# Final Sampling Episode Report Tampa Electric Company’s Big Bend Station Apollo Beach, FL

Episode 6547

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

27 August 2008

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

### i CONTENTS

Page

1. I NTRODUCTION 

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

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

2. P LANT 

### O VERVIEW 

### .............................................................................................................2-1 2.1 FGD Scrubber System .........................................................................................2-2 2.2 FGD Wastewater Treatment System ...................................................................2-3

3. S AMPLE 

### C OLLECTION 

### .......................................................................................................3-1 3.1 Sampling Points, Sample Collection Methods, and Field Measurements ...........3-1

3.1.1 Influent to FGD Wast ewater Treatment ..................................................3-2

3.1.2 Effluent from FGD Wast ewater Treatment .............................................3-4 3.2 List of Analytes and Sample Preservation...........................................................3-6 3.3 Plant Operational Data.........................................................................................3-7 3.4 Deviations from the Sampling and Analysis Plan ...............................................3-7

4. L ABORATORY 

### A NALYTICAL 

### R ESULTS AND 

### D ISCUSSION 

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

4.1 Measured and Calculated Results for FGD Influent Samples .............................4-1 4.2 FGD Wastewater Treatment System ...................................................................4-4

5. D ATA 

### Q UALITY 

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

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

5.2.3 Field Blanks .............................................................................................5-2 5.2.4 Field Duplicates .......................................................................................5-3

6. R EFERENCES 

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

Appendix A: A NALYTICAL 

### R ESULTS



### Appendix B: A NALYTICAL 

### D ATA FOR 

### M ETALS



### , FGD W ASTEWATER



### Appendix C: D ATA 

### R EVIEW 

### N ARRATIVES



### Appendix D: FGD W ASTEWATER 

### T REATMENT 

### S YSTEM 

### F LOW 

### R ATE 

### D ATA



### Appendix E: P ICTURES 

### F ROM THE 

### S AMPLING 

### E PISODE

### ii LIST OF TABLES

Page

2-1 Big Bend NPDES Monitoring Requiremen ts for the FGD Effluent (I-130) ................... 2-6

3-1 Sample Collection Information, Big Bend....................................................................... 3-9

3-2 Number of Samples Collected by Sampling Point, Big Bend ....................................... 3-10

3-3 Field Measurements, Big Bend...................................................................................... 3-11

3-4 Analytical Methods and Procedures for Samples Collected at Big Bend...................... 3-12

3-5 Summary of Sample Containe r and Planned Preservation ............................................ 3-13

3-6 Sample Preservation Summary, Big Bend..................................................................... 3-14

3-7 Generating Unit Operating Characteristics during Sample Collection, Big Bend......... 3-15

3-8 FGD Scrubber System Operati ng Characteristics, Big Bend ........................................ 3-16

3-9 FGD Wastewater Treatment System Op erating Characteristics, Big Bend .................. 3-17

4-1 Biphasic Sample Results for Low-Level Total Metals and Routine Total Metals Measured Above the Report Limit, FGD Influent, Big Bend.......................................... 4-5

4-2 Biphasic Sample Results for Routine To tal Mercury, FGD Influent, Big Bend ............. 4-6

4-3 Biphasic Sample Results for Classical An alytes Measured Above the Report Limit, FGD Influent, Big Bend................................................................................................... 4-6

4-4 Classical Pollutants Measured Above the Report Limit for the FGD Wastewater Treatment System, Big Bend ........................................................................................... 4-6

4-5 Metals Measured Above the Report Li mit for the FGD Wastewater Treatment System, Big Bend............................................................................................................. 4- 7

5-1 Field Blank Results Measured A bove the Report Limit, Big Bend................................. 5-4

5-2 Field Duplicate Re sults, Big Bend................................................................................... 5-5

A-1 FGD Influent Analytic al Data, Big Bend ....................................................................... A-1

A-2 ProChem Biphasic Filtration Blank Analytical Results, Big Bend ................................ A-9

A-3 FGD Effluent Analytic al Data, Big Bend..................................................................... A-10

A-4 Duplicate of FGD Effluent Analytical Data, Big Bend ................................................ A-15

A-5 Bottle Blank and Equipment Bla nk Analytical Data, Big Bend................................... A-19

### LIST OF TABLES (Continued)

Page

iii A-6 FGD Influent Field Blank An alytical Data, Big Bend.................................................. A-24

A-7 FGD Effluent Field Blank An alytical Data, Big Bend ................................................. A-25

B-1 Analytical Results for Metals in the F GD Wastewater Treatment System, Big Bend ....B-1

D-1 Flow Data during FGD Wa stewater Treatment Effluent Sample Collection, Big

Bend ........................................................................................................................... ..... D-1

D-2 Flow Data during FGD Wa stewater Treatment Influent Sample Collection, Big

Bend ........................................................................................................................... ..... D-5

### iv LIST OF FIGURES

Page

2-1 FGD Wastewater Treatment Syst em, Big Bend Power Plant.......................................... 2-7

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

E-2 Three-Way Splitter at the Influent to FGD Wastewater Treatment System....................E-2

E-3 Sampling Set Up at the Influent to F GD Wastewater Treatment System (SP-1) ............E-3

E-4 Pump-Off Station for Dissolved Metals Sample Collection............................................E-4

E-5 Collection of Dissolved Metals Samples at Pump-Off Station........................................E-5

E-6 Three-Way Splitter at the Effluent fr om FGD Wastewater Treatment System...............E-6

E-7 Sampling Set Up at Effluent from FGD Wastewater Treatment System (SP-2).............E-7

E-8 Field Blank Collection at Effluent from FGD Wastew ater Treatment (SP-5).................E-8

### 1-1 1. I NTRODUCTION



### The Engineering and Analysis Division (E AD) of the U.S. Environmental Protection Agency (EPA) has been conducting a program that c onsists of site visits and sampling at steam electric power plants. The purpose of this program is to charact erize raw wastewaters generated by coal-fired steam electric power plants, as well as to evaluate treatment technologies and best management practices used to reduce pollutant discharges. This Sampling Episode Report (SER) describes the sampling activities that took place on July 24 through July 26, 2007 at Tampa Electric Company’s Big Bend Station (Big Bend), located in Apollo Beach, Florida (Sampling Episode 6547). The focus of Episode 6547 was to char acterize the influent to and effluent from the flue gas desulfurization (FGD) wast ewater treatment system at Big Bend.

1.1 Background of Detailed Study

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

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

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

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

1.2 Power Plant Site Selection

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

• 

### Coal-fired boilers;

• 

### Wet FGD scrubber system, including:

— Type of scrubber,

— Sorbent used,

— Year operation began,

— Chemical additives used,

— Forced oxidation process,

— Water cycling, and

— Solids removal process;

### 1-2 • 

### FGD wastewater treatment system;

• 

### Type of coal;

• 

### NO

x 

### controls;

• 

### Ash handling systems;

• 

### Ash treatment system; and

• 

### Mercury air controls.

EPA selected Big Bend for sampling base d on the following site characteristics:

• 

### The plant is a coal-fired pow er plant that burns eastern bituminous coal in all four units;

• 

### The plant operates two wet FGD systems (each system services two units), which are both limestone forced oxidation systems;

• 

### The plant operates a segregated FGD wastewater treatment system, which includes the following steps:

— pH adjustment,

— Ferric chloride addition,

— Polymer addition,

— Clarification, and

— Filtration;

• 

### The plant recently began the operation of a selective catalytic reduction (SCR) system on one of its units; and

• 

### The plant produces a commerc ial-grade gypsum by-product.

1.3 Sampling Episode Overview

On April 27, 2007, EPA and its technical c ontractor, Eastern Research Group, Inc. (ERG), conducted a site visit at Big Bend. The pur pose of the site visit was to learn about the wastewater treatment operations, regarding the FGD scrubber purge, and to gather information in order to collect wastewater samp les at Big Bend. Information colle cted during the site visit was

used to create Sampling Plan, Tampa Electric Company’s Big Bend Station (Sampling Plan) [1], which describes the sample collection pro cedures used during the sampling episode.

For this sampling episode, EPA arrived atBig Bend on Tuesday, July 24, 2007, to review the sampling points, determine the set-up for th e sample collection, label sample bottles, and purchase any additional supplies needed for th e sampling episode. EPA then collected the samples specified in the Sampling Plan on Wednesday, July 25, 2007. The following personnel participated in EPA’s samp le collection activities:

• 

### Ron Jordan, EPA/EAD;

• 

### Josh Hall, EPA/EAD;

• 

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

• 

### TJ Finseth, ERG;

### 1-3 • 

### Sarah Holman, ERG; and

• 

### Jessica Wolford, ERG.

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

### 2-1 2. P LANT 

### O VERVIEW



### The Big Bend Station operates four coal-fir ed steam electric generating units. Units 1 and 2 are wet bottom turbo furnace boilers, each wi th a capacity of 445 megawatts (MW). These units came on line in 1970 and 1973, respectively. Unit 3 is a wet bottom turbo furnace boiler which has a capacity of 465 MW, and came on line in 1976. Finally, Unit 4 is a dry bottom tangentially-fired boiler which has a capacity of 485 MW, and came on line in 1985. The Big Bend Station is located in Apollo Beach, Florida, along the Tampa Bay.

Big Bend burns eastern bituminous coal in all four units. Historically, the coal used in Units 1, 2, and 3 was mined in Kentucky and the coal used in Unit 4 was Illinois Number 6. Currently, Units 1-4 burn all Kentucky coal. Bi g Bend burns approximately four to five million tons of coal per year, which is equivalent to about 450 to 570 tons per hour. In addition to burning coal in the boilers, Big Bend is permitted to burn a blend of coal and petroleum coke, up to 20 percent petroleum coke; however, the plan t typically burns about one to two percent petroleum coke, with a maximum of five per cent. During the sample collection period, no petroleum coke was being burned in the boilers.

Units 1 through 4 have the following configuration:

• 

### Boiler;

• 

### SCR system (Unit 4 only);

• 

### Ammonia injection for sulfur trioxide (SO 3 

### ) control (Unit 4 only);

• 

### Electrostatic precipitator (ESP); and

• 

### FGD system.

Big Bend recently completed the addition of the Unit 4 SCR system, which began operation in May 2007, and is in the process of in stalling SCRs for each of the other three units. SCRs are used to control nitrogen oxide (NO

x 

### ) emissions. The plant intends to install one new SCR each year until all four units have SCRs, with an estimated completion date of May 2010. Once the SCRs are installed on all units, Big Bend will operate the systems year round. The plant estimates that after all four SCRs are in operation, the plant’s NO

x 

### emissions will be reduced by 89 percent, compared to 1998 levels. The SCR operation produces no direct industrial wastewater discharges but by altering the char acteristics of the flue gases it can affect FGD wastewater pollutant characteristics.

During the operation of the SCR system s, some of the sulfur dioxide (SO 2 

### ) in the flue gas

is oxidized to SO 3 

### over the SCR catalyst. The SO 3 

### in the flue gas causes a blue plume; therefore, Big Bend attempts to remove the SO 3 

### from the flue gas. Big Bend injects anhydrous ammonia directly into the flue gas to react with the SO 3 

### and produces ammonium sulfate which is a solid particle. Most of the amm onium sulfate is expected to be removed from the flue gas by the ESPs. Big Bend intends to add excess ammonia to the flue gas to ensure a complete reaction of the SO 3 

### in the flue gas. Some of the ammonia added to th e flue gas is expected to adhere to the fly ash particulates and be removed by the ESPs. In addition, this excess ammonia may be removed from the flue gas in the FGD system, thereby aff ecting the wastewater char acteristics of the FGD

purge stream.

### 2-2 The ESPs at Big Bend are particulate contro l devices that remove the fly ash and other particulates from the flue gas. The ESPs remove approximately 99.5 percent of the particulates in the flue gas. The fly ash and other particulates are collected in hoppers and pneumatically conveyed to storage silos. Prior to the in stallation of the Unit 4 SCR, Big Bend sold approximately 99 percent of the fly ash produced on site. Now that Big Bend is operating the SCR on Unit 4 and injecting ammonia into the flue gas for SO 3 

### control, ammonia adheres to the fly ash produced by Unit 4; therefore, Big Bend is installing a fly ash benefi ciation plant that will strip the ammonia from the fly as h and return it back to the plan t. In addition, the system will separate the ash from the unburned carbon with an electrostatic system. This fly ash beneficiation plant is expected to be operating in April 2008. The ESP operation produces no

direct industrial wast ewater discharges.

Big Bend operates two FGD systems, which are used to control sulfur dioxide (SO 2 

### ) emissions from all four of the generating units. One of the FGD systems scrubs the flue gas for Units 1 and 2, and the other FGD system scrubs th e flue gas for Units 3 and 4. The plant installed the FGD system on Unit 4 in 1985. However, in 1 995, Big Bend retrofitted the system and began scrubbing the flue gas from Unit 3 in the same FGD system. Big Bend also installed a FGD system for Units 1 and 2 in 2000. Plant personnel estimate that the addition of the FGD system for Units 1 and 2 reduces Big Bend’s SO 2 

### emissions by approximately 89 percent, as compared

to 1998 levels.

The wastewater generated from the FGD sc rubber systems is treated on site prior to discharge to Tampa Bay. In 2000, when Big Bend installed the FGD system on Units 1 and 2, the plant also installed a FGD wa stewater treatment system to tr eat the wastewater purge stream (the purge stream is needed to remove chlorides from the FGD systems to keep the system below 30,000 mg/L chlorides). Section 2.1 discusses the FGD scrubber systems and Section 2.2

discusses the FGD wastewat er treatment system.

2.1 FGD Scrubber System

Big Bend has two different FGD scrubber syst ems, one for Units 1 and 2 (“Unit 1&2”), and one for Units 3 and 4 (“Unit 3&4”); however , there are some similarities between the two different systems. Both systems use a limestone sl urry as the sorbent, both are forced oxidation systems, and both use dibasic acids (D BA) as additives in the systems.

The limestone used in both FGD systems is conveyed to three individual day silos for storage, which feed three different ball mills. Each of the three ball mills pulverizes the limestone to the same size and consistency. From th e ball mills, the limestone slurry is sent to a hydroclone that separates the larg er limestone particles from the smaller particles. The particles that are too large to be sent to the absorber ar e returned to the ball mill for further processing and all other particles are sent to a splitter box that splits the feed for the Unit 1&2 FGD system and the Unit 3&4 FGD system. Each FGD system has its own limestone reagent feed tank that holds limestone to be sent to the absorber systems.

The Unit 3&4 FGD system consists of f our double loop, spray/tray absorber towers. Initially, only three of the four towers operated at any given time, with the fourth as a spare; however, once the plant began scrubbing Unit 3 flue gas in the system, they began operating all four towers continuously. Big Bend adds DBA to th e limestone reagent feed tank to increase the

### 2-3 sulfur dioxide removal from the system; therefore, all the limestone slurry that is sent to the absorber contains DBA. The plant adds limestone slurry to the absorbers to keep the pH of the scrubber lower loop at approximately 4.2 and the upper loop at approximately 6.0.

The Unit 1&2 FGD system was installed in 2000. It consists of one single loop spray/tray

tower that is 60 feet in diameter and 60 feet ta ll, with forced oxidation. The absorber tower holds approximately 1.3 million gallons of slurry and is one of the largest scrubbers in the United States. Big Bend feeds the limestone slurry to th e absorbers to keep the pH of the scrubber between 5 and 6. In addition, the plant manages th e blowdown from the scrubber to maintain the scrubber slurry at approximately 20 percen t solids (by weight) in the scrubber.

The blowdown from the Unit 1&2 scrubber is pumped directly to primary hydroclones. The blowdown from the Unit 3&4 scrubber is pu mped to quencher blowdown tanks and then pumped to a separate set of primary hydroc lones. The blowdown from the scrubbers is approximately 20 percent solids. The underflo w from both of the primary hydroclones is transported to the sludge surge ta nk and contains approximately 50 to 55 percent solids. From the sludge surge tank, the gypsum is pumped to rotary drum vacuum filters. As the gypsum is transferred to the vacuum filters, it is washed with Sun City Sewage Treatment Plant effluent

water to reduce the level of chlorides in the gypsum. The rotary drum vacuum filters dry the solids to approximately 90 percent solids gypsum product. The gypsum produced by the plant is transported to the National Gypsum wallboard manufacturing plant adjacent to Big Bend.

The overflows from the two sets of primary hydroclones, which are approximately 6 percent solids, are combined in the chloride purge feed tank. Most of this wastewater is transferred to the return water tank and recycled back to the Unit 1&2 scrubber; however, some of the wastewater is pumped to a seconda ry hydroclone. The underflow from the secondary hydroclone is recycled back to the Unit 1&2 sc rubber and the overflow (i .e., scrubber purge) is transferred to the FGD wastewater treatment system.

2.2 FGD Wastewater Treatment System

The overflow from the secondary hydrocl ones enters the FGD wastewater treatment system continuously during normal operations with a fairly consistent flow rate of approximately 200 to 225 gpm, a solids concentration of approxima tely 1 to 3 percent solids, and a chlorides concentration which varies between 15,000 to 30,000 ppm. When the equalization tank reaches high levels, the plant will dive rt the FGD scrubber purge away from the equalization tank by sending it to the return water tank. The Big Bend FGD wastewater treatment system contains the following operations:

• 

### Equalization tank;

• 

### pH adjustment (lime addition);

• 

### Ferric chloride addition;

• 

### Mixing tank;

• 

### Flocculating polymer addition;

• 

### Clarification;

— Overflow to pH adjustment (hydrochloric acid addition);

— Underflow to filter press; and

• 

### Filtration.

### 2-4 Big Bend estimates that the maximum flow ra te from the equalization tank through the wastewater treatment system is approximately 230 gpm, with a total equalization tank residence time of approximately 8 to 9 hours. Figure 2-1 presents a process flow diagram of the FGD wastewater treatment system, as well as the sa mpling locations for EPA’s sampling episode. Big

Bend estimates that the residence time of the enti re FGD wastewater trea tment system (including the equalization tank) is approximately 24 to 32 hours. The flow rate entering the wastewater treatment system during the sampling episode was approximately 250 gpm; however, 154 gpm was off-specification filter press f iltrate (with pollutant characteristics similar to treated effluent) and only 96 gpm consisted of scrubber pur ge from the secondary hydroclones.

According to Big Bend personnel, the plant cont rols the level in the equalization tank to prevent the tank from overfilling. When the level in the tank reaches high levels, the plant diverts the scrubber purge from the secondary hydroclones away from the equalization tanks and

transfers it to the FGD scrubbers via the return water tank. Because the plant was transferring 154 gpm of off-specification filter press filtrate to the equaliz ation tank, the plant diverted some of the scrubber purge away from the equalizat ion tank and therefore, the 96 gpm of scrubber purge is a lower than normal flow rate. When the filter press filtrate meets the turbidity specifications, it is transferred to the treated water transfer tank a nd discharged from the system.

The secondary hydroclone overflow is transf erred directly to th e equalization tank. The equalization tank also receives effluent from the treatment system if it did not meet the plant’s permit limits and wastewater from the filtrate sump. The filtrate sump wastewater consists of filter backwash from the sand filters, off-specification filter press filtrate, wash water from polymer storage containers, fume scrubber wa stewater from the muriatic acid tank, and occasionally material from the sludge storage tank during maintenance. Big Bend typically transports the filtrate sump wastew ater to the equalization tank 5 tim es a day at a flow rate of 170 gpm for approximately 200 minutes per day.

The wastewater, at a pH of approximately 6.0, flows from the equalization tank to reaction tank 1, where Big Bend adds hydrated lime to raise the pH of the wastewater to 9.0, which facilitates heavy metals precipitation. The r eaction tank is equipped with an agitator to effect rapid mixing and has an aver age residence time of 60 minutes.

From reaction tank 1, the wastewater flow s to reaction tank 2, where Big Bend adds ferric chloride. The ferric chloride produces iron oxyhydroxide, which cause s coprecipitation of

other trace elements in the water. The overflow from reaction tank 2 is transferred to reaction tank 3, which provides low shear agitation. Th e mixing of the wast ewater provides an environment to build floc particle s to settle in the clarifiers.

From reaction tank 3, the wastewater is tr ansferred to the clarifier. A flocculating polymer is added to the clarifier feed pump di scharge. The primary clarifier, which was added after the initial design of the treat ment system, is capable of handli ng all of the wastewater in the FGD wastewater treatment system . The two secondary back-up clar ifiers are from the original design of the FGD wastewater treatment plant a nd can each handle 50 percent of the wastewater. When the primary clarifier was added to the system, Big Bend began using the two secondary clarifiers as back-ups; therefore, the plant uses the secondary b ack-up clarifiers when necessary (i.e., during maintenance of the prim ary clarifier). All thr ee of the clarifiers are designed to have

### 2-5 an overflow stream with a maximum TSS level of 100 mg/L and an underflow slurry of 5 to 10 percent solids. During the sampling episode, th e secondary clarifiers were not operating.

