# Final Sampling Episode Report EME Homer City Generation L.P.’s Homer City Power Plant Homer City, PA

Episode 6548

Prepared for:



# U.S. Environmental Protection Agency

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

Prepared by:



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

26 August 2008

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

### i CONTENTS

Page

1. I NTRODUCTION 

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

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

2. P LANT 

### O VERVIEW 

### .............................................................................................................2-1 2.1 FGD Scrubber System .........................................................................................2-2 2.2 FGD Wastewater Treatment System ...................................................................2-3 2.3 Bottom Ash Treatment System............................................................................2-6

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 Second-Stage Clarifier Overflow in FGD Wastewater Treatment ..........3-4

3.1.3 Effluent from FGD Wast ewater Treatment .............................................3-6

3.1.4 Effluent from Bottom Ash Pond..............................................................3-7 3.2 List of Analytes and Sample Preservation...........................................................3-9 3.3 Plant Operational Data.......................................................................................3-10 3.4 Deviations from the Sampling and Analysis Plan .............................................3-10

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 4.3 Bottom Ash Pond 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 .......................................................................................5-4

6. R EFERENCES 

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

Appendix A: A NALYTICAL 

### R ESULTS



### Appendix B: A NALYTICAL 

### D ATA FOR 

### M ETALS



### , FGD W ASTEWATER AND 

### B OTTOM 

### A SH 

### P OND



### Appendix C: D ATA 

### R EVIEW 

### N ARRATIVES



### Appendix D: P ICTURES 

### F ROM THE 

### S AMPLING 

### E PISODE

### ii LIST OF TABLES

Page

2-1 Homer City NPDES Monitoring Requ irements for the FGD Effluent............................ 2-6

3-1 Sample Collection Information, Homer City................................................................. 3-13

3-2 Number of Samples Collected by Sampling Point, Homer City ................................... 3-14

3-3 Field Measurements, Homer City.................................................................................. 3-15

3-4 Analytical Methods and Procedures for Samples Collected at Homer City.................. 3-16

3-5 Summary of Sample Containe r and Planned Preservation ............................................ 3-17

3-6 Sample Preservation Summary, Homer City................................................................. 3-18

3-7 Generating Unit Operating Ch aracteristics During Sample Collection, Homer City.... 3-20

3-8 FGD Scrubber System Operating Characteristics, Homer City..................................... 3-20

3-9 FGD Wastewater Treatment System Op erating Characteristics, Homer City............... 3-21

3-10 Bottom Ash System Operating Ch aracteristics, Homer City......................................... 3-21

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

4-2 Biphasic Sample Results for Routine To tal Mercury, FGD Influent, Homer City.......... 4-7

4-3 Biphasic Sample Results for Classical An alytes Measured Above the Report Limit, FGD Influent, Homer City............................................................................................... 4-7

4-4 Classical Pollutants Measured Above the Report Limit for the FGD Wastewater Treatment System, Homer City ....................................................................................... 4-8

4-5 Metals Measured Above the Report Li mit for the FGD Wastewater Treatment System, Homer City......................................................................................................... 4-9

4-6 Classical Pollutants Measured Above the Report Limit for the Bottom Ash Pond Effluent, Homer City ..................................................................................................... 4-12

4-7 Metals Measured Above the Report Lim it for the Bottom Ash Pond Effluent, Homer City........................................................................................................................... ...... 4-13

5-1 Field Blank Results Measured Above the Report Limit, Homer City............................. 5-5

5-2 Field Duplicate Resu lts, Homer City............................................................................... 5-6

A-1 FGD Influent Analytical Data, Homer City.................................................................... A-1

### LIST OF TABLES (Continued)

Page

iii A-2 ProChem Biphasic Filtration Blank Analytical Results, Homer City............................. A-9

A-3 FGD Second-Stage Clarifier Overflow Ef fluent Analytical Da ta, Homer City ........... A-10

A-4 FGD Effluent Analytic al Data, Homer City ................................................................. A-14

A-5 Duplicate of FGD Effluent An alytical Data, Homer City ............................................ A-19

A-6 Bottom Ash Effluent Analyt ical Data, Homer City...................................................... A-24

A-7 Bottle Blank and Equipment Blank Analytical Data, Homer City ............................... A-29

A-8 FGD Influent Field Blank Analytical Data, Homer City.............................................. A-36

A-9 FGD Second-Stage Clarifier Overflow Fi eld Blank Analytical Data, Homer City...... A-37

A-10 FGD Effluent Field Blank An alytical Data, Homer City ............................................. A-41

A-11 Bottom Ash Effluent Field Blank Analytical Data, Homer City.................................. A-45

B-1 Analytical Results for Metals in th e FGD Wastewater Trea tment System, Homer City........................................................................................................................... ........B-1

B-2 Analytical Results for Metals in th e Bottom Ash Pond Effluent, Homer City................B-3

### iv LIST OF FIGURES

Page

2-1 FGD Wastewater Treatment Syst em, Homer City Power Plant...................................... 2-8

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

D-2 Sample Tap Splitter at the Influent to FGD Wastewater Treatment System.................. D-2

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

D-4 Sample Collection Point for the 2 nd 

### Stage Clarifier Overflow ....................................... D-4

D-5 Sampling Set Up for the 2 nd 

### Stage Clarifier Overflow (SP-2)........................................ D-5

D-6 Sample Collection Point for the Efflue nt from the FGD Wastewater Treatment System......................................................................................................................... .... D-6

D-7 Sampling Set Up at Effluent from FGD Wastewater Treatment System (SP-3)............ D-7

D-8 Sampling Set Up at Effluent from the Bottom Ash Pond (SP-4) ................................... D-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 to characterize raw wast ewaters generated by coal-fired steam electric power plants, as well as to eval uate treatment technol ogies and best management practices used to reduce pollutant discharges. This Sampling Episode Report (SER) describes the sampling activities that took place on 21 August 2007 th rough 23 August 2007 at EME Homer City Generation L.P.’s Homer City Power Plant (Homer City), located in Homer City, Pennsylvania (Sampling Episode 6548). The focus of Episode 6548 was to characterize the influent to and effluent from the flue gas desu lfurization (FGD) wastewater tr eatment system, as well as the second stage clarifier overflow w ithin the FGD wastewater treatment system and the effluent from the bottom ash ponds at Homer City.

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,

### 1-2 — Water cycling, and

— Solids removal process;

• 

### FGD wastewater treatment system;

• 

### Type of coal;

• 

### NOx controls;

• 

### Ash handling systems;

• 

### Ash treatment system; and

• 

### Mercury air controls.

EPA selected Homer City for sampling ba sed on the following site characteristics:

• 

### The plant is a coal-fired pow er plant that burns eastern bituminous coal in each of its three generating units;

• 

### The plant operates a wet FGD system that is a limestone forced oxidation system;

• 

### The plant adds formic acid to the FGD system to increase the sulfur dioxide removal efficiency;

• 

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

— Equalization;

— First-stage chemical precipitation;

— First-stage clarification;

— Second-stage chemi cal precipitation;

— Second-stage clarification;

— Nutrient/phosphoric acid addition;

— Heat exchange;

— Biological treatment; and

— Sand filtration.

• 

### The plant operates an SCR on the scrubbed unit (Unit 3); and

• 

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

1.3 Sampling Episode Overview

On February 6, 2007, EPA and its technical contractor, Eastern Research Group, Inc. (ERG), conducted a site visit at Homer City. The purpose 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 samples at Homer Cit y. Information collected dur ing the site visit is

documented in Engineering Site Visit Report for EME Ho mer City Generation L.P.’s Homer City

Power Plant [1] and was used to create Sampling Plan, EME Homer City Generation L.P.’s Homer City Power Plant (Sampling Plan) [2], which describes the sample collection procedures used during the sampling episode.

For this sampling episode, EPA arrived at Homer City on Tuesday, August 21, 2007, to review the sampling points, determine the set up for the sample collection, label sample bottles, and purchase any additional supplies needed for the sampling episode. EPA then collected the samples specified in the Sampling Plan on Wednesday, August 22, and Thursday, August 23, 2007. The following personnel participated in EPA’s sample collection activities:

### 1-3 • 

### Ron Jordan, EPA/EAD;

• 

### Josh Hall, EPA/EAD;

• 

### TJ Finseth, ERG;

• 

### 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



### Homer City operates three coal-fired steam electric generating units. Homer City burns approximately five million tons of eastern bituminous coal per year. Units 1 and 2, which came on line in 1969, each have a capacity of 650 mega watts (MW) and burn mid-sulfur coal. Unit 3, which came on line in 1977, has a capacity of 70 0 MW and burns high-sulfur coal. Typically, Homer City produces between 13 and 14 million MW -hrs annually. The Homer City plant is located on approximately 2,400 acres near Homer C ity, Pennsylvania, near Two Lick Creek and

Blacklick Creek.

Homer City is part of the Pennsylvania, Ne w Jersey, and Maryland (PJM) electricity grid and adjusts its MW output based on the grid’s ne eds (typical fluctuation may be 20 to 30 MW). During the summer and winter, Ho mer City typically operates at maximum or close to maximum load 24 hours per day. During the spring and fall, the plant may reduce its load at night to 50 percent of its capacity.

Units 1 through 3 have the following configuration:

• 

### Boiler;

• 

### SCR system;

• 

### Air preheater;

• 

### Electrostatic precipitator (ESP); and

• 

### FGD system (Unit 3 only).

In 2001, Homer City retrofitted Unit 3 with a wet FGD scrubber system to control the sulfur dioxide releases from the plant. Unit 3 is subject to New Source Performance Standards (NSPS) air regulations. Plant pers onnel report that, after installing the FGD scrubber on Unit 3, the total plant sulfur dioxide emissions were reduced by 40 percent to comply with new permit limits, and the mercury emissions were reduced by 55 percent. The mercury reductions are based on the mercury removal across the Unit 3 FGD scr ubber as tested by the Department of Energy (DOE) during 2001. At the time the FGD scrubber was installed on Unit 3, Homer City also

installed an FGD wastewater trea tment system to control the di scharges from the wastewater generated during the operation of the FGD scrubber. Section 2.1 discusses the FGD system and

Section 2.2 discusses the FGD wa stewater treatment system.

Between 2000 and 2001, Homer City retrofitted Units 1 through 3 with selective catalytic reduction (SCR) systems to control nitrogen oxi de (NOx) releases from the plant. Plant personnel report that, after inst alling the SCR systems, the total plant NOx emissions were reduced by 80 percent to comply with new perm it limits. Plant personnel estimate that the SCR systems on Units 1 through 3 remove approximately 60 to 90 percent of th e NOx from the flue gas. Homer City currently operates the SCR systems from May 1 through September 30 each

year.

In the SCR systems, the plant injects only the amount of ammonia needed to convert the NOx in the flue gas to nitrogen and water. Excess unreacted ammonia from the SCR system, caused by flue gas fluctuations, is known as “a mmonia slip.” As the flue gas passes over the catalyst in the SCR process, some of the sulfur dioxide is oxidized to sulfur trioxide, which

combines with unreacted ammonia to form ammo nium bisulfate. Ammonium bisulfate can cause

### 2-2 fouling and corrosion in air preheaters. The plan t typically operates the SCR systems with less than two percent ammonia slip to avoid fouling the air preheate r with the ammonium bisulfate by-product. Typically, without bisulf ate fouling, air preheaters are washed once a year for 8 to 12 hours using ash recycle water at a flow rate of 1,000 gallons per minute (gpm).

Homer City has taken steps to reduce air emissions beyond installing FGD and SCR systems. Homer City also cleans th e coal used in Units 1 and 2 in an on-site process that reduces

the sulfur content of the coal . The boilers in Units 1 through 3 are equipped with low NOx burners and separated overfire air (SOFA) systems, which limit the production of NOx.

Homer City utilizes electros tatic precipitators (ESPs) to remove greater than 99.8 percent of the fly ash from the flue gas emitted from Un its 1 through 3. There is no wastewater generated from the operation of the ESPs or fly ash handling system at Homer City. Fly ash is pneumatically transferred to silos where it is stor ed until it is trucked to the on-site, unlined ash landfill or beneficially used at the on-site, lined coal refuse site.

2.1 FGD Scrubber System

Homer City operates one wet FGD scrubber sy stem on Unit 3, downstream of the ESP, to

control the emission of sulfur dioxide from the un it. The FGD system is a five-level spray tower

that uses limestone as the sorbent.

The plant has a limestone storage pile on si te that contains appr oximately 30,000 tons of Pennsylvania limestone. The plant uses a ball mill to crush the limestone prior to mixing it with blowdown water from the Unit 3 cooling tower to cr eate the absorbent lime stone slurry used in

the FGD scrubber. Storm water from the limest one storage and handling area drains to a pond and the water is pumped into the FGD make up water tank.

The limestone slurry is pumped to the vari ous levels of the scr ubber tower (typically three or four levels out of the five are opera ted at one time) and sprayed downward into the scrubber. As the flue gas flows up through the towe r, countercurrent to the spray, droplets of the absorbent slurry absorbs and reac ts with the sulfur dioxide in the flue gas to produce calcium

sulfite. To increase the sulfur dioxide removal effi ciency of the scrubber, the plant adds formic acid to the system, which buffers the solution and aids in dissolution of the calcium carbonate. The plant previously used dibasic acid (DBA), but found that it reduced the selenium removal efficiency of the FGD wastewater treatment sy stem. According to Homer City personnel, the FGD system removes approximately 97 to 99 percen t of the sulfur dioxide from the Unit 3 flue gas. Adding the formic acid increases the sulfur dioxide removal by approximately two percent and allows the plant to operate the system with one less spray level (i.e., up to four levels instead of all five). The reduction in the FGD operating cost outweighs the additi onal cost to operate a biological reactor to remove the formic acid in the FGD wastewat er treatment system, which is

discussed in Section 2.2.

The slurry that collects at th e bottom of the FGD scrubber is ag itated to keep the solids in suspension. A forced oxidation system, in which compressed air is intr oduced into the bottom slurry, further oxidizes calcium sulfite to calcium sulfate (gypsum). The slu rry is recycled up to the various spray levels until the chlorides conc entration in the slurry reaches approximately 15,000 to 20,000 ppm. The spray tower is constructe d of Inconel, a supe ralloy used in high-

### 2-3 temperature applications that is resistant to oxidation and corro sion. This material can withstand up to 25,000 ppm chlorides. When the slurry reaches the maximum allowable solids concentration, the plant blows down some of the slurry from the scrubber and adds fresh makeup limestone slurry to the scr ubber. Homer City personnel estimat e that blowdown occurs daily for approximately 12 to 18 hours. During blowdown, the solids level of the slurry typically decreases from 15 to 13 percent.

During blowdown, the gypsum slurry is sent to primary hydrocyclones, in which solid gypsum is separated from the water by centrifugal force. The solid gypsum is forced outward to the walls of the hydrocyclones and falls downw ard, while the water ex its the top of the hydrocyclones. The gypsum from the primary hydrocyc lones is transferred to vacuum filter belts. Approximately 80 percent of the supernatant overflow from the primary hydrocyclones is recycled back to the scrubber and the remain ing 20 percent is transferred to secondary hydrocyclones. Homer City recently brought the secondary hydrocyclones on line to further reduce the solids content of the supernatant overflow before it is transferred to the FGD wastewater treatment system. A portion of th e supernatant overflow from the secondary hydrocyclones is transferred to the FGD wastewat er treatment system and a portion is recycled

back to the scrubber.

