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. INTRODUCTION .................................................................................................................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. PLANT OVERVIEW.............................................................................................................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. SAMPLE COLLECTION .......................................................................................................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. LABORATORY ANALYTICAL RESULTS AND DISCUSSION...................................................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. DATA QUALITY.................................................................................................................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. REFERENCES .....................................................................................................................6-1 

Appendix A: ANALYTICAL RESULTS

Appendix B: ANALYTICAL DATA FOR METALS, FGD POND AND ASH POND

Appendix C: DATA REVIEW NARRATIVES

Appendix D: PICTURES FROM THE SAMPLING EPISODE
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 Container and Planned Preservation ............................................ 3-19 

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

3-7 Generating Unit Operating Characteristics during Sample Collection, Widows 

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

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

3-9 FGD Pond System Operating Characteristics, 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 Classicals 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 FGD Pond System, Widows Creek..................................... 4-6 

4-3 Biphasic Sample Results for Classicals 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................................................................................................................ 4-11 

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

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

5-1 Field Duplicate Results, Widows Creek .......................................................................... 5-5 
LIST OF TABLES (Continued) 

Page 

iii

A-1 FGD Pond Influent Analytical Data, Widows Creek...................................................... A-1 

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

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

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

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

A-6 Ash Pond Effluent Analytical 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 Analytical Data, Widows Creek ................................. A-51 

A-11 Ash Pond Effluent Field Blank Analytical Data, 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, Widows Creek Fossil Plant ............................................... 2-8 

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

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

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

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

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

D-6 Sample Collection Set-Up at Effluent from Ash Pond System ...................................... D-6 
1-1

1. INTRODUCTION

 The Engineering and Analysis Division (EAD) of the U.S. Environmental Protection 

Agency (EPA) has been conducting a program that consists of site visits and sampling at steam 

electric power plants. The purpose of this program is to characterize 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 Creek 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 (CWA) requires EPA to develop and publish a 

biennial plan that establishes a schedule for the 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 second-largest discharger of toxic-weighted 

pollutants. EPA’s analyses indicated that the toxic-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 controls. 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 discharges 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 efforts for the 2007/2008 study on better characterizing 

the sources generating the pollutants responsible for the majority of the toxic-weighted pollutant 

loadings and available pollution control technologies/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 characteristics of the plants, as well as the site 

visits conducted for the study. The following characteristics (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 based on the following site characteristics: 

• The plant is a coal-fired power plant that burns eastern bituminous coal; 

• The plant operates two wet FGD systems, 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 visits 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 12th

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 Authority’s Widows Creek Fossil Plant (Sampling Plan) [2], 

which describes the sample collection procedures used during the sampling episode. 

 For this sampling episode, EPA arrived at Widows Creek on Monday, September 10, 

2007, to review the sampling points, determine the set-up for the sample collection, and label 

sample bottles. EPA then collected the samples 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 collected split samples with the Utility Water Act 

Group (UWAG), acting on behalf of the plant. 
2-1

2. PLANT OVERVIEW

 Widows Creek operates eight coal-fired steam electric generating units. Units 1 through 6 

each have a capacity of approximately 115 megawatts (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, Alabama, beside the Guntersville 

Reservoir on the Tennessee River. 

 Widows Creek uses two different types of coal: 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 Illinois 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 precipitator (ESP) as well as boiler optimization controls 

to reduce nitrogen oxide (NOx) 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 installed on both Units 7 

and 8 in 2003-2004. SCRs are used to control NOx emissions by injecting ammonia into the flue 

gas to convert the NOx 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 the 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. Emissions 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 dioxide. Widows Creek injects the sodium sulfite upstream of the air 

preheaters in Unit 7 and injects lime downstream of the air preheaters in Unit 8. 

 ESPs are particulate control devices that remove 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. Section 2.1 discusses the particulate control system 

and Section 2.2 discusses the ash pond system. 

 The FGD scrubber systems were retrofit additions to the plant and were installed on Unit 

8 in 1970 and on Unit 7 in 1981. FGD systems are used to control sulfur dioxide (SO2) 

emissions. The wastewater generated by the FGD systems is treated on site by a series of 

gypsum ponds that allow the gypsum and other particulates to settle out of the wastewater stream 
2-2

prior to discharge. Section 2.3 discusses the FGD system and Section 2.4 discusses the gypsum 

pond system. 

 The FGD system on Unit 8 is not only used to control SO2 emission, but it is also used to 

control the particulates in the flue gas because 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 are 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, solid, 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 particles 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 stream of sluice water that transports 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 during 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 electric charge on the particles contained in the 

flue gas. The charged particles then collect on a metal plate with an opposite electric charge. As 

the particles begin to layer on the metal plates, the plates are tapped/rapped to loosen the 

particles, which fall into collection hoppers. Each unit has multiple hoppers that collect ash from 

different places in the ESP. The hoppers located closer to the inlet of the ESP collect the larger 

fly ash particles that are removed more easily, and the hoppers located closer to the outlet of the 

ESP collect the finer fly ash particles 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 collection hoppers with intake water. The plant 

automatically cycles through the hoppers in Unit 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 sluices the fly ash from the collection hoppers 

with intake water every two hours. A complete sluicing cycle for each unit takes approximately 

one hour; therefore, Units 1 through 6 alternate between sluicing and nonsluicing every other 

hour. As mentioned in Section 2.0, Unit 8 does not have an ESP; therefore, 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 receives both the bottom and the fly ash sluice 

waste streams discussed in Section 2.3, as well as the following other low-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 leading into the main pond, followed by a middle 

stilling pond, and a final pumping basin. Widows Creek transports the ash sluice water from 

Units 1 through 6 to a different part of the diked channel than the ash sluice 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 discharges 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 episode, the plant changed the configuration of 

the diked channels, such that ash sluice water from 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 two 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 large bottom ash particles and some of the fly ash particles settle 

to the bottom of the channel. Widows Creek continuously 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 travels through the diked channels and 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 the “red water” back 

into the diked channel but rather recycles it based 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 through the diked channels, it enters the ash pond, 

decreasing the flow velocity and allowing the finer fly 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 surface of the wastewater. Cenospheres are small, 

lightweight, hollow spheres that are formed in the 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 point, 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 CO2 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 wastewater enters the pumping basin for 

final settling and transport. Based on long-term average data, Widows 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). Widows Creek recycles most of the wastewater 

entering the pumping basin (27.6 MGD 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 recycles 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 often, 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 proportion of bottom ash, 

rather than consisting of a balanced 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 Units 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 limestone 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. The 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 where 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 droplets of the absorbent slurry absorb and react 

with the sulfur dioxide in the flue gas to produce calcium sulfate (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 where 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 spray 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 liquid falls downward, back to the bottom of the FGD system). 

The Unit 8 FGD system removes 94 to 96 percent of sulfur dioxide. In addition to removing 

sulfur dioxide from the flue gas, the Unit 8 scrubber also removes the fly ash 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 gypsum pond system, where the solid particles 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 have an ESP to remove the fly ash and other 

particulates from the flue gas prior to the FGD 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 slurry 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 settling 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 the 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, which 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 slurry. These first two 

gypsum ponds remove most of the gypsum and other 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. Because the gypsum slurry from Unit 8 contains 

fly ash, the gypsum removed from the ponds had not been marketable gypsum; however, 
2-6

Widows Creek has begun marketing some of the 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 little gypsum. The wastewater from 

the last pond is discharged to Widows Creek, which flows into the Tennessee River. Widows 

Creek periodically changes the configuration and operation of the gypsum pond system 

whenever the plant operators think it will facilitate treatment, 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 sampling episode, which is different from the 

configuration during the two previous site visits. Since the time 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 configuration 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; therefore, EPA selected a point approximately 100 feet 

downstream of where both streams combine. In addition, the sample collection point was 

immediately downstream of a metal culvert. EPA decided to collect the sample downstream of 

the metal culvert because the waste stream exhibited a better flow pattern 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 uses 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 

1st Gypsum Pond

3rd Gypsum 

Pond

Gypsum slurry from 

Unit 7 FGD scrubber

Discharge to Widows 

Creek

SP-2

SP-1

Diked Channel Alternate Channel

2nd Gypsum Pond

Gypsum slurry from 

Unit 8 FGD scrubber

Figure 2-2. FGD Gypsum Pond System, Widows Creek Fossil Plant 
3-1 

3. SAMPLE COLLECTION

 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 discusses the plant operational 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 boiler. 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 Collection Methods, and Field Measurements

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

measurements obtained for this sampling episode. Additional details are available in Section 3 of 

the Sampling Plan. Figures 2-1 and 2-2 present flow diagrams of the plant’s two pond systems, 

including sampling point locations. 

 Table 3-1 lists the sampling points, sampling point descriptions, type of sample 

collection, sample collection dates and times, and the EPA Sample Control Center (SCC) sample 

numbers. Table 3-2 lists the sampling point numbers and descriptions, the number of samples 

collected, and the pollutant parameters 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 from FGD Pond System (SP-2); 

• SP-6 Influent to FGD Pond System (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 Pond (SP-4) Field Blank. 

 For all the sampling points, EPA collected 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 the same analyte were collected simultaneously). 

The HEM/SGT-HEM samples were collected using a bottle dipper; therefore, EPA and Widows 
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Creek’s representative collected duplicate samples, with one filling the bottle 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 these samples were collected as “multipour” splits 

because the composite tubing did not have a splitter 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. The 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 procedures, see Section 5.2.3. 

 At each of the nine sampling points, EPA collected 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 addition, 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-bagged, with a clear inner bag enclosed 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 pull 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 possible within the “cleanbox.” 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 metal 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 entering the diked channel from the Unit 8 influent pipe; however, it 

appeared to be at a lower flow rate. According to plant personnel, the Unit 8 absorber modules 

continued to purge water to the FGD pond system during the sampling episode, even though the 

unit was shut down; therefore, the influent sample was likely diluted by this water stream. Based 

on information provided by Widows Creek, approximately 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 was 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 process 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 some 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 night, and because it allowed the samplers enough time 

to ship the samples and meet all sample hold times. In addition, the duration of the composite 

sampling period was considered sufficient for capturing 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 samplers/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 trash 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 for 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 composite container for the classical 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 attached 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 composite 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 through 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 two set-ups for the composites was that, due to 

the difference in preservation requirements for these analytes, the composite container for the 

classicals was placed on ice and 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 automatic compositor (ISCO peristaltic pump) to collect 800 mL 

of sample every 10 minutes for 4 hours, for a total 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 classicals 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 attached 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 composite container 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 protect the containers from rain; however, the lid was not shut down 

completely because it would kink the tubing. Figure 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 samples for each compositor. 

Because both samples were collected successfully, the samplers left the sampling point to collect 

the effluent from the FGD pond samples (SP-2) and did not return to the influent sampling point 

until the compositing time period was complete. 

 When the samplers returned to the sampling point, the compositing period had concluded, 

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 grab 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 sides of the tubing and the composite 

containers. 

 The sampling team then transported the 20-liter composite containers back to the staging 

area to pour off and pump off. The samplers used 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 samplers used a funnel with a short length of 

silicone tubing attached to a “Y” splitter and two additional pieces of silicone tubing to pour the 

samples into the sample bottles. First, two of the samplers (shakers) shook the 20-liter metals 

composite container vigorously for several minutes to resuspend all of the solids settled at the 

bottom of the container. The shakers 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 the “Y” splitter, and into EPA’s and the Widows Creek’s 

representative’s sample bottles. Because 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 same 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 bottles 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 container, 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 samples 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, the 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 (approximately 2 liters) and then collected the low-level 

dissolved metals, routine dissolved metals, and routine hexavalent chromium samples. 

 During the sample collection, the sampling team collected two aliquots 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 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 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 wastewater characteristics should be 

fairly homogeneous. 