The overflow from the clarifiers are commi ngled and transferred to sand gravity filters. As the wastewater is pumped to the gravity filters, the plant adds hydrochloric acid to the wastewater to ensure the pH is between 6.0 a nd 9.0. The gravity filters are designed to produce a filtrate stream having less than 5 mg/L TSS. Th e plant continuously backwashes the filters and

the wastewater from the backwash is transferred to the filtrate sump.

From the gravity filters, the wastewater is transferred to the treated water transfer tank and discharged from the plant. Th e plant has the capability to r ecycle the treated water back to the equalization tank if the treated water does not meet the plant’s limits. The discharge from the treated water transfer tanks is based on level control; therefore, if the tank is less than 30 percent full, the system will not discharge from the trea ted water transfer tank. The plant commingles the

effluent from the FGD wa stewater treatment system (i.e., trea ted water transfer tank) with the plant’s once-through cooling water prior to discharge. During th e sampling episode, the average effluent discharge from the FGD wastewater treatment system (prior to commingling with cooling water) was approximately 104 gpm; however , the discharge flow rate varied widely during the episode, ranging from 2.44 gpm to 253 gpm.

The underflow from all three clarifiers is transferred to the sludge storage tank. Big Bend dewaters the sludge by pumping it through one of tw o filter presses. The filter cake is stored on site and sold as a by-product. The filtrate is tran sferred to the treated water tank or to the filtrate sump if it does not meet plant specifications. Table 2-1 presents Big Bend’s NPDES permit requirements for their internal monitoring point of the effluent from the FGD wastewater treatment system, shown as I-130 on Figure 2-1.

EPA collected a sample of the influent to Big Bend’s FGD wastewater treatment system after the equalization tank, but prior to reaction tank 1 and any chemical addition. EPA also collected a sample of the effluent from Big Be nd’s FGD wastewater trea tment system after the

treated wastewater effluent ta nk, but prior to the wastewater commingling with the once-through cooling water.

### 2-6 Table 2-1. Big Bend NPDES Monitoring Requi rements for the FGD Effluent (I-130)

Parameter Daily

Minimum Daily

Maximum Monthly Average Sample Frequency Sample Type

Total Suspended Solids NA 30 mg/L NA Quarterly Grab

Oil & Grease NA 15 mg/L NA Quarterly Grab

pH 6.0 s.u. 9.0 s.u. NA Quarterly Grab

Arsenic, Total Recoverable Report (ug/L) Quarterly Grab

Chromium, Total Recoverable Report (ug/L) Quarterly Grab

Copper, Total Recoverable Report (ug/L) Quarterly Grab

Lead, Total Recoverable Report (ug/L) Quarterly Grab

Mercury, Total Recoverable Report (ug/L) Quarterly Grab

Nickel, Total Recoverable Report (ug/L) Quarterly Grab

Selenium, Total Recoverable Report (ug/L) Quarterly Grab

Alpha, Gross Particle Activity Report (PCI/L) Quarterly Grab

Radium 226 + Radium 228, Total Report (PCI/L) Quarterly Grab

Flow Rate Monitor (MGD) Continuous Recorder

NA – Not applicable.

### 2-7Figure 2-1. FGD Wastewater TreatmentSystem, Big Bend Power Plant

### 3-1 3. S AMPLE 

### C OLLECTION



### During the Big Bend sampling episode, the sa mpling team followed the sample collection protocols specified in the Sa mpling Plan. Section 3.1 describes the sampling points, sample collection methods, and field measurements. Secti on 3.2 describes the list of analytes and the sample preservation procedures. Section 3.3 discu sses the plant operational data collected during the sampling episode. Finally, Section 3.4 discusse s any deviations from the planned sampling activities described in the Sampling Plan.

During the sampling episode, Unit 3 was shut do wn due to high opacity readings from the

unit’s ESP. The unit was shut down on Monda y, July 23, 2007 and the sampling occurred on Wednesday, July 25, 2007. For more details abou t the Unit 3 shut down, see Section 3.3. In addition, during the sampling episode, the plant wa s transferring off-speci fication filter press filtrate to the FGD wastewater treatment equali zation tank, which caused the plant to transfer less of the secondary hydroclone overflow to the FGD wastewat er treatment system. During the sampling episode 154 gpm of off-sp ecification filter press filtra te and 96 gpm of scrubber purge were entering the equalization tank.

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

This section describes the sampling points, sample collection methods followed, and the field measurements obtained for this sampling episode. Additional details are available in Section 3 of the Sampling Plan. Figure 2-1 pres ents a flow diagram of the plant including sampling point locations.

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

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

The sampling points for this episode were:

• 

### SP-1 Influent to FGD Wastewater Treatment System;

• 

### SP-2 Effluent from FGD Wast ewater Treatment System;

• 

### SP-3 Duplicate of Effluent from FGD Wastewater Treatment System;

• 

### SP-4 Influent to FGD Wastewater Treatme nt System (SP-1) Field Blank; and

• 

### SP-5 Effluent from FGD Wa stewater Treatment System (SP-2) Field Blank.

For SP-1, SP-2, and SP-3, EPA collected split samples with Big Bend’s representative. Prior to the sampling episode, Big Bend personnel installed three-way splitters on the sampling taps at the two sampling locations, which allowe d for split sample collection. The low-level and routine total metals and the classical pollutants were collected as “true” splits (i.e., samples for the same analyte were collected simultaneously) ; however, the low-level and routine dissolved metals samples were collected as “multipour” sp lits, due to difficulties collecting split samples through a filter. The “multipour” splits were coll ected by the following procedure: one-third of the EPA sample bottle was filled and then one-t hird of the “split” bottle was filled. The EPA sample bottle and the “split” sample bottle were each in turn then filled with an additional one-

### 3-2 third sample. Finally, the EPA samp le bottle was filled completely and then the “split” bottle was filled completely.

The field blank samples (SP-4 and SP-5) fo r the low-level and routine total metals samples were not collected as split samples be tween EPA and Big Bend’s representative. These samples were collected using separate blank wa ter and separate tubing. The field blank samples

for the low-level and routine dissolved metals samples were collected using the “multipour” approach, as described previously. For a desc ription of the field bl ank sample collection procedures, see Section 5.2.3.

At each of the five sampling points, EPA co llected low-level metals sample fractions following EPA Method 1669 collection protocols. To collect low-level metals samples, EPA donned Tyvek® suits and dust masks (dust masks we re worn until all low-level mercury samples had been collected). In addition, EPA set up a “c leanbox,” which consists of a portable plastic rectangular box with a shallow lip and a flip-top lid th at secures itself ope n 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 it a nd 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 E-1, in Appendix E, is a picture of a sampler working inside a “cleanbox.” To collect samples, EPA placed th e sample bottles and the inner bag into the “cleanbox” following the protocols specified in Method 1669, also re ferred 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 Wastewater Treatment

The influent to the FGD wastewater treatment system (SP-1) was collected from a sample tap located along the wastewater piping after th e equalization tank, but pr ior to reaction tank 1. The sample tap was connected to the top of the pipe on the suction side of the pump from the equalization tank. Figure 2-1 identifies the sa mpling location for SP-1. This sample was collected as a grab sample, because the batch discharges from the gypsum dewatering process were equalized prior to sample collection and ther efore, were expected to be fairly homogenous.

During the sample collection at the influent to the FGD wastewater treatment system, the sampling team covered the area around the sampling point with tarps to block the sun and cover the samplers in case of rain. There was no rain during the sample collection period; however, there was a periodic light mist that fell from th e return water tank located next to the sampling point. There was also a strong wi nd blowing at the backs of the samplers during portions of the sample collection.

Prior to collecting samples at the influent to the FGD wastewater treatment system (SP-1), the sampling team collected field blanks (SP-4) for low-level total metals and low-level total mercury. See Section 5.2.3 for a description of the field blank sample collection procedures at the influent to the FGD wastewater treatment system.

### 3-3 EPA collected the wastewater samples at th e influent to the FGD wastewater treatment system by attaching a 5-foot leng th of silicone tubing to one of the fittings on the three-way splitter at the sample location (Big Bend’s represen tative attached an identical piece of silicone tubing to one of the other fitti ngs). Figure E-2, in Appendix E, is a picture of the three-way splitter attached to the sample tap at the infl uent to the FGD wastewater treatment system sampling point. The samplers opened the valves of the sample tap and allowed the sample to purge the tubing for four minutes . After the samplers opened the valve to the sampling tap, the valve was left open and the flow from the ta p did not stop until all samples were collected (except HEM/SGT-HEM and the dissolved metals samples).

After the four-minute purge time had elapse d, the samplers filled two 10-liter containers with sample, which were later used to pump off the low-level and routine dissolved metals sample fractions. After filling th e 10-liter containers, a member of the sampling team transported the two 10-liter containers to the FGD laboratory to allow the solids in the wastewater to settle while the remainder of the sampling team stayed at the sample point and continued sample collection. Figure E-3, in Appendix E, is a picture of the sampling set-up at the influent to the FGD wastewater treatment system.

The samplers then collected the low-level total metals, low-level total mercury, low-level dissolved mercury, and arsenic/selenium speciati on samples in a “cleanbox,” as described in Section 3.1. The samplers then collected rou tine total metals, BOD, Group I, and Group II samples by pouring the sample directly from the t ubing into the sample bottl es without the use of a “cleanbox.” To collect the HEM/SGT-HEM sample s, the samplers shut off the valve for the sample tap, removed the tubing from the fitting, reopened the valve, and filled the sample bottles directly from the tap to prevent any oil a nd grease adhering to the sides of the tubing.

During the sample collection, the sampling team collected an aliquot of sample for field testing. Sample pH and temperature were measur ed immediately at the sampling point using a pH meter and four-color pH paper. The four-color pH paper was us ed as an independent check of the pH meter to ensure that similar results were measured. After returning to the staging area, the sampling team took measurements of free and to tal residual chlorine using a colorimeter. Table 3-3 presents the field measurement data fo r the influent to the FGD wastewater treatment system. The samplers noted that the field test jar was initially cloudy and had a brownish-gray appearance when collected. The solids in the sa mple settled after appr oximately four minutes, leaving a one inch layer at the bo ttom of the jar. In a ddition, after the solids settled, the aqueous portion of the samples was yellowish in color.

The sampling team then moved to the FGD laboratory, where a pump- off station was set up, to collect the low-level and ro utine dissolved metals samples. The pump-off station consisted of a length of Teflon® tubing attached to a leng th of silicone tubing, which was threaded through a peristaltic pump. The samplers connected a capsule filter to the end of the silicone tubing. Figures E-4 and E-5, in Appendix E, are pictures of the set-up of the pump-off station. Prior to collecting any dissolved wastewater samples, the samplers collected a field blank sample (SP-4)

for low-level dissolved metals. S ee Section 5.2.3 for a description of the dissolved metals field blank sample collection at the influent to the FGD wastewater treatment system.

After collecting the field blank samples, the samplers transferred the end of the Teflon® tubing into one of the 10-liter containers filled with wastewater from th e influent to the FGD

### 3-4 wastewater treatment system. By this time, the so lids in the wastewater had been settling for approximately 1.5 hours (the 10-lite r containers had been filled approximately 2 hours earlier), and there was approximately a one inch layer of solids at the bottom of the container.

The samplers first purged the tubing and filte r with approximately 600 mL of sample and

then collected the routine hexavalent chromium sample, which was collected first because it was the only other sample that needed to be preserved prior to ship ment. After collecting the routine hexavalent chromium sample, the samplers switched capsule filters, purged the new filter with approximately 500 mL of sample, and collected the low-level dissolved metals sample. The samplers then transferred the end of the Teflon® tubing into the second of the 10-liter containers, switched the capsule filter, and purged the tu bing and filter with a pproximately 600 mL of sample. Finally, the sampling team collected the routine dissol ved metals sample.

3.1.2 Effluent from FGD Wastewater Treatment

The effluent from the FGD wastewater treatment system (SP-2) was collected from a sample tap located along the wastewater piping after the treated wastew ater effluent tank, but prior to commingling with the once-through coo ling water. Figure 2-1 identifies the sampling

location for SP-2.

During the sample collection at the effluent from the FGD wastewater treatment system, the sampling team covered the area around the samp ling point with tents and tarps to block the sun and cover the samplers in case of rain. There was no rain during the sample collection period.

Prior to collecting samples at the effluent from the FGD wastewat er treatment system (SP-2), the samplers collected field blanks (SP-5) for low-level total metals, low-level total mercury, and routine total metals. 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 at the effluent from the FGD wastewater treatment system by attaching a 5-foot leng th of silicone tubing to one of the fittings on the three-way splitter at the sample location (Big Bend’s represen tative attached an identical piece of silicone tubing to one of the other fittings ). Figure E-6, in Appendix E, is a picture of a sampler attaching the silicone tubing to the three-way splitter. The samplers opened the valves of the sample tap and allowed the sample to purge the tubing for 3 minutes. After the samplers opened the valve to the sampling tap, the valve was left open and the flow from the tap did not stop until all samples were collected (except HEM/SGT-HEM and the dissolved metals samples). Figure E-7, in Appendix E, is a picture of the sampling set- up at the effluent from the FGD wastewater

treatment system.

After the three-minute purge time had elap sed, the samplers began collecting the lowlevel total metals samples in a “cleanbox,” as described in Section 3.1. The samplers collected low-level total metals, low-level total mercury, and low-level dissolved mercury, as well as the field duplicates and QC samples for each of the analytes, and the arseni c/selenium speciation samples. Then the samplers filled three 10-liter c ontainers with sample, which were later used to pump off the low-level and routine dissolved meta ls sample fractions. After filling the 10-liter containers, a member of the sampling team tr ansported the three containers to the FGD

### 3-5 laboratory while the remainder of the sampling t eam stayed at the sample point and continued sample collection.

During the sample collection, the sampling team collected an aliquot of sample for field testing. Sample pH and temperature were measur ed immediately at the sampling point using a pH meter. After returning to the staging area, the samplers 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 wastewat er treatment system. The sample rs noted that the sample was clear with a yellowish color.

The samplers then collected the routin e total metals, BOD, Group I, and Group II samples, as well as the field duplicates and QC samples for each analyte, by pouring the sample directly from the tubing into the sample bottles wit hout the use of a “clea nbox.” To collect the HEM/SGT-HEM samples, the samplers shut off the valve for the sample tap, removed the tubing from the fitting, reopened the valve, and f illed the HEM/SGT-HEM and HEM/SGT-HEM QC sample bottles directly from the tap to prevent any oil and grease adheri ng to the sides of the tubing.

The sampling team then moved to the FGD laboratory, where a pump- off station was set up, to collect the low-level and ro utine dissolved metals samples. The pump-off station consisted of a length of Teflon® tubing attached to a leng th of silicone tubing, which was threaded through a peristaltic pump. The samplers connected a capsule filter to the end of the silicone tubing. Figures E-4 and E-5, in Appendix E are pictures of the set-up of the pump-off station. Prior to collecting any dissolved wastewater samples, the samplers collected a field blank sample (SP-5) for low-level dissolved metals, low-level hexavalent chromium, routine dissolved metals, and

routine hexavalent chro mium. See Section 5.2.3 for a descripti on of the dissolved metals field blank sample collection at the effluent to the FGD wastewater treatment system.

After collecting the field blank samples, the samplers transferred the end of the Teflon® tubing into one of the 10-liter containers filled with wastewater from th e effluent to the FGD wastewater treatment system. By this time, the effluent sample had been sitting for approximately two hours.

The samplers first purged the tubing and filter with approximately 1 liter of sample, after which, the samplers collected the low-level dissolved metals sample. Due to the back pressure in the filter, the samplers switched to a new capsule filter. The samplers then purged the new filter with approximately 1 liter of sample and collected the low-level dissolved metals field duplicate and QC samples. The samplers then transferred the end of the Teflon® tubing into the second of the 10-liter containers, switche d the capsule filter, purged the tubing and filter with approximately 1 liter of sample, and collected the low-level hexavalent chromium sample, as well as the field duplicate and QC samples. The sa mplers then switched to a new capsule filter and purged the new filter with approximately 1 liter of sample, after which, the samplers collected the routine dissolved metals sample. Then the samplers transferred the end of the Teflon® tubing into the third of the 10-liter containers, switched the capsule f ilter, purged the tubing and filter with approximately 1 liter of sa mple, and collected the routine dissolved metals field duplicate and QC samples. Finally, the sample rs switched the capsule filter, purged the new filter with approximately 1 liter of sample, and collected the routine dissolved hexavalent chromium sample, as well as the field duplicate and QC samples.

### 3-6 3.2 List of Analytes and Sample Preservation

Analytes in EPA’s Big Bend sampling episode included those in the following classes of pollutants:

• 

### Classicals:

— Biochemical oxygen demand, 5-day (BOD 5 

### ),

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus,

— Hexane extractable material (HEM), and

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

• 

### Metals:

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

— Routine dissolved metals (27 metals),

— Routine hexavalent chromium,

— Low-level total mercury,

— Low-level dissolved mercury,

— Low-level hexavalent chromium,

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

— Low-level dissolved metals (11 metals).

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

concentrations.

Table 3-5 lists the containe rs used for sample collection as well as the preservation requirements for each sample, and Table 3-6 summa rizes the chemical preservation for each of the samples that were preserved on site. The sampling team preserved samples in accordance with procedures described in S ection 3.4 of the Sampling Plan. A ll samples except routine total and dissolved metals, low-level total and dissolved metals, low-level total and dissolved mercury, and low-level hexavalent chromium sa mples were placed on ice and cooled to <6°C immediately following collection. All dissolved metals samples, except low-level dissolved mercury, were filtered in the fi eld. The routine and low-level hexavalent chromium samples were preserved in the field, but all other metals samples were acid-preserved at the laboratory, prior to extraction. The routine hexavalent chromium samp les were supposed to be preserved to a pH between 9.3 and 9.7 using an ammonium sulfate buffer solution; however, the sampling team discontinued preservation for some samples becau se 10 percent of the sample volume was added

### 3-7 before the required pH was achieved (the pH of the preserved samples was approximately 8.7 to 9.0). The low-level hexavalent chromium samples bottles were prepreserved with 4 mL of 50- percent NaOH. The Group II and HEM/SGT-HEM samp les were preserved with sulfur acid to a pH of <2 immediately after colle ction in the staging area, and th e pH was confirmed with fourcolor pH strips.

3.3 Plant Operational Data

During the sampling episode at Big Bend, plant personnel provided the sampling team with operational data for each of the generating units and the F GD scrubber systems, as well as operational and flow data for the FGD wastewater treatment system. Tabl e 3-7 presents the unit operating characteristics, Table 3-8 presents th e FGD scrubber system operating characteristics, and Table 3-9 presents the FGD wastewater trea tment system operating characteristics during the sampling episode. In addition, plant personnel provi ded the sampling team with measured flow

values at the influent and effluent of the F GD wastewater treatment system during the sampling episode. The average flow rate into the FGD wa stewater treatment system was approximately 250 gpm while EPA was collected th e influent samples and the average effluent flow rate was approximately 104 gpm while EPA collected the e ffluent samples. The influent flow rate consisted of approximately 96 gpm of scrubber purge and 154 gpm of wastewater treatment
recirculation flow. The flow rate data from 8: 00 am to 10:30 am (during effluent sampling) and 3:00 pm to 4:30 pm (during influent sampli ng) on the day of sampling is available in Appendix D.

As noted in Section 3.0, Unit 3 was shut dow n during the sampling episode due to a high opacity reading in Unit 3’s ESP, according to plant personnel. Big Bend has a maximum legal limit of 20 percent opacity. The Unit 3 ESP typica lly operates at 3-6 percent opacity; however, on Monday, July 23, 2007, the opacity sensor measurement was 45 percent. Due to the high opacity reading, the operators shut down Unit 3; however, after the unit was shut down, the opacity sensor continued to measure 45 percent op acity. Therefore, the pl ant suspected that the sensor was not operating properly.

Because Unit 3 was not operating during the sampling episode, the scrubber that treats Units 3 & 4 was only treating the flue gas from Unit 4. Therefore, during the episode, the flow

rate of the scrubber blowdown from the sc rubber treating Units 3 & 4 was reduced by approximately 50 percent.

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 Procedures. EPA planned to collect th e influent to the FGD wastewater treatment system (SP-1) and the effluent from the FGD wastewater treatment system (SP-2) by filling the sample bottles directly from the sample tap. Instead, EPA collected the samples by attaching silicone tubing to the sample tap and running the tubing into a “cleanbox” wh ere the sample bottles were filled, as

described in Section 3.1.

### 3-8 • 

### Field Blank Sample Collection Procedures. EPA planned to collect the field

blanks for the influent to the FGD wast ewater treatment system (SP-4) and the

effluent from the FGD wast ewater treatment system (SP-5) by pouring the blank water directly into the sample bottles at the sample location. Because the sample collection procedures cha nged and tubing was used for the for the sample collection, the tubing had to be incorporated into the field blank. Therefore, EPA used a funnel to pour the blank water through the tubing and into the sample bottles, as described in Section 5.2.3.