The gypsum is rinsed on the vacuum filter be lt to reduce the chloride concentration using blowdown from Unit 3’s cooling tower as rinse wate r. As the gypsum is rinsed and dried, water that falls through or around the belt is collected and recycled back to the absorber. There is an optimal gypsum crystal size range for manufactur ing wallboard, and the pores of the vacuum filter belts are sized accordingly. If the gypsum crystals are too small, they pass through the pores and are recycled back to the scrubber wher e they continue to grow. The gypsum typically contains 30 to 40 percent moisture at the beginning of the vacuum filter belt and 10 percent moisture in the final gypsum product. The gypsum falls off the vacuum filter belt and is conveyed to a domed structure for storage. Homer City produces gypsum th at is light in color and contains less than one per cent impurities, which is mostly fly ash. Homer City produces about 1,000 tons of gypsum per day and sells it to a wallboard manufacturer in Pittsburgh for
about $1/ton.

2.2 FGD Wastewater Treatment System

The FGD wastewater treatment system is de signed to receive intermittent discharges of

FGD wastewater from the seconda ry hydrocyclones at a flow ra te of approximately 220 gpm. The intermittent discharges typically occur for 12 to 18 hours per day. The plant operates the FGD wastewater treatment system 24 hours per day. The Homer City FGD wastewater treatment system contains the following treatment operations:

• 

### Equalization;

• 

### First-stage chemical precipitation:

— Lime addition for pH adjustment, and

— Ferric chloride, cationic polymer, and air addition for metals precipitation/coagulation;

• 

### First-stage clarification with anionic polymer addition;

### 2-4 • 

### Second-stage chemi cal precipitation:

— Lime addition for pH adjustment, and

— Ferric chloride, cationic polymer, and air addition for metals precipitation/coagulation;

• 

### Second-stage clarification with anionic polymer addition;

• 

### Micronutrient (typic ally urea), phosphoric acid, and corn syrup addition for biological treatment;

• 

### Heat exchange;

• 

### Aerobic biological treatment; and

• 

### Sand filtration.

Figure 2-1 presents a process flow diagram of the FGD wastewater treatment system, as well as the sampling locations for three of the four sampling points for EPA’s sampling episode.

Overflow from the FGD hydrocyclones is transf erred directly to the feed tank of the FGD wastewater treatment system, where the intermitte nt flows from the hydroc yclones are equalized, allowing the plant to pump a constant flow rate of FGD wastewater through the treatment system. The flow rate exiting the feed tank of th e FGD wastewater treatment system is typically about 110 gpm. Homer City typically adds about 10 to 20 gpm of chemical feed (i.e., lime, ferric chloride, and polymer) to the FGD wastewater treat ment system; therefore, the flow rate exiting the FGD wastewater treatment system averages about 120 gpm. The hydraulic residence time for

the entire FGD wastewater treatm ent system is about 3.5 days. The flow rate into the wastewater treatment system from the equalization tank dur ing the sampling episode was approximately 109 gpm (based on one measurement recorded from the flow meter at 1:11 PM on 22 August 2007, during sample collection). In addition, the flow ra te into the wastewater treatment system from the equalization tank on 21 August 2007, ranged fr om 105 gpm to 113 gpm (based on continuous electronic flow monitoring provi ded to EPA by Homer City).

The feed tank is agitated to prevent ca lcium from settling and scaling the tank. The hydraulic residence time in the 150,000-gallon feed tank is about 22 hours. Homer City typically

maintains the wastewater volume in the feed tank at about 40 to 80 percent of the total tank

volume. Water from the feed tank is transferred continuously (24 hours per day) to a first-stage chemical precipitation tank (referred to hereinafte r as the “first-stage neutralization tank”, as named by Homer City), in which lime is added to adjust the pH of the wastewater from 6.0 to 8.1. The plant also adds ferric chloride for meta ls precipitation, and cationic polymer and air to further enhance the precipitati on/coagulation. From the first- stage neutralization tank, the wastewater is transferred to the first-stage clarifier, in which anionic polymer is added for coagulation. The majority of th e heavy solids (mainly calcium su lfate and calciu m carbonate) are removed in the first-stage clarifier.

Homer City personnel indicated that excess solids entering the firs t-stage clarifier can interfere with metals precipitat ion and removal. In particular, Homer City is concerned about interference with selenium removal, which affect s the plant’s ability to meet its NPDES permit limit of 0.8 mg/L total selenium. In an attempt to reduce this interferen ce, Homer City recently added a second set of hydrocyclones to the gypsum dewatering system for additional gypsum solids removal upstream of the FGD wastewater treatment system, as discussed in Section 2.1. With the secondary hydrocyclones operating, th e wastewater entering the FGD wastewater treatment system contains less than one percent solids.

### 2-5 Water from the first-stage clarifier is transferred to the second-stage chemical precipitation tank (referred to he reinafter as the “second-stage ne utralization tank”, as named by Homer City), in which lime is added to adjust the wastewater pH to 8.1. The plant also adds ferric chloride for metals precipitation, and ai r and occasionally cationic polymer to further enhance the precipitation/coagulation. When the plant initially began operating the FGD wastewater treatment system, it also added orga nosulfide to the second- stage neutralization tank for mercury removal; however, the plant has sinc e determined that sufficient mercury removal

can be achieved without the addition of organosulfide.

From the second-stage neutralization tank, wast ewater is transferre d to the second-stage clarifier, in which anionic polym er is added for coagulation. The hydraulic residence time across each of the 50,000-gallon first- a nd second-stage clarifiers is a pproximately 7.5 hours. Prior to adding the secondary hydrocyclone s, Homer City removed more metals in the second-stage clarifier than the first-stage cl arifier, due to a better iron hydr oxide floc, which plant personnel

attribute to the lower solids content in the sec ond-stage clarifier. Sludge from the clarifiers is

transferred to a thickener and th en to a vacuum filter. Some sludge from the clarifiers and thickener is recycled to the 1st stage neutra lization tank to prevent scaling on the tank walls. Recycling the sludge introduces cr ystals into the tank and scali ng preferentially occurs on the crystal surfaces.

Overflow from the second-stage clarifier is transferred to the pH adjustment tank, in which micronutrients (typically urea), phosphoric acid, and corn syrup are added to ensure growth of microorganisms in the biological reactor. In the past, Homer City has added HCl or lime to adjust the pH to 7.5 to 8.0 prior to biol ogical treatment; however , the overflow from the second-stage clarifier is typically at the appropriate pH and adjustment is not necessary. From the pH adjustment tank, water is transferred through a h eat exchanger to the biological reactor. The microorganisms in the aerobic biological reactor reduce the organic content and the associated biochemical oxygen de mand (BOD) of the wastewater. BOD in the FGD wastewater

is a result of the formic acid that is added to the limestone slurry in the FGD scrubber system. Flow through the biological reactor is con tinuous. The hydraulic residence time in the 350,000- gallon biological reactor is about 2 days. Sludge from the biologica l reactor is transferred to the thickener, where it is combined with the clarifie r sludge and then transferred to the vacuum filter. The vacuum filter reduces the sludge moisture content from approximately 60 to 70 percent down to 20 percent. Homer City generates 25 tons per day of filter cake (mostly calcium sulfate/gypsum) from the vacuum filters, whic h the plant tests to ensure compliance with leachability requirements, and then disposes of th is sludge in the on-site, unlined fly ash landfill. Homer City generates approximately 3,840 gallons per day (gpd) of filtrate from the vacuum filters, which is transferred to the wastewater treatment feed tank. The vacuum filter filtrate accounts for approximately 2.4 percent of the tota l influent to the FGD wastewater treatment
system.

Wastewater from the biologi cal reactor is transferred th rough sand filters. Wastewater from the sand filters is transferred continuously to an effluent tank, except when the filters are backwashed. Homer City backwashes the sand f ilters once every 12 hours for about 15 minutes. The backwash is directed to a sump, which also collects all floor drain wastewater. Wastewater from the sump is transferred to the FGD wastew ater treatment system feed tank a few times per day (about 4,000 gallons per transfer). Home r City generates approximately 2,400 gpd of sand

### 2-6 filter backwash each day, which accounts for 1.5 per cent of the total influent flow to the FGD
wastewater treatment system.

Wastewater from the effluent tank is discharged through NPDES Outfall #027 to Blacklick Creek. The flow rate exiting the effluent tank varies from about 70 to 170 gpm due to the operation of the variable freque ncy drive that maintains a consta nt level in the effluent tank; the average flow rate is about 120 gpm. Homer City estimates that the hydraulic residence time in the 3,000-gallon, agitated effluent tank is about 12 to 13 minutes. The flow rate of the effluent from the wastewater treatment system during the sampling episode was approximately 107 gpm (based on the average of 12 measurements record ed randomly at different frequencies from the flow meter during sample collection on August 22, 2007).

Table 2-1 presents Homer City’s NPDES pe rmit requirements for effluent from the FGD wastewater treatment system, which is Outfall #027.

Table 2-1. Homer City NPDES Monitoring Requirements for the FGD Effluent

Parameter Daily Minimum Daily Maximum Monthly Average

Total Suspended Solids (TSS) NA 100 mg/L 30 mg/L

Carbonaceous Biochemical Oxygen Demand (CBOD5) NA 50 mg/L 25 mg/L

Oil & Grease NA 20 mg/L 15 mg/L

Temperature NA 110 NA

pH 6.0 s.u. 9.0 s.u. NA

Beryllium NA 1.6 mg/L 0.8 mg/L

Lead NA 0.2 mg/L 0.1 mg/L

Selenium NA 1.6 mg/L 0.8 mg/L

Boron Monitor and Report

Methylene Blue Active Substances (MBAS) Monitor and Report

Osmotic Pressure Monitor and Report

Total Dissolved Solids (TDS) Monitor and Report

Flow Rate Monitor and Report

NA – Not applicable.



### EPA collected a sample of the influent to Homer City’s FGD wastewater treatment system downstream of the feed tank and upstream of the first-stage neutralization tank (i.e., the sample was collected prior to any chemical addi tion). EPA collected an interim sample within Homer City’s FGD wastewater treatment system at the overflow of the second-stage clarifier. EPA also collected a sample of the effluent from Homer City’s FGD wastewater treatment system directly from the effluent tank.

2.3 Bottom Ash Treatment System

Homer City uses water to sluice the botto m ash and other slag produced from the bottom of each boiler. Homer City sluices the bottom ash from the Unit 1 and Unit 2 boilers for approximately 90 minutes every 12 hour shift (i .e., two times per day) for both units. In

### 2-7 addition, Homer City sluices the bottom ash from the Unit 3 boiler for approximately 45 minutes every 12 hour shift.

The bottom ash sluice water is piped from th e boilers to hydrobins, which remove 90 to 95 percent of the solids. The dewatered bottom ash from the hydrobins is either used locally for antiskid and road construction or placed in th e on-site, unlined ash la ndfill. The supernatant overflow from the hydrobins drains to ash settling ponds.

Homer City operates four ash settling ponds. The plant typically ope rates two ash settling ponds at one time, which are opera ted in parallel. Each ash pond has an approximate volume of 1.76 million gallons. The ash settling ponds receive overflow from the bottom ash hydrobins, as well as stormwater runoff. Approxi mately six acres of storm water drains into the ponds from the ash handling and precipitator ar eas. Water is transferred from the ash settling ponds to a clear well via weirs, which are on the opposite side of the ponds from the inlet pipes. From the clear well, water is recycled for use as bottom ash slui ce. There is a periodic discharge from the clear well through the NPDES Outfall #00 5, the frequency of which depends on the amount of rainfall that has been received. The discharge from the clear well is limited to less than 30 mg/L average TSS and a pH of 6.0 to 9.0 s.u. The ash settling p onds are cleaned every si x to eight months. The recovered solids are transported to the on-site, unlined fly ash landfill.

EPA collected a sample of the effluent from Homer City’s bottom ash ponds directly

from the clear well.

### 2-8Figure 2-1. FGD Wastewater TreatmentSystem, Homer City Power Plant

### 3-1 3. S AMPLE 

### C OLLECTION



### During the Homer City sampling episode, the sampling team followed the sample collection protocols specified in the Sampling Plan [2]. S ection 3.1 describes the sampling points, sample collection methods, and field m easurements. Section 3.2 describes the list of analytes and the sample preservation procedures . Section 3.3 discusses the plant operational data collected during the sampling ep isode. Finally, Section 3.4 disc usses any deviations from the planned sampling activities described in the Sampling Plan.

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 FGD wastewater treatment plant including sampling point locations. No te that the sampling point at the effluent of Homer City’s bottom ash ponds is not shown in Figure 2-1.

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 of the sampling points.

The sampling points collected during this episode were:

• 

### SP-1: Influent to FGD Wast ewater Treatment System;

• 

### SP-2: Second-Stage Clarifier Overflow in FGD Wastewater Treatment System;

• 

### SP-3: Effluent from FGD Wa stewater Treatment System;

• 

### SP-4: Effluent from Bottom Ash Pond;

• 

### SP-5: Duplicate of Effluent from FGD Wastewater Treatment System (SP-3);

• 

### SP-6: Influent to FGD Wa stewater Treatment System (SP-1) Field Blank;

• 

### SP-7: Second-Stage Clarifier Overflow in FGD Wastewater Treatment System (SP-2) Field Blank;

• 

### SP-8: Effluent from FGD Wa stewater Treatment System (SP-3) Field Blank; and

• 

### SP-9: Effluent from Bottom As h Pond (SP-4) Field Blank.

For all the sampling points (except the tota l mercury and low-level total metals field blank samples at SP-6), EPA collected split sample s with Homer City’s representative. Prior to the sampling episode, Homer City personnel inst alled a splitter on the sampling tap at the influent to the FGD wastewater treatment sy stem (SP-1), which allowed for split sample

collection. At all of the other sa mpling points, EPA inserted a “Y” splitter into the sample tubing configuration to allow for split sample collecti on. For this sampling epis ode, all analytes, other than HEM/SGT-HEM were collected as “true” splits (i.e., samples for the same analyte were collected simultaneously). The HEM/SGT-HEM sa mples were either collected using a bottle dipper, or directly from a sample tap; therefor e, EPA and Homer City’s representative collected duplicate samples, with one filling the bottle i mmediately after the other. However, for the influent to the FGD wastewater treatment system , SP-1, because the splitter was installed in the

### 3-2 sample tap, EPA and Homer City’s representative were able to collect “true” splits for the HEM/SGT-HEM sample.

The field blank samples at the influent to the FGD wastewater treatment system (SP-6) for the low-level total mercury and low-level tota l metals samples were not collected as split samples between EPA and Homer City’s represen tative. These samples were collected using separate blank water and separa te tubing. However, the field blank samples for the low-level dissolved metals samples were collected as “true” split samples. For a description of the field blank sample collection pr ocedures, see Section 5.2.3.