 During the sample collection at the effluent 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 during the sample collection, but the samplers and sample bottles were 

protected, thereby minimizing any potential contamination. However, because the samples were 
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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 effluent from the FGD pond system (SP-2), the 

sampling team collected field blanks (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 chromium. 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 stream into the sample containers. The sampling 

team attached one end of a 25-foot length of Teflon® 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 area and attached 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, with two additional pieces of silicone tubing 

attached to the “Y” splitter. The length of silicone 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 sampling 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 chromium samples, as well as the QC and duplicate 

samples, because the capsule filter was already inline with the tubing configuration from the 

dissolved metals field blank sample collection. The 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 metals 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 samples, 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 total 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 described in Section 3.1. The samplers 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 prevent any oil and grease adhering to the sides of 

the tubing. Therefore, EPA did not collect split samples with Widows Creek’s representative for 

the HEM/SGT-HEM samples, but instead collected 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 contaminating 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 the 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 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 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 effluent from 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 through 6, upstream of where the “red water” is 

pumped back into the diked channel. As discussed in Section 2.4, this sample does not account 

for the wastewaters from Units 7 and 8 that enter 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 the ash pond; therefore, EPA chose to collect a 

composite to account for some of the variability 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 accurately represent the wastewater entering 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 cover 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 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 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 collected 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 field 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 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 for 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 composite container for the classical 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 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 

over the entire composite 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 through 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 two set-ups for the composites 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 automatic compositor (ISCO peristaltic 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 classicals samples. The samplers programmed the 

automatic compositor to collect 800 mL of sample every 30 minutes for 12 hours, calibrated the 

compositor to collect approximately 800 mL, and attached 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 protect the containers from rain; however, the lid was not shut down 

completely because it would kink the tubing. Figure D-5, in Appendix D, is a picture of the 

sampling set up for the composite at the 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 samples 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 sampling point to watch the collection of the second 

grab sample and determined that sample was only collected in one of the 20-liter containers. 

EPA examined the tubing for the other 20-liter container and noticed a kink in the line that must 

have prevented the container from being filled. When attempting to correct the situation by 

collecting a manual aliquot via the automatic compositor, the sampling team accidentally added 

additional sample to the 20-liter container that already received 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 collected in each 20-liter were 

similar. EPA believes that collecting an additional aliquot during one time period will not 

significantly impact the overall sample. The samplers 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 sampling 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 grab 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 sides of the tubing and the composite containers. 

 EPA then retrieved the 20-liter composite containers and transported them back to the 

staging area to pour off and pump off. The samplers 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 then 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 funnel, 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, routine total metals, and the arsenic/selenium 

speciation samples from the 20-liter metals composite container, using 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 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.” Figure D-3, in Appendix D, is a 

picture of the sample collection set-up for the “shake and pour” method at the influent to the ash 

pond system (SP-3). 

 At this point, the sampling team could have collected the dissolved metals sample 

fractions from the metals 20-liter composite container; however, based on visual observation of 

the composite container, the samplers determined that the solids had not completely settled in the 

container. Therefore, to conserve 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 team then 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 

samplers attached a capsule filter 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” 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 samples of the ash pond influent, the samplers collected a field blank sample 

(SP-8) for low-level dissolved metals. See Section 5.2.3 for a description of the dissolved metals 

field blank sample collection at the influent to the ash pond system. 

 After collecting the field blank samples, the 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 sample and then collected the low-level dissolved 

metals, routine dissolved metals, and routine hexavalent chromium samples. 

 During the sample collection, the sampling team collected two aliquots 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 field test sample due to darkness). The four-color 

pH paper was used 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 

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 feet above the water level. Figure 2-1 identifies 

the sampling location for SP-4. This sample was collected as a grab sample, because the 

wastewater is equalized through the long retention 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 tent or tarps to cover 

the samplers/samples from rain because there 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 chromium. See Section 5.2.3 for a description of the 

field blank sample collection at the effluent from the ash pond system. 

 EPA collected the wastewater samples for 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 attached 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, with two additional pieces of silicone tubing attached to the “Y” 

splitter. The length of silicone tubing between the pump and the “Y” splitter consisted of two 

pieces with a small connector, which allowed the samplers 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-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 sampling 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 already inline with the tubing configuration from the dissolved 

metals field blank sample collection. The sampling team then collected the routine dissolved 

metals, routine dissolved metals QC, and routine hexavalent chromium samples. Each of these 

samples was collected in a “cleanbox,” as described in Section 3.1. 

 After collecting all the dissolved metals samples, 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 total and dissolved mercury, routine total metals, 

and arsenic/selenium speciation samples, as well as the QC samples, for each analyte in a 

“cleanbox,” as described in Section 3.1. The sampling team then collected the BOD, Group I, 

and Group II samples, 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 samples directly from 

the pumping basin to prevent any oil and grease adhering to the sides of the tubing. Therefore, 

EPA did not collect split samples with Widows Creek’s representative for the HEM/SGT-HEM 

samples, but instead collected duplicate samples 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 point with the bottle dipper; however, the samplers attempted to 

collect it as close to the same point as possible. 

 During the sample collection, the sampling team collected an aliquot of sample for field 

testing. 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 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 effluent from the ash pond system. 

3.2 List of Analytes and Sample Preservation

 Analytes in EPA’s Widows Creek sampling episode included those in the following 

classes of pollutants: 

• Classicals: 

— Biochemical oxygen demand, 5-day (BOD5), 

— 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, chromium, 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, selenium, silver, thallium, zinc), and 

— Low-level dissolved metals (11 metals). 

 The analytes selected reflect the current understanding of coal-fired power plant air 

pollution control wastewaters, including contributions from coal, scrubber sorbents, treatment 

chemicals, and other sources. Table 3-4 lists the analytical methods used to determine pollutant 

concentrations. 

 Table 3-5 lists the containers used for sample collection as well as the preservation 

requirements for each sample, and Table 3-6 summarizes the chemical preservation for each of 

the samples that were preserved on site. The sampling team preserved samples in accordance 

with procedures described in Section 3.4 of the Sampling Plan. All samples except routine total 

and dissolved metals, low-level total and dissolved metals, low-level total and dissolved 

mercury, and low-level hexavalent chromium samples 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 field. 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 samples 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 because 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 was confirmed with four-color pH 

strips. 

3.3 Plant Operational Data

 During the sampling episode at Widows Creek, plant personnel provided the sampling 

team with operational data for each of the generating 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 characteristics, and Table 3-11 presents the ash pond system 

operating characteristics during 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 issues in the boiler. Unit 8 was shut down on Tuesday, September 11, 

2007 at 0600 and remained down during the entire 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 changed 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 the 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 and 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 configuration of the influent to the ash 

pond system from what EPA had seen during the site visits. EPA planned to 

collect the composite sample of the influent to the ash pond system after the ash 

sluice from Units 1 through 6 was commingled 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 through 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 planned to collect composite samples by 

collecting 24 individual grab samples 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 and ends with a grab sample; therefore, 

EPA collected 800 mL of samples for each individual grab. 

• Pour Off of Influent to the FGD Pond System (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 consideration, EPA determined it would be too 

difficult to shake the composite containers with the tubing (needed for the pump 

off) attached to the cap of the container; 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 describes the “shake and pour” methodology 

in detail. 

• Total Metal Field Blank Sample Collection 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 because 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 partial 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 achieved (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 classicals, 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. 
3-16 

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

Sampling 

Point 

Number Sampling 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

SP-1 Influent to FGD Pond System 1 1 1 1 1 1 1 1 1 SP-2 Effluent from FGD Pond 

System 

1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 

SP-3 Influent to Ash Pond System 1 1 1 1 1 1 1 1 1 SP-4 Effluent from Ash Pond 

System 

1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1 1 1 

SP-5 Duplicate of Effluent from 

FGD Pond System 

1 1 1 1 1 1 1 1 1 1 

SP-6 Influent to FGD Pond System 

Field Blank 

1 1 1 1 1 

SP-7 Effluent from FGD Pond 

System Field Blank 

1 1 1 1 1 1 

SP-8 Influent to Ash Pond System 

Field Blank 

1 1 1 

SP-9 Effluent from Ash Pond 

System Field Blank 

1 1 1 1 

Total Number of Samples 9+2QC 9+2QC 9+2QC 5+2QC 4+2QC 7+2QC 7+2QC 5+1QC 5+1QC 5+1QC 

a – 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 the time this report was finalized and therefore are not inc
3-17 

Table 3-3. Field Measurements, Widows Creek 

Temp oC pH (S.U.) Sampling 

Point 

Number 

Sampling Point 

Description Time Meter Thermometer Meter a Strips 

Free 

Chlorine

(mg/L) 

Total 

Chlorine 

(mg/L) 

Ma

Inte

Re

(m

Influent to FGD Pond (beginning of composite) 

SP-1 0804 35.6 38.5 7.83 7 0.13 0.28 

Influent to FGD Pond (end of composite) 

1328 32.6 34.5 7.15 7 0.00 0.00 

SP-2 Effluent from FGD Pond 1121 28.5 28 8.14 8 0.36 0.13 

Influent to Ash Pond (beginning of composite) 

SP-3 1907 33.1 34 8.82 NA 0.12 0.06 

Influent to Ash Pond (end of composite) 

0705 33.8 35 8.35 7 0.00 0.06 

SP-4 Effluent from Ash Pond 1147 29.3 30 7.82 7 0.00 0.03 

a – 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 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 samplibreeze, 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 (BOD5) Probe 

SM 2540 D Total Suspended Solids (TSS) Gravimetric 

SM 2540 C Total Dissolved Solids (TDS) Gravimetric 

ASTM D516-90 Sulfate 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/Nitrate as Nitrogen Autoanalyzer 

SM 4500—N, C Total Kjeldahl Nitrogen (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 Container and Planned Preservation 

Parameter Sample Container and Volume On-Site Preservation 

Classicals 

BOD5 One 1-L plastic bottle ≤6oC 

Group I a Two 1-L plastic bottles ≤6EC 

Group II b Two 1-L plastic bottles H2SO4 to pH <2, ≤6EC 

HEM/SGT-HEM Two 1-L wide mouth glass jars H2SO4 to pH <2, ≤6oC 

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, ≤6EC 

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, ≤6EC 

Duplicate: HCl to pH <2, ≤6EC 

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 ≤6EC; 

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 buffer 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 H2SO4 7 2 255 drops 

70520 Group II V2 9/11/07 H2SO4 7 2 255 drops 

70520 HEM/SGT-HEM G1 V1 9/11/07 0735 H2SO4 7 2 225 drops 

70520 HEM/SGT-HEM G1 V2 9/11/07 0735 H2SO4 7 2 225 drops 

70520 HEM/SGT-HEM G2 V1 9/11/07 1330 H2SO4 7 2 130 drops 

70520 HEM/SGT-HEM G2 V2 9/11/07 1330 H2SO4 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 H2SO4 8 2 25 drops 

70521 Group II V2 9/11/07 1130 H2SO4 8 2 25 drops 

70521 Group II MS/MSD V1 9/11/07 H2SO4 8 2 25 drops 

70521 Group II MS/MSD V2 9/11/07 H2SO4 8 2 25 drops 

70521 HEM/SGT-HEM V1 9/11/07 1015 H2SO4 8 2 25 drops 

70521 HEM/SGT-HEM V2 9/11/07 1015 H2SO4 8 2 25 drops 

70521 HEM/SGT-HEM MS/MSD 

V1 

9/11/07 1015 H2SO4 8 2 25 drops 

70521 HEM/SGT-HEM MS/MSD 

V2 

9/11/07 1015 H2SO4 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 H2SO4 8 2 20 drops 

70522 Group II V2 9/12/07 0900 H2SO4 8 2 20 drops 

70522 HEM/SGT-HEM G1 V1 9/11/07 2000 H2SO4 8 2 20 drops 

70522 HEM/SGT-HEM G1 V2 9/11/07 2000 H2SO4 8 2 20 drops 

70522 HEM/SGT-HEM G2 V1 9/12/07 0730 H2SO4 8 2 15 drops 

70522 HEM/SGT-HEM G2 V2 9/12/07 0730 H2SO4 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 H2SO4 7 2 20 drops 
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 buffer 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 H2SO4 7 2 20 drops 

70523 HEM/SGT-HEM V1 9/12/07 1100 H2SO4 7 2 25 drops 

70523 HEM/SGT-HEM V2 9/12/07 1100 H2SO4 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 H2SO4 8 2 25 drops 

70524 Group II V2 9/11/07 H2SO4 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 
3-22 

a – Coal usage was calculated as the average amount of the coal used 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, 2007c – Unit 1 was derated when EPA arrived at the plant as a result of a feedwater heater drain line failure, but was brought back up on 9/1

d – Unit 8 was generating approximately 450 MW before it was shut down. Unit 8 was shut down at approximately 6:00 AM on 9/11/0the 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 C

Unit 

ID Boiler Type Coal Type 

Coal 

Usage a

(tpd) 

Source of Coal (Coal 

Region and/or State) 

Capacity 

(MW) 

Electricity 

Production (or 

Percent 

Capacity) b 

SCR (No, 

On, Off) 

Par

Contr

(HS/C

1 c Wall-fired Low-Sulfur 

Eastern Bituminous 

379 20 Mile & Bowie mines 

in CO 

115 65.5 (57%) c No 

2 Wall-fired Low-Sulfur 

Eastern Bituminous 

1,467 20 Mile & Bowie mines 

in CO 

115 96 (83%) No 

3 Wall-fired Low-Sulfur 

Eastern Bituminous 

1,253 20 Mile & Bowie mines 

in CO 

115 81 (70%) No 

4 Wall-fired Low-Sulfur 

Eastern Bituminous 

1,437 20 Mile & Bowie mines 

in CO 

115 111 (97%) No 

5 Wall-fired Low-Sulfur 

Eastern Bituminous 

982 20 Mile & Bowie mines 

in CO 

115 92 (80%) No 

6 Wall-fired Low-Sulfur 

Eastern Bituminous 

1,308 20 Mile & Bowie mines 

in CO 

115 106 (92%) No 

7 TangentiallyFired High-Sulfur Eastern 

Bituminous 

4,439 Warrior, Pattiki, & 

Galitin mines in the Illinois Basin 

480 439 (91%) On ESP 

8 d TangentiallyFired High-Sulfur Eastern 

Bituminous 

2,044 Warrior, Pattiki, & 

Galitin mines in the Illinois Basin 

470 450 d (96%) On F
3-23 

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

Unit ID 

Type of 

Scrubber Sorbent 

Additives (DBA, 

Formic Acid, etc.)