• 

### Dissolved Metals Filtration. EPA planned to filter the influent to the FGD wastewater treatment samples approxim ately one hour after the sample was collected; however, EPA did not filter the samples until approximately two hours

later. For the effluent from the FGD wast ewater treatment, EPA did not filter the samples until two and a half hours after sample collection.

• 

### Collection Containers for Routine Dissolved Metals. For the effluent from the FGD wastewater treatment system, EPA planned to collect volume for the pump

off of routine dissolved metals and routin e hexavalent chromium samples, as well as the field duplicate and QC samples, in to three 1-gallon containers. However, EPA collected the volume into a precleaned 10-liter container.

• 

### Dissolved Metals Sample Collection Order. During the filtration of the influent to the FGD wastewater treatment samples, EPA collected the routine hexavalent chromium sample prior to collecting the low-level and routine dissolved metals samples because it was the only dissolved sample that needed to be preserved prior to shipment.

• 

### Collection of Low-Level Mercury Field Blank Samples at SP-1. During the collection of the low-level total mercury field blank samples at SP-1, the sampling team did not don dust masks as require d by EPA Method 1669. After the field blank sample was collected, EPA reali zed the error and donned the dust masks until the low-level total and dissolved mercury samples were collected.

• 

### Chlorine Field Test Measurements. When EPA performed the chlorine field test

measurements for both the influent to th e FGD wastewater treatment system (SP1) and the effluent from the FGD wast ewater treatment system (SP-2), the reaction of the DPD reagent with the wa stewater formed a precipitate which

caused an interference with the measurement.

• 

### 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 solutio n; however, the samplers discontinued preservation for some samples because 10 percent of the sample volume was added before the required pH was achieved (the pH of the preserved samples was approximately 8.7 to 9.0).

### 3-9 • 

### Nitrate/Nitrite as Nitrogen Analysis. The analysis of nitrate/nitrite as nitrogen was not performed for this sampling ep isode. The laboratory equipment required for the analysis was broken and the equi pment could not be repaired before the

hold time was exceeded.

Table 3-1. Sample Collection Information, Big Bend

Sampling

Point Number Sampling Point Description Type of Sample Sample Collection

Date and Time SCC Number

SP-1 Influent to FGD Wastewater Treatment System Grab 07/25/2007

1510 a and 1710 b 70320

SP-2 Effluent from FGD Wastewater Treatment System Grab 07/25/2007

0815 a and 1140 b 70321

SP-3 Duplicate of Effluent from FGD Wastewater Treatment System Grab 07/25/2007

0815 a and 1140 b 70322

SP-4 Influent to FGD Wastewater Treatment System Field Blank Grab 07/25/2007

1450 a and 1705 b 70323

SP-5 Effluent from FGD Wastewater Treatment System Field Blank Grab 07/25/2007

0745 a and 1110 b 70324

a – Collection of the total metals samples (low-level an d routine), low-level dissolved mercury, and classicals. b – Collection of the dissolved metals samples (except low-level dissolved mercury).

### 3-10Table 3-2. Number of Samples Collected by Sampling Point, Big BendSamplingPointNumberSampling PointDescription Low-Level Total Metals (11 analytes) Low-Level Dissolved Metals (11 analytes) Low-Level Total Mercury Low-Level Dissolved Mercury Low-Level Hexavalent Chromium Routine Total Metals (27 analytes) Routine Dissolved Metals (27 analytes) BOD 5 Group I

a Group II b HEM / SGT-HEM Routine Hexavalent Chromium Selenium/Arsenic S p eciation cSP-1 Influent to FGD WastewaterTreatment System1 1 1 1 1 1 1 1 1 1 1 1 + DupSP-2 Effluent from FGDWastewater TreatmentSystem1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC1+QC 1+QC 1+QC 1+QC 1+QC 1 + DupSP-3 Duplicate of Effluent fromFGD Wastewater TreatmentSystem1 1 1 1 1 1 1 1 1 1 1SP-4 Influent to FGD WastewaterTreatment System FieldBlank1 1 1SP-5 Effluent from FGDWastewater TreatmentSystem Field Blank1 1 1 1 1 1 1Total Number of Samples 5+1QC 5+1QC 5+1QC 3+1QC 3+1QC 5+1QC 5+1QC 3+1QC 3+1QC 3+1QC 2+1QC 5+1QC 2+2Dupa – Group I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate and chloride.b – Group II includes ammonia as nitrogen,nitrate/nitrite as nitrogen, total Kjeldahl nitrogen (TKN), and total phosphorus.c – The selenium/arsenic speciation results from the sampling episode were not available at thetime this report was finalizedand therefore are not included in this report.

### 3-11Table 3-3. Field Measurements, Big BendpH(S.U.)Sampling PointNumberSampling PointDescriptionTimeTemp°CMeterMeteraStripsFree Chlorine(mg/L)Total Chlorine(mg/L)Waste StreamFlow Rate (GPM)SP-1 Influent to FGDWastewater Treatment1601 38.2 8.08 8.3 LimitbNA 250cSP-2 Effluent from FGDWastewater Treatment0942 35.7 6.91 NA 0.15dNA 104ea – The pH meter was calibrated on the morning of July 25, 2007 using pre-packaged buffer solutions at pHs 4.0, 7.0, and 10.0.b – After the N,N’-diethyl-p-phenylenediamine (DPD) powder was added to the sample, a precipitate formed which EPA could not rinse from the cell. The testwas performed for free residual chlorine, but resulted in a “limit” reading. EPA did not perform the analysis for total residual chlorine.c – Based on the average of monitored flow rate data in one minute intervals provided by Big Bend from 3:00 pm to 4:30 pm (thetime FGD wastewatertreatment system influent samples were collected).d – After the DPD powder was added to the sample, a precipitateformed; however, it settled to the bottom of the vial prior tothe reading. EPA did not performthe analysis for total residual chlorine.e – Based on the average of monitored flow rate data in one minute intervals provided by Big Bend from 8:00 am to 10:30 am (thetime FGD wastewatertreatment system effluent samples were collected).NA – Not analyzed.Note: At SP-2, the plant has a turbidity meter that is continuously measuring the turbidity of the effluent. During the sampling collection period, the samplingteam recorded the following turbidity readings: 11.20 to 11.57 NTU at 0756; 10.83 to 11.12 NTU at 0825; and 9.39 NTU at 0928.

### 3-12 Table 3-4. Analytical Methods and Proce dures for Samples Collected at Big Bend

Method Number Parameter Method Type

Classicals

SM 5210 B Biochemical Oxygen Demand (BOD 5 ) Probe

SM 2540 D Total Suspended Solids (TSS) Gravimetric

SM 2540 C Total Dissolved Solids (TDS) Gravimetric

ASTM D516-90 Sulf ate Turbidimetric

SM 4500–Cl–C Chloride Titrimetric, mercuric

nitrate

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

SM 4500—NO3 -H Nitrate/Nitr ate as Nitrogen Autoanalyzer

SM 4500—N,C (18th ed.) 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 (SGTHEM) Gravimetric

Metals

EPA 1631 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 Atomic Absorption Spectroscopy ICP and CVAA

ASTM D1687-92 Hexavalent Chromium Colorimetric

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

### 3-13 Table 3-5. Summary of Sample Co ntainer and Planned Preservation

Parameter Sample Container and Volume On-Site Preservation

Classicals

BOD 5 One 1-L plastic bottle ≤ 6 o C

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

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

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

Metals

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

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

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

Routine hexavalent chromium One 250-mL plastic bottle 0.45 μm filter (performed in field) Ammonium sulfate buffer to pH 9.3 – 9.7, ≤ 6 E C

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

Low-level total elements by ICP/MS (11 elements, Method 1638) One 1-L LDPE (ultraclean), fluoropolymer lined cap None (acid preserve at laboratory)

Low-level dissolved elements by ICP/MS (11 elements, Method 1638) One 1-L LDPE (ultraclean), fluoropolymer lined cap 0.45 μm filter (performed in field) (acid preserve at laboratory)

Low-level hexavalent chromium (Method 1636) One 500-mL LDPE (ultraclean), fluoropolymer lined cap 0.45 μm filter (performed in field) 4 mL 50% NaOH per 500 mL sample (performed in field) c

Selenium/arsenic speciation Two 125-mL amber glasses (ultraclean) None for original sample, ≤ 6 E C Duplicate: HCl to pH <2, ≤ 6 E C

a – Group I includes TSS, TDS, sulfate, and chloride. b – Group II includes ammonia as nitrogen, nitrate/nitrite as nitrogen, TKN, and total phosphorus. c – Method 1636 has a preservation requirement that the low-level hexavalent chromium sample be cooled to ≤ 6 E C; however, EPA did not cool the low-level hexavalent chromium samples due to contamination concerns.

### 3-14 Table 3-6. Sample Preservation Summary, Big Bend

Sampling

Point

Number Analysis Date and

Time Chemical Initial pH Final pH Amount Added

70320 Group II V1 7/25/07 1935 H 2 SO 4 9 2 175 drops

70320 Group II V2 7/25/07 1937 H 2 SO 4 9 2 175 drops

70320 HEM/SGT-HEM 7/25/07 1938 H 2 SO 4 9 2 175 drops

70320 Routine Hexavalent

Chromium 7/25/07 1940 Ammonium

Sulfate Buffer 8.5 8.7 250 drops a

70320 Arsenic/Selenium Speciation (Duplicate) 7/25/07 2015 HCl 9 2 50 drops

70321 Group II V1 7/25/07 1145 H 2 SO 4 7 2 70 drops

70321 Group II V2 7/25/07 1147 H 2 SO 4 7 2 70 drops

70321 Group II QC V1 7/25/07 1148 H 2 SO 4 7 2 70 drops

70321 Group II QC V2 7/25/07 1149 H 2 SO 4 7 2 70 drops

70321 HEM/SGT-HEM 7/25/07 1150 H 2 SO 4 7 2 70 drops

70321 HEM/SGT-HEM QC V1 7/25/07 1152 H 2 SO 4 7 2 70 drops

70321 HEM/SGT-HEM QC V2 7/25/07 1153 H 2 SO 4 7 2 70 drops

70321 Routine Hexavalent

Chromium 7/25/07 1205 Ammonium

Sulfate Buffer 7.5 9.0 200 drops a

70321 Routine Hexavalent Chromium QC 7/25/07 1210 Ammonium

Sulfate Buffer 7.5 9.0 200 drops a

70321 Arsenic/Selenium Speciation (Duplicate) 7/25/07 2030 HCl 7.5 2 30 drops

70322 Group II V1 7/25/07 1154 H 2 SO 4 7 2 70 drops

70322 Group II V2 7/25/07 1155 H 2 SO 4 7 2 70 drops

70322 Routine Hexavalent

Chromium 7/25/07 1300 Ammonium

Sulfate Buffer 7.5 9.0 200 drops a

70324 Routine Hexavalent

Chromium 7/25/07 1200 Ammonium

Sulfate Buffer 6.5 9.5 73 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 buff er solution; therefore, the preservation was stopped to prevent the sample from being diluted by the preservative.

### 3-15Table 3-7. Generating Unit Operating Characteristics during Sample Collection, Big BendUnitIDBoiler TypeCoal typeCoal Usagea(tons/day)Source of Coal(coal regionand/or state)Capacity(MW)ElectricityProduction (orpercentcapacity)SCR(No, On,Off)ParticulateControl System(HS/CS ESP, orBH)Wet FGDSystem(Yes/No)1 Opposite wallfired/SubcriticalEasternBituminousblend3,735(3.26%Sulfur)EasternIllinois/WesternKentuckyBituminous coal400 360 MW (90%)@Approximately10 AM on7/25/2007No SCR ESP Yes2 Opposite wallfired/SubcriticalEasternBituminousblend2,916(3.00%Sulfur)EasternIllinois/WesternKentuckyBituminous coal410 350 MW (85%)@Approximately10 AM on7/25/2007No SCR ESP Yes3 Opposite wallfired/SubcriticalEasternBituminousblendN/A N/A 430 0 MW(Unit was shutdown)No SCR ESPbYes4 Tangentiallyfired /SubcriticalEasternBituminousblend4,265(3.30%Sulfur)EasternIllinois/WesternKentuckyBituminous coal460 435 MW (95%)@Approx 10 AMon 7/25/2007SCR on ESP Yesa – Average of the tons burned on July 24 and July 25, 2007, as provided by Big Bend.b – Unit 3 was not operating due to an issue with the ESP.HS ESP – Hot-side electrostatic precipitator.CS ESP – Cold-side electrostatic precipitator.BH – Baghouse.

### 3-16Table 3-8. FGD Scrubber System Operating Characteristics, Big BendUnit IDType of ScrubberSorbentAdditives(DBA, FormicAcid, etc.)FGD Make-up WaterSourceSO2RemovalPercentage(%)ForcedOxidation(Yes/No)Percent Solidsin Slurry(%)Type of SolidsSeparation1-2a1 single-loop spraytray absorber towerLimestone DBA Plant recycle water andcounty effluent mixture96.3 Yes 22.0 Primary andsecondaryhydroclones3-4b4 double-loop spraytray absorber towersLimestone DBA Plant recycle water andcounty effluent mixture95.8 Yes 19.1 Primary andsecondaryhydroclonesa – The flue gas from Units 1 and 2 are combined and fed to single absorber tower.b – The flue gas from Units 3 and 4 are combined and then split into the four absorber towers.Note: The plant estimates that the percent solids in the effluent from the primary hydroclones is 5 percent solids and the effluent from the secondary hydroclonesis 2 percent solids.

### 3-17 Table 3-9. FGD Wastewater Treatment System Operating Characteristics, Big Bend

FGD Solids Dewatering (for last cycle prior to sampling or while sampling)

Scrubber slurry blowdown flow rate 1,758 gpm (average) a

Scrubber slurry blowdown duration Varies

Scrubber slurry blowdown percent solids 20.6% b

Dewatering cycle frequency Varies

Time since last cycle Unit 1&2 scrubber: 07/25/2007 @ 8:00 am Unit 3&4 scrubber: 07/25/2007 @ 8:50 am

Percent hydroclone overfl ow recycled back to

scrubber Unable to estimate

FGD Wastewater Treatment System Op eration During Sa mple Collection

Scrubber purge flow rate 96 gpm (average)

Scrubber purge duration Continuous

Lime addition 7,852 gpd (35% solids)

Ferric chloride addition 70 gpd c

Chemtreat Polymer P813E addition 4.8 gpd

Hydrochloric acid addition 532 gpd (35.7%)

Amount of solids generated 12 tpd

Effluent flow rate 109 gpm (average)

Frequency of effluent discharge Approximately 40% of the time

Retention time of equalization tank 8.7 hrs

Retention time of primary clarifier 18.5 hrs

Retention time of chemical reaction tanks 2.2 hrs

Retention time of second ary clarifier Not used during sampling episode

a – The average scrubber blowdown flow rate for both scrubbers combined. b – Average of the percent solids in Unit 1&2 scrubber blowdown (22%) and Unit 3&4 scrubber blowdown (19.1%). c – 38.6 percent ferric chloride in aqueous solution.

### 4-1 4. L ABORATORY 

### A NALYTICAL 

### R ESULTS AND 

### D ISCUSSION



### This section summarizes and di scusses the analytical data co llected during this sampling episode. Section 4.1 discusses the methods used by the laboratories for th e biphasic analysis of SP-1 and presents the results of the analyses. Sec tion 4.2 presents the labora tory analytical data

for the influent to and effluent from the FGD wastewater treatment system.

Appendix A provides all analytical results for all samples collected at Big Bend, including all qualified results a nd all results that were measur ed above the method detection limit, but below the reporting limit (i.e., J-values). Appendix B presents the analytical results in a format similar to that used in Section 4.2, but w ith the J-values shown (J-values are not included in the tables presented in Section 4.2).

4.1 Measured and Calculated Results for FGD Influent Samples

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

concentrations for the follo wing phases of the sample:

• 

### Aqueous phase;

• 

### Solid phase; and

• 

### Total sample.

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

Routine Metals and Selected Classicals Analyses

ProChem used EPA Method 200.7 to analyze th e wastewater samples for routine metals, and EPA Method 245.1 to analyze for routine mercury. EPA Method 200.7 states, “Aqueous samples containing total suspended solids ≥ 1% (w/v) should be extracted as a solid type sample.” (U.S. EPA, 2001) Because EPA expect ed the solids content to be greater than one percent, ProChem developed an approach for th e 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 concen tration from the solid and aqueous phase results, the laboratory also needed to measure the or iginal sample volume, solid phase weight, and filtrate volume. EPA developed the following equa tion to calculate the individual metal total concentrations for the sample.

### 4-2 Sample Solid Solid Filtrate Filtrate 

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

= (4-1)

where:

C Filtrate 

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

V Filtrate 

### = Volume of the filtrate;

C Solid 

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

Wt Solid 

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

V Sample 

### = Volume of the original sample.

ProChem used the same approach for the five clas sical pollutants that were analyzed as biphasic samples: ammonia as nitrogen, chloride, sulfat e, total Kjeldahl ni trogen (TKN), and total phosphorus.

Low-Level Metals Analyses

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

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

To calculate the solid phase concentration from the total and dissolved phase results,

Battelle also measured the TSS level in the to tal metals sample bottle. EPA used the following equation to calculate the individual metal solid phase concentrations for the sample:

TSS Diss Total

Solid 

### C C

- C C = 

### (4-2)

where:

C Solid 

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

C Total 

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

C Diss 

### = Concentration of the metal in the dissolved phase of the sample; and

C TSS 

### = TSS concentration of the sample.

Analytical Deviations

During the analysis of the Big Bend FGD infl uent samples, ProChem did not measure the original sample volume and filtrate volume for the routine total metals samples, which were needed for the calculation of the total sample concentration. Because ProChem did not have extra sample volume to reanalyze the samples, extra sample volume from the low-level total metals sample bottles at Battelle were shipped to ProChem for the reanalysis of routine total metals. When performing the reanalysis using Ba ttelle’s extra sample volume, ProChem used the same approach as Battelle (i.e., analyzing the total sample directly), because the laboratory

### 4-3 determined that the suspended soli ds present in the sample were at a concentration less than one percent; therefore, th e phase separation was not require d by EPA Method 200.7. The laboratory analyzed the total metals directly from the sa mple bottle. The laboratory had already analyzed the dissolved metals concentration; therefore, a solid concentration was calculated using Equation 4-2.

Table 4-1 presents the results of the bipha sic analysis for low-level total metals and routine total metals (except routine total mercury, which is discussed below) in the FGD influent samples. Only those analytes that were detected at the influent to the FGD wastewater treatment system (at levels above the repor ting limit) are included in the tabl e. Results are rounded to three significant figures. Appendix Table A- 1 presents all the analytical results from the FGD influent (SP-1) sample analysis, includi ng results that were measured above the method detection limit, but below the reporting limit (i.e., J-values ).

For the biphasic classical analyses, ProChe m did not measure the original sample volume and filtrate volume, which were needed for the ca lculation of the total sample concentration, and they did not have extra sample volume to rean alyze the classicals. Although additional sample volume was available for the reanalysis of merc ury, by the time the error was recognized, the holding time for the mercury analysis had expired.

To determine the total sample results fo r the classical analytes, EPA calculated the sample volume using the sample weight and sample density. EPA was also able to calculate the filtrate volume using data that had already been collected by the laboratory. Therefore, the classical analytes total concen trations were calculated using Equation 4-1 without making any assumptions. For the routine total mercury co ncentration, EPA had to estimate the sample

volume to calculate the filtrate volume needed for the calculation. As a best available estimate, EPA assumed that the sample volume was 500 mL, based on the sample bottle size, knowing that the actual volume of sample collected may have been less than or greater than 500 mL

Table 4-2 presents the results of the bipha sic analysis for routine total mercury and Table 4-3 presents the results of the biphasic analysis for ammoni a as nitrogen, chloride, sulfate, TKN, and total phosphorus in the FGD influent samp les. Only those analytes that were detected

at the influent to the FGD wast ewater treatment system (at leve ls above the reporting limit) are

included in the table. Results are rounded to three significant figures. Appendix Table A-1 presents all the analytical results from the F GD influent (SP-1) samp le analysis, including Jvalues.

ProChem performed a filtration blank associ ated with the biphasic sample separation process for the FGD influent (SP-1) sample an alysis. For the blank, Pr oChem poured blank water through the filter used for the separation and an alyzed the filtered blank water for routine mercury (note: routine mercury is the only analyt ical result from the filtration blank that is applicable to the biphasic analys is because all other metals were analyzed without the biphasic separation). Mercury was not measured in the fi ltration blank sample above the reporting limit, indicating that there was no contamination from the filtration process. Appendix Table A-2 presents the routine mercury analytic al result from the filtration blank.

### 4-4 4.2 FGD Wastewater Treatment System

Table 4-4 presents the analytical results of the classical pollutants at the influent to and

effluent from the FGD wastewat er treatment system (SP-1 and SP-2). Table 4-5 presents the analytical results of the routine and low-level meta ls at the influent to an d effluent from the FGD wastewater treatment system (SP- 1 and SP-2). Only those analytes that were detected in one or more samples (at levels above the reporting limit) for the sampling episod e 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 limi t, “NQ” is reported followed by the samplespecific report limit in parenthe ses. If an analyte was not detect ed in a sample above the method detection limit, “ND” is reported followed by th e 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 sy stem was not timed to reflect the amount of time it takes the wastewater to pass through the treatment system (approximately 24-32 hours).