At each of the nine sampling points, EPA co llected low-level metals sample fractions following EPA Method 1669 collection protocols. To collect low-level metals samples, EPA samplers donned Tyvek® suits and dust masks (dust masks were worn until all low-level mercury samples had been collected) during sample collection. In addition, EPA set up a “cleanbox,” which consists of a portable plastic r ectangular box with a sh allow lip and a flip-top

lid that secures itself open with clips. The “cleanbox” is double-bagged with a clear inner bag, enclosed in a translucent outer bag. The “cleanbox” is handled using “clean hands / dirty hands” techniques, whereby the inner bag is handled only by the “cle an hands” sampler. When the “cleanbox” is opened, the sampler is able to position his/her hands in the box and pull the bag over the opening of the box, but is still able to see the sample bottles and tubing. The “cleanbox” minimizes potential atmospheric contaminati on during sample collection. Figure D-1, in Appendix D, presents a picture of a sampler work ing inside a “cleanbox.” To collect samples, EPA placed the sample bottles and the inner bag into the “cleanbox” following the protocols specified in Method 1669, also referred to as “clean hands / dirty hands” protocols. Sampling staff filled the sample container and closed the sample bottle lid and inner bag as quickly as possible within the “cleanbox.” The sample bo ttles 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 FGD wastewater treatment sy stem (SP-1) was collected from a sample tap located on the wastewater piping downstream of the feed tank on the discharge side of the transfer pump, and upstream of the first-stag e neutralization tank. The sample point thus represents a mixture of FGD purge and backwash from the sand filters. Based on average flow rates and frequency of the FGD purge, vacuum fi lter filtrate, and filter backwash, the effluent from the feed tank is approximately 110 gpm, comprised of approximately 96 percent FGD purge, 2.5 percent vacuum filter filtra te, and 1.5 percent filter backwash.

Homer City’s sample tap and valve at SP-1 (as normally configured) is located approximately 15 feet above the ground. To aid in sample collection, Ho mer City installed a length of stainless steel pipe (Swagelok tubing) from the sample tap (15 feet above the ground) to just below waist level. In addition, Homer City installed a stainless steel splitter, with samplevalves, to allow split samples to be collected. Figure 2-1 identifies the sampling location for SP1. This sample was collected as a grab sample because the batch discharges from the gypsum dewatering process were equalized in the feed ta nk prior to sample collection and were expected to be fairly homogeneous. The sampling point was located inside ; therefore, there were no wind or rain concerns during the sample collection.

### 3-3 Prior to collecting the samples at the influe nt to the FGD wastewater treatment system (SP-1), the sampling team purged the newly installed stainless steel piping for five minutes (about 10 gallons of wastewater pu rged). The sampling team then collected field blanks (SP-6) for low-level total mercury and low-level total metals. See Section 5.2.3 for a description of the field blank sample collection pro cedures at the influent to the FGD wastewater treatment system.

EPA collected the wastewater samples at th e influent to the FGD wastewater treatment system by attaching a 5-foot length of silicone tubing to one of th e fittings on the splitter at the sample location (Homer City’s re presentative attached an identical piece of silicone tubing to the other fitting). Figure D-2, in Appendix D, presents a picture of the sample ta p splitter installed at the influent to the FGD wastewater treatment sy stem by Homer City. After the samplers attached the silicone tubing, they opened the valves of the sample tap to purge the tubing. While the tubing was being purged, the end of the EPA tubing fell on the ground. EPA removed the previous piece of tubing from th e tap and attached a new, identic al piece of precleaned tubing to the tap. Although this newly attached piece of tubi ng was not used to collect the field blanks, EPA does not expect it to be an issue because th e tubing sets were identical and were cleaned during the same batch. In addition, the supplier of the tubing provided equipment blank results for the tubing sets (see Section 5.2.2).

After the new tubing was attached, EPA purge d the new tubing for four minutes before beginning sample collection. Flow from the tap did not stop until all samples were collected (except HEM/SGT-HEM and the dissolved metals samples).

After the four-minute purge time had elapsed, the samplers filled three 10-liter containers with sample, which were later used to pump off the low-level and routine dissolved metals sample fractions. Once the 10-liter containers we re filled, one member of the sampling team transported the three 10-liter containers to the stag ing area to allow the solids in the wastewater to settle while the remainder of the sampling t eam stayed at the sampling point and continued sample collection. Figure D-3, in Appendix D, pres ents a picture of the sampling set up at the influent to the FGD wastewater treatment system.

EPA then collected the low-level total metals, low-level total mercury, low-level dissolved mercury, routine total metals, as well as the QC samples for each analyte, and the arsenic/selenium speciation samples in a “clean box,” as described in Section 3.1. The sampling team then collected BOD, Group I, and Group II samples by pouring the sample directly from the tubing into the sample bottles without us ing a “cleanbox.” 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 filled the sample bottles directly from the tap to prevent any oil and 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 tota l residual chlorine using a colorimeter. Table 3-3 presents the field measurement data for the in fluent to the FGD wastewater treatment system. The samplers noted that the field test ja r was initially cloudy and had a brownish-gray

### 3-4 appearance when collected. However, the solids in the sample settled quick ly, leaving a layer of solids at the bottom of the jar.

The sampling team then moved to the stag ing area, where a pump -off station was set up,

to collect the low-level and routine dissolved me tals samples. The pump-off station consisted of a length of Teflon® tubing attached to a length of silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team att ached a capsule filter to the silicone tubing, which was a short distance downstream of the pum p. The sampling team attached another short length of silicone tubing to the capsule filter e ffluent, which was attached to a “Y” splitter and two lengths of silicone tubing. Th is set-up allowed EPA to colle ct “true” split samples with Homer City’s representatives. Prior to collecting any dissolved metals samples of the FGD wastewater influent, the samplers collected a fi eld blank sample (SP-6) for low-level dissolved metals. See Section 5.2.3 for a description of the dissolved metals field blank sample collection at the influent to the FGD wastewater treatment system.

After the field blank sample was collected, the sampling team transferred the end of the Teflon® tubing into one of the 10-liter containers filled with wastewater from the influent to the FGD wastewater treatment system. By this time, the solids in the wastewater had been settling for approximately 2.5 hours, and there was appr oximately a one-inch layer of solids at the

bottom of the container.

The sampling team first purged the tubing and filter with sample for 30 seconds (approximately 1 L). The samplers then collected the low-level dissolved metals sample, as well as the low-level dissolved metals QC sample. Af ter the low-level dissolved metals samples were collected, the samplers transferre d the end of the Teflon® tubing in to another 10-liter container, installed a new capsule filter, and purged the tubing and filter for 30 seconds (approximately 1 L of sample). The samplers then collected the routine dissolved metals sample, the routine dissolved metals QC sample, and the routine hexavalent chromium sample.

3.1.2 Second-Stage Clarifier Overflow in FGD Wastewater Treatment

The second-stage clarifier overflow in the F GD wastewater treatment system (SP-2) was collected from the overflow weir of the clarifier, at the point where the wastewater enters the pipe to transfer the wastewater to the pH adjustment tank. To aid in sample collection, Homer City constructed scaffolding dir ectly against the clarifier to allow the samplers easy access the overflow weir. Figure 2-1 identifies the sampling location for SP-2. This sample was collected as a grab sample, because the flow through the F GD wastewater treatment system is continuous; therefore, the wastewater characteris tics should be fairly homogeneous.

During the sample collection at the sec ond-stage clarifier in the FGD wastewater treatment system, the sampling team covered the sa mple collection area with a tarp to cover the samplers and sample bottles in case of rain, and prevent debris from falling on the sample

collection area. There was no rain during the sample collection period.

Prior to collecting the samp les for the second-stage clarifier overflow in the FGD wastewater treatment system (SP-2), the sampli ng team collected field blanks (SP-7) for lowlevel total mercury, low-level total metals, routin e total metals, low-level dissolved metals, lowlevel hexavalent chromium, routine dissolved metals, and routine hexavalent chromium. See

### 3-5 Section 5.2.3 for a description of the field bla nk sample collection procedures for the secondstage clarifier overflow in the F GD wastewater treatment system.

EPA collected the wastewater samples for th e second-stage clarifie r overflow in the FGD wastewater treatment system by pumping sample s from the overflow weir into the sample

containers. EPA attached one end of a 25-foot le ngth of Teflon® tubing to a piece of PVC pipe. A sampling team member stood on the scaffolding and submerged the open end of the PVC pipe and tubing in the overflow weir. Figure D-4, in Appendix D, presents a picture of the tubing submerged in the second-stage clarifier weir . The sampling team positioned the tubing along the side of the scaffolding to reach the sampling t eam at ground level and att ached it to a piece of silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team attached a “Y” splitter to the e nd of the silicone tubing, with two additional pieces of silicone tubing attached to the “Y” splitter. The length of silicone tubing between the pump and the “Y” splitter consisted of two pieces with a small connector, which allowed EPA to attach and detach a capsule filter inline with the tubing configur ation. The “Y” splitter allowed EPA to collect “true” split samples with Homer City’s repres entative. Figure D-5, in Appendix D, presents a picture of the sampling set up for the second-stag e clarifier overflow in the FGD wastewater
treatment system.

After EPA configured the tubing for the sa mpling point, the samplers purged the tubing with sample. After approximately 20 seconds of purging, the tubing detached from the filter due to backpressure. The samplers were able to r ecover the filter and tubi ng without contaminating any equipment. The samplers reat tached the tubing to the filter and continued purging for two

minutes.

After the tubing was purged, the samplers first collected the low-level dissolved metals and low-level hexavalent chromium samples becau se the capsule filter was already inline with the tubing configuration from the dissolved meta ls field blank sample collection. The sampling team then installed a new capsule filter, purged the filter for one minute, and collected the

routine dissolved metals and rout ine hexavalent chromium samples. Each of these samples was collected in a “cleanbox,” as described in Section 3.1.

After collecting the routine hexavalent ch romium sample, the samplers dropped EPA’s silicone tubing on the ground. The samplers recove red the tubing from the ground, but the end of tubing was contaminated. The sampling team re moved the connector piece on the end of the tubing and used Homer City’s representatives’ tubing to pour sample over the end of EPA’s tubing for two minutes. EPA did not replace the sa mple tubing, but rather continued to use the tubing for the remainder of the sample collection.

After collecting all the dissolved metals sa mples, the sampling team removed the capsule filter from the tubing configuration, and purged the tubing for one minute. The samplers then collected the low-level total metals, low-level total mercury, low-level dissolved mercury, routine total metals, and arsenic/selenium speciat ion samples in a “cleanbox,” as described in Section 3.1. The sampling team then collected the BOD, Group I, and Group II samples by pouring the samples directly from the tubing into the samples bottl es without using a “cleanbox.” To collect the HEM/SGT-HEM samples, the samplers dipped the sample bottles directly into the overflow weir to prevent any oil and grease adhe ring to the sides of the tubing. Therefore, EPA

### 3-6 did not collect split samples with Homer City’s representative for the HEM/SGT-HEM samples, but instead, collected duplicate samples with Homer City’s representative.

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

3.1.3 Effluent from FGD Wastewater Treatment

The effluent from the FGD wa stewater treatment system ( SP-3) was collected directly from the effluent tank. Figure 2-1 identifies th e sampling location for SP-3. This sample was collected as a grab sample, because all the wastew ater entering the efflue nt tank has been treated in the FGD wastewater treatment system and is discharged from the tank; therefore, the

wastewater characteristics shoul d be fairly homogeneous. The sampling point was located inside, next to the staging area; therefore, there we re no wind or rain con cerns during the sample

collection.

Prior to collecting samples at the effluent from the FGD wastewat er treatment system (SP-3), the sampling team collect ed field blanks (SP-8) for lo w-level total mercury, low-level total metals, routine total metals, low-level dissolved metals, low-level hexavalent chromium, routine dissolved metals, and routine hexavale nt chromium. See Section 5.2.3 for a description of the field blank sample collect ion at the effluent from the F GD wastewater treatment system.

EPA collected the wastewater samples fo r the effluent from the FGD wastewater treatment system by pumping samples from the e ffluent tank into the sample containers. The sampling team attached one end of a 25-foot leng th of Teflon® tubing to a piece of PVC pipe and inserted the PVC pipe tubing into the effluent tank through a hole in the top of the tank. The sampling team positioned the tubing to reach the sa mpling team at the staging area and attached it to a piece of silicone tubi ng, which was threaded through an ISCO peristaltic pump. The sampling team attached a “Y” splitter to the othe r end of the silicone tubi ng, with two additional pieces of silicone tubing attached to the “Y” splitter. The length of silicone tubing between the pump and the “Y” splitter consisted of two pieces with a small connector, which allowed EPA to attach and detach a capsule filt er inline with the tubing configuration. Th e “Y” splitter allowed EPA to collect “true” split samples with Homer City’s representative. Figures D-6 and D-7, in Appendix D, present pictures of the sampling se t up for the effluent from the FGD wastewater
treatment system.

After EPA configured the tubing for the sa mpling point, the samplers purged the tubing and filter with sample for approximately one minut e. The samplers first collected the low-level dissolved metals sample, as well as the QC and duplicate samples because the capsule filter was already inline with the tubing configuration from the dissolved metals field blank sample collection. The sampling team then installed a ne w capsule filter and purged the filter with approximately one-half liter of sample. After pur ging the filter, the samplers collected the lowlevel hexavalent chromium, routine dissolved metals, and the routine hexavalent chromium

### 3-7 samples, as well as the QC and duplicate sample s for each analyte. Each of these samples was collected in a “cleanbox,” as described in Section 3.1.

After collecting all the dissolved metals sa mples, the sampling team removed the capsule filter from the tubing configuration, and purged the tubing for one minute. The samplers then collected the low-level total metals, low-level total mercury, low-level dissolved mercury, routine total metals, and arsenic/selenium speci ation samples, as well as the QC and duplicate samples for each analyte in a “cleanbox,” as de scribed in Section 3.1. Th e sampling team then collected the BOD, Group I, and Group II samples, as well as the QC and duplicate samples for each analyte, by pouring the samples directly from the tubing into the samples bottles without using a “cleanbox.” To aid in the collection of the HEM/SGT-HEM samples, Homer City

installed a stainless steel tap off of the effluent tank to al low EPA to collect samples without using tubing. The samplers flushed the stainless steel tap for four minutes , because the initial 20 seconds of sample from the tap appeared to contain high solids, but by the end of the four minutes, the sample looked similar to the efflue nt collected for the other samples. EPA then collected the HEM/SGT-HEM samples directly from the stainless steel sample tap to prevent any oil and grease adhering to the sides of the tubi ng. Therefore, EPA did not collect split samples with Homer City’s representative for the HEM/SGT-HEM samples, but instead, collected duplicate samples with Homer City’s representative.

