Dissolved Zn

70521

Dissolved Zn

70521 Total Zn

70524

Dissolved Zn

70524 Total Zn Report in database

as non-detect Sample result <5x blank

result NA

70521

Dissolved Ni

70522 Total Sb

70523

Dissolved Cr

70523 Total Cr

70524

Dissolved Ni Maximum value Sample result >5x and

<10x blank result NA See Database

NA = Not applicable

### Appendix D

PICTURES FROM THE SAMPLING EPISODE

### D-1 Figure D-1. Sampler Working Inside a “Cleanbox”

### D-2 Figure D-2. Composite Set-Up at th e Influent to FGD Pond System

### D-3 Figure D-3. “Shake and Pour” Sample Collection Set-Up

### D-4 Figure D-4. Sample Collection Set-Up at Effluent from FGD Pond System

### D-5 Figure D-5. Composite Set-Up at th e Influent to Ash Pond System

### D-6 Figure D-6. Sample Collection Set-Up at Effluent from Ash Pond System