Appendix Tables A-1, A-3, and A-4 present all the analytical results from the FGD influent (SP-1), FGD effluent (SP-2), and FGD effluent duplic ate (SP-3) 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 include results where analytes were measured above the method detection limit, but below the reporting limit (i.e., J-values).

### 4-5 Table 4-1. Biphasic Sample Results for Low-Le vel Total Metals and Routine Total Metals Measured Above the Report Li mit, FGD Influent, Big Bend

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

Low-level Total Metals

Antimony 21.9 NQ (0.837) 24.9

Arsenic 137 NQ (6.28) 165

Cadmium 190 10.0 238

Chromium ND (160) 136 651 L

Copper NQ (40.0) 16.2 103

Lead ND (10.0) 14.6 69.9

Mercury 0.206 3.38 16.4

Nickel 1,030 322 2,570

Selenium 3,280 NQ (41.8) 3,470

Thallium 39.4 NQ (0.837) 39.8

Zinc ND (100) 391 1,870

Routine Total Metals

Aluminum ND (50.0) 6,280 31,200

Antimony 33.9 5.75 62.5

Arsenic 18.6 11.4 75.5

Barium 1,820 ND (0.402) 1,590

Beryllium NQ (5.00) 2.07 12.9

Boron 618,000 NQ (2,010) 626,000

Cadmium 179 9.05 224

Calcium 4,470,000 447,000 6,690,000

Chromium NQ (10.0) 151 757

Cobalt NQ (50.0) 28.2 172

Copper 27.2 18.7 120

Iron NQ (100) 4,730 23,500

Lead NQ (50.0) 12.6 69.1

Magnesium 4,110,000 145,000 4,830,000

Manganese 9,610 2,470 21,900

Molybdenum 581 7.44 618

Nickel 851 249 2,090

Selenium 3,610 109 4,150

Sodium 1,970,000 113,000 2,530,000

Thallium 14.3 ND (2.01) ND (10.0)

Titanium 12.5 82.0 420

Vanadium 108 124 724

Yttrium ND (5.00) 49.3 245

Zinc 16.8 306 1,540

L – Sample result between 5x and 10x blank result. 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.

### 4-6 Table 4-2. Biphasic Sample Results for Rout ine Total Mercury, FGD Influent, Big Bend

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

Routine Total Metals

Mercury ND (10.0) 0.220 NJ (10.0)

ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filt ered aqueous and/or the filtered solid analytical results, including J-values, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculate d result is presented in Appendix A with a CJ flag designation.



### Table 4-3. Biphasic Sample Results for Clas sical Analytes Measured Above the Report Limit, FGD Influent, Big Bend

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

Classical Pollutants

Ammonia As Nitrogen (NH 3 -N) 31.7 20.4 31.5

Total Kjeldahl Nitrogen (TKN) 47.4 319 51.6

Chloride 24,500 11,000 24,200

Sulfate 2,300 67,600 3,590

Total Phosphorus 0.390 39.4 0.990



### Table 4-4. Classical Pollutants Measured Above the Report Limit for the FGD Wastewater Treatment System, Big Bend

Analyte Method Unit FGD Influent (SP-1) FGD Effluent (SP-2/SP-3) a

Classical Pollutants

Ammonia As Nitrogen (NH 3 -N) 4500-NH 3 F MG/L 31.5 24.1

Total Kjeldahl Nitrogen (TKN ) 4500-N,C MG/L 51.6 98.7

Biochemical Oxygen Demand (BOD) 5210B MG/L 1,370 >1,720

Chloride 4500-CL-C MG/L 24,200 22,500

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

Sulfate D516-90 MG/L 3,590 1,920

Total Dissolved Solids (TDS) 2540 C MG/L 44,600 40,600

Total Phosphorus 365.3 MG/L 0.990 0.355

Total Suspended Solids (TSS) 2540 D MG/L 4,970 31.5

a – The FGD effluent results represent the average of the FGD effluent and the duplicate of the FGD effluent analytical measurements. > – Result above measurement range. NA – Not analyzed. ND – Not detected (number in parenthesis is the report limit). Note: Results shown are not pair ed samples. See Section 4.2.

### 4-7a – The FGD effluent results represent the average of the FGD effluent and the duplicate of the FGD effluent analytical measurements.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 wasdetermined to be less than the calculated sample-specific reportlimit (number in parenthesis is the report limit). The calculated result is presented in Appendix Awith 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 ispresented in Appendix A with a J flag designation. A designation of “NQ” for the average FGD effluent indicates that the original FGD effluent and/or theduplicate of the FGD effluent is flagged asa J-value. The analytical result for the original FGD effluent and/or the duplicateof the FGD effluent is presented inAppendix A with a J flag designation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).L – Sample result between 5x and 10x blank result.Note: Results shown are not paired samples. See Section 4.2.Table 4-5. Metals Measured Above the Report Limit for the FGD Wastewater Treatment System, Big BendFGD Influent (SP-1)FGD Effluent (SP-2/SP-3)aAnalyteMethodUnitTotalDissolvedTotalDissolvedRoutine MetalsAluminum 200.7 UG/L 31,200 ND (50.0) ND (50.0) ND (50.0)Antimony 200.7 UG/L 62.5 33.9 22.1 R 20.8 TArsenic 200.7 UG/L 75.5 18.6 NQ (10.0) 10.8 R,TBarium 200.7 UG/L 1,590 1,820 1,490 1,410Beryllium 200.7 UG/L 12.9 NQ (5.00) NQ (5.00) NQ (5.00)Boron 200.7 UG/L 626,000 618,000 369,000 397,000Cadmium 200.7 UG/L 224 179 24.9 19.3Calcium 200.7 UG/L 6,690,000 4,470,000 4,420,000 5,210,000Chromium 200.7 UG/L 757 NQ (10.0) NQ (10.0) NQ (10.0)Hexavalent Chromium D1687-92 UG/L NA 24.0 NA ND (2.00)Cobalt 200.7 UG/L 172 NQ (50.0) NQ (50.0) NQ (50.0)Copper 200.7 UG/L 120 27.2 <10.3 NQ (10.0)Iron 200.7 UG/L 23,500 NQ (100) NQ (100) NQ (100)Lead 200.7 UG/L 69.1 NQ (50.0) NQ (50.0) NQ (50.0)Magnesium 200.7 UG/L 4,830,000 4,110,000 2,510,000 2,930,000Manganese 200.7 UG/L 21,900 9,610 60.1 55.6

### 4-8a – The FGD effluent results represent the average of the FGD effluent and the duplicate of the FGD effluent analytical measurements.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 wasdetermined to be less than the calculated sample-specific reportlimit (number in parenthesis is the report limit). The calculated result is presented in Appendix Awith 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 ispresented in Appendix A with a J flag designation. A designation of “NQ” for the average FGD effluent indicates that the original FGD effluent and/or theduplicate of the FGD effluent is flagged asa J-value. The analytical result for the original FGD effluent and/or the duplicateof the FGD effluent is presented inAppendix A with a J flag designation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).L – Sample result between 5x and 10x blank result.Note: Results shown are not paired samples. See Section 4.2.Table 4-5. Metals Measured Above the Report Limit for the FGD Wastewater Treatment System, Big BendFGD Influent (SP-1)FGD Effluent (SP-2/SP-3)aAnalyteMethodUnitTotalDissolvedTotalDissolvedMercury 245.1 UG/L NJ (10.0) ND (10.0) ND (10.0) ND (10.0)Molybdenum 200.7 UG/L 618 581 450R 430 TNickel 200.7 UG/L 2,090 851 221 210Selenium 200.7 UG/L 4,150 3,610 2,910R 2,860 RSodium 200.7 UG/L 2,530,000 1,970,000 1,590,000 1,880,000Thallium 200.7 UG/L ND (10.0) 14.3 16.8 12.5Titanium 200.7 UG/L 420 12.5 13.5 13.7Vanadium 200.7 UG/L 724 108 NQ (20.0) NQ (20.0)Yttrium 200.7 UG/L 245 ND (5.00) ND (5.00) ND (5.00)Zinc 200.7 UG/L 1,540 16.8 ND (10.0) ND (10.0)Low-Level MetalsAntimony 1638 UG/L 24.9 21.9 14.2 13.7Arsenic 1638 UG/L 165 137 68.0 72.4Cadmium 1638 UG/L 238 190 25.8 22.2Chromium 1638 UG/L 651 L ND (160) NQ (80.0) NQ (80.0)Hexavalent Chromium 1636 UG/L NA NA NA ND (5.00)Copper 1638 UG/L 103 NQ (40.0) NQ (20.0) NQ (20.0)

### 4-9a – The FGD effluent results represent the average of the FGD effluent and the duplicate of the FGD effluent analytical measurements.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 wasdetermined to be less than the calculated sample-specific reportlimit (number in parenthesis is the report limit). The calculated result is presented in Appendix Awith 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 ispresented in Appendix A with a J flag designation. A designation of “NQ” for the average FGD effluent indicates that the original FGD effluent and/or theduplicate of the FGD effluent is flagged asa J-value. The analytical result for the original FGD effluent and/or the duplicateof the FGD effluent is presented inAppendix A with a J flag designation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).L – Sample result between 5x and 10x blank result.Note: Results shown are not paired samples. See Section 4.2.Table 4-5. Metals Measured Above the Report Limit for the FGD Wastewater Treatment System, Big BendFGD Influent (SP-1)FGD Effluent (SP-2/SP-3)aAnalyteMethodUnitTotalDissolvedTotalDissolvedLead 1638 UG/L 69.9 ND (10.0) ND (5.00) ND (5.00)Mercury 1631E UG/L 16.4 0.206 0.156 0.0688Nickel 1638 UG/L 2,570 1,030 381 396Selenium 1638 UG/L 3,470 3,280 2,500 2,560Thallium 1638 UG/L 39.8 39.4 31.1 31.5Zinc 1638 UG/L 1,870 ND (100) NQ (50.0) NQ (50.0)

### 5-1 5. D ATA 

### Q UALITY



### QA/QC procedures applicable to the Big Bend sampling episode are outlined in the Quality Assurance Project Plan for the Steam Electric Detailed Study (QAPP) [2]. This section describes the QC procedures used to assess th e precision and accuracy of the analytical data presented in Section 4 and Appendices A and B. QC practices used for this sampling episode include the analysis of matrix spikes, blanks , duplicate samples, and QC standard checks.

5.1 Analytical Quality Control

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

5.2 Field Quality Control

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

5.2.1 Bottle Blanks

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

Albion Environmental collected the bottle blan ks for the low-level metals sample bottles (1000 mL LDPE), the low-level hexavalent chro mium samples bottles (500 mL LDPE), and the speciation sample bottles (125 mL amber glass bottl es) by filling the pre-cleaned bottle to the neck with ASTM Type 1 water, preserving the sa mple with nitric acid to a pH <2, and allowing the sample to sit for at least 72 hours. Albion Environmental then analyzed the samples using

EPA Method 1638.

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

at least 72 hours. Albion E nvironmental then analyzed th e samples using EPA Method 1638.

Albion Environmental collected the bottle blanks for the low-level mercury sample bottles (250 flint glass bottles a nd 1-L borosilicate glass bottles) by filling the pre-cleaned bottle to the neck with ASTM Type 1 water, preservi ng the sample with bromine monochloride, and

### 5-2 allowing the sample to sit for at least 24 hours. Albion Environmental then analyzed the samples using EPA Method 1631E.

Albion Environmental collected the bottle bl ank for the 10-liter composite containers by filling the container with approximately two liters of ASTM Type 1 water and allowing it to soak for approximately 24 hours. During this pe riod, Albion Environmental shook the container periodically and changed its orientation to e xpose all surfaces of the container to the ASTM Type 1 water. Albion Environmental then shook the 10-liter container 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., EP A Method 1638 or 1631E), as described above for the other bottle blank samples.

No metals were detected in the bottle blank, indicating th at there was no contamination from the sample containers. Appendix Table A-5 pr esents all of the analy tical results from the bottle blank and equipment blank analyses for al l of the equipment used for the collection of low-level samples.

5.2.2 Equipment Blanks

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

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

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

No metals were detected in the equi pment blanks, indicating that there was no contamination from the sampling equipment. Appe ndix Table A-5 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.

5.2.3 Field Blanks

The sampling team collected field blanks (SP-4 and SP-5) to evaluate possible contamination caused by sampling equipment, sa mpling equipment decontamination procedures,

### 5-3 sample collection procedures, or atmospheric contamination. EPA analyzed the field blank samples for the low-level and routine metals an alyses, including both total and dissolved metals 1



### .

The low-level and routine total metals field blank samples for the influent to the FGD Wastewater Treatment System (SP-4) and the effluent from the FGD Wastewater Treatment System (SP-5) were collected by pouring AS TM Type 1 water through a precleaned funnel attached to the silicone tubing used for sample collection. The sampling team shrouded the blank water and funnel with a plastic bag while pouring the blank wate r into the funnel to prevent potential atmospheric deposition. In addition, the sample bottles were placed in a “cleanbox” to prevent potential atmospheric depos ition. Figure E-8, in Appendix E, is a picture of the samplers collecting the field blanks at th e effluent from the FGD wastewat er treatment system. The ASTM Type 1 water flowed through the funnel and tubi ng, and was poured into the sample bottles. EPA collected the field blank sample s separately from the Big Bend representative’s field blank samples. Split samples were not collected for th e field blank samples because the sample split was performed at the tap outlet, not within the sample tubing.

The low-level and routine dissolved metals field blank samples for the influent to the FGD Wastewater Treatment Syst em (SP-4) and the effluent from the FGD Wastewater Treatment System (SP-5) were collected by pumping ASTM Type 1 water through the pump-off tubing used for the dissolved metals sample colle ction and a capsule filt er. The container holding the ASTM Type 1 water was placed in a large plas tic 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 poured into the sample bottles. EPA collected the field blank samples as “multipour ” split samples with Big Bend’s representative, using the same procedure discussed in the sa mple collection descri ption (Section 3.1).

Table 5-1 presents the field blank analyt ical results for SP-4 and SP-5. Only those analytes that were detected in the field bla nk samples at levels above the reporting limit are

included in the table. Results are rounded to th ree significant digits. Ap pendix Tables A-6 and A7 present all the analytical results for the fiel d blanks from the FGD influent (SP-1) and FGD effluent (SP-2) 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 duplicat e samples to assess the sampling measurement precision for the episode. Field dupl icate samples are separate samp les collected from the same location as the original sample. The duplicate is filled immediately after the original sample, and is stored and analyzed independently. The re lative percent difference (RPD) between the two sample results is examined to determine the precision of the data. EPA used the following equation to calculate the RPD for the duplicate sample results.

1 EPA did not collect a low-level dissolved mercury field blan k sample in the field because the sample filtration was performed at the laboratory to minimize potential mercury contamination. The laboratory performed a filtration blank prior to filtering the sample, which is assessed as th e field blank for the low-level dissolved mercury sample. Mercury was detected at a concentration of 0.000334 ug/L in the filtration blank; however, this concentration is below the report limit of 0.0005 ug/L. Therefore, this sample result is flagged as a J-value.

### 5-4 100

2 D S D S (%) RPD × ⎟ ⎠ ⎞ ⎜ ⎝ ⎛ + −

= 

### (5-1)

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

result.

During this sampling episode, duplicate sa mples (SP-3) for all analytes (except HEM/SGT-HEM) were collected from the effluent from the FGD Wastewat er Treatment System (SP-2). Table 5-2 presents an alytical results and the RPD for SP-2 and SP-3 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 si gnificant digits. Appendix Tables A-3 and A-4 present all the analytical results for the F GD effluent and FGD effluent duplicate 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).

Table 5-1. Field Blank Results Measured Above the Report Limit, Big Bend

Analyte Sample Point Method Unit Concentration (ug/L)

Routine Total Metals

Calcium FGD Effluent 200.7 UG/L 863

Magnesium FGD Effluent 200.7 UG/L 750

Routine Dissolved Metals

Boron FGD Effluent 200.7 UG/L 2,430

Calcium FGD Effluent 200.7 UG/L 20,200

Magnesium FGD Effluent 200.7 UG/L 17,800

Sodium FGD Effluent 200.7 UG/L 8,730

Low-Level Dissolved Metals

Chromium FGD Effluent 1638 UG/L 2.15

Copper FGD Effluent 1638 UG/L 1.11

Hexavalent Chromium FGD Effluent 1636 UG/L 6.27

Zinc FGD Effluent 1638 UG/L 0.650

### 5-5> – Result above measurement range.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).Table 5-2. Field Duplicate Results, Big BendAnalyteOriginal FGD EffluentConcentrationDuplicate FGD EffluentConcentrationAverage ResultRelative PercentDifference (%)UnitsClassical PollutantsAmmonia As Nitrogen (NH3-N)23.924.224.11.2MG/LTotal Kjeldahl Nitrogen (TKN)10295.398.76.8MG/LBiochemical Oxygen Demand(BOD)1,440>2,000>1,72033MG/LChloride22,00023,00022,5004.4MG/LHexane Extractable Material(HEM)6.00NA 6.00NCMG/LSilica Gel Treated HEM (SGTHEM)ND (6.00) NA ND (6.00) NC MG/LSulfate1,8202,0201,92010MG/LTotal Dissolved Solids (TDS)40,70040,40040,6000.74MG/LTotal Phosphorus0.3900.3200.35520MG/LTotal Suspended Solids (TSS)42.021.031.567MG/LRoutine Total MetalsAluminumND (50.0)ND (50.0)ND (50.0)NCUG/LAntimony22.3R 21.922.11.8UG/LArsenicNQ (10.0)NQ (10.0)ND (10.0)NCUG/LBarium1,5701,4101,49011UG/LBerylliumNQ (5.00)NQ (5.00)ND (5.00)NCUG/LBoron346,000391,000369,00012UG/LCadmium26.023.724.99.3UG/L

### 5-6> – Result above measurement range.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).Table 5-2. Field Duplicate Results, Big BendAnalyteOriginal FGD EffluentConcentrationDuplicate FGD EffluentConcentrationAverage ResultRelative PercentDifference (%)UnitsCalcium4,210,0004,620,0004,420,0009.3UG/LChromiumNQ (10.0)NQ (10.0)ND (10.0)NCUG/LCobaltNQ (50.0)NQ (50.0)ND (50.0)NCUG/LCopper10.5NQ (10.0)< 10.3NCUG/LIronNQ (100)NQ (100)ND (100)NCUG/LLeadNQ (50.0)NQ (50.0)ND (50.0)NCUG/LMagnesium2,470,0002,550,0002,510,0003.2UG/LManganese63.157.060.110UG/LMercuryND (10.0)ND (10.0)ND (10.0)NCUG/LMolybdenum470R 4294509.1UG/LNickel2312102219.5UG/LSelenium3,020R 2,7902,9107.9UG/LSodium1,530,0001,650,0001,590,0007.5UG/LThallium17.416.216.87.1UG/LTitanium13.713.213.53.7UG/LVanadiumNQ (20.0)NQ (20.0)ND (20.0)NCUG/LYttriumND (5.00)ND (5.00)ND (5.00)NCUG/LZincND (10.0)ND (10.0)ND (10.0)NCUG/LRoutine Dissolved MetalsAluminumND (50.0)ND (50.0)ND (50.0)NCUG/LAntimony21.1T 20.4 20.83.4UG/LArsenic11.1R,T 10.510.85.6UG/L

### 5-7> – Result above measurement range.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).Table 5-2. Field Duplicate Results, Big BendAnalyteOriginal FGD EffluentConcentrationDuplicate FGD EffluentConcentrationAverage ResultRelative PercentDifference (%)UnitsBarium1,4001,4101,4100.71UG/LBerylliumNQ (5.00)NQ (5.00)ND (5.00)NCUG/LBoron401,000392,000397,0002.3UG/LCadmium19.519.119.32.1UG/LCalcium5,180,0005,240,0005,210,0001.2UG/LChromiumNQ (10.0)NQ (10.0)ND (10.0)NCUG/LHexavalent ChromiumND (2.00)ND (2.00)ND (2.00)NCUG/LCobaltNQ (50.0)NQ (50.0)ND (50.0)NCUG/LCopperNQ (10.0)NQ (10.0)ND (10.0)NCUG/LIronNQ (100)NQ (100)ND (100)NCUG/LLeadNQ (50.0)NQ (50.0)ND (50.0)NCUG/LMagnesium2,910,0002,940,0002,930,0001.0UG/LManganese55.655.555.60.18UG/LMercuryND (10.0)ND (10.0)ND (10.0)NCUG/LMolybdenum431T 4294300.47UG/LNickel2102092100.48UG/LSelenium2,860R 2,8602,8600.0 UG/LSodium1,850,0001,910,0001,880,0003.2UG/LThallium14.210.812.527UG/LTitanium13.214.113.76.6UG/LVanadiumNQ (20.0)NQ (20.0)ND (20.0)NCUG/LYttriumND (5.00)ND (5.00)ND (5.00)NCUG/L

### 5-8> – Result above measurement range.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).Table 5-2. Field Duplicate Results, Big BendAnalyteOriginal FGD EffluentConcentrationDuplicate FGD EffluentConcentrationAverage ResultRelative PercentDifference (%)UnitsZincND (10.0)ND (10.0)ND (10.0)NCUG/LLow-Level Total MetalsAntimony14.114.214.20.71UG/LArsenic67.068.968.02.8UG/LCadmium25.725.925.80.78UG/LChromiumNQ (80.0)NQ (80.0)ND (80.0)NCUG/LCopperNQ (20.0)NQ (20.0)ND (20.0)NCUG/LLeadND (5.00)ND (5.00)ND (5.00)NCUG/LMercury0.1540.1570.1561.9UG/LNickel3633993819.4UG/LSelenium2,5002,5002,5000.0UG/LThallium31.031.231.10.64UG/LZincNQ (50.0)NQ (50.0)ND (50.0)NCUG/LLow-Level Dissolved MetalsAntimony13.314.113.75.8UG/LArsenic73.071.772.41.8UG/LCadmium22.122.222.20.45UG/LChromiumNQ (80.0)NQ (80.0)ND (80.0)NCUG/LHexavalent ChromiumND (5.00)ND (5.00)ND (5.00)NCUG/LCopperNQ (20.0)NQ (20.0)ND (20.0)NCUG/LLeadND (5.00)ND (5.00)ND (5.00)NCUG/LMercury0.07080.06680.06885.8UG/L

### 5-9> – Result above measurement range.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).Table 5-2. Field Duplicate Results, Big BendAnalyteOriginal FGD EffluentConcentrationDuplicate FGD EffluentConcentrationAverage ResultRelative PercentDifference (%)UnitsNickel4023903963.0UG/LSelenium2,5602,5502,5600.39UG/LThallium31.331.631.50.95UG/LZincNQ (50.0)NQ (50.0)ND (50.0)NCUG/L

### 6-1 6. R EFERENCES



### 1. Eastern Research Group, Inc., 2007. Sampli ng Plan, Tampa Electric Company’s Big Bend Station. July 10. DCN 04815 A1. EPA-HQ-OW-2006-0071-0630.1.