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

3.1.4 Effluent from Bottom Ash Pond

EPA collected the effluent from the botto m ash pond (SP-4), from the clear well, which receives water from the two bottom ash ponds. Homer City collects its bottom ash effluent monitoring samples at the clearwell overflow weir. However, EPA collected samples from the middle area of the clear well, aw ay from the skimmer and overflow weir, which were rusty and had the potential to contaminate the samples with metal. Figure D-8, in Appendix D, shows the sampling point location upstream of the skimmer. EPA felt that the sampling point selected, although prior to the skimmer and weir, still re presented the effluent from a bottom ash pond. The sample was collected as a grab sample because the residence time of the ash ponds and the clear well equalize the wa stewater discharges.

The sampling point for the effluent from the bottom ash pond was located outside near the clear well. At the time the sampling team went out to the sampling point, a vacuum truck was skimming solids from the surface of the clear well. According to th e truck operator, the skimming had started approximately two hours before the samplers arrived at the sampling point. After approximately 10 minutes, the vacuum truck left the sampling area. At the time the truck finished skimming, Unit 3 was sluicing the bottom ash to the ash ponds. Because the plant uses

water from the clear well as the source for bottom ash sluice water, water was being removed from the clear well, and therefore, the plan t was not discharging. The sampling team waited

### 3-8 approximately one hour before setting up the sampli ng point so that none of the three units were sluicing bottom ash and the plant was discharging from the clear well.

Prior to collecting samples at the effluent from the bottom ash pond (SP-4), the sampling team collected field blanks (SP-9) for low-leve l total mercury, low-level total metals, routine total metals, low-level dissolved metals, low- level hexavalent chromium, routine dissolved metals, and routine hexavalent chromium. See Section 5.2.3 for a de scription of the field blank sample collection at the effluent from the bottom ash pond.

EPA collected the wastewater samples for the effluent from the bottom ash pond by pumping samples from the clear well into the sa mple containers. EPA attached one end of a 25- foot length of Teflon® tubing to a piece of PVC pi pe and inserted the tubing into the clear well at a point where there was no residue floating on the top of the water. The sampling team secured the PVC pipe along a rail, so that the tubing was approximately two feet below the surface of the water (the clearwell has a depth of 18 feet). The sampling team positioned the tubing to reach the set-up location near the clear well and att ached it to a piece of silicone tubing, which was threaded through an ISCO peristaltic pump. The sa mpling team attached a “Y” splitter to the end of the silicone tubing, with two additional pieces of silicone tubing attached to the “Y” splitter. The length of silicone tubing between the pump and the “Y” splitter consiste d of two pieces with a small connector, which allowed EPA to attach a nd detach a capsule filter inline with the tubing configuration. The “Y” splitter allowed EPA to co llect “true” split samples with Homer City’s representative. Figure D-8, in Appendix D, pres ents a picture of the sampling set up for the effluent from the bottom ash pond.

After EPA configured the tubing for the sa mpling point, the samplers purged the tubing and filter with sample for approximately 1.5 minut es. The samplers first collected the low-level dissolved metals sample and the QC sample because the capsule filter was already inline with the tubing configuration from the dissolved metals field blank sample collection. The sampling team then installed a new capsule filter and purged the filter with sample for one minute. After purging the filter, the samplers collected the lo w-level hexavalent chromium, routine dissolved metals, the routine hexavalent chromium samples, and the QC sample for each analyte. Each of these samples was collected in a “cl eanbox”, as described in Section 3.1.

After collecting all the dissolved metals sa mples, the sampling team removed the capsule filter from the tubing configuration, and purged the tubing for one minute. The samplers then collected the low-level total metals, low-level total mercury, low-level dissolved mercury, routine total metals, as well as the QC sample for each analyte, and arsenic/selenium speciation samples in a “cleanbox,” as described in Section 3.1. The sampling team then collected the BOD, Group I, and Group II samples, as well as the QC sample for each analyte, by pouring the samples directly from the tubing into the sa mples bottles without using a “cleanbox.” The samplers collected the HEM/SGT-HEM and HEM/SGT-HEM QC samples by using a bottle dipper to collect the samples directly from the clear well to prevent any oil and grease adhering to the sides of the tubing. Therefore, EPA di d not collect split samples with Homer City’s representative for the HEM/SGT-HEM samples, but instead, collected duplicate samples with Homer City’s representative. The samplers co llected the HEM/SGT-HEM samples as close to the location where the tubing had been co llecting the other sa mples as possible.

### 3-9 During the sample collection, the sampling team collected an aliquot of sample for field testing. Sample pH and temperature were measur ed immediately at the sampling point using a pH meter and four-color pH paper. The four-color pH paper was us ed as an independent check of the pH meter to ensure that similar results were measured. After returning to the staging area, the sampling team took measurements of free and tota l residual chlorine using a colorimeter. Table 3-3 presents the field measurement data for the effluent from the bottom ash pond.

3.2 List of Analytes and Sample Preservation

Analytes in EPA’s Homer City sampling epis ode included those in the following classes of pollutants:

• 

### Classicals:

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

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus,

— Hexane extractable material (HEM), and

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

• 

### 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

### 3-10 mercury, and low-level hexavalent chromium sa mples were placed on ice and cooled to <6°C immediately following collection. All dissolved metals samples, except low-level dissolved mercury, were filtered in the fi eld. The routine and low-level hexavalent chromium samples were preserved in the field, but all other metals samples were acid-preserved at the laboratory, prior to extraction. The routine hexavalent chromium samp les were supposed to be preserved to a pH between 9.3 and 9.7 using an ammonium sulfate buffer solution; however, the sampling team discontinued preservation for some samples becau se 10 percent of the sample volume was added before the required pH was achieved (the pH of these preserved samples was approximately 9.0). The low-level hexavalent chromium sample bottles were prepreserved with 4 mL of 50-percent NaOH. The Group II and HEM/SGT-HEM samples were preserved with sulfur acid to a pH of <2 immediately after collection in the staging area, and the pH wa s confirmed with four-color pH strips.

3.3 Plant Operational Data

During the sampling episode at Homer Cit y, plant personnel provided the sampling team with operational data for each of the generating units, the FGD scrubber system, and the bottom ash collection system, as well as operational and flow data for the FGD wastewater treatment system. Table 3-7 presents the unit operating characteristics, Table 3-8 presents the FGD scrubber system operating characteristics, Tabl e 3-9 presents the FGD wastewater treatment system operating characteristics, and Table 3-10 presents the bottom ash system operating characteristics during the sampling episode.

3.4 Deviations from the Sampling and Analysis Plan

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

described below:

• 

### Collection Containers for Dissolved Metals at SP-1. For the influent to the FGD wastewater treatment system, EPA planned to collect volume for the pumpoff of routine and low-level dissolved me tals and routine hexavalent chromium samples, as well as the QC samples, in to two precleaned 10-liter containers. However, EPA collected the volume into th ree precleaned 10-liter container, to ensure that enough volume was collected.

• 

### Dissolved Metals Sample Fi ltration Time at SP-1. For the influent to the FGD
wastewater treatment system , EPA planned to filter the dissolved metals samples approximately one hour after filling the 10- liter containers wi th sample; however,

the filtration did not occur unt il approximately 2.5 hours later.

• 

### Dissolved Metals Sample Collection at all Sampling Points. EPA planned to collect the dissolved metals samples at all sampling points as “multipour” splits, by partially filling the EPA bottle, then f illing the split bottle, and then repeating the partial filling of both bottles two more times until both bottles are completely full. Instead, EPA collected “true” split sa mples with Homer City’s representative at all sampling points by placing a filter directly after the peristaltic pump and then having a splitter after the filter.

### 3-11 • 

### Low-Level Total Mercury Field Blank Sa mple Collection at all Sampling

Points. EPA planned to collect the low-leve l total mercury field blank samples after the low-level total metals field blank samples at all sampling points; however, EPA decided to collect the low- level total mercury field blank samples first. The low-level total metals field blank water was held in a plastic container, while the low-level mercury field blank water was held in a borosilicate glass container (because the glass is easier to clean for mercury contamination). The borosilicate glass has the potential to leach into the mercury field blank water, and therefore, could potentially contaminate the samples for the boron analysis. For this reason, EPA decided that the low-leve l total metals field blanks should be collected after the low-level mercury field blanks because then the field blank and the wastewater sample are both exposed to the same potential boron contamination from the low-level total mercury field blank water.

• 

### Sample Collection at the Second-Stage Clarifier (SP-2). EPA planned to collect the samples of the second-stag e clarifier overflow by setting up the sampling point on the clarifier brid ge; however, EPA set up the sampling equipment on the ground, at the bottom of the clarifier. One sampler stood on the scaffolding set up by Homer City holding the tubing in the clarifier overflow weir.

• 

### Second-Stage Clarifier Fl ow Rate Estimation. EPA planned to estimate the

flow rate of the second-s tage clarifier overflow by measuring the time required to fill a 1-L jar placed at the overflow weir, if possible. However, EPA decided that this flow value would likely not produce a re liable result and that the influent flow rate into the treatment system would be a more accurate representation of the flow

rate.

• 

### HEM/SGT-HEM Sample Collection at Second-Stage Clarifier. EPA planned to collect the HEM/SGT-HEM samples at the second-stage cl arifier by using a bottle dipper to place the bo ttle near the overflow weir and filling the bottle with the water flowing over the weir. However, because Homer City built the scaffolding along the clarifier wall, EPA was able to dip the bottles directly into

the overflow weir where the water was coll ected prior to being transported to the pH adjustment tank.

• 

### Sample Collection at the FGD Effluent (SP-3). EPA planned to collect the samples of the effluent from the FGD wastewater treatment system by using Homer City’s ISCO pump and tubing and attaching new tubing to the end of the preexisting tubing. However, EPA decide d to use new Teflon® and silicone tubing cleaned according to EPA Method 1669 protocols and a rented ISCO pump to collect the samples.

• 

### HEM/SGT-HEM Sample Collection at FGD Effluent. EPA planned to collect the HEM/SGT-HEM samples by dipping the bottl es directly into the effluent tank using a bottle dipper; however, Homer City determined it would be inconvenient to remove the top of the effluent tank. Therefore, prior to the sampling episode, Homer City installed a stainless steel ta p at the bottom of the effluent tank to allow EPA to collect samples without the use of tubing. EPA collected the

### 3-12 HEM/SGT-HEM samples at the effluent from the FGD wastewater treatment system by filling bottles directly from a stainless steel tap th at Homer City had

installed.

• 

### Sample Tubing Dropped During Sample Collection. During the collection of the influent to the FGD wastewater treatment system (SP-1) and the second-stage

clarifier overflow in the FGD wastewater treatment system (SP-2), EPA dropped the sample tubing on the ground. For the influent sample, EPA replaced the tubing with an identical piece of pr e-cleaned tubing and resumed sample collection. For the second-stage clarif ier overflow sample, EPA removed the connector on the end of the sample t ubing and rinsed the tubing for 2 minutes with sample, prior to resuming sample collection.

• 

### Sample Tubing Detached During Sample Collection at SP-2. While purging the sample tubing at the second-stage clar ifier overflow in the FGD wastewater treatment system (SP-2), the tubing detached from the filter due to backpressure. The samplers were able to recover the filter and tubing without contaminating any equipment. The samplers reattached the tubing to the filter and continued purging

for two minutes.

• 

### Chlorine Field Test Measurements. EPA did not perform the chlorine field test

measurement for the influent to the F GD wastewater treatment system (SP-1) immediately after sample co llection because the color of the sample would have prevented an accurate measurement; theref ore, EPA performed the analysis on a filtered sample collected during the pump-off. Because this test was performed on a filtered sample and because the chlorine may have dissipated during the time between initial sample collection and pump-off, the result may not represent the

actual wastewater characteristics. In addition, EPA was unable to perform the chlorine field test measurement for the effluent from the bottom ash pond immediately after sample collection.

• 

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

### 3-13 Table 3-1. Sample Collection Information, Homer City

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 08/22/2007

1153 a and 1442 b 70420

SP-2 Second-Stage Clarifier Overflow in FGD Wastewater Treatment System Grab 08/23/2007

0750 70421

SP-3 Effluent from FGD Wastewater Treatment System Grab 08/22/2007

0813 70422

SP-4 Effluent from Bottom Ash Pond Grab 08/23/2007

1130 70423

SP-5 Duplicate of Effluent from FGD Wastewater Treatment System Grab 08/22/2007

0813 70424

SP-6 Influent to FGD Wastewater Treatment System Field Blank Grab 08/22/2007

1127 a and 1430 b 70425

SP-7 Second-Stage Clarifier Overflow in FGD Wastewater Treatment System Field

Blank Grab 08/23/2007

0718 70426

SP-8 Effluent from FGD Wastewater Treatment System Field Blank Grab 08/22/2007

0731 70427

SP-9 Effluent from Bottom Ash Pond Field

Blank Grab 08/23/2007

1102 70428

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).

### 3-14Table 3-2. Number of Samples Collectedby Sampling Point, Homer CitySamplingPointNumberSampling Point Description Low-Level Total Metals (11 analytes) Low-Level Dissolved Metals (11 analytes) Low-Level Total Mercury Low-Level Dissolved Mercury Low-Level Hexavalent Chromium Routine Total Metals (27 analytes) Routine Dissolved Metals (27 analytes) BOD 5 Group I

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

cSP-1 Influent to FGD WastewaterTreatment System1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1 1 1 1 1 1+dupSP-2 Second-Stage Clarifier Overflow inFGD Wastewater Treatment System1 1 1 1 1 1 1 1 1 1 1 1 1+dupSP-3 Effluent from FGD WastewaterTreatment System1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+dupSP-4 Bottom Ash Pond Effluent 1+QC 1+QC 1+QC 1+QC1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+QC 1+dupSP-5 Duplicate of Effluent from FGDWastewater Treatment System1 1 1 1 1 1 1 1 1 1 1SP-6 Influent to FGD WastewaterTreatment System Field Blank1 1 1SP-7 Second-Stage Clarifier Overflow inFGD Wastewater Treatment SystemField Blank1 1 1 1 1 1 1SP-8 Effluent from FGD WastewaterTreatment System Field Blank1 1 1 1 1 1 1SP-9 Bottom Ash Pond Effluent FieldBlank1 1 1 1 1 1 1Total Number of Samples 9+3QC 9+3QC 9+3QC 5+3QC7+2QC 8+3QC 8+3QC 5+2QC 5+2QC 5+2QC 4+2QC 8+2QC 4+4dupa – Group I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate and chloride.b – Group II includes ammonia as nitrogen,nitrate/nitrite as nitrogen, total Kjeldahl nitrogen (TKN), and total phosphorus.c –The selenium/arsenic speciation results from the sampling episodewere not available at the timethis report was finalized andtherefore are not included in this report.