FGD Make-up 

Water Source 

SO2 Removal 

Percentage 

Forced Oxidation 

(Yes/No) 

Percent 

in Slu

7 Spray Limestone NA Intake 85-90% Yes 15 % 

8 a Spray/ 

Fountain 

Limestone NA Intake 94-96% Yes 15 % 

a – 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 dilute 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 Operating 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, the 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. 
3-25 

Table 3-10. Ash System Operating Characteristics During Sample Collection, Widows Cr

Unit 

ID 

Fly Ash 

Generation 

(tph) 

Fly Ash 

Sluice Water 

Flow Rate 

(gph) 

Source of 

Fly Ash 

Sluice 

Water 

Sluice Cycle 

Duration and 

Frequency 

Continuous 

Sluicing 

(Yes/No) 

Bottom Ash 

Generation 

(tph) 

Bottom Ash 

Sluice Water 

Flow Rate 

(gph) 

Source of 

Bottom 

Ash Sluice 

Water 

Slui

Dura

Fre

1 1.39 ≈ 28,000 Intake Approx. 1 hr 

1x every 2 hrs 

No 0.35 ≈ 56,000 Intake App

1x ev

2 5.38 ≈ 28,000 Intake Approx. 1 hr 

1x every 2 hrs 

No 1.34 ≈ 56,000 Intake App

1x ev

3 4.59 ≈ 28,000 Intake Approx. 1 hr 

1x every 2 hrs 

No 1.15 ≈ 56,000 Intake App

1x ev

4 5.27 ≈ 28,000 Intake Approx. 1 hr 

1x every 2 hrs 

No 1.32 ≈ 56,000 Intake App

1x ev

5 3.60 ≈ 28,000 Intake Approx. 1 hr 

1x every 2 hrs 

No 0.90 ≈ 56,000 Intake App

1x ev

6 4.80 ≈ 28,000 Intake Approx. 1 h 

1x every 2 hrs 

No 1.20 ≈ 56,000 Intake App

1x ev

7 16.65 ≈ 180,000 Intake Approx. 30 

min/cycle, 

continuously 

Yes 5.55 ≈ 180,000 Intake App

min 1

8 7.67 N/A N/A N/A N/A 2.56 ≈ 180,000 Intake App

min 1

N/A – Not applicable. 
3-26 

Table 3-11. Ash Pond System Operating 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 CO2 injection in middle stilling pond 

Chemicals added to pond system CO2

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. LABORATORY ANALYTICAL RESULTS AND DISCUSSION

 This section summarizes and discusses the analytical data collected during this sampling 

episode. Section 4.1 discusses the methods used by the laboratories for the 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 and all results that were measured 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 presented 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 wastewater treatment system were expected to 

contain significant amounts of readily settleable solids, to a large degree consisting of gypsum, 

unreacted limestone, and fly ash. Because of this, 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 solids loads. Therefore, EPA directed its contract 

laboratories to separate the aqueous and solid phases of the sample 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 following phases of the sample: 

• Aqueous phase; 

• Solid phase; and 

• Total sample. 

The routine metals laboratory, ProChem Analytical (ProChem), and the low-level laboratory, 

Battelle Marine Sciences Laboratory (Battelle), used two different approaches for the biphasic 

analysis because of the different methods used for routine versus low-level metals analyses. This 

section describes the approaches used by each laboratory and presents the results of the analyses. 

Routine Metals and Selected Classicals Analyses for FGD Influent 

 ProChem used EPA Method 200.7 to analyze the 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 content 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 aqueous phase results, the laboratory also needed 

to measure the original sample volume, solid phase weight, and filtrate volume. EPA developed 

the following equation to calculate the individual metal total concentrations for the sample. 
4-2 

Sample

Filtrate Filtrate Solid Solid

V

(C V ) (C Wt ) Total SampleConcentration × + × = (4-1) 

where: 

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

VFiltrate = volume of the filtrate; 

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

WtSolid = weight of the solids in the sample; and 

VSample = volume of the original sample. 

ProChem used the same approach for the six classical 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 biphasic analysis for the routine total metals, 

ammonia as nitrogen, nitrate/nitrite, chloride, sulfate, TKN, and total phosphorus. Only those 

analytes that were detected at the influent to the FGD pond system (at levels above the reporting 

limits) are included in the table. Results are rounded to three significant figures. Appendix Table 

A-1 presents all the analytical results from the influent to the 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-level 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 the 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 using this approach, the 

laboratory did not have to perform an extra filtration step to determine the individual metals 

concentrations for the various phases in the sample. 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 the individual metal solid phase concentrations for the sample: 

TSS

Total Diss

Solid C

C - C C = (4-2) 

where: 

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

CTotal = total concentration of the metal in the sample; 

CDiss = concentration of the metal in the dissolved phase of the sample; and 

CTSS = TSS concentration of the sample. 
4-3 

 Table 4-2 presents the results of the biphasic analysis for low-level total metals. Only 

those analytes that were detected at the influent to the FGD pond system (at levels above the 

reporting limits) are included in the table. Results are rounded to three significant figures. 

Appendix Table A-1 presents all the analytical results from the influent to the FGD pond system 

(SP-1) sample analysis, including results where analytes were measured above the detection 

level, but below the reporting 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 total 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 the original sample, which were all measured by 

the laboratory. Therefore, the routine metals total concentrations were calculated 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 sample volume and the filtrate volume using the 

original sample weight, solid-phase weight, filtrate weight, and the density of the original 

sample, which were all measured by the laboratory. Therefore, the classical analytes total 

concentrations were calculated using Equation 4-1 without making any assumptions. 

Ash Pond Influent 

 Prior to analyzing the ash pond influent samples, ProChem determined that the sample 

contained a solids content greater than one percent solids; therefore, ProChem performed the 

phase separation prior to the analysis 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 experienced during the analysis of the 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, chloride, 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 all the analytical results from 

the influent to the ash pond system (SP-3) sample analysis, including J-values. 

 ProChem performed a filtration blank associated with the biphasic sample separation 

process for the FGD influent (SP-1) and the ash pond influent (SP-3) sample analyses. For the 

blank, ProChem poured blank water through the filter used for the 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, indicating that there was no contamination from the 

filtration process. Appendix Table A-3 presents all the analytical results from the filtration blank. 

The filtration blank results apply to both the FGD 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 were detected in one or more samples (at levels 

above the reporting limits) for the sampling episode are included in the table. Results are 

rounded to three significant digits. If an analyte was measured 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 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-1, A-4, and A-5 present all the 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 metal 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 routine and low-level metals for these same sampling points. Only those 

analytes that were detected in one or more samples (at levels above the reporting limits) for the 

sampling episode are included in the table. Results are rounded to three significant digits. If an 

analyte was measured 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 samplespecific report limit in parentheses. Note that the 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 analytical 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 Classicals and Routine Total Metals Measured 

Above the Report Limit for the Influent to the FGD 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 (NH3-N) 0.530 25.2 2.26 

Nitrate/Nitrite (NO3-N + NO2-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, including 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 Low-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 Classicals 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 (NH3-N) 0.180 14.3 0.400 

Nitrate/Nitrite (NO3-N + NO2-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, including 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 (NH3-N) 4500-NH3F MG/L 2.26 0.220 

Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1.00 0.0945 

Total Kjeldahl Nitrogen (TKN) 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 paired 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 outside 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 filtered 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 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. A “NQ” for the average 

FGD effluent indicates that the original FGD effluent and/or the duplicate 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 paired 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 outside 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 filtered 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 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. A “NQ” for the average 

FGD effluent indicates that the original FGD effluent and/or the duplicate 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 paired 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-NH3F MG/L 0.400 0.160 

Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H 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 paired samples. See Section 4.3. 
R – MS/MSD % Recovery outside 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 filtered 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 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. 

Note: Results shown are not paired 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 4.45 
R – MS/MSD % Recovery outside 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 filtered 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 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. 

Note: Results shown are not paired 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. DATA QUALITY

 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 the 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 laboratories 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 was 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 blanks, field blanks, and field 

duplicate sample results. Section 3.8 of the Sampling 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 detected during the sampling episode). Appendix A 

contains the results for all analytes, both detected and nondetected. 

5.2.1 Bottle Blanks 

 EPA collects bottle blanks to evaluate possible contamination from the sample collection 

bottles. Bottle blanks were collected and analyzed for 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 analyzed the samples using EPA Method 1638. 

 Albion Environmental collected the bottle blanks 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 representative aliquot into a pre-cleaned LDPE 

sample bottle, preserved the sample with nitric acid to a pH <2, and allowed the sample to sit for 

at least 24 hours. Albion Environmental then analyzed the samples using EPA Method 1638. 

 Albion Environmental collected the bottle blanks for the low-level mercury sample 

bottles (250 flint glass bottles and 1-L borosilicate glass bottles) by filling the pre-cleaned bottle 

to the neck with ASTM Type 1 water, preserving 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 blank for the 10-liter and 20-liter composite 

containers by filling the containers with approximately 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 orientation to expose all surfaces of the container to 

the ASTM Type 1 water. Albion Environmental then shook the 10-liter and 20-liter containers 

and poured a representative sample into a pre-cleaned 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 analytical methods (i.e., EPA Method 1638 or 1631E), as described 

above for the other bottle blank samples. 

 No metals were detected in the bottle blank, indicating that there was no contamination 

from the sample containers. Appendix 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. 

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 Environmental collected and analyzed equipment 

blanks for low-level metals for each type of pre-cleaned equipment supplied for the episode. 

 Albion Environmental collected the equipment blanks for the capsule filters and 

fabricated tubing sets by pumping approximately 500 mL of ASTM Type 1 water through the 

pre-cleaned filter or tubing set and discarding the water. Albion Environmental then pumped 

additional water through the pre-cleaned filter or tubing set into a pre-cleaned 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 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 equipment 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 the tubing sets. Barium was not detected above the 

report limit in the equipment blanks for the other 12 analyses. In addition, barium was not 

detected in any of the field blank samples (above the report limit), as described in Section 5.2.3. 

Finally, barium was measured at a concentration greater than 300 times the equipment blank 

result at all of the sampling points for both the total and dissolved phases. Therefore, the 

potential contamination from the sampling equipment did not significantly affect the sampling 

results. 

 No other metals were detected in the equipment blanks, indicating that there was no other 

contamination from the sample equipment. Appendix 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 the barium equipment blank concentration to be 
5-3 

0.490 ug/L for all tubing sets containing #73 silicone tubing because the tubing set may have 

been fabricated using #73 silicone from the cleaning batch that had a detection 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 equipment, sampling equipment decontamination 

procedures, sample collection procedures, or atmospheric contamination. EPA analyzed the field 

blank samples for the low-level and routine metals analyses, including both total and dissolved 

metals1. 