2. 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.

3. U.S. EPA. 2001. Method 200.7: Trace Elements in Water, Solids, and Biosolids, by Inductively Coupled Plasma-A tomic Emission Spectrometry . Revision 5.0. EPA-821-R01-010. January.

### Appendix A

ANALYTICAL RESULTS

### A-1CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.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.Table A-1. FGD Influent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationClassical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L NA NP NP 31.5Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L NA NP NP 51.6Biochemical Oxygen Demand (BOD) 5210B MG/L 300 NP NP 1,370Chloride 4500-CL-C MG/L NA NP NP 24,200Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP ND (6.00) USulfate D516-90 MG/L NA NP NP 3,590Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 44,600Total Phosphorus 365.3 MG/L NA NP NP 0.990Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 4,970Classical Pollutants – Solid (wet weight)Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/KG 1 NP NP 20.4Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/KG 1 NP NP 319Chloride 4500-CL-C MG/KG 1 NP NP 11,000Sulfate D516-90 MG/KG 50 NP NP 67,600Total Phosphorus 365.3 MG/KG 1 NP NP 39.4Classical Pollutants – Filtered AqueousAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 31.7Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 47.4

### A-2CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.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.Table A-1. FGD Influent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationChloride 4500-CL-C MG/L 50 NP NP 24,500Sulfate D516-90 MG/L 100 NP NP 2,300Total Phosphorus 365.3 MG/L 1 NP NP 0.390Routine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 31,200Antimony 200.7 UG/L 1 0.700 20.0 62.5Arsenic 200.7 UG/L 1 0.500 10.0 75.5Barium 200.7 UG/L 1 0.100 2.00 1,590Beryllium 200.7 UG/L 1 0.500 5.00 12.9Boron 200.7 UG/L 100 270 10,000 626,000Cadmium 200.7 UG/L 1 0.100 5.00 224Calcium 200.7 UG/L 100 510 5,000 6,690,000Chromium 200.7 UG/L 1 0.200 10.0 757Cobalt 200.7 UG/L 1 0.600 50.0 172Copper 200.7 UG/L 1 0.200 10.0 120Iron 200.7 UG/L 1 5.40 100 23,500Lead 200.7 UG/L 1 0.700 50.0 69.1Magnesium 200.7 UG/L 10 89.0 2,000 4,830,000Manganese 200.7 UG/L 10 2.00 150 21,900

### A-3CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.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.Table A-1. FGD Influent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationMercury 245.1 UG/L NA NC 10.0 0.968 CJMolybdenum 200.7 UG/L 1 0.200 10.0 618Nickel 200.7 UG/L 1 1.10 50.0 2,090Selenium 200.7 UG/L 1 0.600 5.00 4,150Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 10 405 5,000 2,530,000Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 9.48 JTitanium 200.7 UG/L 1 0.200 10.0 420Vanadium 200.7 UG/L 1 0.600 20.0 724Yttrium 200.7 UG/L 1 0.200 5.00 245Zinc 200.7 UG/L 1 0.200 10.0 1,540Routine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 33.9Arsenic 200.7 UG/L 1 0.500 10.0 18.6Barium 200.7 UG/L 1 0.100 2.00 1,820Beryllium 200.7 UG/L 1 0.500 5.00 2.60 JBoron 200.7 UG/L 100 270 10,000 618,000

### A-4CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.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.Table A-1. FGD Influent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationCadmium 200.7 UG/L 1 0.100 5.00 179Calcium 200.7 UG/L 100 510 5,000 4,470,000Chromium 200.7 UG/L 1 0.200 10.0 7.84 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 24.0Cobalt 200.7 UG/L 1 0.600 50.0 32.0 JCopper 200.7 UG/L 1 0.200 10.0 27.2Iron 200.7 UG/L 1 5.40 100 16.5 JLead 200.7 UG/L 1 0.700 50.0 6.33 JMagnesium 200.7 UG/L 100 890 20,000 4,110,000Manganese 200.7 UG/L 1 0.200 15.0 9,610Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 581Nickel 200.7 UG/L 1 1.10 50.0 851Selenium 200.7 UG/L 1 0.600 5.00 3,610Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,970,000Thallium 200.7 UG/L 1 0.500 10.0 14.3Tin 200.7 UG/L 1 0.400 30.0 4.89 JTitanium 200.7 UG/L 1 0.200 10.0 12.5

### A-5CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.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.Table A-1. FGD Influent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationVanadium 200.7 UG/L 1 0.600 20.0 108Yttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 16.8Routine Metals – Filtered AqueousMercury 245.1 UG/L 50 2.50 10.0 ND (10.0) URoutine Metals – Solid (wet weight)Mercury 245.5 MG/KG 1 0.00600 0.0200 0.220Routine Metals – Solid (dry weight)Aluminum 200.7 MG/KG NA 2.13 10.1 6,280Antimony 200.7 MG/KG NA 0.141 4.02 5.75Arsenic 200.7 MG/KG NA 0.101 2.01 11.4Barium 200.7 MG/KG NA 0.0201 0.402 ND (0.402) UBeryllium 200.7 MG/KG NA 0.101 1.01 2.07Boron 200.7 MG/KG NA 54.3 2,010 1,610 JCadmium 200.7 MG/KG NA 0.0201 1.01 9.05Calcium 200.7 MG/KG NA 103 1,010 447,000Chromium 200.7 MG/KG NA 0.0402 2.01 151Cobalt 200.7 MG/KG NA 0.121 10.1 28.2Copper 200.7 MG/KG NA 0.0402 2.01 18.7

### A-6CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.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.Table A-1. FGD Influent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationIron 200.7 MG/KG NA 1.09 20.1 4,730Lead 200.7 MG/KG NA 0.141 10.1 12.6Magnesium 200.7 MG/KG NA 179 4,020 145,000Manganese 200.7 MG/KG NA 0.402 30.2 2,470Molybdenum 200.7 MG/KG NA 0.0402 2.01 7.44Nickel 200.7 MG/KG NA 0.221 10.1 249Selenium 200.7 MG/KG NA 0.121 1.01 109Silver 200.7 MG/KG NA 0.0805 4.02 ND (4.02) USodium 200.7 MG/KG NA 815 10,100 113,000Thallium 200.7 MG/KG NA 0.101 2.01 ND (2.01) UTin 200.7 MG/KG NA 0.0805 6.04 ND (6.04) UTitanium 200.7 MG/KG NA 0.0402 2.01 82.0Vanadium 200.7 MG/KG NA 0.121 4.02 124Yttrium 200.7 MG/KG NA 0.0402 1.01 49.3Zinc 200.7 MG/KG NA 0.0402 2.01 306Low-Level Metals – TotalAntimony 1638 UG/L 200 1.40 4.00 24.9Arsenic 1638 UG/L 200 3.04 30.0 165Cadmium 1638 UG/L 200 0.200 20.0 238

### A-7CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.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.Table A-1. FGD Influent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationChromium 1638 UG/L 200 16.6 160 651 LCopper 1638 UG/L 200 0.800 40.0 103Lead 1638 UG/L 200 0.200 10.0 69.9Mercury 1631E UG/L 1,000 0.188 0.500 16.4Nickel 1638 UG/L 200 2.60 200 2,570Selenium 1638 UG/L 200 3.20 200 3,470Silver 1638 UG/L 200 0.400 20.0 ND (20.0) UThallium 1638 UG/L 200 0.0800 4.00 39.8Zinc 1638 UG/L 200 41.8 100 1,870Low-Level Metals – DissolvedAntimony 1638 UG/L 200 1.40 4.00 21.9Arsenic 1638 UG/L 200 3.04 30.0 137Cadmium 1638 UG/L 200 0.200 20.0 190Chromium 1638 UG/L 200 16.6 160 ND (160) UCopper 1638 UG/L 200 0.800 40.0 25.4 JLead 1638 UG/L 200 0.200 10.0 ND (10.0) UMercury 1631E UG/L 100 0.0188 0.0500 0.206Nickel 1638 UG/L 200 2.60 200 1,030Selenium 1638 UG/L 200 3.20 200 3,280

### A-8CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.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.Table A-1. FGD Influent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationSilver 1638 UG/L 200 0.400 20.0 ND (20.0) UThallium 1638 UG/L 200 0.0800 4.00 39.4Zinc 1638 UG/L 200 41.8 100 ND (100) ULow-Level Metals – Solid (dry weight)Antimony 1638 MG/KG NA 0.293 0.837 0.628 JArsenic 1638 MG/KG NA 0.636 6.28 5.86 JCadmium 1638 MG/KG NA 0.0460 4.19 10.0Chromium 1638 MG/KG NA 3.47 33.5 136Copper 1638 MG/KG NA 0.167 8.37 16.2Lead 1638 MG/KG NA 0.0418 2.09 14.6Mercury 1631E MG/KG NA 0.105 0.0393 3.38Nickel 1638 MG/KG NA 0.544 41.8 322Selenium 1638 MG/KG NA 0.667 41.8 39.8 JSilver 1638 MG/KG NA 0.0837 4.19 ND (4.19) UThallium 1638 MG/KG NA 0.0167 0.837 0.0837 JZinc 1638 MG/KG NA 8.75 20.9 391

### A-9 Table A-2. ProChem Biphasic Filtration Blank Analytical Results, Big Bend

Analyte Method Unit Dilution

Factor Sample-Specific

MDL Sample-Specific

RL Concentration

Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) 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-10ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. Number shown in parentheses is the reporting limit).R – MS/MSD % Recovery outside method acceptance criteria.J – Result measured above the MDL, but less than the reporting limit.T – MS/MSD RPD outside method acceptance criteria.Table A-3. FGD Effluent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSampleSpecific MDLSample-Specific RLConcentrationClassical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 23.9Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 102Biochemical Oxygen Demand (BOD) 5210B MG/L 300 NP NP 1,440Chloride 4500-CL-C MG/L 50 NP NP 22,000Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP 6.00Silica Gel Treated HEM (SGT-HEM) 1664A MG/L 1 NP NP ND (6.00) USulfate D516-90 MG/L 50 NP NP 1,820Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 40,700Total Phosphorus 365.3 MG/L 1 NP NP 0.390Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 42.0Routine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 22.3 RArsenic 200.7 UG/L 1 0.500 10.0 9.73 JBarium 200.7 UG/L 1 0.100 2.00 1,570Beryllium 200.7 UG/L 1 0.500 5.00 1.80 JBoron 200.7 UG/L 100 270 10,000 346,000Cadmium 200.7 UG/L 1 0.100 5.00 26.0Calcium 200.7 UG/L 100 510 5,000 4,210,000Chromium 200.7 UG/L 1 0.200 10.0 1.31 JCobalt 200.7 UG/L 1 0.600 50.0 3.05 J

### A-11ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. Number shown in parentheses is the reporting limit).R – MS/MSD % Recovery outside method acceptance criteria.J – Result measured above the MDL, but less than the reporting limit.T – MS/MSD RPD outside method acceptance criteria.Table A-3. FGD Effluent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSampleSpecific MDLSample-Specific RLConcentrationCopper 200.7 UG/L 1 0.200 10.0 10.5Iron 200.7 UG/L 1 5.40 100 57.4 JLead 200.7 UG/L 1 0.700 50.0 4.97 JMagnesium 200.7 UG/L 100 890 20,000 2,470,000Manganese 200.7 UG/L 1 0.200 15.0 63.1Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 470 RNickel 200.7 UG/L 1 1.10 50.0 231Selenium 200.7 UG/L 1 0.600 5.00 3,020 RSilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,530,000Thallium 200.7 UG/L 1 0.500 10.0 17.4Tin 200.7 UG/L 1 0.400 30.0 3.48 RTitanium 200.7 UG/L 1 0.200 10.0 13.7Vanadium 200.7 UG/L 1 0.600 20.0 9.64 RYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) URoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 21.1 TArsenic 200.7 UG/L 1 0.500 10.0 11.1 R,TBarium 200.7 UG/L 1 0.100 2.00 1,400

### A-12ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. Number shown in parentheses is the reporting limit).R – MS/MSD % Recovery outside method acceptance criteria.J – Result measured above the MDL, but less than the reporting limit.T – MS/MSD RPD outside method acceptance criteria.Table A-3. FGD Effluent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSampleSpecific MDLSample-Specific RLConcentrationBeryllium 200.7 UG/L 1 0.500 5.00 1.81 JBoron 200.7 UG/L 100 270 10,000 401,000Cadmium 200.7 UG/L 1 0.100 5.00 19.5Calcium 200.7 UG/L 100 510 5,000 5,180,000Chromium 200.7 UG/L 1 0.200 10.0 1.24 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 2.30 JCopper 200.7 UG/L 1 0.200 10.0 7.82 JIron 200.7 UG/L 1 5.40 100 44.6 JLead 200.7 UG/L 1 0.700 50.0 3.96 JMagnesium 200.7 UG/L 100 890 20,000 2,910,000Manganese 200.7 UG/L 1 0.200 15.0 55.6Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 431 TNickel 200.7 UG/L 1 1.10 50.0 210Selenium 200.7 UG/L 1 0.600 5.00 2,860 RSilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,850,000Thallium 200.7 UG/L 1 0.500 10.0 14.2Tin 200.7 UG/L 1 0.400 30.0 2.84 JTitanium 200.7 UG/L 1 0.200 10.0 13.2Vanadium 200.7 UG/L 1 0.600 20.0 8.38 J

### A-13ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. Number shown in parentheses is the reporting limit).R – MS/MSD % Recovery outside method acceptance criteria.J – Result measured above the MDL, but less than the reporting limit.T – MS/MSD RPD outside method acceptance criteria.Table A-3. FGD Effluent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSampleSpecific MDLSample-Specific RLConcentrationYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) ULow-Level Metals – TotalAntimony 1638 UG/L 100 0.700 2.00 14.1Arsenic 1638 UG/L 100 1.52 15.0 67.0Cadmium 1638 UG/L 100 0.100 10.0 25.7Chromium 1638 UG/L 100 8.30 80.0 35.7 JCopper 1638 UG/L 100 0.400 20.0 13.8 JLead 1638 UG/L 100 0.100 5.00 ND (5.00) UMercury 1631E UG/L 1 0.000188 0.000500 0.154Nickel 1638 UG/L 100 1.30 100 363Selenium 1638 UG/L 100 1.60 100 2,500Silver 1638 UG/L 100 0.200 10.0 2.07 JThallium 1638 UG/L 100 0.0400 2.00 31.0Zinc 1638 UG/L 100 20.9 50.0 34.1 JLow-Level Metals – DissolvedAntimony 1638 UG/L 100 0.700 2.00 13.3Arsenic 1638 UG/L 100 1.52 15.0 73.0Cadmium 1638 UG/L 100 0.100 10.0 22.1Chromium 1638 UG/L 100 8.30 80.0 29.0 JHexavalent Chromium 1636 UG/L 10 3.50 5.00 ND (5.00) UCopper 1638 UG/L 100 0.400 20.0 13.6 J

### A-14ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. Number shown in parentheses is the reporting limit).R – MS/MSD % Recovery outside method acceptance criteria.J – Result measured above the MDL, but less than the reporting limit.T – MS/MSD RPD outside method acceptance criteria.Table A-3. FGD Effluent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSampleSpecific MDLSample-Specific RLConcentrationLead 1638 UG/L 100 0.100 5.00 ND (5.00) UMercury 1631E UG/L 1 0.000188 0.000500 0.0708Nickel 1638 UG/L 100 1.30 100 402Selenium 1638 UG/L 100 1.60 100 2,560Silver 1638 UG/L 100 0.200 10.0 2.92 JThallium 1638 UG/L 100 0.0400 2.00 31.3Zinc 1638 UG/L 100 20.9 50.0 31.0 J

### A-15> – Result above measurement range.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.Table A-4. Duplicate of FGD Effluent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 24.2Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 95.3Biochemical Oxygen Demand (BOD) 5210B MG/L 300 NP NP >2,000Chloride 4500-CL-C MG/L 50 NP NP 23,000Sulfate D516-90 MG/L 50 NP NP 2,020Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 40,400Total Phosphorus 365.3 MG/L 1 NP NP 0.320Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 21.0Routine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 21.9Arsenic 200.7 UG/L 1 0.500 10.0 9.01 JBarium 200.7 UG/L 1 0.100 2.00 1,410Beryllium 200.7 UG/L 1 0.500 5.00 1.77JBoron 200.7 UG/L 100 270 10,000 391,000Cadmium 200.7 UG/L 1 0.100 5.00 23.7Calcium 200.7 UG/L 100 510 5,000 4,620,000Chromium 200.7 UG/L 1 0.200 10.0 1.49 JCobalt 200.7 UG/L 1 0.600 50.0 2.68 JCopper 200.7 UG/L 1 0.200 10.0 8.56 JIron 200.7 UG/L 1 5.40 100 54.7 JLead 200.7 UG/L 1 0.700 50.0 2.97 JMagnesium 200.7 UG/L 100 890 20,000 2,550,000Manganese 200.7 UG/L 1 0.200 15.0 57.0

### A-16> – Result above measurement range.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.Table A-4. Duplicate of FGD Effluent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationMercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 429Nickel 200.7 UG/L 1 1.10 50.0 210Selenium 200.7 UG/L 1 0.600 5.00 2,790Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,650,000Thallium 200.7 UG/L 1 0.500 10.0 16.2Tin 200.7 UG/L 1 0.400 30.0 2.08 JTitanium 200.7 UG/L 1 0.200 10.0 13.2Vanadium 200.7 UG/L 1 0.600 20.0 8.09 JYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) URoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 20.4Arsenic 200.7 UG/L 1 0.500 10.0 10.5Barium 200.7 UG/L 1 0.100 2.00 1,410Beryllium 200.7 UG/L 1 0.500 5.00 1.76 JBoron 200.7 UG/L 100 270 10,000 392,000Cadmium 200.7 UG/L 1 0.100 5.00 19.1Calcium 200.7 UG/L 100 510 5,000 5,240,000Chromium 200.7 UG/L 1 0.200 10.0 1.24 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 2.61 JCopper 200.7 UG/L 1 0.200 10.0 7.77 J

### A-17> – Result above measurement range.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.Table A-4. Duplicate of FGD Effluent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationIron 200.7 UG/L 1 5.40 100 41.5 JLead 200.7 UG/L 1 0.700 50.0 4.74 JMagnesium 200.7 UG/L 100 890 20,000 2,940,000Manganese 200.7 UG/L 1 0.200 15.0 55.5Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 429Nickel 200.7 UG/L 1 1.10 50.0 209Selenium 200.7 UG/L 1 0.600 5.00 2,860Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,910,000Thallium 200.7 UG/L 1 0.500 10.0 10.8Tin 200.7 UG/L 1 0.400 30.0 3.38 JTitanium 200.7 UG/L 1 0.200 10.0 14.1Vanadium 200.7 UG/L 1 0.600 20.0 8.53 JYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) ULow-Level Metals – TotalAntimony 1638 UG/L 100 0.700 2.00 14.2Arsenic 1638 UG/L 100 1.52 15.0 68.9Cadmium 1638 UG/L 100 0.100 10.0 25.9Chromium 1638 UG/L 100 8.30 80.0 38.5 JCopper 1638 UG/L 100 0.400 20.0 13.5 JLead 1638 UG/L 100 0.100 5.00 ND (5.00) UMercury 1631E UG/L 1 0.000188 0.000500 0.157Nickel 1638 UG/L 100 1.30 100 399

### A-18> – Result above measurement range.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.U – Result below the MDL. Number shown in parentheses is the reporting limit).J – Result measured above the MDL, but less than the reporting limit.Table A-4. Duplicate of FGD Effluent Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationSelenium 1638 UG/L 100 1.60 100 2,500Silver 1638 UG/L 100 0.200 10.0 3.74 JThallium 1638 UG/L 100 0.0400 2.00 31.2Zinc 1638 UG/L 100 20.9 50.0 31.8 JLow-Level Metals – DissolvedAntimony 1638 UG/L 100 0.700 2.00 14.1Arsenic 1638 UG/L 100 1.52 15.0 71.7Cadmium 1638 UG/L 100 0.100 10.0 22.2Chromium 1638 UG/L 100 8.30 80.0 41.2 JHexavalent Chromium 1636 UG/L 10 3.50 5.00 ND (5.00) UCopper 1638 UG/L 100 0.400 20.0 12.5 JLead 1638 UG/L 100 0.100 5.00 ND (5.00) UMercury 1631E UG/L 1 0.000188 0.000500 0.0668Nickel 1638 UG/L 100 1.30 100 390Selenium 1638 UG/L 100 1.60 100 2,550Silver 1638 UG/L 100 0.200 10.0 2.10 JThallium 1638 UG/L 100 0.0400 2.00 31.6Zinc 1638 UG/L 100 20.9 50.0 35.3 JND – Not detected (number in parenthesis is the report limit).