### 3-15Table 3-3. Field Measurements, Homer CitypH(S.U.)SamplingPointNumberSampling PointDescriptionDate andTimeTemp°CMeterMeteraStripsFree Chlorine(mg/L)Total Chlorine(mg/L)ManganeseInterferenceReading(mg/L)WasteStreamFlow Rate(GPM)SP-1 Influent to FGDWastewater Treatment08/22/07124938.2 6.78 NA 0.00b0.00bNA 109cSP-2 Second-Stage ClarifierOverflow in FGDWastewater TreatmentSystem08/23/07082332.8 8.09 8.5 0.00d0.00dNASP-3 Effluent from FGDWastewater Treatment08/22/07092129.4 7.37 7 0.33 0.33 0.00 107eSP-4 Bottom Ash Pond Effluent 08/23/07120737.8 8.46 NA 0.00f0.00fNAa – The pH meter was calibrated on the morning of August 22 and 23, 2007 using pre-packaged buffer solutions at pHs 4.0, 7.0, and 10.0.b – EPA did not initially perform a free and total chlorine measurement because the color of the sample would prevent an accurate colorimetric reading. EPAlater performed a reading of the filtered sample after settling,which resulted in 0.00 mg/L for both free and total chlorine.c – Flow rate based on one measurement recorded from the influent flow meter during sample collection at 1:11 PM on August 22,2007.d – The free and total chlorine measurements were 0.00 mg/L; however, the samplers observed that the sample looked cloudy afterthe N,N’-diethyl-pphenylenediamine (DPD) reagent addition (as compared tothe colorless sample prior to reagent addition).e – Flow rate based on the average of 12 measurements recorded from the effluent flow meter during sample collection on August22, 2007.NA – Not analyzed.f – EPA performed the free and total chlorine measurements at 5:00 pm; therefore, the chlorine in the sample may have dissipated.

### 3-16 Table 3-4. Analytical Methods and Procedu res for Samples Collected at Homer City

Method Number Parameter Method Type

Classicals

SM 5210 B Biochemical Oxygen Demand (BOD5) Probe

SM 2540 D Total Suspended Solids (TSS) Gravimetric

SM 2540 C Total Dissolved Solids (TDS) Gravimetric

ASTM D516-90 Sulf ate Turbidimetric

SM 4500–Cl–C Chloride Titrimetric, mercuric

nitrate

SM 4500—NH 3 F (18th ed.) Ammonia as Nitrogen Distillation, potentiometric

SM 4500—NO 3 -H Nitrate/Nitrate 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 (SGT-HEM) 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. ICP/MS – Inductively coupled plasma with mass spectrometry. ICP – Inductively coupled plasma. CVAA – Cold vapor atomic adsorption.

### 3-17 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)

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

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 caps None (acid preserve at laboratory)

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

Low-level hexavalent chromium (Method 1636) One 500-mL LDPE (ultraclean), fluoropolymer lined caps 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.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. b – The sample bottle was filled too full to preserve initia lly; therefore, EPA removed some excess volume with a pipet prior to preserving the sample. The bottle was shaken well prior to removing the excess volume.



### 3-18 Table 3-6. Sample Preservation Summary, Homer City

Sampling

Point

Number Analysis Date and

Time Chemical Initial pH Final pH Amount Added

70420 Group II V1 08/22/07 H 2 SO 4 7 2 50 drops

70420 Group II V2 08/22/07 H 2 SO 4 7 2 50 drops

70420 HEM/SGT-HEM V1 08/22/07 H 2 SO 4 7 2 65 drops

70420 HEM/SGT-HEM V2 08/22/07 H 2 SO 4 7 2 65 drops

70420 Routine Hexavalent

Chromium 08/22/07 Ammonium

Sulfate Buffer 7 9 250 drops a

70420 Arsenic/Selenium Speciation (Duplicate) 08/22/07 HCl 7 2 15 drops

70421 Group II V1 08/23/07 H 2 SO 4 8.5 2 50 drops

70421 Group II V2 08/23/07 H 2 SO 4 8.5 2 50 drops

70421 HEM/SGT-HEM V1 08/23/07 H 2 SO 4 8.5 2 70 drops

70421 HEM/SGT-HEM V2 08/23/07 H 2 SO 4 8.5 2 70 drops

70421 Routine Hexavalent

Chromium 08/23/07 Ammonium

Sulfate Buffer 8.5 9.5 250 drops

70421 Arsenic/Selenium Speciation (Duplicate) 08/23/07 HCl 8.5 2 30 drops

70422 Group II V1 08/22/07 H 2 SO 4 7 2 60 drops

70422 Group II V2 08/22/07 H 2 SO 4 7 2 60 drops

70422 Group II V1 MS/MSD 08/22/07 H 2 SO 4 7 2 60 drops

70422 Group II V2 MS/MSD 08/22/07 H 2 SO 4 7 2 60 drops

70422 HEM/SGT-HEM V1 08/22/07 H 2 SO 4 7 2 100 drops

70422 HEM/SGT-HEM V2 08/22/07 H 2 SO 4 7 2 100 drops

70422 HEM/SGT-HEM V1

MS/MSD 08/22/07 H 2 SO 4 7 2 100 drops

70422 HEM/SGT-HEM V2

MS/MSD 08/22/07 H 2 SO 4 7 2 100 drops

70422 Routine Hexavalent

Chromium 08/22/07 Ammonium

Sulfate Buffer 7 9 250 drops b

70422 Routine Hexavalent

Chromium MS/MSD 08/22/07 Ammonium

Sulfate Buffer 7 9 250 drops b

70422 Arsenic/Selenium Speciation (Duplicate) 08/22/07 HCl 7 2 20 drops

70423 Group II V1 08/23/07 H 2 SO 4 6.5 2 50 drops

70423 Group II V2 08/23/07 H 2 SO 4 6.5 2 50 drops

70423 Group II V1 MS/MSD 08/23/07 H 2 SO 4 6.5 2 50 drops

70423 Group II V2 MS/MSD 08/23/07 H 2 SO 4 6.5 2 50 drops

70423 HEM/SGT-HEM V1 08/23/07 H 2 SO 4 6.5 2 80 dropsa – Preservation of this sample was stopped due to excessive buffering of the sample. The pH of the sample was not changing with the addition of the ammonium sulfate buff er solution; therefore, the preservation was stopped to prevent the sample from being diluted by the preservative. b – The sample bottle was filled too full to preserve initia lly; therefore, EPA removed some excess volume with a pipet prior to preserving the sample. The bottle was shaken well prior to removing the excess volume.



### 3-19 Table 3-6. Sample Preservation Summary, Homer City

Sampling

Point

Number Analysis Date and

Time Chemical Initial pH Final pH Amount Added

70423 HEM/SGT-HEM V2 08/23/07 H 2 SO 4 6.5 2 80 drops

70423 HEM/SGT-HEM V1 08/23/07 H 2 SO 4 6.5 2 90 drops

70423 HEM/SGT-HEM V2 08/23/07 H 2 SO 4 6.5 2 90 drops

70423 Routine Hexavalent

Chromium 08/23/07 Ammonium

Sulfate Buffer 6.5 9.5 250 drops

70423 Routine Hexavalent

Chromium MS/MSD 08/23/07 Ammonium

Sulfate Buffer 6.5 9.5 250 drops

70423 Arsenic/Selenium Speciation (Duplicate) 08/22/07 HCl 5.5 2 20 drops

70424 Group II V1 (Duplicate) 08/22/07 H 2 SO 4 7 2 60 drops

70424 Group II V2 (Duplicate) 08/22/07 H 2 SO 4 7 2 60 drops

70424 Routine Hexavalent Chromium (Duplicate) 08/22/07 Ammonium

Sulfate Buffer 7 9 250 drops b

70426 Routine Hexavalent Chromium (Field Blank) 08/23/07 Ammonium

Sulfate Buffer 7 9.5 80 drops

70427 Routine Hexavalent Chromium (Field Blank) 08/22/07 Ammonium

Sulfate Buffer 7 9.5 90 drops

70428 Routine Hexavalent Chromium (Field Blank) 08/23/07 Ammonium

Sulfate Buffer 7 9.5 140 drops

### 3-20Table 3-7. Generating Unit Operating Characteristics During Sample Collection, Homer CityUnitIDBoiler TypeCoal typeCoalUsage(tons)aSource 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 Supercriticalwall fired boilerEasternBituminous blend11,429 See note below. 650 646 (99%) SCR on. ESP No2 Supercriticalwall fired boilerEasternBituminous blend10,939 See note below. 650 618 (95%) SCR on. ESP No3 Babcock &Wilson drumboilerEasternBituminous blend12,097 See note below. 700 675 (96%) SCR on. ESP YesNote: Homer City was burning an Eastern Bituminous blend of mostly coal from the upper and lower Freeport seam and the upper,middle, and lower Kittanningseam. In addition a lesser amount of coal from the Pittsburgh seam is also used.a – Total amount of coal burned in the units from 12 AM 8/22/07 through 11 PM 8/23/07 (48 hours average).Table 3-8. FGD Scrubber System Operating Characteristics, Homer CityUnit IDType ofScrubberSorbentAdditives(DBA, FormicAcid, etc.)FGD Make-up WaterSourceSO2RemovalPercentage(%)ForcedOxidation(Yes/No)Percent Solidsin Slurry(%)Type of SolidsSeparation3 Spray tray Limestone Formic Acid Open cycle usingclarified river water andcooling water blowdownfrom unit 3 only.Typically 95-98%95.4% Average for8/22-23Yes Typically13-15%aPrimary andSecondaryHydroclonesa – The solids concentration in the scrubber purge, after the primary and secondary hydroclones, during the sampling episode was 9,900 mg/L on 8/22/07 and21,700 mg/L on 8/23/07.

### 3-21 Table 3-9. FGD Wastewater Treatment System Operating Characteristics, Homer City

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

Scrubber slurry blowdown flow rate 1444 gpm

Scrubber slurry blowdown duration 12 - 13 hours

Scrubber slurry blowdown percent solids 16 percent to 13 percent (start to finish)

FGD Wastewater Treatment System Op eration During Sa mple Collection

Scrubber purge flow rate 230 gpm

Scrubber purge duration 12 – 13 hours

Lime addition 2.78 gpm for pH of 8.1

Ferric chloride addition 63 ppm (set-point in first-stage neutralization tank) 60 ppm (set-point in second-stage neutralization tank)

Anionic Polymer (Nalco Pol-E-Z 2706) addition 14 ppm (set-point in fi rst-stage clarifier) 6.5 ppm (set-point in second-stage clarifier)

Cationic Polymer (Nalcolyte 8100) addition 20 ppm (set-point in first stage neutralization tank)

Hydrochloric acid addition Not used during sampling episode

Effluent flow rate (average) 110 gpm

Frequency of effluent discharge Continuous

Retention time of first-stage neutralization tank 38 minutes

Retention time of first-stage clarifier 60 minutes

Retention time of second-stage neutralization tank 38 minutes

Retention time of second-stage clarifier 60 minutes

Note: Data regarding the FGD solids dewatering frequency were not provided by Homer City.



### Table 3-10. Bottom Ash System Operating Characteristics, Homer City

Unit ID Bottom Ash Generation (tph) Bottom Ash Sluice

Water Flow Rate (gph) Source of Bottom

Ash Sluice Water Sluice Cycle

Duration and

Frequency Continuous Sluicing (Yes/No)

1 8.09 168,000 Units 1, 2, and 3

circulation water cooling towers. 90 minutes each 12

hour shift No

2 8.09 168,000 Units 1, 2, and 3

circulation water cooling towers. 90 minutes each 12

hour shift No

3 4.62 168,000 Units 1, 2, and 3

circulation water cooling towers. 45 minutes each 12

hour shift No

### 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 F GD wastewater treatment system, as well as the second-stage clarifier overflow w ithin the system. Section 4.3 presents the laboratory analytical data for the effluent from the bottom ash pond.

Appendix A provides all analytical results for all samples collected at Homer City, 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 Sections 4.2 and 4.3, but with the J-values shown (J -values are not included in the tables presen ted in Sections 4.2 and 4.3).

4.1 Measured and Calculated Results for FGD Influent Samples

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

concentrations for the follo wing phases of the sample:

• 

### Aqueous phase;

• 

### Solid phase; and

• 

### Total sample.

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

Routine Metals and Selected Classicals Analyses

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

### 4-2 Sample Solid Solid Filtrate Filtrate 

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

= (4-1)

where:

C Filtrate 

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

V Filtrate 

### = volume of the filtrate;

C Solid 

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

Wt Solid 

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

V Sample 

### = volume of the original sample.

ProChem used the same approach for the six cla ssical pollutants that were analyzed as biphasic samples: ammonia as nitrogen, chloride, nitrate/ni trite, sulfate, total Kjeldahl nitrogen (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 analyses for the Homer City 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 th e dissolved phase of the sample; and

C TSS 

### = TSS concentration of the sample.

Analytical Deviations

During the analysis of the Homer City FGD influent 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

### 4-3 same approach as Battelle (i.e., analyzing the total sample directly), because the laboratory 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 re sults from the influent to the FGD wastewater treatment system (SP-1) sample analysis, including 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 biphasi c analysis for routine total mercury and Table 4-3 presents the results of the biphasic analysis for ammonia as nitrogen, chloride, sulfate, nitrate/nitrite, TKN, and total phos phorus in the FGD influent samp les. Only those analytes that

were detected at the influent to the FGD wast ewater treatment system (at levels above the reporting limit) are included in the tables. Resu lts are rounded to three significant figures. Appendix Table A-1 presents all th e analytical results from the in fluent to the FGD wastewater treatment system (SP-1) sample analysis, including J-values.

ProChem performed a filtration blank associ ated with the biphasic sample separation process for the FGD influent (SP-1) sample analysis. For the blank, ProChem poured blank water through the filter used for the separation and analyzed 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 filtration blank sample above the reporting limit, indicating that there was no contamination from the filtration process. Appendix Table A-2 presents all the routine mercury anal ytical 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 the FGD wastewater treatment system (SP-1), the second-stage clarifier overflow from the FGD wastewater treatment system (SP-2), and the effl uent from the FGD wastewater treatment system (average of SP-3 and SP-5 results). Table 4-5 presents the analyti cal results of the routine and low-level metals for these same sampling points. Only those analytes that we re detected in one or more samples (at levels above the reporting 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 treatme nt system (approximately 3.5 days).

Appendix Tables A-1, A-3, A-4, and A-5 pres ent all the analytical results from the influent to the FGD wastewater treatment syst em (SP-1), the second-st age clarifier overflow from the FGD wastewater treatment system ( SP-2), the effluent from the FGD wastewater treatment system (SP-3), and the duplicate of th e effluent from the F GD wastewater treatment system (SP-5) sample analyses, including J-valu es. Appendix Table B-1 presents the analytical results for the metal analytes in a format simila r to Table 4-5; however, Table B-1 also include results where analytes were measured above th e method detection level, but below the reporting limit (i.e., J-values).

4.3 Bottom Ash Pond Treatment System

Table 4-6 presents the analytical results of th e classical pollutants at the effluent from the bottom ash treatment system (SP-4). Table 4-7 pres ents the analytical resu lts of the routine and low-level metals at the effluent from the bottom ash treatment system (SP-4). Only those analytes that were detected in one or more sa mples (at levels above th e reporting limit) for the sampling episode are included in the table. Result s are rounded to three si gnificant digits. If an analyte was measured above the method detectio n limit, but below the report limit, “NQ” is reported followed by the sample-specific report limit in parentheses. If an analyte was notdetected in a sample above the method detection limit, “ND” is reported followed by the samplespecific report limit in parenthe ses. Appendix Table A-6 presents all the analytical results from the effluent from the bottom ash treatment system (SP-4) sample analys is, including J-values. Appendix Table B-2 presents the an alytical results for the metal an alytes in a format similar to Table 4-7; however, Table B-2 also include results where analytes were measured above the method detection level, but below th e reporting limit (i.e., J-values).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. R – MS/MSD % Recovery outsid e method acceptance criteria.