 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 tubing consisting of 25 feet of Teflon® tubing 

attached to a length of silicone tubing. The container holding the ASTM Type 1 water was 

placed in a large plastic bag and the end of the Teflon® tubing was placed directly into the 

container. The large plastic bag was closed off 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 into 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 description (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 minimize 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 poured 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 sample collection description (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 ash 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 off 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 blank 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 the 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 the 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” splitter, and poured into the sample bottles. The 

low-level and routine dissolved metals field blank 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 pumping ASTM Type 1 water 

through the tubing, capsule filter, and “Y” splitter, and into the sample bottles. EPA collected all 

analytes for the effluent sample field blanks as “true” split samples with Widows Creek’s 

representative, using the same procedure discussed in the sample collection description 

(Section 3.1). 

 No metals were detected in the field blank samples above the reporting limit, indicating 

that there was no contamination from the sample 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), influent 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 above the method detection limit, but below the 

reporting limit (i.e., J-values). 

5.2.4 Field Duplicates 

 The sampling team collected field duplicate samples to assess the sampling measurement 

precision for the episode. Field duplicate samples are separate samples 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 relative 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

S D

S D

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 samples (SP-5) for all analytes (except 

HEM/SGT-HEM) were collected from the effluent from the FGD pond system (SP-2). Table 5-1 

presents analytical results and the RPD for SP-2 and SP-5 and includes analytical results for only 

those analytes that were detected in one or more samples for the sampling episode. Results are 

rounded to three significant digits. 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, including 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 at least one non-detect value. (Calculation uses detection 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). Thpresented in Appendix A with a J flag designation. 

Table 5-1. Field Duplicate Results, Widows Creek 

Analyte

Original FGD Effluent 

Concentration (SP-2) 

Duplicate FGD Effluent 

Concentration (SP-5) Average Result 

Relat

Diffe

Classical Pollutants Ammonia As Nitrogen (NH3-N) 0.210 0.230 0.220 Nitrate/Nitrite (NO3-N + NO2-N) 0.100 0.0890 0.0945 Total Kjeldahl Nitrogen (TKN) 2.47 2.54 2.51 Biochemical Oxygen Demand (BOD) 

ND (9.00) 11.0 < 10.0 

Chloride 1,120 1,110 1,120 Hexane Extractable Material (HEM) 

ND (5.00) NA ND (5.00) 

Sulfate 1,840 2,270 2,060 Total Dissolved Solids (TDS) 6,040 5,620 5,830 Total Phosphorus 0.0100 E 0.0130 E 0.0115 Total Suspended Solids (TSS) 8.00 8.00 E 8.00 Routine Total Metals Aluminum 117 105 111 Antimony NQ (20.0) NQ (20.0) ND (20.0) Arsenic 50.2 48.8 49.5 Barium 186 171 179 Beryllium NQ (5.00) NQ (5.00) ND (5.00) Boron 31,700 31,200 31,500 Cadmium NQ (5.00) NQ (5.00) ND (5.00) 
5-6 

< – Average result includes at least one non-detect value. (Calculation uses detection 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). Thpresented in Appendix A with a J flag designation. 

Table 5-1. Field Duplicate Results, Widows Creek 

Analyte

Original FGD Effluent 

Concentration (SP-2) 

Duplicate FGD Effluent 

Concentration (SP-5) Average Result 

Relat

Diffe

Calcium 987,000 986,000 987,000 Chromium NQ (10.0) NQ (10.0) ND (10.0) Copper NQ (10.0) NQ (10.0) ND (10.0) Iron NQ (100) NQ (100) ND (100) Lead ND (50.0) ND (50.0) ND (50.0) Magnesium 193,000 185,000 189,000 Manganese 636 609 623 Mercury ND (2.00) ND (2.00) ND (2.00) Molybdenum 1,530 1,470 1,500 Nickel NQ (50.0) NQ (50.0) ND (50.0) Selenium 241 230 236 Sodium 69,200 69,700 69,500 Thallium NQ (10.0) NQ (10.0) ND (10.0) Titanium NQ (10.0) NQ (10.0) ND (10.0) Vanadium 42.7 41.4 42.1 Yttrium ND (5.00) ND (5.00) ND (5.00) Zinc NQ (10.0) NQ (10.0) ND (10.0) Routine Dissolved Metals Aluminum NQ (50.0) NQ (50.0) ND (50.0) Antimony NQ (20.0) NQ (20.0) ND (20.0) Arsenic 47.2 46.1 46.7 
5-7 

< – Average result includes at least one non-detect value. (Calculation uses detection 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). Thpresented in Appendix A with a J flag designation. 

Table 5-1. Field Duplicate Results, Widows Creek 

Analyte

Original FGD Effluent 

Concentration (SP-2) 

Duplicate FGD Effluent 

Concentration (SP-5) Average Result 

Relat

Diffe

Barium 191 191 191 Beryllium NQ (5.00) NQ (5.00) ND (5.00) Boron 28,700 29,700 29,200 Cadmium NQ (5.00) NQ (5.00) ND (5.00) Calcium 934,000 929,000 932,000 Chromium NQ (10.0) NQ (10.0) ND (10.0) Hexavalent Chromium ND (2.00) ND (2.00) ND (2.00) Copper NQ (10.0) NQ (10.0) ND (10.0) Iron NQ (100) NQ (100) ND (100) Lead ND (50.0) ND (50.0) ND (50.0) Magnesium 182,000 186,000 184,000 Manganese 543 R 542 543 Mercury ND (2.00) ND (2.00) ND (2.00) Molybdenum 1,480 1,450 1,470 Nickel NQ (50.0) NQ (50.0) ND (50.0) Selenium 231 221 226 Sodium 66,900 65,500 66,200 Thallium NQ (10.0) NQ (10.0) ND (10.0) Titanium ND (10.0) ND (10.0) ND (10.0) Vanadium 39.7 40.2 40.0 Yttrium ND (5.00) ND (5.00) ND (5.00) 
5-8 

< – Average result includes at least one non-detect value. (Calculation uses detection 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). Thpresented in Appendix A with a J flag designation. 

Table 5-1. Field Duplicate Results, Widows Creek 

Analyte

Original FGD Effluent 

Concentration (SP-2) 

Duplicate FGD Effluent 

Concentration (SP-5) Average Result 

Relat

Diffe

Zinc ND (10.0) ND (10.0) ND (10.0) Low-Level Total Metals Antimony 11.8 11.8 11.8 Arsenic 47.3 47.9 47.6 Cadmium 3.66 3.80 3.73 Chromium NQ (16.0) NQ (16.0) ND (16.0) Copper NQ (4.00) NQ (4.00) ND (4.00) Lead NQ (1.00) NQ (1.00) ND (1.00) Mercury 0.0428 0.0448 0.0438 Nickel 35.6 36.7 36.2 Selenium 205 211 208 Thallium 11.1 11.1 11.1 Zinc ND (10.0) ND (10.0) ND (10.0) Low-Level Dissolved Metals Antimony 11.8 11.9 11.9 Arsenic 47.0 46.0 46.5 Cadmium 3.76 3.71 3.74 Chromium NQ (16.0) NQ (16.0) ND (16.0) Hexavalent Chromium 3.29 3.10 3.20 Copper NQ (4.00) NQ (4.00) ND (4.00) Lead ND (1.00) ND (1.00) ND (1.00) 
5-9 

< – Average result includes at least one non-detect value. (Calculation uses detection 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). Thpresented in Appendix A with a J flag designation. 

Table 5-1. Field Duplicate Results, Widows Creek 

Analyte

Original FGD Effluent 

Concentration (SP-2) 

Duplicate FGD Effluent 

Concentration (SP-5) Average Result 

Relat

Diffe

Mercury 0.0106 0.0107 0.0107 Nickel 32.8 L 33.8 L 33.3 Selenium 213 373 293 Thallium 11.0 10.9 11.0 Zinc ND (10.0) ND (10.0) ND (10.0) 
6-1

6. REFERENCES

1. Eastern Research Group, Inc., 2007. Engineering Site Visit Report for Tennessee Valley 

Authority’s Widows Creek Fossil Plant. July 18. DCN 04714. EPA-HQ-OW-2006-0071-

0399. 

2. Eastern Research Group, Inc., 2007. Sampling Plan, Tennessee Valley Authority’s 

Widows Creek Fossil Plant. September 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 Emission Spectrometry. Revision 5.0. EPA-821-R01-010. January. 
Appendix A 