### A-19 Table A-5. Bottle Blank and Equipmen t Blank Analytical Data, Big Bend

Analyte Method Process Units Concentration

LDPE 1000 ml Plastic Bottles – Bottl e Blank (for low-level metals 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)

LDPE 500 ml Plastic Bottles – Bottle Blank (for 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)ND – Not detected (number in parenthesis is the report limit).



### A-20 Table A-5. Bottle Blank and Equipmen t Blank Analytical Data, Big Bend

Analyte Method Process Units Concentration

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)

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

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

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

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

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

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)ND – Not detected (number in parenthesis is the report limit).



### A-21 Table A-5. Bottle Blank and Equipmen t Blank Analytical Data, Big Bend

Analyte Method Process Units Concentration

Zinc EPA 1638 Dissolved UG/L ND (0.50)

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

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

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

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

LDPE 10 L Composite Bottles – Bottle Blank (sample composite bottle for dissolved/filtration pump-off)

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



### A-22 Table A-5. Bottle Blank and Equipmen t Blank Analytical Data, Big Bend

Analyte Method Process Units Concentration

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Pump-Off Tubing Set – Equipment Bl ank (Teflon® and 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 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)

C-Flex Tubing Set – Equi pment Blank (silicone tubing for sample collection for low-level mercury and metals from sample taps)

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



### A-23 Table A-5. Bottle Blank and Equipmen t Blank Analytical Data, Big Bend

Analyte Method Process Units Concentration

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-24ND – Not detected (number in parenthesis is the report limit).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.Table A-6. FGD Influent Field Blank Analytical Data, Big BendAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationLow-Level Metals – TotalAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND (0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.198 JCopper 1638 UG/L 1 0.00400 0.200 ND (0.200) ULead 1638 UG/L 1 0.00100 0.0500 ND (0.0500) UMercury 1631E UG/L 1 0.000188 0.000500 0.000268 JNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 ND (0.100) UThallium 1638 UG/L 1 0.000400 0.0200 ND (0.0200) UZinc 1638 UG/L 1 0.209 0.500 ND (0.500) ULow-Level Metals – DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 0.00430 JChromium 1638 UG/L 1 0.0830 0.800 ND (0.800) UCopper 1638 UG/L 1 0.00400 0.200 0.0651 JLead 1638 UG/L 1 0.00100 0.0500 0.00360 JNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 0.0643 JSilver 1638 UG/L 1 0.00200 0.100 0.00270 JThallium 1638 UG/L 1 0.000400 0.0200 0.000500 JZinc 1638 UG/L 1 0.209 0.500 ND (0.500) U

### A-25ND – Not detected (number in parenthesis is the report limit).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).Table A-7. FGD Effluent Field Blank Analytical Data, Big BendAnalyteMethodUnitDilution FactorSampleSpecific MDLSample-SpecificRLConcentrationRoutine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 ND (20.0) UArsenic 200.7 UG/L 1 0.500 10.0 ND (10.0) UBarium 200.7 UG/L 1 0.100 2.00 ND (2.00) UBeryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 90.9 JCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 863Chromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND (10.0) UIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 750Manganese 200.7 UG/L 1 0.200 15.0 ND (15.0) UMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 ND (10.0) UNickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND (5.00) USilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 360 JThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) U

### A-26ND – Not detected (number in parenthesis is the report limit).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).Table A-7. FGD Effluent Field Blank Analytical Data, Big BendAnalyteMethodUnitDilution FactorSampleSpecific MDLSample-SpecificRLConcentrationYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) URoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 ND (20.0) UArsenic 200.7 UG/L 1 0.500 10.0 ND (10.0) UBarium 200.7 UG/L 1 0.100 2.00 ND (2.00) UBeryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 2,430Cadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 20,200Chromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND (10.0) UIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 17,800Manganese 200.7 UG/L 1 0.200 15.0 0.345 JMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 ND (10.0) UNickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND (5.00) USilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 8,730Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) U

### A-27ND – Not detected (number in parenthesis is the report limit).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).Table A-7. FGD Effluent Field Blank Analytical Data, Big BendAnalyteMethodUnitDilution FactorSampleSpecific MDLSample-SpecificRLConcentrationTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) UYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 0.310 JLow-Level Metals – TotalAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND (0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.254 JCopper 1638 UG/L 1 0.00400 0.200 0.0102 JLead 1638 UG/L 1 0.00100 0.0500 0.00150 JMercury 1631E UG/L 1 0.000188 0.000500 0.000291 JNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 0.00280 JThallium 1638 UG/L 1 0.000400 0.0200 ND (0.0200) UZinc 1638 UG/L 1 0.209 0.500 0.221 JLow-Level Metals – DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 0.0183 JArsenic 1638 UG/L 1 0.0152 0.150 0.0711 JCadmium 1638 UG/L 1 0.00100 0.100 0.0152 JChromium 1638 UG/L 1 0.0830 0.800 2.15Hexavalent Chromium 1636 UG/L 5 1.75 2.50 6.27Copper 1638 UG/L 1 0.00400 0.200 1.11Lead 1638 UG/L 1 0.00100 0.0500 0.0162 J

### A-28ND – Not detected (number in parenthesis is the report limit).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).Table A-7. FGD Effluent Field Blank Analytical Data, Big BendAnalyteMethodUnitDilution FactorSampleSpecific MDLSample-SpecificRLConcentrationNickel 1638 UG/L 1 0.0130 1.00 0.0696 JSelenium 1638 UG/L 1 0.0160 1.00 0.956 JSilver 1638 UG/L 1 0.00200 0.100 0.0390 JThallium 1638 UG/L 1 0.000400 0.0200 0.00410 JZinc 1638 UG/L 1 0.209 0.500 0.650

### Appendix B

ANALYTICAL DATA FOR METALS, FGD WASTEWATER

### B-1CJ – 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 thesample fraction analyticalresults (i.e., filtered aqueous and/or filtered solid concentration)was measured above the method detection limit, and the calculated total sampleconcentration is less than the calculated sample-specific report limit.L – Sample result between5x and 10x blank result.J - Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD 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 Resultsfor Metals in the FGD Wastewater Treatment System, Big BendFGD Influent (SP-1)Original FGD Effluent (SP-2)Duplicate FGD Effluent (SP-3)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedRoutine MetalsAluminum 200.7 UG/L 31,200 ND (50.0) U ND (50.0) U ND (50.0) U ND (50.0) U ND (50.0) UAntimony 200.7 UG/L 62.5 33.9 22.3 R 21.1 T 21.920.4Arsenic 200.7 UG/L 75.5 18.69.73 J 11.1 R,T 9.01 J 10.5Barium 200.7 UG/L 1,590 1,8201,570 1,400 1,410 1,410Beryllium 200.7 UG/L 12.92.60 J 1.80 J 1.81 J 1.77J 1.76 JBoron 200.7 UG/L 626,000 618,000 346,000401,000 391,000 392,000Cadmium 200.7 UG/L 224 17926.0 19.5 23.7 19.1Calcium 200.7 UG/L 6,690,000 4,470,000 4,210,000 5,180,000 4,620,0005,240,000Chromium 200.7 UG/L 757 7.84J 1.31 J 1.24 J 1.49 J 1.24 JHexavalent Chromium D1687-92 UG/L NA 24.0 NA ND (2.00) U NA ND (2.00) UCobalt 200.7 UG/L 172 32.0 J3.05 J 2.30 J 2.68 J 2.61 JCopper 200.7 UG/L 120 27.210.5 7.82 J 8.56 J 7.77 JIron 200.7 UG/L 23,500 16.5 J57.4 J 44.6 J 54.7 J 41.5 JLead 200.7 UG/L 69.1 6.33 J4.97 J 3.96 J 2.97 J 4.74 JMagnesium 200.7 UG/L 4,830,000 4,110,000 2,470,000 2,910,000 2,550,000 2,940,000Manganese 200.7 UG/L 21,900 9,61063.1 55.6 57.0 55.5Mercury 245.1 UG/L 0.968 CJ ND (10.0) U ND (10.0) U ND (10.0) U ND (10.0) U ND (10.0) UMolybdenum 200.7 UG/L 618 581 470 R 431 T 429 429Nickel 200.7 UG/L 2,090 851 231 210 210 209Selenium 200.7 UG/L 4,150 3,6103,020 R 2,860 R 2,790 2,860Silver 200.7 UG/L ND (20.0) U ND (20.0) U ND (20.0) U ND (20.0) U ND(20.0) U ND (20.0) U

### B-2CJ – 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 thesample fraction analyticalresults (i.e., filtered aqueous and/or filtered solid concentration)was measured above the method detection limit, and the calculated total sampleconcentration is less than the calculated sample-specific report limit.L – Sample result between5x and 10x blank result.J - Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD 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 Resultsfor Metals in the FGD Wastewater Treatment System, Big BendFGD Influent (SP-1)Original FGD Effluent (SP-2)Duplicate FGD Effluent (SP-3)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedSodium 200.7 UG/L 2,530,000 1,970,0001,530,000 1,850,0001,650,000 1,910,000Thallium 200.7 UG/L ND (10.0) U14.3 17.4 14.2 16.2 10.8Tin 200.7 UG/L 9.48 J 4.89 J3.48 R 2.84 J 2.08 J 3.38 JTitanium 200.7 UG/L 420 12.513.7 13.2 13.2 14.1Vanadium 200.7 UG/L 724 1089.64 R 8.38 J 8.09 J 8.53 JYttrium 200.7 UG/L 245 ND (5.00) U ND (5.00)U ND (5.00) U ND (5.00) U ND (5.00) UZinc 200.7 UG/L 1,540 16.8 ND (10.0) UND (10.0) U ND (10.0) U ND (10.0) ULow-Level MetalsAntimony 1638 UG/L 24.9 21.9 14.1 13.314.2 14.1Arsenic 1638 UG/L 165 137 67.0 73.0 68.9 71.7Cadmium 1638 UG/L 238 190 25.7 22.125.9 22.2Chromium 1638 UG/L 651 L ND (160)U 35.7 J 29.0 J 38.5 J 41.2 JHexavalent Chromium 1636 UG/L NA NANA ND (5.00) U NA ND (5.00) UCopper 1638 UG/L 103 25.4 J 13.8 J 13.6 J 13.5 J 12.5 JLead 1638 UG/L 69.9 ND (10.0) U ND (5.00)U ND (5.00) U ND (5.00) U ND (5.00) UMercury 1631E UG/L 16.4 0.2060.154 0.0708 0.157 0.0668Nickel 1638 UG/L 2,570 1,030 363 402 399 390Selenium 1638 UG/L 3,470 3,2802,500 2,560 2,500 2,550Silver 1638 UG/L ND (20.0) U ND (20.0) U 2.07 J 2.92 J 3.74 J 2.10 JThallium 1638 UG/L 39.8 39.431.0 31.3 31.2 31.6Zinc 1638 UG/L 1,870 ND (100)U 34.1 J 31.0 J 31.8 J 35.3 J

### Appendix C

DATA REVIEW NARRATIVESComputer Sciences Corporation

www.csc.com

6101 Stevenson Avenue Alexandria, Virginia 22304

703.461.2000 Fax 703.461.2020 

### MEMORANDUM

DATE: December 5, 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 Study, Episode 6547

OVERVIEW

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

data for four samples in Episode 6547. Sample 70320, identified as FGD influent, was expected to contain a significant and variable particulate con centration. 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, for some classical analyses (those with a phase listed in Table 1) , the laboratory was directed by EPA to separate the FGD influent sample into an aqueous-phase a nd a solid-phase and analyze each. The two sets of results (filtered aqueous and filtered solid phases) are provided in the analytical database, as are calculated total results (derived by combining filtered aqueous and filte red solid phase results).

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

Table 1 - Sample Identifiers, Descri ptions, Sampling Dates and Analytes

EPA Sample # Matrix Sample Description Sampling

Date Phase Analytes

70320 Aqueous SP-1 – FGD Influent 7/25/07 NA BOD (SM 5210B), HEM (1664A), SGT-HEM (1664A), Hexavalent Chromium (ASTM D1687- 92), TSS (SM 2540D), and TDS (SM 2540C)

70320 Aqueous SP-1 – FGD Influent 7/25/07 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)

70320 Aqueous SP-1 – FGD Influent 7/25/07 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)2 Table 1 - Sample Identifiers, Descri ptions, Sampling Dates and Analytes

EPA Sample # Matrix Sample Description Sampling

Date Phase Analytes

70320 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)

70321 Aqueous SP-2 – FGD

Effluent 7/25/07 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), 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)

70322 Aqueous SP-3 – FGD Effluent Duplicate 7/25/07 NA BOD (SM 5210B),

Hexavalent Chromium (ASTM D1687-92), 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)

70324 Aqueous SP-4 – FGD

Effluent Field Blank 7/25/07 NA Hexavalent Chromium (ASTM D1687-92)

NA= Not Applicable. In the Phase column, only one result exists in the EPA database for this sample/analyte

combination.



### 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. All data are of acceptable quality with th e qualifiers described below and detailed in the data review summary table (Table 2).

SUMMARY

All samples were analyzed within the contract-sp ecified holding times for all classical wet chemistry parameters as directed on the accompanying traffic reports, except for Nitrate/Nitrite analysis. Nitrate/Nitrite analysis was requested for sampl es 70320 filtered solid and f iltered aqueous phases, 70321,

and 70322. Data were not subm itted due to instrument failure.3 

### The calibration and continuing calibration standards were successfully analyzed. Laboratory blanks were performed for each analysis, and there was no contam ination detected above the laboratory reporting limits with the exception of the samples described be low. An effluent field blank was analyzed for hexavalent chromium and the analyte was not detect ed above the ML. 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 exception of the samples described below.

DATA ISSUES

SGT-HEM

The MS and MSD recoveries for sample 70321 were 161% and 176% respectively, above the contract acceptance criteria range of 64-132%. Because the sa mple result was a non-detect respectively, the high bias did not affect the data; CSC considers the sa mple result to be considered acceptable without qualification.

The OPR recovery (170%) associated with sample 70321 was above the contract acceptance criteria range of 64-132%. The sample result was a non-detect, theref ore the high recovery does not affect the data; the sample result is considered acceptable without qualification.

TKN

TKN was detected in the laboratory preparation blank at a concentration of 0.17 mg/L, which is greater than the ML of .1 mg/L. The TKN results for the sam ples are greater than ten times the preparation blank result. Because the presence of the an alyte in the blank does not adversely affect the data when the result is greater than ten times the associated blank, the TK N data are acceptable without qualification for the following associated samples: 70320 filtered aque ous and filtered solid phases, 70321, and 70322.

TSS

The TSS result for the FGD effluent sample 70321 was 42 mg/L. The laboratory duplicate result for this sample was 21 mg/L. The relative percent differen ce (RPD) value for sample 70321 and the duplicate is 66.7%, which is above the contract acceptance cr iteria of 20%. A reanalysis for sample 70321 was performed with similar results confirming the initial analysis. CSC believes that this difference was caused by the fact that the laboratory performed the initial and duplicate analyses from different bottles. Based on the high RPD, CSC considers the TSS result fo r sample 70321 to be an estimated value.

BOD

The field duplicate effluent sample 70322 BOD resu lt was > 2000 mg/L, due to insufficient sample

dilution. CSC recommends that the value be qualified as a minimum in the EPA database.

The BOD sample result for the effluent sample 70321 was 1440 mg/L. The laboratory duplicate result for this sample was > 2000 mg/L (again, a minimum due to insufficient dilution). The RPD for sample 70321 and the laboratory duplicate is > 32%, which is above the contract acceptance criteria of 20%; the field duplicate result+ would indicate a similar high RPD. Based on this, CSC recommends that the BOD result for sample 70321 be considered an estimated value.4 

### Field Duplicate

The RPD between samples 70321 (FGD effluent) and 70322 (FGD effluent duplicate) for the following analytes were: BOD (33%), total phosphorus (22% ) and TSS (67%). CSC does not routinely qualify results based on field duplicate RPD.

TECHNICAL NOTES

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 In fluent sample using the following formula:

Several variables were not recorded by the labor atory 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, and the solid phase wei ght. This series of calculations are as follows and detailed in the phase separation data elements table (Table 3):

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

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

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

In generating the classicals “Calculated Total” resu lts 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. Ne gative values submitted by the laboratory were not used

in the calculations.

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

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

sample original phase solid phase solid Filtrate Filtrate × +

=5 

### 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 laboratory was asked to provide separate percent solids measurements for each sample bottle that was phase-separated. However, because th is request was received after samp le analysis was initiated, the laboratory was unable to measure a valid percent solid s for the Group 2 bottle. In Table 3, the percent solid result is provided for the Group 1 bottle to conver t solid phase wet weight basis values to dry weight results, and was 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 Marla Smith, EPA Brian Englert, EPA Beverly Randolph, EPA Nelson Andrews, EPA Deb Bartram, ERG TJ Finseth, ERG 

### Lynn Walters, CSC Barbara Beard, CSC

Table 2 Data Review Summary Table

Episode: 6547 Analysis: Classicals

Industry: Steam Electric Study Reviewer: Sara Clark

Sample Analyte Action Reason CSC Qual Level

70321 TSS Estimated value RPD exceeds the contract-specified

criteria NA 42 mg/L

70321 BOD Estimated value RPD exceeds the contract-specified

criteria NA 1440 mg/L

70322 BOD Minimum value Result above

measurement range > 2000 mg/L

NA= Not Applicable6 

### Table 3 Phase Separation Data Elements

Episode: 6547 Analysis: Classicals

Industry: Steam Electric Study Reviewer: Sara Clark

Group number I II

Sample number 70320 70320

Original sample vol (mL) 928 a 952 a

Net weight of solid phase on the filter (g) 18.33 14.75

Density (g/mL) 1.0022 1.0022

Original sample weight (g) 930 954

Filtrate weight (g) 912 a 939 a

Filtrate volume (mL) 910 a 937 a

Percent Solid (of solid phase) (%) 45.4 NA

a 

### Derived value. Calculated using lab measured results (if available), or otherwise estimated NA: Not applicableComputer Sciences Corporation

www.csc.com

6101 Stevenson Avenue Alexandria, Virginia 22304

703.461.2000 Fax 703.461.2020 

### MEMORANDUM

DATE: December 5, 2007

TO: Ron Jordan, Work Assignment Manager

EPA EAD

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

SUBJECT: Data Review Narrative for Total and Dissolv ed Metals Analyses for the Steam Electric Study, Episode 6547

Under EPA contract number 68-C-03-0 44, ProChem Analytical submitted da ta for the analysis of metals by EPA Method 200.7 and mercury by Method 245.1. Four aqueous samples in this episode were analyzed for total and dissolved metals. Sample 70320, identified as FGD influent, was expected to contain a significant and variable particulate con centration. 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) le ad to analytical interferences. Therefore the laboratory was directed by EPA to separate the FGD influent sample into an aqueous-phase and a solidphase, and analyze each for 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, desc riptions, sampling dates, phases, and the required analytical methods.