Exclude – Results were excluded because the MS/MSD sa mples had a zero percent recovery for total thallium.



### 4-5 Table 4-1. Biphasic Sample Results for Low-Le vel Total Metals and Routine Total Metals Measured Above the Report Limit, FGD Influent, Homer City

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

Low-level Total Metals

Antimony ND (0.400) 2.67 31.1

Arsenic 24.2 R 103 1,220

Cadmium 24.5 2.43 52.8 R

Chromium ND (16.0) 109 1,270

Copper 11.3 63.2 747

Lead ND (1.00) 30.2 351

Mercury 0.0809 50.8 533

Nickel 1,450 119 2,840

Selenium 584 253 3,530

Thallium 23.2 1.21 37.3

Zinc 34.7 180 2,130

Routine Total Metals

Aluminum ND (50.0) 21,700 289,000

Antimony NQ (20.0) 5.11 86.4

Arsenic NQ (10.0) 119 1,590

Barium 149 R 884 11,900 R

Beryllium 10.5 1.38 28.8

Boron 254,000 ND (1,500) 224,000

Cadmium 26.2 9.31 150

Calcium 1,990,000 92,500 3,220,000

Chromium ND (10.0) 105 1,400

Cobalt 201 12.6 369

Copper 14.5 59.9 811

Iron ND (100) 62,000 824,000

Lead NQ (50.0) 24.7 340

Magnesium 3,100,000 ND (1,500) 2,760,000

Manganese 173,000 3,910 225,000

Molybdenum 30.6 25.9 375

Nickel 1,350 91.0 2,560

Selenium 656 251 4,000

Sodium 1,440,000 ND (3,760) 1,430,000

Thallium 61.2 Exclude Exclude

Titanium ND (10.0) 97.7 1,300

Vanadium ND (20.0) 57.6 766ND – 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. R – MS/MSD % Recovery outsid e method acceptance criteria.

Exclude – Results were excluded because the MS/MSD sa mples had a zero percent recovery for total thallium.



### 4-6 Table 4-1. Biphasic Sample Results for Low-Le vel Total Metals and Routine Total Metals Measured Above the Report Limit, FGD Influent, Homer City

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

Yttrium 6.28 43.6 586

Zinc ND (10.0) 143 1,900

### 4-7 Table 4-2. Biphasic Sample Results for Routine Total Mercury, FGD Influent, Homer City

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

Routine Total Metals

Mercury ND (10.0) 14.5 243

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



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

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

Classical Pollutants

Ammonia As Nitrogen (NH 3 -N) 3.62 23.8 4.12

Nitrate/Nitrite (NO 3 -N + NO 2 -N) 44.0 467 54.5

Total Kjeldahl Nitrogen (TKN) 9.52 199 14.2

Chloride 12,000 4,000 11,800

Sulfate 5,900 46,900 6,920

Total Phosphorus 0.680 79.6 2.64

### 4-8Table 4-4. Classical Pollutants Measured Above the ReportLimit for the FGD Wastewater Treatment System, Homer CityAnalyteMethodUnitFGD Influent (SP-1)FGD Second-stageClarifier OverflowEffluent (SP-2)FGD Effluent(SP-3/SP-5)aClassical PollutantsAmmonia As Nitrogen (NH3-N)4500-NH3FMG/L4.123.800.295Nitrate/Nitrite (NO3-N + NO2-N) 353.2 MG/L 54.5 6.00 36.5 RTotal Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 14.2 13.1 3.04Chloride4500-CL-CMG/L11,80011,50011,800SulfateD516-90MG/L6,9202,9202,790Total Dissolved Solids (TDS)2540 CMG/L23,20020,50022,600Total Phosphorus365.3MG/L2.640.3500.520Total Suspended Solids (TSS)2540 DMG/L13,3008.00<5.50a – The FGD effluent results represent the average of the FGD effluent and the duplicate of the FGD effluent analytical measurements.R – MS/MSD % Recovery outside method acceptance criteria.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).Note: Results shown are not paired samples. See Section 4.2.

### 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).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 “NQ” forthe average FGD effluent indicatesthat the original FGD effluent and/or the duplicate of theFGD effluent is a J-value. Theanalytical result for the original FGD effluent and/or the duplicate of the FGD effluent is presented in Appendix A with a J flagdesignation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).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, Homer CityFGD Influent (SP-1)FGD Second-stage ClarifierOverflow Effluent (SP-2)FGD Effluent (SP-3/SP-5)aAnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedRoutine MetalsAluminum 200.7 UG/L 289,000 ND (50.0) ND (50.0) ND (50.0) ND (50.0) ND (50.0)Antimony 200.7 UG/L 86.4 NQ (20.0) 20.1 NQ (20.0) <20.8 NQ (20.0)Arsenic 200.7 UG/L 1,590 NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0)Barium 200.7 UG/L 11,900 R 149 R 112 116 71.3 R 70.6 R,TBeryllium 200.7 UG/L 28.8 10.5 7.69 7.90 7.68 7.71Boron 200.7 UG/L 224,000 254,000 191,000 187,000 191,000 184,000Cadmium 200.7 UG/L 150 26.2 NQ (5.00) NQ (5.00) NQ (5.00) NQ (5.00)Calcium 200.7 UG/L 3,220,000 1,990,000 1,740,000 1,520,000 2,000,000 1,930,000Chromium 200.7 UG/L 1,400 ND (10.0) ND (10.0) NQ (10.0) ND (10.0) ND (10.0)HexavalentChromiumD1687-92 UG/L NA ND (2.00) NA ND (2.00) NA ND (2.00)Cobalt 200.7 UG/L 369 201 NQ (50.0) NQ (50.0) NQ (50.0) NQ (50.0)Copper 200.7 UG/L 811 14.5 12.3 12.0 12.5 11.8Iron 200.7 UG/L 824,000 ND (100) NQ (100) NQ (100) <117 166 RLead 200.7 UG/L 340 NQ (50.0) NQ (50.0) ND (50.0) NQ (50.0) NQ (50.0)Magnesium 200.7 UG/L 2,760,000 3,100,000 2,640,000 2,630,000 2,610,000 2,510,000Manganese 200.7 UG/L 225,000 173,000 47,700 47,000 30,100 29,100

### 4-10a – 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).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 “NQ” forthe average FGD effluent indicatesthat the original FGD effluent and/or the duplicate of theFGD effluent is a J-value. Theanalytical result for the original FGD effluent and/or the duplicate of the FGD effluent is presented in Appendix A with a J flagdesignation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).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, Homer CityFGD Influent (SP-1)FGD Second-stage ClarifierOverflow Effluent (SP-2)FGD Effluent (SP-3/SP-5)aAnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedMercury 245.1 UG/L 243 ND (10.0) ND (10.0) ND (10.0) ND (10.0) ND (10.0)Molybdenum 200.7 UG/L 375 30.6 36.7 35.9 37.6 35.8Nickel 200.7 UG/L 2,560 R 1,350 56.9 56.9 NQ (50.0) NQ (50.0)Selenium 200.7 UG/L 4,000 R 656 R 187 179 771 741 RSodium 200.7 UG/L 1,430,000 1,440,000 1,140,000 1,130,000 1,280,000 1,230,000Thallium 200.7 UG/L Exclude 61.2 ND (10.0)ND (10.0) ND (10.0) ND (10.0)Titanium 200.7 UG/L 1,300 R ND (10.0) ND (10.0) ND (10.0) ND (10.0) ND (10.0)Vanadium 200.7 UG/L 766 ND (20.0) ND (20.0) ND (20.0) ND (20.0) NQ (20.0)Yttrium 200.7 UG/L 586 6.28 NQ (5.00) NQ (5.00) NQ (5.00) NQ (5.00)Zinc 200.7 UG/L 1,900 ND (10.0) ND (10.0) ND (10.0) ND (10.0) NQ (10.0)Low-Level MetalsAntimony 1638 UG/L 31.1 ND (0.400) ND (0.400) ND (0.400) ND (0.400) ND (0.400)Arsenic 1638 UG/L 1,220 24.2 R 20.6 21.8 23.0 22.5Cadmium 1638 UG/L 52.8 R 24.5 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.00)Chromium 1638 UG/L 1,270 ND (16.0) NQ (16.0) NQ (16.0) NQ (16.0) NQ (16.0)HexavalentChromium1636 UG/L NA NA NA ND (2.50) NA ND (2.50)Copper 1638 UG/L 747 11.3 10.9 9.22 9.67 9.39

### 4-11a – 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).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 “NQ” forthe average FGD effluent indicatesthat the original FGD effluent and/or the duplicate of theFGD effluent is a J-value. Theanalytical result for the original FGD effluent and/or the duplicate of the FGD effluent is presented in Appendix A with a J flagdesignation.R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).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, Homer CityFGD Influent (SP-1)FGD Second-stage ClarifierOverflow Effluent (SP-2)FGD Effluent (SP-3/SP-5)aAnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedLead 1638 UG/L 351 ND (1.00) NQ (1.00) NQ (1.00) NQ (1.00) NQ (1.00)Mercury 1631E UG/L 533 0.0809 0.125 0.0245 0.117 0.0542Nickel 1638 UG/L 2,840 1,450 111 116 92.1 93.5Selenium 1638 UG/L 3,530 584 238 241 613 620Thallium 1638 UG/L 37.3 23.2 16.8 16.6 16.0 15.8Zinc 1638 UG/L 2,130 34.7 15.0 14.4 15.2 15.7

### 4-12 Table 4-6. Classical Pollutants Measured Ab ove the Report Limit for the Bottom Ash

Pond Effluent, Homer City

Analyte Method Unit Bottom Ash Pond Effluent (SP-4)

Classical Pollutants

Ammonia As Nitrogen (NH 3 -N) 4500-NH 3 F MG/L 0.340

Nitrate/Nitrite (NO 3 -N + NO 2 -N) 353.2 MG/L 37.0

Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1.36

Chloride 4500-CL-C MG/L 90.0

Sulfate D516-90 MG/L 1,290

Total Dissolved Solids (TDS) 2540 C MG/L 1,250

Total Phosphorus 365.3 MG/L 1.09

Total Suspended Solids (TSS) 2540 D MG/L 5.00L – Sample result between 5x and 10x blank result. NA – Not analyzed.
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.



### 4-13 Table 4-7. Metals Measured Above the Report Limit for the Bottom Ash Pond Effluent, Homer City

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

Routine Total Metals

Aluminum 200.7 UG/L 323 231

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

Arsenic 200.7 UG/L NQ (10.0) NQ (10.0)

Barium 200.7 UG/L 101 106

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

Boron 200.7 UG/L 396 397

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

Calcium 200.7 UG/L 186,000 192,000

Chromium 200.7 UG/L NQ (10.0) NQ (10.0)

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

Cobalt 200.7 UG/L NQ (50.0) NQ (50.0)

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

Iron 200.7 UG/L 355 106

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

Magnesium 200.7 UG/L 31,800 32,600

Manganese 200.7 UG/L 128 129

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

Molybdenum 200.7 UG/L 19.7 20.2

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

Selenium 200.7 UG/L 6.02 6.10 L

Sodium 200.7 UG/L 106,000 106,000

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

Titanium 200.7 UG/L NQ (10.0) NQ (10.0)

Vanadium 200.7 UG/L NQ (20.0) NQ (20.0)

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

Zinc 200.7 UG/L 21.6 35.2

Low-Level Metals

Antimony 1638 UG/L 1.09 0.990

Arsenic 1638 UG/L 6.52 5.00

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

Chromium 1638 UG/L NQ (4.00) NQ (4.00)

Hexavalent Chromium 1636 UG/L NA 3.01

Copper 1638 UG/L 2.37 2.08

Lead 1638 UG/L NQ (0.250) NQ (0.250)L – Sample result between 5x and 10x blank result. NA – Not analyzed.
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.



### 4-14 Table 4-7. Metals Measured Above the Report Limit for the Bottom Ash Pond Effluent, Homer City

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

Mercury 1631E UG/L 0.00511 0.00141

Nickel 1638 UG/L 10.7 10.4

Selenium 1638 UG/L 5.74 5.16

Thallium 1638 UG/L 1.32 1.31

Zinc 1638 UG/L 24.2 15.0

### 5-1 5. D ATA 

### Q UALITY



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

5.1 Analytical Quality Control

EPA contracted directly with analytical labor atories for the analysis of samples collected during this episode. EPA’s Sample Control Center (SCC) verified that the performances of the laboratories selected by EPA wa s acceptable by conducting QC checks of the analytical data as specified by SCC’s Quality Assurance Project Plan dated 15 February 2008. SCC data review chemists prepared written data review narrative s describing any qualifications of the analytical data from this episode. The data revi ew 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 ch romium samples bottles (500 mL LDPE), the speciation sample bottles (125 mL amber glass bo ttles), and the 2-L blank water bottles by filling the pre-cleaned bottle to the neck with ASTM T ype 1 water, preserving the sample with nitric acid to a pH <2, and allowing the sample to sit for at least 24 hours. Albion Environmental then analyzed the samples using EPA Method 1638.

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

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

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

### 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-7 pr esents all of the analy tical results from the bottle blank and equipment blank analyses for al l of the equipment used for the collection of low-level samples.

5.2.2 Equipment Blanks

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

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

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

No metals were detected in the equi pment blanks, indicating that there was no contamination from the sampling equipment. Appe ndix Table A-7 presents all of the analytical results from the bottle blank and equipment blank analyses for all of the equipment used for the collection of low-level samples.

5.2.3 Field Blanks

The sampling team collected field blanks (SP-6, SP-7, SP-8, and SP-9) to evaluate possible contamination caused by sampling equi pment, sampling equipment decontamination procedures, sample collection procedures, or at mospheric contamination. EPA analyzed the field

### 5-3 blank samples for the low-level and routine meta ls analyses, including both total and dissolved

metals 1



### .

The low-level total metals field blank samples for the influent to the FGD Wastewater Treatment System (SP-6) were collected by pour ing ASTM Type 1 water through a precleaned funnel attached to the silicone tubing used fo r sample collection. The sampling team shrouded the blank water and funnel with a plastic bag while pouring the blank wa ter into the funnel to prevent potential atmospheric de position. In addition, the sample bottles were placed in a “cleanbox” to prevent potential atmospheric deposition. The ASTM Type 1 water flowed through the funnel and tubing, and was poured into the sample bottles. EPA collected the field blank samples separately from the Homer City representative’s field blank samples. Split samples were not collected for the field blank sa mples because the sample split was performed at the tap outlet, not with in the sample tubing.