ANALYTICAL RESULTS 
A-1 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Classical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L NA NP NP Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L NA NP NP Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L NA NP NP Biochemical Oxygen Demand (BOD) 5210B MG/L 30 NP NP Chloride 4500-CL-C MG/L NA NP NP Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP Silica Gel Treated HEM (SGT-HEM) 1664A MG/L 1 NP NP Sulfate D516-90 MG/L NA NP NP Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP Total Phosphorus 365.3 MG/L NA NP NP Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP Classical Pollutants – Solid (wet weight) Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/KG 1 NP NP Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/KG 1 NP NP Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/KG 1 NP NP Chloride 4500-CL-C MG/KG 1 NP NP Sulfate D516-90 MG/KG 50 NP NP 
A-2 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Total Phosphorus 365.3 MG/KG 20 NP NP Classical Pollutants – Filtered Aqueous Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1 NP NP Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP Chloride 4500-CL-C MG/L 1 NP NP Sulfate D516-90 MG/L 50 NP NP Total Phosphorus 365.3 MG/L 5 NP NP Routine Metals – Total Aluminum 200.7 UG/L NA NC 217 Antimony 200.7 UG/L NA NC 86.9 Arsenic 200.7 UG/L NA NC 43.4 Barium 200.7 UG/L NA NC 8.69 Beryllium 200.7 UG/L NA NC 21.7 Boron 200.7 UG/L NA NC 1,000 Cadmium 200.7 UG/L NA NC 21.7 Calcium 200.7 UG/L NA NC 2,170 Chromium 200.7 UG/L NA NC 43.4 
A-3 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Cobalt 200.7 UG/L NA NC 217 Copper 200.7 UG/L NA NC 43.4 Iron 200.7 UG/L NA NC 434 Lead 200.7 UG/L NA NC 217 Magnesium 200.7 UG/L NA NC 869 Manganese 200.7 UG/L NA NC 65.2 Mercury 245.1 UG/L NA NC 2.00 Molybdenum 200.7 UG/L NA NC 43.4 Nickel 200.7 UG/L NA NC 217 Selenium 200.7 UG/L NA NC 21.7 Silver 200.7 UG/L NA NC 86.9 Sodium 200.7 UG/L NA NC 2,170 Thallium 200.7 UG/L NA NC 43.4 Tin 200.7 UG/L NA NC 130 Titanium 200.7 UG/L NA NC 43.4 Vanadium 200.7 UG/L NA NC 86.9 Yttrium 200.7 UG/L NA NC 21.7 Zinc 200.7 UG/L NA NC 43.4 
A-4 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Routine Metals – Dissolved Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 10 27.0 1,000 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 10 51.0 500 Chromium 200.7 UG/L 1 0.200 10.0 Hexavalent Chromium D1687-92 UG/L 1 1.00 2.00 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 10 0.500 2.00 
A-5 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Routine Metals – Filtered Aqueous Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 10 27.0 1,000 
A-6 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 20 102 1,000 Chromium 200.7 UG/L 1 0.200 10.0 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 10 0.500 2.00 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 
A-7 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Routine Metals – Solid (wet weight) Aluminum 200.7 MG/KG 1 1.75 5.00 Antimony 200.7 MG/KG 1 0.110 2.00 Arsenic 200.7 MG/KG 1 0.110 1.00 Barium 200.7 MG/KG 1 0.0200 0.200 Beryllium 200.7 MG/KG 1 0.0100 0.500 Boron 200.7 MG/KG 1 0.200 10.0 Cadmium 200.7 MG/KG 1 0.0200 0.500 Calcium 200.7 MG/KG 10 4.00 50.0 Chromium 200.7 MG/KG 1 0.0200 1.00 Cobalt 200.7 MG/KG 1 0.360 5.00 Copper 200.7 MG/KG 1 0.0300 1.00 Iron 200.7 MG/KG 1 1.06 10.0 Lead 200.7 MG/KG 1 0.100 5.00 Magnesium 200.7 MG/KG 1 2.18 20.0 
A-8 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Manganese 200.7 MG/KG 1 0.0200 1.50 Mercury 245.5 MG/KG 1 0.00600 0.0250 Molybdenum 200.7 MG/KG 1 0.0600 1.00 Nickel 200.7 MG/KG 1 0.0800 5.00 Selenium 200.7 MG/KG 1 0.170 0.500 Silver 200.7 MG/KG 1 0.100 2.00 Sodium 200.7 MG/KG 1 6.23 50.0 Thallium 200.7 MG/KG 1 0.110 1.00 Tin 200.7 MG/KG 1 0.100 3.00 Titanium 200.7 MG/KG 1 0.120 1.00 Vanadium 200.7 MG/KG 1 0.0800 2.00 Yttrium 200.7 MG/KG 1 0.0300 0.500 Zinc 200.7 MG/KG 1 0.200 1.00 Low-Level Metals – Total Antimony 1638 UG/L 200 1.40 4.00 Arsenic 1638 UG/L 200 3.04 30.0 Cadmium 1638 UG/L 200 0.200 20.0 Chromium 1638 UG/L 200 16.6 160 
A-9 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Copper 1638 UG/L 200 0.800 40.0 Lead 1638 UG/L 200 0.200 10.0 Mercury 1631E UG/L 1,000 0.188 0.500 Nickel 1638 UG/L 200 2.60 200 Selenium 1638 UG/L 200 3.20 200 Silver 1638 UG/L 200 0.400 20.0 Thallium 1638 UG/L 200 0.0800 4.00 Zinc 1638 UG/L 200 41.8 100 Low-Level Metals - Dissolved Antimony 1638 UG/L 20 0.140 0.400 Arsenic 1638 UG/L 20 0.304 3.00 Cadmium 1638 UG/L 20 0.0200 2.00 Chromium 1638 UG/L 20 1.66 16.0 Copper 1638 UG/L 20 0.0800 4.00 Lead 1638 UG/L 20 0.0200 1.00 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 20 0.260 20.0 Selenium 1638 UG/L 100 1.60 100 
A-10 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-1. FGD Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific Silver 1638 UG/L 20 0.0400 2.00 Thallium 1638 UG/L 20 0.00800 0.400 Zinc 1638 UG/L 20 4.18 10.0 Low-Level Metals – Solid (dry weight) Antimony 1638 MG/KG NA 0.0408 0.117 Arsenic 1638 MG/KG NA 0.0885 0.874 Cadmium 1638 MG/KG NA 0.00640 0.583 Chromium 1638 MG/KG NA 0.484 4.66 Copper 1638 MG/KG NA 0.0233 1.17 Lead 1638 MG/KG NA 0.00580 0.291 Mercury 1631E MG/KG NA 0.00490 0.0129 Nickel 1638 MG/KG NA 0.0757 5.83 Selenium 1638 MG/KG NA 0.0932 5.83 Silver 1638 MG/KG NA 0.0116 0.583 Thallium 1638 MG/KG NA 0.00230 0.117 Zinc 1638 MG/KG NA 1.22 2.91 
A-11 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Classical Pollutants – Total Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/L NA NP NP Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L NA NP NP Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L NA NP NP Biochemical Oxygen Demand (BOD) 5210B MG/L 30 NP NP Chloride 4500-CL-C MG/L NA NP NP Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP Sulfate D516-90 MG/L NA NP NP Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP Total Phosphorus 365.3 MG/L NA NP NP Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP Classical Pollutants – Solid (wet weight) Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/KG 1 NP NP Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/KG 1 NP NP Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/KG 1 NP NP Chloride 4500-CL-C MG/KG 1 NP NP Sulfate D516-90 MG/KG 1 NP NP Total Phosphorus 365.3 MG/KG 50 NP NP 
A-12 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Classical Pollutants – Filtered Aqueous Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1 NP NP Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP Chloride 4500-CL-C MG/L 1 NP NP Sulfate D516-90 MG/L 2 NP NP Total Phosphorus 365.3 MG/L 10 NP NP Routine Metals – Total Aluminum 200.7 UG/L NA NC 95.0 Antimony 200.7 UG/L NA NC 38.0 Arsenic 200.7 UG/L NA NC 19.0 Barium 200.7 UG/L NA NC 3.80 Beryllium 200.7 UG/L NA NC 9.50 Boron 200.7 UG/L NA NC 190 Cadmium 200.7 UG/L NA NC 9.50 Calcium 200.7 UG/L NA NC 95.0 Chromium 200.7 UG/L NA NC 19.0 Cobalt 200.7 UG/L NA NC 95.0 
A-13 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Copper 200.7 UG/L NA NC 19.0 Iron 200.7 UG/L NA NC 190 Lead 200.7 UG/L NA NC 95.0 Magnesium 200.7 UG/L NA NC 380 Manganese 200.7 UG/L NA NC 28.5 Mercury 245.1 UG/L NA NC 0.475 Molybdenum 200.7 UG/L NA NC 19.0 Nickel 200.7 UG/L NA NC 95.0 Selenium 200.7 UG/L NA NC 9.50 Silver 200.7 UG/L NA NC 38.0 Sodium 200.7 UG/L NA NC 950 Thallium 200.7 UG/L NA NC 19.0 Tin 200.7 UG/L NA NC 57.0 Titanium 200.7 UG/L NA NC 19.0 Vanadium 200.7 UG/L NA NC 38.0 Yttrium 200.7 UG/L NA NC 9.50 Zinc 200.7 UG/L NA NC 19.0 
A-14 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Routine Metals – Dissolved Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 1 2.70 100 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 1 5.10 50.0 Chromium 200.7 UG/L 1 0.200 10.0 Hexavalent Chromium D1687-92 UG/L 1 1.00 2.00 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 1 0.0500 0.200 
A-15 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Routine Metals – Filtered Aqueous Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 1 2.70 100 
A-16 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 1 5.10 50.0 Chromium 200.7 UG/L 1 0.200 10.0 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 1 0.0500 0.200 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 
A-17 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Routine Metals – Solid (wet weight) Aluminum 200.7 MG/KG 1 1.75 5.00 Antimony 200.7 MG/KG 1 0.110 2.00 Arsenic 200.7 MG/KG 1 0.110 1.00 Barium 200.7 MG/KG 1 0.0200 0.200 Beryllium 200.7 MG/KG 1 0.0100 0.500 Boron 200.7 MG/KG 1 0.200 10.0 Cadmium 200.7 MG/KG 1 0.0200 0.500 Calcium 200.7 MG/KG 1 0.400 5.00 Chromium 200.7 MG/KG 1 0.0200 1.00 Cobalt 200.7 MG/KG 1 0.360 5.00 Copper 200.7 MG/KG 1 0.0300 1.00 Iron 200.7 MG/KG 1 1.06 10.0 Lead 200.7 MG/KG 1 0.100 5.00 Magnesium 200.7 MG/KG 1 2.18 20.0 
A-18 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Manganese 200.7 MG/KG 1 0.0200 1.50 Mercury 245.5 MG/KG 1 0.00600 0.0250 Molybdenum 200.7 MG/KG 1 0.0600 1.00 Nickel 200.7 MG/KG 1 0.0800 5.00 Selenium 200.7 MG/KG 1 0.170 0.500 Silver 200.7 MG/KG 1 0.100 2.00 Sodium 200.7 MG/KG 1 6.23 50.0 Thallium 200.7 MG/KG 1 0.110 1.00 Tin 200.7 MG/KG 1 0.100 3.00 Titanium 200.7 MG/KG 1 0.120 1.00 Vanadium 200.7 MG/KG 1 0.0800 2.00 Yttrium 200.7 MG/KG 1 0.0300 0.500 Zinc 200.7 MG/KG 1 0.200 1.00 Low-Level Metals – Total Antimony 1638 UG/L 200 1.40 4.00 Arsenic 1638 UG/L 200 3.04 30.0 Cadmium 1638 UG/L 200 0.200 20.0 Chromium 1638 UG/L 200 16.6 160 
A-19 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Copper 1638 UG/L 200 0.800 40.0 Lead 1638 UG/L 200 0.200 10.0 Mercury 1631E UG/L 52 0.00978 0.0260 Nickel 1638 UG/L 200 2.60 200 Selenium 1638 UG/L 200 3.20 200 Silver 1638 UG/L 200 0.400 20.0 Thallium 1638 UG/L 200 0.0800 4.00 Zinc 1638 UG/L 200 41.8 100 Low-Level Metals - Dissolved Antimony 1638 UG/L 20 0.140 0.400 Arsenic 1638 UG/L 20 0.304 3.00 Cadmium 1638 UG/L 20 0.0200 2.00 Chromium 1638 UG/L 20 1.66 16.0 Copper 1638 UG/L 20 0.0800 4.00 Lead 1638 UG/L 20 0.0200 1.00 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 20 0.260 20.0 Selenium 1638 UG/L 100 1.60 100 
A-20 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

calculated 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 RL are only provided for the metal analytes because EPA is presentmetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-2. Ash Pond Influent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific R

Silver 1638 UG/L 20 0.0400 2.00 Thallium 1638 UG/L 20 0.00800 0.400 Zinc 1638 UG/L 20 4.18 10.0 
A-21 

Table A-3. ProChem Biphasic Filtration Blank 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-22 

U – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-4. FGD Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific RL 

Classical Pollutants Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1 NP NP Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP Biochemical Oxygen Demand (BOD) 5210B MG/L 6 NP NP Chloride 4500-CL-C MG/L 1 NP NP Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP Sulfate D516-90 MG/L 50 NP NP Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP Total Phosphorus 365.3 MG/L 1 NP NP Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP Routine Metals – Total Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 10 27.0 1,000 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 10 51.0 500 Chromium 200.7 UG/L 1 0.200 10.0 
A-23 

U – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-4. FGD Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific RL 

Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 10 0.500 2.00 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Routine Metals – Dissolved Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 
A-24 

U – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-4. FGD Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific RL 

Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 10 27.0 1,000 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 10 51.0 500 Chromium 200.7 UG/L 1 0.200 10.0 Hexavalent Chromium D1687-92 UG/L 1 1.00 2.00 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 10 0.500 2.00 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 
A-25 

U – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-4. FGD Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific RL 

Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Low-Level Metals – Total Antimony 1638 UG/L 20 0.140 0.400 Arsenic 1638 UG/L 20 0.304 3.00 Cadmium 1638 UG/L 20 0.0200 2.00 Chromium 1638 UG/L 20 1.66 16.0 Copper 1638 UG/L 20 0.0800 4.00 Lead 1638 UG/L 20 0.0200 1.00 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 20 0.260 20.0 Selenium 1638 UG/L 100 1.60 100 Silver 1638 UG/L 20 0.0400 2.00 Thallium 1638 UG/L 20 0.00800 0.400 Zinc 1638 UG/L 20 4.18 10.0 Low-Level Metals - Dissolved Antimony 1638 UG/L 20 0.140 0.400 Arsenic 1638 UG/L 20 0.304 3.00 
A-26 

U – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-4. FGD Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific RL 

Cadmium 1638 UG/L 20 0.0200 2.00 Chromium 1638 UG/L 20 1.66 16.0 Hexavalent Chromium 1636 UG/L 5 1.75 2.50 Copper 1638 UG/L 20 0.0800 4.00 Lead 1638 UG/L 20 0.0200 1.00 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 20 0.260 20.0 Selenium 1638 UG/L 100 1.60 100 Silver 1638 UG/L 20 0.0400 2.00 Thallium 1638 UG/L 20 0.00800 0.400 Zinc 1638 UG/L 20 4.18 10.0 
A-27 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, 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 Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific R

Classical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1 NP NP Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP Biochemical Oxygen Demand (BOD) 5210B MG/L 6 NP NP Chloride 4500-CL-C MG/L 1 NP NP Sulfate D516-90 MG/L 100 NP NP Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP Total Phosphorus 365.3 MG/L 1 NP NP Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP Routine Metals – Total Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 10 27.0 1,000 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 10 51.0 500 Chromium 200.7 UG/L 1 0.200 10.0 Cobalt 200.7 UG/L 1 0.600 50.0 
A-28 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, 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 Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific R

Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 10 0.500 2.00 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Routine Metals – Dissolved Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 
A-29 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, 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 Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific R

Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 10 27.0 1,000 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 10 51.0 500 Chromium 200.7 UG/L 1 0.200 10.0 Hexavalent Chromium D1687-92 UG/L 1 1.00 2.00 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 10 0.500 2.00 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 
A-30 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, 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 Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific R

Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Low-Level Metals – Total Antimony 1638 UG/L 20 0.140 0.400 Arsenic 1638 UG/L 20 0.304 3.00 Cadmium 1638 UG/L 20 0.0200 2.00 Chromium 1638 UG/L 20 1.66 16.0 Copper 1638 UG/L 20 0.0800 4.00 Lead 1638 UG/L 20 0.0200 1.00 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 20 0.260 20.0 Selenium 1638 UG/L 100 1.60 100 Silver 1638 UG/L 20 0.0400 2.00 Thallium 1638 UG/L 20 0.00800 0.400 Zinc 1638 UG/L 20 4.18 10.0 Low-Level Metals - Dissolved Antimony 1638 UG/L 20 0.140 0.400 Arsenic 1638 UG/L 20 0.304 3.00 Cadmium 1638 UG/L 20 0.0200 2.00 Chromium 1638 UG/L 20 1.66 16.0 Hexavalent Chromium 1636 UG/L 5 1.75 2.50 Copper 1638 UG/L 20 0.0800 4.00 
A-31 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, 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 Creek 

Analyte Method Unit 

Dilution 

Factor Sample-Specific MDL Sample-Specific R

Lead 1638 UG/L 20 0.0200 1.00 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 20 0.260 20.0 Selenium 1638 UG/L 100 1.60 100 Silver 1638 UG/L 20 0.0400 2.00 Thallium 1638 UG/L 20 0.00800 0.400 Zinc 1638 UG/L 20 4.18 10.0 
A-32 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-6. Ash Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific 

Classical Pollutants – Total Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 1 NP NP Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP Biochemical Oxygen Demand (BOD) 5210B MG/L 1.2 NP NP Chloride 4500-CL-C MG/L 1 NP NP Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP Silica Gel Treated HEM (SGT-HEM) 1664A MG/L 1 NP NP Sulfate D516-90 MG/L 5 NP NP Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP Total Phosphorus 365.3 MG/L 1 NP NP Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP Routine Metals – Total Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 1 2.70 100 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 1 5.10 50.0 Chromium 200.7 UG/L 1 0.200 10.0 Cobalt 200.7 UG/L 1 0.600 50.0 
A-33 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-6. Ash Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific 

Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 1 0.0500 0.200 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Routine Metals – Dissolved Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 
A-34 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-6. Ash Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific 

Boron 200.7 UG/L 1 2.70 100 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 1 5.10 50.0 Chromium 200.7 UG/L 1 0.200 10.0 Hexavalent Chromium D1687-92 UG/L 1 1.00 2.00 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 1 0.0500 0.200 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 
A-35 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-6. Ash Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific 

Low-Level Metals – Total Antimony 1638 UG/L 5 0.0350 0.100 Arsenic 1638 UG/L 5 0.0760 0.750 Cadmium 1638 UG/L 5 0.00500 0.500 Chromium 1638 UG/L 5 0.415 4.00 Copper 1638 UG/L 5 0.0200 1.00 Lead 1638 UG/L 5 0.00500 0.250 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 5 0.0650 5.00 Selenium 1638 UG/L 5 0.0800 5.00 Silver 1638 UG/L 5 0.0100 0.500 Thallium 1638 UG/L 5 0.00200 0.100 Zinc 1638 UG/L 5 1.05 2.50 Low-Level Metals - Dissolved Antimony 1638 UG/L 5 0.0350 0.100 Arsenic 1638 UG/L 5 0.0760 0.750 Cadmium 1638 UG/L 5 0.00500 0.500 Chromium 1638 UG/L 5 0.415 4.00 Hexavalent Chromium 1636 UG/L 5 1.75 2.50 Copper 1638 UG/L 5 0.0200 1.00 Lead 1638 UG/L 5 0.00500 0.250 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 5 0.0650 5.00 
A-36 

E – 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 RL are only provided for the metal analytes because EPA is present

metals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was nolimit, the report limit is presented in parentheses in the concentration column. 

Table A-6. Ash Pond Effluent Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific 

Selenium 1638 UG/L 5 0.0800 5.00 Silver 1638 UG/L 5 0.0100 0.500 Thallium 1638 UG/L 5 0.00200 0.100 Zinc 1638 UG/L 5 1.05 2.50 
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-37 

Table A-7. Bottle Blank and Equipment Blank 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 Blank 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 dissolved 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 Blank (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 Blank 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 Bottles – 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 (alternative sample composite bottle 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 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) 
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 Blank 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 Blank (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® tubing 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 Blank 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® tubing, 5 feet #73 silicone tubing, Y-splitter, two pieces 

of 5 feet #24 silicone tubing for sample collection for 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 tubing for sample collection for low-level total and dissolved mercury and 

total metals at the FGD influent 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 Blank 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-43 

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). ND – Not detected (number in parenthesis is the report limit). 

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

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Routine Metals – Total Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 1 2.70 100 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 1 5.10 50.0 Chromium 200.7 UG/L 1 0.200 10.0 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 1 0.0500 0.200 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 
A-44 

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). ND – Not detected (number in parenthesis is the report limit). 

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

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Routine Metals – Dissolved Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 1 2.70 100 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 1 5.10 50.0 Chromium 200.7 UG/L 1 0.200 10.0 Hexavalent Chromium D1687-92 UG/L 1 1.00 2.00 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 1 0.0500 0.200 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 
A-45 

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). ND – Not detected (number in parenthesis is the report limit). 

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

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Low-Level Metals – Total Antimony 1638 UG/L 1 0.00700 0.0200 Arsenic 1638 UG/L 1 0.0152 0.150 Cadmium 1638 UG/L 1 0.00100 0.100 Chromium 1638 UG/L 1 0.0830 0.800 Copper 1638 UG/L 1 0.00400 0.200 Lead 1638 UG/L 1 0.00100 0.0500 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 1 0.0130 1.00 Selenium 1638 UG/L 1 0.0160 1.00 Silver 1638 UG/L 1 0.00200 0.100 Thallium 1638 UG/L 1 0.000400 0.0200 Zinc 1638 UG/L 1 0.209 0.500 Low-Level Metals - Dissolved Antimony 1638 UG/L 1 0.00700 0.0200 Arsenic 1638 UG/L 1 0.0152 0.150 Cadmium 1638 UG/L 1 0.00100 0.100 Chromium 1638 UG/L 1 0.0830 0.800 Copper 1638 UG/L 1 0.00400 0.200 Lead 1638 UG/L 1 0.00100 0.0500 Nickel 1638 UG/L 1 0.0130 1.00 
A-46 

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). ND – Not detected (number in parenthesis is the report limit). 

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

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Selenium 1638 UG/L 1 0.0160 1.00 Silver 1638 UG/L 1 0.00200 0.100 Thallium 1638 UG/L 1 0.000400 0.0200 Zinc 1638 UG/L 1 0.209 0.500 
A-47 

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). ND – Not detected (number in parenthesis is the report limit). 

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

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Routine Metals – Total Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 1 2.70 100 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 1 5.10 50.0 Chromium 200.7 UG/L 1 0.200 10.0 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 1 0.0500 0.200 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 
A-48 

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). ND – Not detected (number in parenthesis is the report limit). 

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

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Routine Metals – Dissolved Aluminum 200.7 UG/L 1 10.6 50.0 Antimony 200.7 UG/L 1 0.700 20.0 Arsenic 200.7 UG/L 1 0.500 10.0 Barium 200.7 UG/L 1 0.100 2.00 Beryllium 200.7 UG/L 1 0.500 5.00 Boron 200.7 UG/L 1 2.70 100 Cadmium 200.7 UG/L 1 0.100 5.00 Calcium 200.7 UG/L 1 5.10 50.0 Chromium 200.7 UG/L 1 0.200 10.0 Hexavalent Chromium D1687-92 UG/L 1 1.00 2.00 Cobalt 200.7 UG/L 1 0.600 50.0 Copper 200.7 UG/L 1 0.200 10.0 Iron 200.7 UG/L 1 5.40 100 Lead 200.7 UG/L 1 0.700 50.0 Magnesium 200.7 UG/L 1 8.90 200 Manganese 200.7 UG/L 1 0.200 15.0 Mercury 245.1 UG/L 1 0.0500 0.200 Molybdenum 200.7 UG/L 1 0.200 10.0 Nickel 200.7 UG/L 1 1.10 50.0 Selenium 200.7 UG/L 1 0.600 5.00 Silver 200.7 UG/L 1 0.400 20.0 Sodium 200.7 UG/L 1 40.5 500 Thallium 200.7 UG/L 1 0.500 10.0 
A-49 

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). ND – Not detected (number in parenthesis is the report limit). 

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

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Tin 200.7 UG/L 1 0.400 30.0 Titanium 200.7 UG/L 1 0.200 10.0 Vanadium 200.7 UG/L 1 0.600 20.0 Yttrium 200.7 UG/L 1 0.200 5.00 Zinc 200.7 UG/L 1 0.200 10.0 Low-Level Metals – Total Antimony 1638 UG/L 1 0.00700 0.0200 Arsenic 1638 UG/L 1 0.0152 0.150 Cadmium 1638 UG/L 1 0.00100 0.100 Chromium 1638 UG/L 1 0.0830 0.800 Copper 1638 UG/L 1 0.00400 0.200 Lead 1638 UG/L 1 0.00100 0.0500 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 1 0.0130 1.00 Selenium 1638 UG/L 1 0.0160 1.00 Silver 1638 UG/L 1 0.00200 0.100 Thallium 1638 UG/L 1 0.000400 0.0200 Zinc 1638 UG/L 1 0.209 0.500 Low-Level Metals - Dissolved Antimony 1638 UG/L 1 0.00700 0.0200 Arsenic 1638 UG/L 1 0.0152 0.150 Cadmium 1638 UG/L 1 0.00100 0.100 Chromium 1638 UG/L 1 0.0830 0.800 Hexavalent Chromium 1636 UG/L 5 1.75 2.50 Copper 1638 UG/L 1 0.00400 0.200 Lead 1638 UG/L 1 0.00100 0.0500 
A-50 

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). ND – Not detected (number in parenthesis is the report limit). 

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

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Nickel 1638 UG/L 1 0.0130 1.00 Selenium 1638 UG/L 1 0.0160 1.00 Silver 1638 UG/L 1 0.00200 0.100 Thallium 1638 UG/L 1 0.000400 0.0200 Zinc 1638 UG/L 1 0.209 0.500 
A-51 

Table A-10. Ash Pond Influent Field Blank Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Low-Level Metals – Total Antimony 1638 UG/L 1 0.00700 0.0200 Arsenic 1638 UG/L 1 0.0152 0.150 Cadmium 1638 UG/L 1 0.00100 0.100 Chromium 1638 UG/L 1 0.0830 0.800 Copper 1638 UG/L 1 0.00400 0.200 Lead 1638 UG/L 1 0.00100 0.0500 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 1 0.0130 1.00 Selenium 1638 UG/L 1 0.0160 1.00 Silver 1638 UG/L 1 0.00200 0.100 Thallium 1638 UG/L 1 0.000400 0.0200 Zinc 1638 UG/L 1 0.209 0.500 Low-Level Metals – Dissolved Antimony 1638 UG/L 1 0.00700 0.0200 Arsenic 1638 UG/L 1 0.0152 0.150 Cadmium 1638 UG/L 1 0.00100 0.100 Chromium 1638 UG/L 1 0.0830 0.800 Copper 1638 UG/L 1 0.00400 0.200 Lead 1638 UG/L 1 0.00100 0.0500 Nickel 1638 UG/L 1 0.0130 1.00 Selenium 1638 UG/L 1 0.0160 1.00 Silver 1638 UG/L 1 0.00200 0.100 Thallium 1638 UG/L 1 0.000400 0.0200 Zinc 1638 UG/L 1 0.209 0.500 

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). ND – Not detected (number in parenthesis is the report limit). 
A-52 

Table A-11. Ash Pond Effluent Field Blank Analytical Data, Widows Creek 

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific RL 

Low-Level Metals – Total Antimony 1638 UG/L 1 0.00700 0.0200 Arsenic 1638 UG/L 1 0.0152 0.150 Cadmium 1638 UG/L 1 0.00100 0.100 Chromium 1638 UG/L 1 0.0830 0.800 Copper 1638 UG/L 1 0.00400 0.200 Lead 1638 UG/L 1 0.00100 0.0500 Mercury 1631E UG/L 1 0.000188 0.000500 Nickel 1638 UG/L 1 0.0130 1.00 Selenium 1638 UG/L 1 0.0160 1.00 Silver 1638 UG/L 1 0.00200 0.100 Thallium 1638 UG/L 1 0.000400 0.0200 Zinc 1638 UG/L 1 0.209 0.500 Low-Level Metals – Dissolved Antimony 1638 UG/L 1 0.00700 0.0200 Arsenic 1638 UG/L 1 0.0152 0.150 Cadmium 1638 UG/L 1 0.00100 0.100 Chromium 1638 UG/L 1 0.0830 0.800 Hexavalent Chromium 1636 UG/L 5 1.75 2.50 Copper 1638 UG/L 1 0.00400 0.200 Lead 1638 UG/L 1 0.00100 0.0500 Nickel 1638 UG/L 1 0.0130 1.00 Selenium 1638 UG/L 1 0.0160 1.00 Silver 1638 UG/L 1 0.00200 0.100 Thallium 1638 UG/L 1 0.000400 0.0200 Zinc 1638 UG/L 1 0.209 0.500 

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). ND – Not detected (number in parenthesis is the report limit) 
Appendix B 

ANALYTICAL DATA FOR METALS, FGD POND AND ASH POND 
B-1 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

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. R – MS/MSD % Recovery outside method acceptance criteria. 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 paired samples. See Section 4.2. 