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

EPA Sample # Matrix Sample Description Sampling

Date Phase Methods

7/25/2007 Dissolved 200.7, 245.1

7/25/2007 Filtered Solid 7/25/2007 Filtered Aqueous 70320 Aqueous FGD Influent

NA Calculated Total 245.1

Dissolved 70321 Aqueous FGD Effluent 7/25/2007 Total 200.7, 245.1

Dissolved

70322 Aqueous FGD Effluent-Duplicate 7/25/2007 Total 200.7, 245.1

Dissolved 70324 Aqueous FGD Effluent-Field Blank 7/25/2007 Total 200.7, 245.1

NA= Not applicable



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

### SUMMARY

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

criteria.

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

issues described below and summarized in Table 2. The MS/MSD analyses were performed on the total and dissolved fractions of sample 70321.

DATA ISSUES

Method and Analytical Blanks

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

follows:

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

detail.

ML Standards

The recovery of mercury (135%) in the aqueous minimu m level standard was above the contract-specified criteria of 120%. However, because mercury was not det ected in any of the samples in this episode, CSC considers the results to be unaffected by this potential high recovery.

Quarterly Quality Control Samples (QCS)

The recovery of calcium (106%) in the quarterly qual ity control sample (QCS) was marginally above the contract-specified criteria (95-105%). The QCS r ecovery of nickel (94%) and thallium (94%) were slightly below the contract-specified criteria (95- 105%). However, because the OPR and CCVs were all within contract specified criteria, and they are each prepared from separate standard sources, CSC recommends that sample data be included in the database without qualification.

Field Duplicate

The relative percent difference (R PD) between samples 70322 (FGD effluent duplicate) and 70321 (FGD effluent) for dissolved thallium was 27%. CSC does not routinely qualify results based on field duplicate

RPD.3 

### Matrix Performance

The relative percent difference (RPD) between the matr ix spike and matrix spik e duplicate for dissolved cadmium (21%) in sample 70321 was marginally above th e contract-specified acceptance criteria of 20%.

CSC considers the result for dissolved cadmium in sample 70321 to be of acceptable quality.

The MS recovery of dissolved antimony (133%) and molybdenum (135%) in sample 70321 were above the contract-specified acceptance criteria of 125% . The MSD recovery of dissolved antimony (162%) and molybdenum (255%) in sample 70321 were also above the acceptance criteria. CSC recommends that the results for dissolved antimony and molybd enum in sample 70321 be considered of acceptable quality but may be maximum values.

The MS recovery of dissolved arsenic (140%) in sample 70321 was above the contract-specified acceptance criteria of 125%. The related MSD recove ry (177%) and RPD (22%) were also above the acceptance criteria. CSC recommends that the result fo r dissolved arsenic in sample 70321 be considered

an estimated value.

The MS recovery of dissolved yttrium (37%) in sample 70321 was below the contract-specified acceptance criteria of 75%. The related MSD r ecovery (135%) and RPD (114%) were above the acceptance criteria. Because dissolved yttrium was not detected, CSC recommends that the result in sample 70321 be included in the database without qualification.

The MS recovery of dissolved selenium (126%) in sample 70321 was marginally above the contractspecified criteria of 125%. CSC recommends that th e result for dissolved selenium in sample 70321 be considered of acceptable quality but may be a maximum value.

The MS recovery of dissolved aluminum (112%) in sample 70321 was within the contract-specified criteria of 75-125%. The related MSD recovery (6 1%) was below the acceptance criteria. The RPD (60%) between the MS and MSD was above the 20% criteria. Since dissolved aluminum was not detected, CSC recommends that the result for alumi num in sample 70321 be included in the database without qualification.

The MS recoveries of total antimony (139%) and arsenic (146%) in sample 70321 were above the contract-specified acceptance criteria of 125%. The MSD recoveries of total antimony (129%) and arsenic (134%) in sample 70321 were also above the acceptance criteria. Since total arsenic was not detected, CSC recommends that the result in sam ple 70321 be included in the database without qualification. CSC recommends that the total antimony result in sample 70321 be considered of acceptable quality but may be a maximum value.

The MS recovery of total molybdenum (102%) in sample 70321 was within the contract-specified acceptance criteria of 75-125%. The related MSD rec overy (69%) was below the acceptance criteria. The RPD (6%) between the MS and MSD was within the c ontract-specified criteria. CSC recommends that the result for total molybdenum in sample 70321 be considered a minimum value.

The MS recovery of total selenium (123%) in samp le 70321 was within the co ntract-specified acceptance criteria of 75-125%. The related MSD recovery (131%) was above the acceptance criteria. CSC

recommends that the result for total selenium in sample 70321 be considered a maximum value.4 

### Serial Dilutions

The serial dilution percent differences for dissolv ed copper in sample 70321 (55%) and total copper (22%) were above the contract-specified criteria of 10%. However, the MS/MSD recoveries were within the criteria for both total and dissolved copper. CSC does not qualify sample data based on serial dilution

results alone and believes that no further action is required

.



### Field Blanks/Filter Blanks

Boron, calcium, magnesium, and sodium were detected in the dissolved field filter blank sample (70324) at concentrations greater than the contract-speci fied MLs. Calcium and magnesium were the only two analytes detected in the total field filter blank (7 0324). Per EPA request, CSC does not qualify sample

data or results based on field and filter blanks results.

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

The laboratory failed to provide those items listed in bold above.

CSC calculated the total result for the FGD In fluent sample using the following formula:

Since the laboratory provided only the solid-phase wei ght, CSC estimated the original sample volume to be 500 mL, based on the bottle size, and because the la boratory reported that the bottles were full upon receipt. The filtrate volume was calculated using this estimated original volume, solid-phase weight, and the density of the original sample measured by the la boratory. This series of calculations are as follows and detailed in the phase separation data elements table (Table 3):

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

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

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

As a result, calculated total data for mercury will be qualified as estimated for sample 70320.

Additionally, CSC requested that the laboratory meas ure the volume of a 500-mL bottle of the type used for these samples, to further refine the sample volume estimate. A discussion of the uncertainty introduced by the volume assumption is included below. 

### L Vol. kg) Wt. x μg/mg 1000 mg/kg (Conc. L) Vol. x μg/L (Conc. μg/L ion Concentrat Sample Total

sample original solid solid Filtrate Filtrate 

### × +

=5 

### • According to the laboratory, a 500-mL bottle filled to the rim holds about 510 mL (to the nearest mL).

• Allowing for some variability among the 500-mL bottl es and the levels to which each was filled in the field, we assume that a “full” bottle holds 500 mL ± 10 mL.

• Recalculating the results from Episode 6547 using 510 mL as the original volume yields results that are 4 % higher than those calculated assuming 490 mL.

• Therefore, for the metals results in Episode 6547, th e volume estimation introduces an error of ± 4 %. That difference is well within the expected analy tical uncertainty and at least 5 times lower than typical acceptance limits for laboratory duplicate analyses (i.e., 20%).

In the generation of the routine metals “Calcula ted Total” results, at EPA's request, CSC included concentrations that were greater than the MDL but le ss 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 w ill 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 50-fold dilutions for mercury. The affected samples are as follows: filte red aqueous phase and dissolved mercury for sample 70320; total and dissolved mercury for sample 70321; a nd total and dissolved mercury for sample 70322. Reporting limits for these results have been adjusted for dilution.

Percent Solids



### CSC notes that there was so little particulate in the bottles sent for the metals analysis of sample 70320 that ProChem could not determine the percent solids on the filtered solid phase of that sample because the majority of the original sample was consumed in an alysis. Therefore, for this sample, a percent solids evaluation was performed from the Group I influent bo ttle and summarized in Table 3. The percent solid result is provided to convert if desired, solid phase we t weight basis values to dry weight results, and was not used to generate the “C alculated 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, EPA6 

### Table 2 Data Review Summary Table

Episode: 

### 6547 Analysis: 

### Metals

Industry: 

### Steam Electric Study Reviewer: 

### Maria A. Vargas

Sample Analyte Action Reason CSC Qual Level

70320

calculated total Hg Estimated value Estimated value used in

calculation of total. NA ND

70321 total Sb Maximum value MS/MSD %R above contract-specified criteria NA 22.3 μg/L

70321 total Mo Minimum value MSD %R below contractspecified criteria NA 470 μg/L

70321 total Se Maximum value MSD %R above contractspecified criteria NA 3,020 μg/L

Sb 21.1 μg/L 70321 dissolved

Mo Maximum value MS/MSD %R above contract-specified criteria NA 431 μg/L

70321 dissolved As Estimated value MS/MSD and RPD above contract-specified criteria NA 11.1 μg/L

70321 dissolved Se Maximum value MS %R above contractspecified criteria NA 2,860 μg/L

NA= Not Applicable

ND= Not detected7 

### Table 3 Phase Separation Data Elements

Episode: 

### 6547 Analysis: 

### Metals

Industry: 

### Steam Electric Study Reviewer: 

### Maria A. Vargas

Sample number 70320

Original sample vol (mL) 500 a

Net weight of solid phase on the filter (g) 2.2

Density (g/mL) 1.0022

Original sample weight (g) 501.1 a

Filtrate weight (g) 498.9 a

Filtrate volume (mL) 497.8 a

Percent Solid (of solid phase) (%) 45.4 b

a 

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

b 

### Value calculated from the Group I bottleC o m put er Sci e nces C o r p orat i on

ww w.csc

. com



### MEMORANDUM

DATE: January 0 8 , 2 008

TO: Ron Jordan, Work Assignment Manager

EPA EAD

FROM: Lisa White, Quality Assurance Chem i s t
Co m puter Sciences Corporation

SUBJECT: Data R e view Narrative for Total Metals Anal y ses for the Stea m Ele c tric Study

, Episodes

6547 and 6 5 4 8

Under EPA contract num ber 68-C-03-044, ProChem Anal y tical subm itted data for the anal y s is of total metals by E P A Method 20 0.7 for aq ueo u s sam p le 70320 i n Episo d e 6547 an d aq ueous sam p le 704 20 in Episode 6548. Because inf l uent sa m p les for this stu dy were expect e d to be highly variable in solids
content, EPA chose to obtai n results for t h e solid phas e as well. The solid phase results for sam p l e 70320

and 70420 w e re not directly anal y zed, but rather calculated from t o tal, dissolve d , and TSS re sults.

Please note that the results for mercury by Method 24 5.1 and dissol v ed m e t a ls by Method 200.7 for these

sam p les were previousl y d e livered unde r a separate Data Review Narrative.

Table 1 provides a list of sa m p les, episo d es, m a tric es, descriptions, sa m p ling dates, phase, and the required analy tical m e thods.

Table 1 - Sam p le Identifiers , Des criptions , Sa mpling Da tes, a nd A n a l ysis M e thods

EPA Sample # Episo d e # Ma trix Sample Descri ption Sa mpling

Da te P h a s e M e t h o d

7 / 25 /07 T o t a l 70 3 20 65 4 7 A q ue o u s FG D I n fl ue nt N A C a l c u l ated So lid 20 0. 7

8 / 22 /07 T o t a l 70 4 20 65 4 8 A q ue o u s FG D I n fl ue nt N A C a l c u l ated So lid 20 0. 7

NA = No t Ap plicab le



### These data ha ve been reviewed in accor d ance with CSC's Data Review Guidelines for Metals Analyses (Novem b er 2004); t h e EAD contract; and with the s p ecifi cations listed in EPA Methods 20 0

. 7 (Rev. 5.0)

. All data are o f acceptable q u ality with the qualifiers described below and detailed in the data review

su mmary table (Table 2).

SUMMARY

All sam p les were successful l y anal y zed within the method-specified holdi ng ti mes. The method detection

lim it (M DL) studies and initial precision and recovery (IPR) analy s es were perform ed and m e t the

contract-spec i fied criteria. Calibration curves, calibration standards

, and calibration blan ks were successfully a n aly zed. Preparation blanks perfor m ed f o r each analysis detected n o contam inati on above

the laborator y’s reportin g li mits. QC sam p les, in cluding o ngoi ng p r ecision and recovery (OP R ) sam p les, matrix spike (MS) sa m p les, matrix spike duplicate (MSD) sam p les, and laborator y serial diluti on sam ples

de m onstrated that laboratory perform an ce for these a n aly ses was a cceptable, wit h the exception of the

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

7 0 3

. 46 1.200 0 Fax 703 .4 61 .20 2 02 

### issues described below and summarized in Table 2. The MS/MSD analyses were performed on sample

70420.

DATA ISSUES

Method and Analytical Blanks

Several analytes were detected in the preparation bl anks (PBs), initial calibration blanks (ICBs), and continuing calibration blanks (CCBs) asso ciated with the samples in this episode at concentrations greater than the respective MDLs, but less than the method- specified MLs. The data quality is affected as

follows:

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

detail.

Matrix Performance

MS/MSD and Serial Dilution analyses were performed on samples 70420.

The percent recoveries for total barium in the MS and MSD (18% and 9% respectively) for sample 70420 were below contract-specified criteria of 75%. In ad dition, the serial dilution percent difference for total barium (16%) was above the contract-specified crite ria of 10%. The combination of spike recovery

failure and serial dilution failure indicates severe matr ix interferences. Therefore, CSC recommends that the result for total barium in sample 70420 be considered an estimated value.

The percent recovery for total titanium (126%) in the MS for sample 70420 was slightly above the contract-specified criteria of 125%. In addition, the serial dilution percent difference (19%) was above the contract-specified criteria of 10%. The combination of spike recovery failure and serial dilution failure indicates severe matrix interferences. Therefore, CS C recommends that the result for total titanium in sample 70420 be considered an estimated value.

The percent recovery for total nickel (73%) in the MSD for sample 70420 was slightly below the contract-specified criteria of 75%. In addition, the serial dilution percent difference (16%) was above the contract-specified criteria of 10%. The combination of spike recovery failure and serial dilution failure indicates severe matrix interferences. Therefore, CS C recommends that the result for total nickel in sample 70420 be considered an estimated value.

The percent recovery for total selenium (47%) in the MSD for sample 70420 was below the contractspecified criteria of 75%. CSC recommends that the result for total selenium in sample 70420 be considered of acceptable quality, but may be a minimum value.

Total thallium was not recovered in the MS or MSD for sample 70420. In addition, the analyte was not detected in the unspiked sample. The laboratory suspected that the increased solids in the sample (chloride in particular) were likely the cause. Zero percent recoveries in the matrix spike samples indicate significant methodological problems that preclude su ccessful analysis of thallium. Therefore, CSC

recommends that the results for total thallium and calculated solid thallium in sample 70420 be excluded

from the database.3 

### The serial dilution percent differences fo r several anal y t es were above the contract-specified criteria of

10% in sam p le 70420 . The se instances are as follows: total chrom i um (14% ), co balt (17% ), copper (15%), lead (12%), m o ly bdenum (12% )

, sodium (11%), vanadium (26 % ), and zinc (17%). In these cas es
, MS/MSD percent recoveri es wer e within acceptable cr iteria. CSC reco mmends that the results for these analy t es be included in the database with out qualification.

TECHNICAL NOTES

Solid Phase Calculations

CSC calculat e d the solid phase results u s ing the following form ula :



### mg ug kg mg

L mg TSS L g Conc L g Conc

sample original Dissolved Total 

### / 10 / 10

/ ) /

. /

. ( (mg/kg) ion concentrat phase Solid 3 6



### × −

= μ μ

In the generation of t h e Calculated Solid result, at EPA's r e quest, CSC included Total and Dissolved concentrations that were gr eater than the MDL but less than the ML unless both factors in the calculations

were le ss tha n the ML. H o wever, if any concentra tion was affect ed by contamination in an associat ed

blank at less than 5 tim es t h e associat ed blank result, i t was changed to a zero be fore going thr ough the calculation, per CSC' s data review protocols. Ne gative values submitted by the laborator y were not used

in the calculations.

The results for the various phases will be labeled in the PROCEDUR field of the EPA database as

“DISSOLVE D ”, “TOT AL ”, and “CAL CULATED S O LID (DRY WEIGHT)”.

The TSS result for sam p le 70320 in E p is ode 6547 is 4970 m g /L. T h e TSS result for sam p le 70420 in Episode 65 48 is 1330 0 m g /L.

Minimum L e v e ls

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

In order to alleviate expect ed matrix eff ects, th e laboratory performed a 2-fold di lution on sample 704 20 in Episode 6548. MLs are adjusted appropriately.

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

bbeard2@csc.com

.

cc: Brian D’Am ico, EPA Deb Bartram, ERG Beverly Rand olph, EPA TJ Finseth, ERG

Marla Sm ith, EPA Lynn Watlers, CSC Nelson Andrews, EPA Barbara B ear d, CSC Brian Englert, EPA4 Table 2 Data Review Summary Table

Episode: 6547, 6548 Analysis: Metals

Industry: Steam Electric Study Reviewer: Lisa White

Sample Analyte Action Reason CSC Qual Level

70420 Total Ba Estimated Value MS and MSD %R below contract-specified criteria;

Serial Dilution %D above contract-specified criteria NA See Database

70420

Calculated solid Ba Estimated Value Dissolved component is a Minimum Value;

Total component is an

Estimated Value NA See Database

70420 Total Tl Exclude Zero %R in MS and MSD EXCLUDE NA

70420

Calculated Solid Tl Exclude Not Calculable EXCLUDE NA

70420 Total Ti Estimated Value MS %R above contractspecified criteria;

Serial Dilution %D above contract-specified criteria NA See Database

70420

Calculated solid Ti Estimated Value Total component is an

Estimated Value NA See Database

70420 Total Ni Estimated Value MSD %R below contractspecified criteria;

Serial Dilution %D above contract-specified criteria NA See Database

70420

Calculated solid Ni Estimated Value Total component is an

Estimated Value NA See Database

70420 Total Se Minimum Value MSD %R below contractspecified criteria NA See Database

70420

Calculated solid Se Estimated Value Total component is a Minimum value;

Dissolved component is

an Estimated Value NA See Database

NA= Not applicableComputer Sciences Corporation

www.csc.com

6101 Stevenson Avenue Alexandria, Virginia 22304

703.461.2000 Fax 703.461.2020 

### MEMORANDUM

DATE: December 4, 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

6547

Under EPA contract number 68-C-03- 046, Battelle Marine Sciences submitted data for the analyses of trace metals. All five aqueous samples in this epis ode were analyzed for total mercury (Hg) by Method 1631E. Three of the five (effluent, effluent duplicat e, and effluent field blank) were analyzed for hexavalent chromium by Method 1636 and total meta ls 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). Several samp les were analyzed for dissolved metals as well as total. Because FGD influent samples for this study were expected to be highly va riable in solids content, EPA chose to obtain results for this phase as well. The solid-phase results for sample 70320 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 7/25/07 Dissolved 1631E 70320 Aqueous FGD influent

NA Calculated Solid 1631E

Total 1631E, 1638

Dissolved 1631E, 1638 70321 Aqueous FGD effluent 7/25/07

NA 1636

Total 1631E, 1638

Dissolved 1631E, 1638 70322 Aqueous FGD effluent duplicate 7/25/07

NA 1636

70323 Aqueous FGD influent field blank 7/25/07 NA 1631E

Total 1631E, 1638

Dissolved 1636, 1638 70324 Aqueous FGD effluent field blank 7/25/07

NA 1636

NA = Not applicable



### These data have been reviewed in accordance with CSC's Data Review Guidelines for Metals Analyses (November 2004), with the EAD contract, and with the specifications listed in EPA Methods 1631E (Aug 2002), 1636 (Jan 1996), and 1638 (Jan 1996). All data are of acceptable quality with the qualifiers

described below.2 

### SUMMARY

All 5 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. Except for instances detailed below, 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 analysis was performed on sample 70321.

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). Some 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 (PB), initial calib ration blanks (ICBs), and continuing calibration blanks (CCBs) asso ciated with the samples in this episode at concentrations greater than the respective MDLs, but less than the method- specified MLs. The data quality is affected as

follows:

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

detail.

Field Blanks

CSC reviewed results from two field blanks. Sample 70323 (influent field blank) exhibited no results above the ML. Dissolved chromium, dissolved copper and dissolved zinc were detected at levels above the ML in field-filtered sample 70324 (effluent field blank). Hexavalent chromium was detected above the ML in sample 70324. Per EPA request, CSC does not qualify results based on field blank

contamination.

TSS Duplicate

Due to lab error, a duplicate for TSS analyses was not performed. Blank and LCS results for TSS were acceptable. Because TSS is a secondary analyte used only in the calculation of solid-phase mercury results, CSC has not qualified the TSS results because of this omission.

Laboratory Duplicate

The RPD for chromium (32%) for a laboratory duplicate performed on dissolved metals sample 70321 was above the internal laboratory limit (25%). Howe ver, because the MS/MSD performed on this sample produced an acceptable RPD, and Method 1638 does not specify limits for laboratory duplicates, CSC considers the associated result acceptable without qualification.3 

### Field Duplicate

Field duplicate RPD values were above the method- specified limit (20%) fo r the following duplicate pairs:

• 70321 and 70322 (effluent and effluent field duplicat e) total metals results for Ag (58%) and Cr (35%). Note that because Method 1638 does not list chromium as an analyte, there are no method-specified limits for chromium field duplicat e RPD. In these cases, CSC defaults to the limit specified for the other analytes in the method—20%.