The low-level and routine total metals field blank samples for the second-stage clarifier overflow in the FGD wastewater treatment system (SP-7), the effluent from the FGD Wastewater Treatment System (SP-8), and the effluent fr om the bottom ash pond (SP-9) were collected by pumping ASTM Type 1 water through the tubing used for the sample collection. The container holding the ASTM Type 1 water was placed in a large plastic bag and the tubing was placed directly into the container. Th e large plastic bag was closed off as quickly as possible to minimize potential atmospheric deposition. The sample bottles were placed in a “cleanbox” and the ASTM Type 1 water was pumped through the tubing and “Y” splitter, and poured into the sample bottles. EPA collected the field blank samp les as “true” split samples with Homer City’s representative, using the same procedure discusse d in the sample collect ion description (Section 3.1).

The low-level and routine dissolved metals field blank samples for the influent to the FGD Wastewater Treatment Syst em (SP-6), the second-stage cl arifier overflow in the FGD wastewater treatment system (SP-7), the efflue nt from the FGD Wastewater Treatment System (SP-8), and the effluent from the bottom ash pond (SP-9) were collected by pumping ASTM Type 1 water through the tubing used for the diss olved metals sample collection and a capsule filter. The container holding the ASTM Type 1 wa ter was placed in a large plastic bag and the tubing was placed directly into the container. The large plastic bag was closed off as quickly as possible to minimize potential atmospheric depo sition. The sample bottles were placed in a “cleanbox” and the ASTM Type 1 water was pumped through the tubing, capsule filter, and “Y” splitter, and poured into the samp le bottles. EPA collected the fiel d blank samples as “true” split samples with Homer City’s representative, using the same procedure discussed in the sample collection descripti on (Section 3.1).

1 EPA did not collect a low-level dissolved mercury field bl ank 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 0.000315 ug/L in the filtration blank performed for the first day of samples, which includes the influent to the FGD wast ewater treatment system, th e effluent from the FGD wastewater treatment system, and the dup licate of the effluent from the FGD wastewater treatment system; however, this concentration is below the report limit of 0.0005 ug/L. Therefore, this sample result is flagged as a J-value. Mercury was not detected above the met hod detection limit (0.000188 ug/L) in the filtration blank performed for the second day of samples, which includes the FGD second-stage clarifier overflow effluent and the bottom ash pond

effluent.

### 5-4 Table 5-1 presents the fiel d blank analytical results fo r SP-6 through SP-9. 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 three significant digits . Appendix Tables A-8 through A-11 present all the analytical results for the field blanks from the influent to the FGD wastewater treatment system ( SP-6), second-stage clarifier over flow in the FGD wastewater treatment system (SP-7), effluent from the FGD wastewater treatment system (SP-8), and effluent from the bottom ash pond (SP-9) sample analyses, including all qualified results and all

results that were measured above the method de tection limit, but below the reporting limit (i.e., J-values).

5.2.4 Field Duplicates

The sampling team collected field duplicate samples (SP-5) to assess the sampling measurement precision for the episode. Field du plicate samples are separate samples collected from the same location as the original sample . The duplicate is filled immediately after the original sample, and is stored and analyzed in dependently. The relative percent difference (RPD) between the two sample results is examined to determine the precision of the data. EPA used the following equation to calculate the RPD for the duplicate sample results.

100

2 D S D S (%) RPD × ⎟ ⎠ ⎞ ⎜ ⎝ ⎛ + −

= 

### (5-1)

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

result.

During this sampling episode, duplicate sa mples (SP-5) for all analytes (except HEM/SGT-HEM) were collected from the effluent from the FGD wastewater treatment system (SP-3). Table 5-1 presents an alytical results and the RPD for SP-3 and SP-5 and includes analytical results for only those analytes that were detected in one or more samples for the sampling episode. Results are rounded to three significant figures. Appendi x Tables A-4 and A-5 present all the analytical results for the effluentfrom the FGD wastewater treatment system (SP3) and the duplicate of the effluent from the FGD wastewater treatment system (SP-5) sample analyses, including all qualified results and all results that were measured above the method detection limit, but below the reporting limit (i.e., J-values).

### 5-5 Table 5-1. Field Blank Results Measured Above the Report Limit, Homer City

Analyte Sample Point Method Unit Concentration (ug/L)

Routine Total Metals

Calcium FGD Effluent 200.7 UG/L 141

Calcium Bottom Ash Effluent 200.7 UG/L 86.3

Magnesium Bottom Ash Effluent 200.7 UG/L 220

Routine Dissolved Metals

Barium FGD Effluent 200.7 UG/L 4.70

Calcium FGD Effluent 200.7 UG/L 193

Magnesium FGD Effluent 200.7 UG/L 221

Molybdenum FGD Effluent 200.7 UG/L 55.8

Selenium FGD Effluent 200.7 UG/L 15.1

Low-Level Dissolved Metals

Hexavalent Chromium FGD Second-stage Clarifier

Overflow 1636 UG/L 3.17

Hexavalent Chromium FGD Effluent 1636 UG/L 2.56

Copper Bottom Ash Effluent 1638 UG/L 0.240

Hexavalent Chromium Bottom Ash Effluent 1636 UG/L 4.36

### 5-6< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-2. Field Duplicate Results, Homer CityAnalyteOriginal FGD EffluentConcentration (SP-3)Duplicate FGD EffluentConcentration (SP-5)Average ResultRelative PercentDifference (%)UnitsClassical PollutantsAmmonia As Nitrogen (NH3-N) 0.360 0.230 0.295 44 MG/LNitrate/Nitrite (NO3-N + NO2-N) 37.0 36.0 R 36.5 2.7 MG/LTotal Kjeldahl Nitrogen (TKN) 2.96 3.11 3.04 4.9 MG/LChloride 12,000 11,500 11,800 4.3 MG/LSulfate 2,520 3,050 2,790 19 MG/LTotal Dissolved Solids (TDS) 23,800 21,300 22,600 11 MG/LTotal Phosphorus 0.720 0.320 0.520 77 MG/LTotal Suspended Solids (TSS) ND (5.00) 6.00 < 5.50 NC MG/LRoutine Total MetalsAluminum ND (50.0) ND (50.0) ND (50.0) NC UG/LAntimony NQ (20.0) 21.5 < 20.8NC UG/LArsenic NQ (10.0) NQ (10.0) ND (10.0) NC UG/LBarium 71.1 R 71.4 71.3 0.42 UG/LBeryllium 7.61 7.74 7.68 1.7 UG/LBoron 188,000 193,000 191,000 2.6 UG/LCadmium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LCalcium 1,920,000 2,070,000 2,000,000 7.5 UG/LChromium ND (10.0) ND (10.0) ND (10.0) NC UG/LCobalt NQ (50.0) NQ (50.0) ND (50.0) NC UG/LCopper 13.0 12.0 12.5 8.0 UG/LIron 134 NQ (100) < 117 NC UG/LLead NQ (50.0) NQ (50.0) ND (50.0) NC UG/L

### 5-7< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-2. Field Duplicate Results, Homer CityAnalyteOriginal FGD EffluentConcentration (SP-3)Duplicate FGD EffluentConcentration (SP-5)Average ResultRelative PercentDifference (%)UnitsMagnesium 2,560,000 2,650,000 2,610,000 3.5 UG/LManganese 29,800 30,300 30,100 1.7 UG/LMercury ND (10.0) ND (10.0) ND (10.0) NC UG/LMolybdenum 37.9 37.2 37.6 1.9 UG/LNickel NQ (50.0) NQ (50.0) ND (50.0) NC UG/LSelenium 773 768 771 0.65 UG/LSodium 1,280,000 1,270,000 1,280,000 0.78 UG/LThallium ND (10.0) ND (10.0) ND (10.0) NC UG/LTitanium ND (10.0) ND (10.0) ND (10.0) NC UG/LVanadium ND (20.0) ND (20.0) ND (20.0) NC UG/LYttrium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LZinc ND (10.0) ND (10.0) ND (10.0) NC UG/LRoutine Dissolved MetalsAluminum ND (50.0) ND (50.0) ND (50.0) NC UG/LAntimony NQ (20.0) NQ (20.0) ND (20.0)NC UG/LArsenic NQ (10.0) NQ (10.0) ND (10.0) NC UG/LBarium 71.9 R,T 69.2 70.6 3.8 UG/LBeryllium 7.74 7.68 7.71 0.78 UG/LBoron 182,000 185,000 184,000 1.6 UG/LCadmium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LCalcium 1,970,000 1,880,000 1,930,000 4.7 UG/LChromium ND (10.0) ND (10.0) ND (10.0) NC UG/LHexavalent Chromium ND (2.00) ND (2.00) ND (2.00) NC UG/L

### 5-8< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-2. Field Duplicate Results, Homer CityAnalyteOriginal FGD EffluentConcentration (SP-3)Duplicate FGD EffluentConcentration (SP-5)Average ResultRelative PercentDifference (%)UnitsCobalt NQ (50.0) NQ (50.0) ND (50.0) NC UG/LCopper 11.6 11.9 11.8 2.6 UG/LIron 134 R 197 166 38 UG/LLead NQ (50.0) NQ (50.0) ND (50.0) NC UG/LMagnesium 2,520,000 2,500,000 2,510,000 0.80 UG/LManganese 29,200 29,000 29,100 0.69 UG/LMercury ND (10.0) ND (10.0) ND (10.0) NC UG/LMolybdenum 36.3 35.2 35.8 3.1 UG/LNickel NQ (50.0) NQ (50.0) ND (50.0) NC UG/LSelenium 766 R 715 741 6.9 UG/LSodium 1,250,000 1,210,000 1,230,000 3.3 UG/LThallium ND (10.0) ND (10.0) ND (10.0) NC UG/LTitanium ND (10.0) ND (10.0) ND (10.0) NC UG/LVanadium ND (20.0) NQ (20.0) ND (20.0) NC UG/LYttrium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LZinc NQ (10.0) ND (10.0) ND (10.0) NC UG/LLow-Level Total MetalsAntimony ND (0.400) ND (0.400) ND (0.400) NC UG/LArsenic 23.5 22.4 23.0 4.8 UG/LCadmium NQ (2.00) NQ (2.00) ND (2.00)NC UG/LChromium NQ (16.0) NQ (16.0) ND (16.0) NC UG/LCopper 9.44 9.90 9.67 4.8 UG/LLead NQ (1.00) NQ (1.00) ND (1.00) NC UG/L

### 5-9< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).R – MS/MSD % Recovery outside method acceptance criteria.T – MS/MSD RPD outside method acceptance criteria.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-2. Field Duplicate Results, Homer CityAnalyteOriginal FGD EffluentConcentration (SP-3)Duplicate FGD EffluentConcentration (SP-5)Average ResultRelative PercentDifference (%)UnitsMercury 0.117 0.117 0.117 0.0 UG/LNickel 92.0 92.2 92.1 0.22 UG/LSelenium 621 605 613 2.6 UG/LThallium 15.9 16.0 16.0 0.63 UG/LZinc 15.2 15.2 15.2 0.0 UG/LLow-Level Dissolved MetalsAntimony ND (0.400) ND (0.400) ND (0.400) NC UG/LArsenic 22.5 22.4 22.5 0.45 UG/LCadmium NQ (2.00) NQ (2.00) ND (2.00) NC UG/LChromium NQ (16.0) NQ (16.0) ND (16.0)NC UG/LHexavalent Chromium ND (2.50) ND (2.50) ND (2.50) NC UG/LCopper 9.26 9.52 9.39 2.8 UG/LLead ND (1.00) NQ (1.00) ND (1.00) NC UG/LMercury 0.0556 0.0528 0.0542 5.2 UG/LNickel 93.7 93.3 93.5 0.43 UG/LSelenium 606 634 620 4.5 UG/LThallium 15.8 15.8 15.8 0.0 UG/LZinc 15.2 16.2 15.7 6.4 UG/L

### 6-1 6. R EFERENCES



### 1. Eastern Research Group, Inc., 2007. Final Engi neering Site Visit Report for EME Homer City Generation L.P.’s, Homer City Po wer Plant. August 9. DCN 04718. EPA-HQ-OW2006-0071-0695.

2. Eastern Research Group, Inc., 2007. Sampling Plan, EME Homer City Generation L.P.’s Homer City Power Plant. August 17. DCN 04860A1. EPA-HQ-OW-2006-0071-0649.1.

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

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

### Appendix A

ANALYTICAL RESULTS

### A-1NA – 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-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Table A-1. FGD Influent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-SpecificMDLSampleSpecific RLConcentrationClassical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L NA NP NP 4.12Nitrate/Nitrite (NO3-N + NO2-N) 353.2 MG/L NA NP NP 54.5Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L NA NP NP 14.2Biochemical Oxygen Demand (BOD) 5210B MG/L 120 NP NP ND (120) UChloride 4500-CL-C MG/L NA NP NP 11,800Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP ND (5.00) USulfate D516-90 MG/L NA NP NP 6,920Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 23,200Total Phosphorus 365.3 MG/L NA NP NP 2.64Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 13,300Classical Pollutants – Solid (wet weight)Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/KG 1 NP NP 23.8Nitrate/Nitrite (NO3-N + NO2-N) 1685 MG/KG 1 NP NP 467Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/KG 1 NP NP 199Chloride 4500-CL-C MG/KG 1 NP NP 4,000Sulfate D516-90 MG/KG 5,000 NP NP 46,900Total Phosphorus 365.3 MG/KG 1 NP NP 79.6Classical Pollutants – Filtered AqueousAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 3.62

### A-2NA – 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-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Table A-1. FGD Influent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-SpecificMDLSampleSpecific RLConcentrationNitrate/Nitrite (NO3-N + NO2-N) 353.2 MG/L 10 NP NP 44.0Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 9.52Chloride 4500-CL-C MG/L 50 NP NP 12,000Sulfate D516-90 MG/L 200 NP NP 5,900Total Phosphorus 365.3 MG/L 1 NP NP 0.680Routine Metals – TotalAluminum 200.7 UG/L 20 212 1,000 289,000Antimony 200.7 UG/L 2 1.40 40.0 86.4Arsenic 200.7 UG/L 2 1.00 20.0 1,590Barium 200.7 UG/L 20 2.00 40.0 11,900 RBeryllium 200.7 UG/L 2 1.00 10.0 28.8Boron 200.7 UG/L 200 540 20,000 224,000Cadmium 200.7 UG/L 2 0.200 10.0 150Calcium 200.7 UG/L 20 102 1,000 3,220,000Chromium 200.7 UG/L 2 0.400 20.0 1,400Cobalt 200.7 UG/L 2 1.20 100 369Copper 200.7 UG/L 2 0.400 20.0 811Iron 200.7 UG/L 20 108 2,000 824,000Lead 200.7 UG/L 2 1.40 100 340Magnesium 200.7 UG/L 20 178 4,000 2,760,000

### A-3NA – 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-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Table A-1. FGD Influent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-SpecificMDLSampleSpecific RLConcentrationManganese 200.7 UG/L 200 40.0 3,000 225,000Mercury 245.1 UG/L NA NC 22.0 243Molybdenum 200.7 UG/L 2 0.400 20.0 375Nickel 200.7 UG/L 2 2.20 100 2,560 RSelenium 200.7 UG/L 2 1.20 10.0 4,000 RSilver 200.7 UG/L 2 0.800 40.0 34.6 JSodium 200.7 UG/L 20 810 10,000 1,430,000Thallium 200.7 UG/L 2 1.00 20.0 ExcludeTin 200.7 UG/L 2 0.800 60.0 38.1 JTitanium 200.7 UG/L 2 0.400 20.0 1,300 RVanadium 200.7 UG/L 2 1.20 40.0 766Yttrium 200.7 UG/L 2 0.400 10.0 586Zinc 200.7 UG/L 2 0.400 20.0 1,900Routine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 18.4 JArsenic 200.7 UG/L 1 0.500 10.0 7.51 JBarium 200.7 UG/L 1 0.100 2.00 149 RBeryllium 200.7 UG/L 1 0.500 5.00 10.5Boron 200.7 UG/L 100 270 10,000 254,000