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

FGD Pond Influent (SP-1) Original FGD Pond Effluent (SP-2) Duplicate FG

Analyte Method Unit Total Dissolved Total Dissolved Total 

Routine Metals Aluminum 200.7 UG/L 234,000 86.6 117 46.8 J 105 Antimony 200.7 UG/L 76.2 CJ 12.3 J 15.8 J 14.8 J 15.2 Arsenic 200.7 UG/L 523 13.9 50.2 47.2 48.8 Barium 200.7 UG/L 7,200 257 186 191 171 Beryllium 200.7 UG/L 44.3 1.58 J 1.95 J 1.79 J 1.85 Boron 200.7 UG/L 28,900 24,100 31,700 28,700 31,200 Cadmium 200.7 UG/L 89.2 0.991 J 0.525 J 0.272 J 0.479 Calcium 200.7 UG/L 5,990,000 849,000 987,000 934,000 986,000 Chromium 200.7 UG/L 1,360 18.7 1.65 J 1.10 J 1.54 Hexavalent Chromium 

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

Cobalt 200.7 UG/L 138 CJ 1.61 J 2.22 J 1.77 J 2.15 Copper 200.7 UG/L 653 3.79 J 2.98 J 2.43 J 2.82 Iron 200.7 UG/L 299,000 17.9 J 64.8 J 21.1 J 55.3 Lead 200.7 UG/L 436 ND (50.0) U ND (50.0) U ND (50.0) U ND (50.0) Magnesium 200.7 UG/L 321,000 176,000 193,000 182,000 185,000 Manganese 200.7 UG/L 2,780 583 636 543 R 609 Mercury 245.1 UG/L 26.5 ND (2.00) U ND (2.00) U ND (2.00) U ND (2.00) Molybdenum 200.7 UG/L 1,340 876 1,530 1,480 1,470 
B-2 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

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. R – MS/MSD % Recovery outside method acceptance criteria. 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 paired samples. See Section 4.2. 

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

FGD Pond Influent (SP-1) Original FGD Pond Effluent (SP-2) Duplicate FG

Analyte Method Unit Total Dissolved Total Dissolved Total 

Nickel 200.7 UG/L 489 25.0 J 32.0 J 29.7 J 30.8 Selenium 200.7 UG/L 652 366 241 231 230 Silver 200.7 UG/L 9.82 CJ ND (20.0) U ND (20.0) U ND (20.0) U ND (20.0) Sodium 200.7 UG/L 104,000 76,700 69,200 66,900 69,700 Thallium 200.7 UG/L 16.2 CJ 14.3 1.45 J 1.61 J 1.67 Tin 200.7 UG/L 21.2 CJ ND (30.0) U ND (30.0) U ND (30.0) U ND (30.0) Titanium 200.7 UG/L 8,180 ND (10.0) U 1.48 J ND (10.0) U 1.21 Vanadium 200.7 UG/L 1,580 15.8 J 42.7 39.7 41.4 Yttrium 200.7 UG/L 217 ND (5.00) U ND (5.00) U ND (5.00) U ND (5.00) Zinc 200.7 UG/L 3,140 ND (10.0) U 0.335 J ND (10.0) U 0.702 Low-Level Metals Antimony 1638 UG/L 51.8 8.90 11.8 11.8 11.8 Arsenic 1638 UG/L 617 18.0 47.3 47.0 47.9 Cadmium 1638 UG/L 86.0 3.16 3.66 3.76 3.80 Chromium 1638 UG/L 1,380 ND (16.0) U 14.6 J 14.4 J 14.7 Hexavalent Chromium 

1636 UG/L NA NA NA 3.29 NA 

Copper 1638 UG/L 826 2.83 J 1.46 J 0.842 J 1.27 Lead 1638 UG/L 545 ND (1.00) U 0.0828 J ND (1.00) U 0.129 Mercury 1631E UG/L 24.7 0.0761 0.0428 0.0106 0.0448 
B-3 

CJ – Calculated J-value. The J-value was calculated using the filtered aqueous and/or the filtered solid analytical results, including J-va

one of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method d

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. R – MS/MSD % Recovery outside method acceptance criteria. 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 paired samples. See Section 4.2. 

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

FGD Pond Influent (SP-1) Original FGD Pond Effluent (SP-2) Duplicate FG

Analyte Method Unit Total Dissolved Total Dissolved Total 

Nickel 1638 UG/L 634 29.6 35.6 32.8 L 36.7 Selenium 1638 UG/L 651 325 205 213 211 Silver 1638 UG/L 5.10 J ND (2.00) U 0.0449 J ND (2.00) U ND (2.00) Thallium 1638 UG/L 93.8 22.5 11.1 11.0 11.1 Zinc 1638 UG/L 2,720 ND (10.0) U ND (10.0) U ND (10.0) U ND (10.0) 
CJ – 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 the sample fraction analytical results (i.e., filtered aqueous 

and/or filtered solid concentration) was measured above the 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 paired 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 14.7 
CJ – 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 the sample fraction analytical results (i.e., filtered aqueous 

and/or filtered solid concentration) was measured above the 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 paired 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 NARRATIVES 
Computer Sciences Corporation 

www.csc.com

MEMORANDUM

DATE: December 14, 2007 

TO: Ron Jordan, Project Officer 

 EPA EAD 

FROM: Sara Clark, Quality Assurance Chemist 

Computer Sciences Corporation 

SUBJECT: Data Review Narrative for Classical Analyses for the Steam Electric Power Study, 

Episode 6549

OVERVIEW

Under EPA Contract Number 68-C-03-058, ProChem Analytical, Inc. submitted classical wet chemistry

data for seven samples in Episode 6549. Samples 70520 and 70522, identified as FGD Influent and Ash 

Pond Influent respectively, were expected to contain a significant and variable particulate concentration. 

EPA and industry representatives were concerned that the variable nature of the samples would 1) 

complicate the collection of a representative sample for both EPA and industry analyses and 2) lead to 

analytical interferences. Therefore, for some classical analyses (those with a listed phase in Table 1), 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. The two sets of results (aqueous and solid phases) are 

provided in the analytical database, as are calculated total results (derived by combining aqueous and 

solid phases results). 

Table 1 provides a complete listing of samples, matrices, descriptions, sampling dates, phases, and the 

required analytes. 

Table 1 - Sample Identifiers, Descriptions, Sampling Dates and Analytes

EPA Sample # Matrix Sample Description Sampling

Date Phase Analytes

70520 Aqueous SP-1 – FGD Influent 9/11/07 NA

BOD (SM 5210B), HEM 

(1664A), SGT-HEM 

(1664A), Hexavalent

Chromium (ASTM D1687-

92), TSS (SM 2540D), and 

TDS (SM 2540C)

70520 Aqueous SP-1 – FGD Influent 9/11/07 Filtered

Aqueous 

Chloride (SM 4500-Cl-

 C), 

Sulfate (ASTM D516-90), 

TKN (SM 4500-N C), 

Ammonia (SM 4500-NH3 

F), Total Phosphorus

(365.3), and Nitrate/Nitrite 

(SM 4500-NO3 H)

6101 Stevenson Avenue 

Alexandria, Virginia 22304 

703.461.2000 Fax 703.461.2020
Table 1 - Sample Identifiers, Descriptions, Sampling Dates and Analytes

EPA Sample # Matrix Sample Description Sampling

Date Phase Analytes

70520 Aqueous SP-1 – FGD Influent 9/11/07 Filtered

Solid

Chloride (SM 4500-Cl- C), 

Sulfate (ASTM D516-90), 

TKN (SM 4500-N C), 

Ammonia (SM 4500-NH3 

F), Total Phosphorus

(365.3), Nitrate/Nitrite (SM 

4500-NO3 H), and Total 

Solids (2540B) 

70520 Aqueous SP-1 – FGD Influent NA Calculated 

Total 

Chloride (SM 4500-Cl-

 C), 

Sulfate (ASTM D516-90), 

TKN (SM 4500-N C), 

Ammonia (SM 4500-NH3 

F), Total Phosphorus

(365.3), and Nitrate/Nitrite 

(SM 4500-NO3 H)

70521 Aqueous 

SP-2 – FGD 

Effluent 9/11/07 NA

BOD (SM 5210B), HEM 

(1664A), SGT-HEM 

(1664A), Hexavalent

Chromium (ASTM D1687-

92), TSS (SM 2540D), 

TDS (SM 2540C), 

Chloride (SM 4500-Cl-

 C), 

Sulfate (ASTM D516-90), 

Total Phosphorus (365.3),

TKN (SM 4500-N C), 

Nitrate/Nitrite (SM 4500-

NO3 H), and Ammonia 

(SM 4500-NH3 F)

70522 Aqueous 

SP-3 – Ash Pond

Influent 9/12/07 NA

BOD (SM 5210B), HEM 

(1664A), SGT-HEM 

(1664A), Hexavalent

Chromium (ASTM D1687-

92), TSS (SM 2540D), and 

TDS (SM 2540C)

70522 Aqueous 

SP-3 – Ash Pond

Influent 9/12/07 Filtered

Aqueous 

Chloride (SM 4500-Cl-

 C), 

Sulfate (ASTM D516-90), 

TKN (SM 4500-N C), 

Ammonia (SM 4500-NH3 

F), Total Phosphorus

(365.3), and Nitrate/Nitrite 

(SM 4500-NO3 H)

2
Table 1 - Sample Identifiers, Descriptions, Sampling Dates and Analytes

EPA Sample # Matrix Sample Description Sampling

Date Phase Analytes

70522 Aqueous 

SP-3 – Ash Pond

Influent 9/12/07 Filtered

Solid

Chloride (SM 4500-Cl-

 C), 

Sulfate (ASTM D516-90), 

TKN (SM 4500-N C), 

Ammonia (SM 4500-NH3 

F), Total Phosphorus

(365.3), Total Solids 

(2540B), and 

Nitrate/Nitrite (SM 4500-

NO3 H)

70522 Aqueous 

SP-3 – Ash Pond

Influent NA Calculated 

Total 

Chloride (SM 4500-Cl-

 C), 

Sulfate (ASTM D516-90), 

TKN (SM 4500-N C), 

Ammonia (SM 4500-NH3 

F), Total Phosphorus

(365.3), and Nitrate/Nitrite 

(SM 4500-NO3 H)

70523 Aqueous 

SP-4 – Ash Pond

Effluent 9/12/07 NA

BOD (SM 5210B), TSS 

(SM 2540D), TDS (SM

2540C), Chloride (SM 

4500-Cl

-

 C), Total 

Phosphorus (365.3), TKN

(SM 4500-N C), 

Nitrate/Nitrite (SM 4500-

NO3 H), Ammonia (SM

4500-NH3 F), Sulfate 

(ASTM D516-90), HEM 

(1664A), SGT-HEM 

(1664A), and Hexavalent

Chromium (ASTM D1687-

92) 

9/11/07 NA

BOD (SM 5210B), 

Hexavalent Chromium

(ASTM D1687-92)

70524 Aqueous 

SP-5 – FGD 

Effluent Duplicate 

9/12/07 NA

TSS (SM 2540D), TDS 

(SM 2540C), Chloride (SM

4500-Cl

-

 C), Total 

Phosphorus (365.3), TKN

(SM 4500-N C), 

Nitrate/Nitrite (SM 4500-

NO3 H), Ammonia (SM

4500-NH3 F), and Sulfate 

(ASTM D516-90)

70525 Aqueous 

SP-6 - FGD Influent

Field Blank 9/11/07 NA Hexavalent Chromium

(ASTM D1687-92)

70526 Aqueous 

SP-7 – FGD 

Effluent Field Blank 9/11/07 NA Hexavalent Chromium

(ASTM D1687-92)

 NA= Not applicable 

3
These data have been reviewed in accordance with CSC’s Data Review Guidelines for Classical Wet 

Chemistry Analyses (DR-02 Revision 2, September 1, 2007) and with the specifications listed in the 

contract. A summary of the results of the data review process is provided below, followed by detailed 

descriptions of data issues identified with these samples. Based on this review, all data in this episode are 

considered to be of acceptable quality with the qualifications described below and detailed in the attached 

data review summary table (Table 2). 