• 70321 and 70322 (effluent and effluent field duplicat e) dissolved metals results for Ag (32%).

CSC does not routinely qualify results based on field duplicate RPD failure.

TECHNICAL NOTES

Sample Temperature

Trace metals samples were not chille d during shipment for this study.

Additional Analytes

Two additional analytes, arsenic and chromium, were included for evaluation by Method 1638. Because they are not specified in the method, the MLs for th ese (0.15 μg/L and 0.80 μg/L, respectively) were set well above the laboratory-determined MDL.

Minimum Levels

A precipitate formed after preservation in dissolved field samples for Method 1638 analysis. Therefore, in order to alleviate expected matrix effects, the laboratory performed a 100-fold dilution on all samples on which Method 1638 was performed, except the FGD effluent field blank sample 70324. MLs are adjusted appropriately.

Solid-Phase Calculations

CSC calculated the solid-phase results 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)”.

In the generation of the Calculated Solid result, at EPA's request, CSC included Total and Dissolved concentrations that were greater than the MDL but l ess than the ML. However, if any concentration was affected by contamination in an associated blank at less than 5 times the associated blank result, it was changed to a zero before going through the calculation, per CSC's data review protocols. Negative values submitted by the laboratory were not used in the calculations. sample original Dissolved Total


### L mg TSS g ng L g Conc L g Conc

/ / 1000 ) /

. /

. ( μg/g) or (ng/mg ion concentrat phase Solid μ μ μ ×

−

=4 

### 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.

The TSS result for the sample 70320 bottle analyzed for mercury is 4779 mg/L.

If you have any questions regarding the analyses of these samples or the review of these data, please contact Barbara Beard by telephone at (703) 461-21 54, facsimile at (703) 461-8056, or via email at

bbeard2@csc.com.

cc: Brian Damico, EPA Beverly Randolph, EPA Marla Smith, EPA Nelson Andrews, EPA Brian Englert, EPA Deb Bartram, ERG TJ Finseth, ERG Lynn Walters, CSC Barbara Beard, CSCComputer Sciences Corporation

www.csc.com

6101 Stevenson Avenue Alexandria, Virginia 22304

703.461.2000 Fax 703.461.2020 

### MEMORANDUM

DATE: December 10, 2007

TO: Ron Jordan, Work Assignment Manager

EPA EAD

FROM: Cris Robinson, Quality Assurance Chemist Computer Sciences Corporation

SUBJECT: Data Review Narrative for Method 1638 Tr ace Metals Analyses for the Steam Electric Study, Episode 6547, FGD Influent Samples

Under EPA contract number 68-C-03- 046, Battelle Marine Sciences submitted data for the analyses of trace metals. Analysis of the two samples reviewed in this narrative by Method 1638 was requested by EPA at a later date than the rest of the samples in Episode 6547. This narrative only evaluates Method 1638 results for sample 70320 and 70323. Other an alyses for these and other samples in Episode 6547 are covered in a previous narrative.

These two samples were analyzed for total metals in cluding 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). Sample 70320 was an alyzed for dissolved and total metals. Because the FGD influent samples for this study were expected to be highly variable in solids content, EPA chose to obtain results for this phase as well. The solid -phase results for sample 70320 were not directly analyzed, but rather calculated from the 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 7/25/07 Dissolved 70320 Aqueous FGD Influent

NA Calculated Solid

Total 70323 Aqueous FGD Influent Field Blank 7/25/07 Dissolved 1638

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 Method 1638 (Jan 1996). All data are of acceptable quality with the qua lifiers described below and detailed in the data review summary table (Table 2).

SUMMARY

Both 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. Except for instances detailed below, all QC samples, in cluding laboratory control samples (LCS), matrix spike and matrix spike duplicate (MS/MSD) sampl es, and quality control samples (QCS) were within contract-specified criteria. The MS/MSD analy ses for this Episode were performed on samples 703212 

### and 70322, and evaluated in a previous narrative. All method preparation blanks detected no contamination above the laboratory’s reporting limits. All calibration blanks were free of contamination above the report limit (minimum level or ML). These blanks are discussed in detail below.

DATA ISSUES

Method and Analytical Blanks

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

follows:

• Sample Results 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. One instance of blank

contamination at this level is detailed below. The affected samples and analytes are as follows:

70320 total Cr.

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

detail.

CCV

One continuing calibration verification standard (CCV) recovery for silver (108)% was slightly above method-specified limits (81-107). However, all reporte d sample results associated with this CCV were not detected; therefore no samples are qualified.

TSS Duplicate

Due to lab error, a duplicate for TSS analyses was not performed. Blank and LCS results for TSS were acceptable. Because TSS is a secondary analyte used onl y in the calculation of solid-phase metals results, no data will be qualified by this omission.

TECHNICAL NOTES

Sample Temperature

Trace metals samples were not chille d during shipment for this study.

Additional Analytes

Two additional analytes, arsenic and chromium, were included for evaluation by Method 1638. Because they are not specified in the method, the MLs for th ese (0.15 μg/L and 0.80 μg/L, respectively) were set well above the laboratory-determined MDL.3 

### Minimum Levels

For dissolved and total sample 70320, the lab diluted 200-fo ld in order to alleviate expected matrix effects caused by high dissolved solids (d issolved solids content was assu med to be high because the lab observed precipitation in dissolved sample bottles). MLs are adjusted appropriately.

Solid-Phase Calculations

CSC calculated the solid-phase resu lts by the following formula:

The results for the various phases will be labeled in the PROCEDUR field of the EPA database as “DISSOLVED”, “TOTAL”, and “CALCULATED SOLID (DRY WEIGHT)”.

When two results are mathematically combined to obtain a Calculated Solid result, CSC will report the larger of the two MLs associated with each result as the Calculated Solid ML.

In the generation of the Calculated Solid result, at EPA's request, CSC included Total and Dissolved concentrations that were greater than the MDL but l ess than the ML. However, if any concentration was affected by contamination in an associated blank at less than 5 times the associated blank result, it was changed to a zero before going through the calculation, per CSC's data review protocols. Negative values submitted by the laboratory were not used in the calculations.

Note that because the Method 1638 samples in this episode were held and analyzed at a later time at the request of EPA, the bottles had been preserved befo re a TSS was requested. Because preservation affects the solids content of a sample, a TSS was not perfo rmed; rather, the TSS result from the sample 70320 bottle analyzed for mercury (4779 mg/L) was used in calculation of Method 1638 solid phase 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) 461-21 54, facsimile at (703) 461-8056, or via email at

bbeard2@csc.com.

cc: Brian Damico, EPA Beverly Randolph, EPA Marla Smith, EPA Nelson Andrews, EPA Brian Englert, EPA Deb Bartram, ERG TJ Finseth, ERG Lynn Walters, CSC Barbara Beard, CSC sample original Dissolved Total


### L mg TSS L ng Conc L ng Conc

/ ) /

. /

. ( μg/g) or (ng/mg ion concentrat phase Solid −

=4 Table 2 Data Review Summary Table

Episode: 6547 Analysis: Trace Metals

Industry: STELEC Study Reviewer: Cris Robinson

Sample Analyte Action Reason CSC Qual Level

70320 Total Cr Maximum value Sample result >5x and

<10x blank result NA See Database

70320

Calculated Solid Cr Maximum value Associated total result is a

maximum NA See Database

NA = Not applicable

### Appendix D

FGD WASTEWATER TREATMENT SYSTEM FLOW RATE DATA

### D-1 Table D-1. Flow Data during FGD Wastewater Treatment Effluent Sample Collection, Big Bend

Date Time FGD WWT Influent Flow Rate (gpm) FGD WWT Effluent Flow Rate (gpm)

July 25, 2007 8:00 AM 252 14

July 25, 2007 8:01 AM 252 14

July 25, 2007 8:02 AM 251 251

July 25, 2007 8:03 AM 251 248

July 25, 2007 8:04 AM 251 245

July 25, 2007 8:05 AM 251 242

July 25, 2007 8:06 AM 251 65

July 25, 2007 8:07 AM 251 17

July 25, 2007 8:08 AM 251 16

July 25, 2007 8:09 AM 251 16

July 25, 2007 8:10 AM 251 15

July 25, 2007 8:11 AM 251 15

July 25, 2007 8:12 AM 251 14

July 25, 2007 8:13 AM 251 239

July 25, 2007 8:14 AM 250 242

July 25, 2007 8:15 AM 250 245

July 25, 2007 8:16 AM 250 249

July 25, 2007 8:17 AM 250 13

July 25, 2007 8:18 AM 250 13

July 25, 2007 8:19 AM 250 13

July 25, 2007 8:20 AM 250 14

July 25, 2007 8:21 AM 250 14

July 25, 2007 8:22 AM 250 14

July 25, 2007 8:23 AM 250 14

July 25, 2007 8:24 AM 250 249

July 25, 2007 8:25 AM 250 249

July 25, 2007 8:26 AM 249 250

July 25, 2007 8:27 AM 249 250

July 25, 2007 8:28 AM 249 6

July 25, 2007 8:29 AM 249 7

July 25, 2007 8:30 AM 249 9

July 25, 2007 8:31 AM 249 10

July 25, 2007 8:32 AM 249 11

July 25, 2007 8:33 AM 249 13

July 25, 2007 8:34 AM 249 252

July 25, 2007 8:35 AM 249 252

July 25, 2007 8:36 AM 249 253

July 25, 2007 8:37 AM 249 253

July 25, 2007 8:38 AM 248 212

### D-2 Table D-1. Flow Data during FGD Wastewater Treatment Effluent Sample Collection, Big Bend

Date Time FGD WWT Influent Flow Rate (gpm) FGD WWT Effluent Flow Rate (gpm)

July 25, 2007 8:39 AM 248 7

July 25, 2007 8:40 AM 248 8

July 25, 2007 8:41 AM 248 9

July 25, 2007 8:42 AM 248 10

July 25, 2007 8:43 AM 248 12

July 25, 2007 8:44 AM 248 13

July 25, 2007 8:45 AM 248 250

July 25, 2007 8:46 AM 248 251

July 25, 2007 8:47 AM 248 251

July 25, 2007 8:48 AM 248 252

July 25, 2007 8:49 AM 248 253

July 25, 2007 8:50 AM 247 12

July 25, 2007 8:51 AM 247 13

July 25, 2007 8:52 AM 247 14

July 25, 2007 8:53 AM 247 15

July 25, 2007 8:54 AM 247 16

July 25, 2007 8:55 AM 247 17

July 25, 2007 8:56 AM 247 251

July 25, 2007 8:57 AM 247 251

July 25, 2007 8:58 AM 247 252

July 25, 2007 8:59 AM 247 252

July 25, 2007 9:00 AM 247 25

July 25, 2007 9:01 AM 247 23

July 25, 2007 9:02 AM 246 21

July 25, 2007 9:03 AM 246 19

July 25, 2007 9:04 AM 246 17

July 25, 2007 9:05 AM 246 15

July 25, 2007 9:06 AM 246 249

July 25, 2007 9:07 AM 246 250

July 25, 2007 9:08 AM 12 251

July 25, 2007 9:09 AM 7 252

July 25, 2007 9:10 AM 7 253

July 25, 2007 9:11 AM 6 15

July 25, 2007 9:12 AM 6 15

July 25, 2007 9:13 AM 166 14

July 25, 2007 9:14 AM 243 14

July 25, 2007 9:15 AM 243 14

July 25, 2007 9:16 AM 243 14

July 25, 2007 9:17 AM 243 14

### D-3 Table D-1. Flow Data during FGD Wastewater Treatment Effluent Sample Collection, Big Bend

Date Time FGD WWT Influent Flow Rate (gpm) FGD WWT Effluent Flow Rate (gpm)

July 25, 2007 9:18 AM 243 14

July 25, 2007 9:19 AM 243 14

July 25, 2007 9:20 AM 243 14

July 25, 2007 9:21 AM 243 14

July 25, 2007 9:22 AM 243 14

July 25, 2007 9:23 AM 243 14

July 25, 2007 9:24 AM 244 14

July 25, 2007 9:25 AM 244 14

July 25, 2007 9:26 AM 244 14

July 25, 2007 9:27 AM 244 14

July 25, 2007 9:28 AM 244 14

July 25, 2007 9:29 AM 244 14

July 25, 2007 9:30 AM 244 13

July 25, 2007 9:31 AM 244 13

July 25, 2007 9:32 AM 244 13

July 25, 2007 9:33 AM 244 13

July 25, 2007 9:34 AM 244 110

July 25, 2007 9:35 AM 244 250

July 25, 2007 9:36 AM 244 248

July 25, 2007 9:37 AM 244 245

July 25, 2007 9:38 AM 244 243

July 25, 2007 9:39 AM 244 240

July 25, 2007 9:40 AM 244 31

July 25, 2007 9:41 AM 244 18

July 25, 2007 9:42 AM 244 23

July 25, 2007 9:43 AM 244 28

July 25, 2007 9:44 AM 245 33

July 25, 2007 9:45 AM 245 245

July 25, 2007 9:46 AM 245 247

July 25, 2007 9:47 AM 245 249

July 25, 2007 9:48 AM 245 250

July 25, 2007 9:49 AM 245 252

July 25, 2007 9:50 AM 245 4

July 25, 2007 9:51 AM 245 9

July 25, 2007 9:52 AM 245 14

July 25, 2007 9:53 AM 245 19

July 25, 2007 9:54 AM 245 24

July 25, 2007 9:55 AM 245 198

July 25, 2007 9:56 AM 245 244

### D-4 Table D-1. Flow Data during FGD Wastewater Treatment Effluent Sample Collection, Big Bend

Date Time FGD WWT Influent Flow Rate (gpm) FGD WWT Effluent Flow Rate (gpm)

July 25, 2007 9:57 AM 245 246

July 25, 2007 9:58 AM 245 248

July 25, 2007 9:59 AM 245 251

July 25, 2007 10:00 AM 245 13

July 25, 2007 10:01 AM 245 13

July 25, 2007 10:02 AM 245 13

July 25, 2007 10:03 AM 245 13

July 25, 2007 10:04 AM 246 13

July 25, 2007 10:05 AM 246 13

July 25, 2007 10:06 AM 246 13

July 25, 2007 10:07 AM 246 13

July 25, 2007 10:08 AM 246 247

July 25, 2007 10:09 AM 246 248

July 25, 2007 10:10 AM 246 250

July 25, 2007 10:11 AM 246 252

July 25, 2007 10:12 AM 246 2

July 25, 2007 10:13 AM 246 5

July 25, 2007 10:14 AM 246 7

July 25, 2007 10:15 AM 246 9

July 25, 2007 10:16 AM 246 11

July 25, 2007 10:17 AM 246 13

July 25, 2007 10:18 AM 246 249

July 25, 2007 10:19 AM 246 250

July 25, 2007 10:20 AM 246 251

July 25, 2007 10:21 AM 246 252

July 25, 2007 10:22 AM 246 14

July 25, 2007 10:23 AM 247 14

July 25, 2007 10:24 AM 247 14

July 25, 2007 10:25 AM 247 14

July 25, 2007 10:26 AM 247 14

July 25, 2007 10:27 AM 247 13

July 25, 2007 10:28 AM 247 235

July 25, 2007 10:29 AM 247 248

July 25, 2007 10:30 AM 247 249

### D-5 Table D-2. Flow Data during FGD Wastewater Treatment Influent Sample Collection, Big Bend

Date Time FGD WWT Influent Flow Rate (gpm) FGD WWT Effluent Flow Rate (gpm)

July 25, 2007 3:00 PM 251 4

July 25, 2007 3:01 PM 251 6

July 25, 2007 3:02 PM 251 8

July 25, 2007 3:03 PM 251 10

July 25, 2007 3:04 PM 251 12

July 25, 2007 3:05 PM 251 245

July 25, 2007 3:06 PM 251 243

July 25, 2007 3:07 PM 251 242

July 25, 2007 3:08 PM 251 241

July 25, 2007 3:09 PM 251 239

July 25, 2007 3:10 PM 251 13

July 25, 2007 3:11 PM 251 13

July 25, 2007 3:12 PM 251 13

July 25, 2007 3:13 PM 251 13

July 25, 2007 3:14 PM 251 13

July 25, 2007 3:15 PM 251 122

July 25, 2007 3:16 PM 251 250

July 25, 2007 3:17 PM 251 250

July 25, 2007 3:18 PM 251 250

July 25, 2007 3:19 PM 251 250

July 25, 2007 3:20 PM 251 14

July 25, 2007 3:21 PM 251 14

July 25, 2007 3:22 PM 251 14

July 25, 2007 3:23 PM 251 13

July 25, 2007 3:24 PM 251 13

July 25, 2007 3:25 PM 251 13

July 25, 2007 3:26 PM 251 13

July 25, 2007 3:27 PM 251 250

July 25, 2007 3:28 PM 251 250

July 25, 2007 3:29 PM 251 251

July 25, 2007 3:30 PM 251 251

July 25, 2007 3:31 PM 251 10

July 25, 2007 3:32 PM 251 11

July 25, 2007 3:33 PM 251 12

July 25, 2007 3:34 PM 251 14

July 25, 2007 3:35 PM 251 15

July 25, 2007 3:36 PM 251 16

July 25, 2007 3:37 PM 251 246

July 25, 2007 3:38 PM 251 247

### D-6 Table D-2. Flow Data during FGD Wastewater Treatment Influent Sample Collection, Big Bend

Date Time FGD WWT Influent Flow Rate (gpm) FGD WWT Effluent Flow Rate (gpm)

July 25, 2007 3:39 PM 251 249

July 25, 2007 3:40 PM 251 250

July 25, 2007 3:41 PM 251 252

July 25, 2007 3:42 PM 251 3

July 25, 2007 3:43 PM 251 5

July 25, 2007 3:44 PM 251 7

July 25, 2007 3:45 PM 251 9

July 25, 2007 3:46 PM 251 11

July 25, 2007 3:47 PM 251 238

July 25, 2007 3:48 PM 251 241

July 25, 2007 3:49 PM 251 243

July 25, 2007 3:50 PM 251 246

July 25, 2007 3:51 PM 251 248

July 25, 2007 3:52 PM 251 10

July 25, 2007 3:53 PM 251 2

July 25, 2007 3:54 PM 251 4

July 25, 2007 3:55 PM 251 7

July 25, 2007 3:56 PM 251 9

July 25, 2007 3:57 PM 251 11

July 25, 2007 3:58 PM 251 249

July 25, 2007 3:59 PM 251 248

July 25, 2007 4:00 PM 251 247

July 25, 2007 4:01 PM 251 246

July 25, 2007 4:02 PM 251 36

July 25, 2007 4:03 PM 251 17

July 25, 2007 4:04 PM 251 16

July 25, 2007 4:05 PM 251 15

July 25, 2007 4:06 PM 251 14

July 25, 2007 4:07 PM 251 13

July 25, 2007 4:08 PM 251 204

July 25, 2007 4:09 PM 251 252

July 25, 2007 4:10 PM 251 252

July 25, 2007 4:11 PM 251 252

July 25, 2007 4:12 PM 250 252

July 25, 2007 4:13 PM 250 3

July 25, 2007 4:14 PM 250 4

July 25, 2007 4:15 PM 250 6

July 25, 2007 4:16 PM 250 8

July 25, 2007 4:17 PM 250 10

### D-7 Table D-2. Flow Data during FGD Wastewater Treatment Influent Sample Collection, Big Bend

Date Time FGD WWT Influent Flow Rate (gpm) FGD WWT Effluent Flow Rate (gpm)

July 25, 2007 4:18 PM 250 11

July 25, 2007 4:19 PM 250 242

July 25, 2007 4:20 PM 250 247

July 25, 2007 4:21 PM 250 246

July 25, 2007 4:22 PM 250 244

July 25, 2007 4:23 PM 250 243

July 25, 2007 4:24 PM 250 20

July 25, 2007 4:25 PM 250 21

July 25, 2007 4:26 PM 250 22

July 25, 2007 4:27 PM 250 23

July 25, 2007 4:28 PM 250 24

July 25, 2007 4:29 PM 250 25

July 25, 2007 4:30 PM 250 244

### Appendix E

PICTURES FROM THE SAMPLING EPISODE

### E-1 Figure E-1. Sampler Working Inside a “Cleanbox”

### E-2 Figure E-2. Three-Way Splitter at the Influent to FGD Wastewater Treatment System

### E-3 Figure E-3. Sampling Set Up at the Influent to FGD Wastewater Treatment System (SP-1)

### E-4 Figure E-4. Pump-Off Station for Di ssolved Metals Sample Collection

### E-5 Figure E-5. Collection of Dissolved Metals Samples at Pump-Off Station

### E-6 Figure E-6. Three-Way Splitter at the Effluent from FGD Wastewater Treatment System

### E-7 Figure E-7. Sampling Set Up at Effluent from FGD Wastewater Treatment System (SP-2)

### E-8 Figure E-8. Field Blank Collect ion at Effluent from FGD Wastewater Treatment (SP-5)