SUMMARY

All samples were analyzed within the contract-specified holding times for all classical wet chemistry

parameters specified in the sampling and analysis plan, except for the total phosphorus, SGT-HEM, and 

TSS analyses as described below. The calibration and continuing calibration standards were successfully

analyzed. Laboratory blanks were performed for each analysis, and there was no contamination detected 

above the minimum level (ML). Effluent and influent field blanks were analyzed for hexavalent 

chromium. The analyte was not detected above the ML in either blank. The QC samples, including the 

ongoing precision and recovery sample (OPR) and matrix spike/matrix spike duplicate (MS/MSD) 

samples, demonstrated that laboratory performance for these analyses was acceptable with the exceptions 

described below. 

DATA ISSUES 

Nitrate and Nitrite 

The MS and MSD recoveries (60% and 27%, respectively) for sample 70521 were below the contractspecified acceptance criteria of 75-125%. The RPD (77%) was above the criteria of 20%. Because 

nitrate/nitrite was not detected in the sample, CSC recommends that the result be included in the database 

without qualification. 

Total Phosphorus 

The following samples were analyzed for total phosphorus less than one day (4-6 hours) past holding 

time: samples 70521, 70523, and 70524; filtered solid and filtered aqueous samples 70520 and 70522. 

CSC considers these results to be estimated values. 

HEM 

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

acceptance criteria of 20%. The MS/MSD percent recoveries were within contract specified acceptance 

criteria. Because HEM was not detected in the sample, CSC considers the result to be acceptable without 

qualification. 

SGT-HEM 

The analysis of SGT-HEM for sample 70520 was performed one day out of holding time. CSC considers 

the SGT-HEM result for this sample to be an estimated value. 

TSS 

The following samples analyzed for TSS were analyzed one day past holding time: 70520, 70522, 70523, 

and 70524. CSC considers the TSS results for these samples to be estimated values. 

4
BOD 

FGD Effluent sample 70521 did not meet the contract-specified minimum dissolved oxygen depletion of 

2.0 mg/L, indicating that a less dilute sample aliquot should have been analyzed. Therefore, the BOD 

result for sample 70521 is reported in the database as not detected at an elevated ML of 9 mg/L. 

TECHNICAL NOTES: 

SGT-HEM 

Although HEM/SGT-HEM analyses were requested for samples 70521 and 70522, SGT-HEM analysis 

was not required because HEM was not detected in these samples.

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 

These data were required elements of the formula used to calculate a total result; there should be one set 

of these records for each of Group I and Group II analyses. The laboratory failed to provide those items

listed in bold above. 

CSC calculated the total results for the FGD Influent and Ash Pond Influent samples using the following 

formula: 

Vol. L

(Conc. mg/L x Vol. L) (Conc. mg/kg Wt. kg) Total SampleConcentration mg/L

original sample

Filtrate Filtrate + solid phase × solid phase =

Several variables were not recorded by the laboratory as requested—most importantly, the original 

sample volume and filtrate volume. In discussion with the lab, CSC was able to calculate the missing 

variables based on other information that the laboratory was able to provide including the original sample 

density, original sample weight, solid phase weight, and the filtrate weight. This series of calculations 

follows and is detailed in the phase separation data elements table (Table 3): 

• Original sample weight = (Original sample volume) x (Original sample density)

• Filtrate weight = (Original sample weight) - (Solid-phase weight) 

• Filtrate volume = (Filtrate weight) / (Original sample density)

In generating the classicals “Calculated Total” results for the Steam Electric Study, CSC used all values 

greater 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. 

5
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. 

Percent Solids

The percent solid results in Table 3 are provided if needed by EPA to convert solid phase wet weight 

basis values to dry weight results. Percent solids 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 Beverly Randolph, EPA 

Marla Smith, EPA Nelson Andrews, EPA 

Brian Englert, EPA Deb Bartram, ERG 

TJ Finseth, ERG Lynn Walters, CSC 

Barbara Beard, CSC 

6
Table 2

Data Review Summary Table 

Episode: 6549 Analysis: Classicals 

Industry: Steam Electric Power Study Reviewer: Sara Clark 

Sample Analyte Action Reason CSC Qual Level

70520 25,300 mg/L 

70522 9,190 mg/L

70523 12 mg/L

70524 

TSS 

8 mg/L

70520 Filtered 

Solid 119 mg/kg 

70520 Filtered 

Aqueous 

2.3 mg/L

70521 0.01 mg/L

70522 Filtered 

Solid 854 mg/kg 

70522 Filtered 

Aqueous 

3.12 mg/L

70523 0.252 mg/L

70524 

Total 

Phosphorus 

0.013 mg/L

70520 SGT-HEM

Samples analyzed 

outside holding time 

NA 

20 mg/L

70520 

Calculated 

Total 

NA 10.5 mg/L

70522 

Calculated 

Total 

Total 

Phosphorus 

Estimated value 

Associated phaseseparated result

estimated

NA 16.6 mg/L

NA= Not Applicable 

ND= Non detect

7
Table 3 

 Phase Separation Data Elements

Episode: 6549 Analysis: Classicals 

Industry: Steam Electric Study Reviewer: Sara Clark 

Group number I II I II

Sample number 70520 70520 70522 70522

Original sample vol (mL) 916.0a 948.2a 937.9 a 919.7 a

Net weight of solid phase on the filter (g) 63.40 66.43 14.93 14.61

Density (g/mL) 1.0125 1.0125 1.0030 1.0030

Original sample weight (g) 927.5 960.1 940.8 922.5

Filtrate weight (g) 864.1 a 893.7 a 925.9 a 907.9 a

Filtrate volume (mL) 853.4 a 882.6 a 923.1 a 905.2 a

Percent Solid (of solid phase) (%) 71.9 65.9 71.9 70.2

a

 Derived value. Calculated using lab measured results

8
Computer 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 Dissolved Metals Analyses for the Steam Electric 

Study, Episode 6549 

Under EPA contract number 68-C-03-044, ProChem Analytical submitted data 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 representatives 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 (filtered aqueous and filtered solid phases) are provided in 

the analytical database, including the calculated total result (derived by combining filtered aqueous and 

filtered solid phase results). 

Table 1 provides a list of samples, matrices, descriptions, 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, 245.1 
2 

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 specifications 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) analyses were performed and were within the contract 

criteria. 

Calibration curves, calibration standards, and calibration blanks were successfully analyzed, with the 

exceptions noted below. Preparation blanks performed for each analysis detected no contamination above 

the laboratory’s reporting limits. QC samples, including 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 analyses was acceptable, with the exception of the 

issues described below and summarized in Table 2. The 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 calibration 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 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. 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 they 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 the 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 the filtered solid phase samples 70520 and 70522; therefore, 

their results are not affected by this low OPR. Because aluminum was detected in both the filtered solid 

phase samples 70520 and 70522, CSC considers the results 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 recommends that the result for 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 marginally 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 and 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 and 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 Influent 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 series of calculations are as follows and detailed in the 

phase separation data elements table (Table 3): 

• Original sample weight = (Original sample 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 “Calculated Total” results, at EPA's request, CSC included 

concentrations that were greater than the MDL but less than the ML unless both factors in the calculations 

were less 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. 

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 analyzed several samples at 10-fold dilutions for 

mercury. The affected samples are as follows: dissolved and filtered 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 have been adjusted for dilution. 

Percent Solids 

Percent solids evaluations were performed for samples 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 

Vol. L

(Conc. μg/L x Vol. L) (Conc. mg/kg 1000μg/mg x Wt. kg) Total SampleConcentration μg/L

originalsample

Filtrate Filtrate + solid × solid =
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 detected 

 
6

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) 459.26a

 497.90 a

Filtrate weight (g) 439.28a

 488.4 a

Filtrate volume (mL) 439.98a

 490.46 a

Percent Solid (of solid phase) (%) 60.5 65.1 

 

 a

 Derived value. Calculated using lab measured results (if available), or otherwise estimated 

 
Computer 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 dissolved 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). Five of the nine (FGD and Ash Pond effluents, FGD 

effluent duplicate, and FGD and Ash Pond effluent field blanks) were analyzed for hexavalent chromium 

by Method 1636. Five samples were analyzed for dissolved mercury. Because influent samples for this 

study were expected to be highly variable in solids content, EPA chose to obtain 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 

70520 Aqueous FGD influent Dissolved 1631E, 1638

NA Calculated Solid 1631E, 1638

Total 1631E, 1638

70521 Aqueous FGD effluent 9/11/07 Dissolved 1631E, 1638

NA 1636 

Total 1631E, 1638

70522 Aqueous Ash Pond influent 9/12/07 

Dissolved 1631E, 1638

Total 1631E, 1638

70523 Aqueous Ash Pond effluent 9/12/07 Dissolved 1631E, 1638

NA 1636 

Total 1631E, 1638

70524 Aqueous FGD effluent duplicate 9/11/07 Dissolved 1631E, 1638

NA 1636 

Total 1631E, 1638

70525 Aqueous FGD influent field blank 9/11/07 

Dissolved 1638 

 
2 

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

EPA Sample # Matrix Sample Description Sampling Date Phase Methods

Total 1631E, 1638

70526 Aqueous FGD effluent field blank 9/11/07 Dissolved 1638 

NA 1636 

Total 1631E, 1638

70527 Aqueous Ash Pond influent field blank 9/11/07 

Dissolved 1638 

Total 1631E, 1638

70528 Aqueous Ash Pond effluent field blank 9/12/07 Dissolved 1638 

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 data review summary table (Table 2). 

SUMMARY

All nine samples were successfully analyzed within the method-specified holding times, and initial 

precision and recovery (IPR) analyses and method detection limit (MDL) studies were acceptably 

performed. All QC samples, including ongoing precision and recovery samples (OPR), matrix spike and 

matrix spike duplicate (MS/MSD) samples, and quality control samples (QCS) were within method 

specified criteria. The MS/MSD analyses were performed on samples 70521 and 70523. Calibration 

curves and calibration verification standards 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 blanks (PBs), initial calibration 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 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 the 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 sample 70523 total Ag (48%). However, because the 

MS/MSD for these analytes produced an acceptable RPD, and Method 1638 does not specify limits for 

laboratory duplicates, CSC considers the associated results acceptable without qualification. 

Field Duplicate 

Field duplicate RPD values were above the method-specified limit (20%) for the following duplicate 

pairs: 

• 70521 and 70524 (FGD effluent and FGD effluent field duplicate) total metals results for Ag 

(25%) and Pb (43%). 

• 70521 and 70524 (FGD effluent and FGD effluent field 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 chilled 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 these (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 levels 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 less 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 Method 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) 461-2154, 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 

original sample

Total Dissolved

TSS mg L

Conc ng L Conc ng L

/

( . / . / ) Solid phase concentration (ng/mg or μg/g) − =
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

70520 Cr 

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 the 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 the Influent to Ash Pond System 
D-6 

Figure D-6. Sample Collection Set-Up at Effluent from Ash Pond System