### A-4NA – 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-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Table A-1. FGD Influent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-SpecificMDLSampleSpecific RLConcentrationCadmium 200.7 UG/L 1 0.100 5.00 26.2Calcium 200.7 UG/L 100 510 5,000 1,990,000Chromium 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 201Copper 200.7 UG/L 1 0.200 10.0 14.5Iron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 11.5 JMagnesium 200.7 UG/L 100 890 20,000 3,100,000Manganese 200.7 UG/L 100 20.0 1,500 173,000Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 30.6Nickel 200.7 UG/L 1 1.10 50.0 1,350Selenium 200.7 UG/L 1 0.600 5.00 656 RSilver 200.7 UG/L 1 0.400 20.0 7.93 JSodium 200.7 UG/L 100 4,050 50,000 1,440,000Thallium 200.7 UG/L 1 0.500 10.0 61.2Tin 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-5NA – 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-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Table A-1. FGD Influent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-SpecificMDLSampleSpecific RLConcentrationYttrium 200.7 UG/L 1 0.200 5.00 6.28Zinc 200.7 UG/L 1 0.200 10.0 ND (10.0) URoutine 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 50 0.300 1.25 14.5Routine Metals – Solid (dry weight)Aluminum 200.7 MG/KG NA 15.9 75.2 21,700Antimony 200.7 MG/KG NA 0.105 3.01 5.11Arsenic 200.7 MG/KG NA 0.0752 1.50 119Barium 200.7 MG/KG NA 0.150 3.01 884Beryllium 200.7 MG/KG NA 0.0752 0.752 1.38Boron 200.7 MG/KG NA 40.6 1,500 ND (1,500) UCadmium 200.7 MG/KG NA 0.0150 0.752 9.31Calcium 200.7 MG/KG NA 38.3 376 92,500Chromium 200.7 MG/KG NA 0.0301 1.50 105Cobalt 200.7 MG/KG NA 0.0902 7.52 12.6Copper 200.7 MG/KG NA 0.0301 1.50 59.9Iron 200.7 MG/KG NA 8.12 150 62,000Lead 200.7 MG/KG NA 0.105 7.52 24.7

### A-6NA – 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-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Table A-1. FGD Influent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-SpecificMDLSampleSpecific RLConcentrationMagnesium 200.7 MG/KG NA 66.9 1,500 ND (1,500) UManganese 200.7 MG/KG NA 3.01 226 3,910Molybdenum 200.7 MG/KG NA 0.0301 1.50 25.9Nickel 200.7 MG/KG NA 0.165 7.52 91.0Selenium 200.7 MG/KG NA 0.0902 0.752 251Silver 200.7 MG/KG NA 0.0602 3.01 ND (3.01) USodium 200.7 MG/KG NA 305 3,760 ND (3,760) UThallium 200.7 MG/KG NA 0.0752 1.50 ExcludeTin 200.7 MG/KG NA 0.0602 4.51 ND (4.51) UTitanium 200.7 MG/KG NA 0.0301 1.50 97.7Vanadium 200.7 MG/KG NA 0.0902 3.01 57.6Yttrium 200.7 MG/KG NA 0.0301 0.752 43.6Zinc 200.7 MG/KG NA 0.0301 1.50 143Low-Level Metals – TotalAntimony 1638 UG/L 200 1.40 4.00 31.1Arsenic 1638 UG/L 200 3.04 30.0 1,220Cadmium 1638 UG/L 200 0.200 20.0 52.8 RChromium 1638 UG/L 200 16.6 160 1,270Copper 1638 UG/L 200 0.800 40.0 747Lead 1638 UG/L 200 0.200 10.0 351

### A-7NA – 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-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Table A-1. FGD Influent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-SpecificMDLSampleSpecific RLConcentrationMercury 1631E UG/L 1,000 0.188 0.500 533Nickel 1638 UG/L 200 2.60 200 2,840Selenium 1638 UG/L 200 3.20 200 3,530Silver 1638 UG/L 200 0.400 20.0 ND (20.0) UThallium 1638 UG/L 200 0.0800 4.00 37.3Zinc 1638 UG/L 200 41.8 100 2,130Low-Level Metals - DissolvedAntimony 1638 UG/L 20 0.140 0.400 ND (0.400) UArsenic 1638 UG/L 20 0.304 3.00 24.2 RCadmium 1638 UG/L 20 0.0200 2.00 24.5Chromium 1638 UG/L 20 1.66 16.0 ND (16.0) UCopper 1638 UG/L 20 0.0800 4.00 11.3Lead 1638 UG/L 20 0.0200 1.00 ND (1.00) UMercury 1631E UG/L 100 0.0188 0.0500 0.0809Nickel 1638 UG/L 20 0.260 20.0 1,450Selenium 1638 UG/L 20 0.320 20.0 584Silver 1638 UG/L 20 0.0400 2.00 ND (2.00) UThallium 1638 UG/L 20 0.00800 0.400 23.2Zinc 1638 UG/L 20 4.18 10.0 34.7

### A-8NA – 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-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.J – Result measured above the MDL, but less than the reporting limit.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Table A-1. FGD Influent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-SpecificMDLSampleSpecific RLConcentrationLow-Level Metals – Solid (dry weight)Antimony 1638 MG/KG NA 0.120 0.344 2.67Arsenic 1638 MG/KG NA 0.261 2.58 103Cadmium 1638 MG/KG NA 0.0189 1.72 2.43Chromium 1638 MG/KG NA 1.43 13.8 109Copper 1638 MG/KG NA 0.0688 3.44 63.2Lead 1638 MG/KG NA 0.0172 0.859 30.2Mercury 1631E MG/KG NA 0.0179 0.0477 50.8Nickel 1638 MG/KG NA 0.224 17.2 119Selenium 1638 MG/KG NA 0.275 17.2 253Silver 1638 MG/KG NA 0.0344 1.72 ND (1.72) UThallium 1638 MG/KG NA 0.00690 0.344 1.21Zinc 1638 MG/KG NA 3.59 8.59 180

### A-9 Table A-2. ProChem Biphasic Filtration Bl ank Analytical Results, Homer City

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-10J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-3. FGD Second-Stage Clarifier Overflow Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical PollutantsAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 3.80Nitrate/Nitrite (NO3-N + NO2-N) 353.2 MG/L 5 NP NP 6.00Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 13.1Biochemical Oxygen Demand (BOD) 5210B MG/L 60 NP NP ND (73.0) UChloride 4500-CL-C MG/L 50 NP NP 11,500Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP ND (5.00) USulfate D516-90 MG/L 100 NP NP 2,920Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 20,500Total Phosphorus 365.3 MG/L 1 NP NP 0.350Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 8.00Routine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 20.1Arsenic 200.7 UG/L 1 0.500 10.0 3.81 JBarium 200.7 UG/L 1 0.100 2.00 112Beryllium 200.7 UG/L 1 0.500 5.00 7.69Boron 200.7 UG/L 100 270 10,000 191,000Cadmium 200.7 UG/L 1 0.100 5.00 3.93 JCalcium 200.7 UG/L 100 510 5,000 1,740,000Chromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UCobalt 200.7 UG/L 1 0.600 50.0 10.8 JCopper 200.7 UG/L 1 0.200 10.0 12.3Iron 200.7 UG/L 1 5.40 100 85.9 J

### A-11J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-3. FGD Second-Stage Clarifier Overflow Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLead 200.7 UG/L 1 0.700 50.0 3.17 JMagnesium 200.7 UG/L 100 890 20,000 2,640,000Manganese 200.7 UG/L 100 20.0 1,500 47,700Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 36.7Nickel 200.7 UG/L 1 1.10 50.0 56.9Selenium 200.7 UG/L 1 0.600 5.00 187Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,140,000Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 0.938 JTitanium 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 1.52 JZinc 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 14.0 JArsenic 200.7 UG/L 1 0.500 10.0 3.05 JBarium 200.7 UG/L 1 0.100 2.00 116Beryllium 200.7 UG/L 1 0.500 5.00 7.90Boron 200.7 UG/L 100 270 10,000 187,000Cadmium 200.7 UG/L 1 0.100 5.00 3.58 JCalcium 200.7 UG/L 100 510 5,000 1,520,000

### A-12J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-3. FGD Second-Stage Clarifier Overflow Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationChromium 200.7 UG/L 1 0.200 10.0 2.46 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 10.7 JCopper 200.7 UG/L 1 0.200 10.0 12.0Iron 200.7 UG/L 1 5.40 100 85.4 JLead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 100 890 20,000 2,630,000Manganese 200.7 UG/L 100 20.0 1,500 47,000Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 35.9Nickel 200.7 UG/L 1 1.10 50.0 56.9Selenium 200.7 UG/L 1 0.600 5.00 179Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,130,000Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 1.88 JTitanium 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 1.62 JZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) ULow-Level Metals – TotalAntimony 1638 UG/L 20 0.140 0.400 ND (0.400) UArsenic 1638 UG/L 20 0.304 3.00 20.6Cadmium 1638 UG/L 20 0.0200 2.00 1.74 J

### A-13J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-3. FGD Second-Stage Clarifier Overflow Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationChromium 1638 UG/L 20 1.66 16.0 8.76 JCopper 1638 UG/L 20 0.0800 4.00 10.9Lead 1638 UG/L 20 0.0200 1.00 0.0512 JMercury 1631E UG/L 5 0.000940 0.00250 0.125Nickel 1638 UG/L 20 0.260 20.0 111Selenium 1638 UG/L 20 0.320 20.0 238Silver 1638 UG/L 20 0.0400 2.00 0.0413 JThallium 1638 UG/L 20 0.00800 0.400 16.8Zinc 1638 UG/L 20 4.18 10.0 15.0Low-Level Metals - DissolvedAntimony 1638 UG/L 20 0.140 0.400 ND (0.400) UArsenic 1638 UG/L 20 0.304 3.00 21.8Cadmium 1638 UG/L 20 0.0200 2.00 1.69 JChromium 1638 UG/L 20 1.66 16.0 9.27 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 ND (2.50) UCopper 1638 UG/L 20 0.0800 4.00 9.22Lead 1638 UG/L 20 0.0200 1.00 0.0485 JMercury 1631E UG/L 5 0.000940 0.00250 0.0245Nickel 1638 UG/L 20 0.260 20.0 116Selenium 1638 UG/L 20 0.320 20.0 241Silver 1638 UG/L 20 0.0400 2.00 0.0891 JThallium 1638 UG/L 20 0.00800 0.400 16.6Zinc 1638 UG/L 20 4.18 10.0 14.4

### A-14J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.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).Table A-4. FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical PollutantsAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 0.360Nitrate/Nitrite (NO3-N + NO2-N) 353.2 MG/L 10 NP NP 37.0Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 2.96Biochemical Oxygen Demand (BOD) 5210B MG/L 120 NP NP ND (120) UChloride 4500-CL-C MG/L 50 NP NP 12,000Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP ND (5.00) USulfate D516-90 MG/L 100 NP NP 2,520Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 23,800Total Phosphorus 365.3 MG/L 1 NP NP 0.720Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP ND (5.00) URoutine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 13.6 JArsenic 200.7 UG/L 1 0.500 10.0 3.60 JBarium 200.7 UG/L 1 0.100 2.00 71.1 RBeryllium 200.7 UG/L 1 0.500 5.00 7.61Boron 200.7 UG/L 100 270 10,000 188,000Cadmium 200.7 UG/L 1 0.100 5.00 3.24 JCalcium 200.7 UG/L 100 510 5,000 1,920,000Chromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UCobalt 200.7 UG/L 1 0.600 50.0 6.36 JCopper 200.7 UG/L 1 0.200 10.0 13.0

### A-15J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.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).Table A-4. FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationIron 200.7 UG/L 1 5.40 100 134Lead 200.7 UG/L 1 0.700 50.0 0.987 JMagnesium 200.7 UG/L 100 890 20,000 2,560,000Manganese 200.7 UG/L 100 20.0 1,500 29,800Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 37.9Nickel 200.7 UG/L 1 1.10 50.0 34.0 JSelenium 200.7 UG/L 1 0.600 5.00 773Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,280,000Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 3.41 JTitanium 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 1.46 JZinc 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 14.0 JArsenic 200.7 UG/L 1 0.500 10.0 3.56 JBarium 200.7 UG/L 1 0.100 2.00 71.9 R, TBeryllium 200.7 UG/L 1 0.500 5.00 7.74Boron 200.7 UG/L 100 270 10,000 182,000

### A-16J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.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).Table A-4. FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCadmium 200.7 UG/L 1 0.100 5.00 3.30 JCalcium 200.7 UG/L 100 510 5,000 1,970,000Chromium 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 6.27 JCopper 200.7 UG/L 1 0.200 10.0 11.6Iron 200.7 UG/L 1 5.40 100 134 RLead 200.7 UG/L 1 0.700 50.0 2.58 JMagnesium 200.7 UG/L 100 890 20,000 2,520,000Manganese 200.7 UG/L 100 20.0 1,500 29,200Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 36.3Nickel 200.7 UG/L 1 1.10 50.0 31.7 JSelenium 200.7 UG/L 1 0.600 5.00 766 RSilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,250,000Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 4.41 JTitanium 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 1.53 JZinc 200.7 UG/L 1 0.200 10.0 9.62 J

### A-17J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.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).Table A-4. FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLow-Level Metals – TotalAntimony 1638 UG/L 20 0.140 0.400 ND (0.400) UArsenic 1638 UG/L 20 0.304 3.00 23.5Cadmium 1638 UG/L 20 0.0200 2.00 1.77 JChromium 1638 UG/L 20 1.66 16.0 10.4 JCopper 1638 UG/L 20 0.0800 4.00 9.44Lead 1638 UG/L 20 0.0200 1.00 0.0362 JMercury 1631E UG/L 100 0.0188 0.0500 0.117Nickel 1638 UG/L 20 0.260 20.0 92.0Selenium 1638 UG/L 20 0.320 20.0 621Silver 1638 UG/L 20 0.0400 2.00 0.0672 JThallium 1638 UG/L 20 0.00800 0.400 15.9Zinc 1638 UG/L 20 4.18 10.0 15.2Low-Level Metals - DissolvedAntimony 1638 UG/L 20 0.140 0.400 ND (0.400) UArsenic 1638 UG/L 20 0.304 3.00 22.5Cadmium 1638 UG/L 20 0.0200 2.00 1.61 JChromium 1638 UG/L 20 1.66 16.0 10.2 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 ND (2.50) UCopper 1638 UG/L 20 0.0800 4.00 9.26Lead 1638 UG/L 20 0.0200 1.00 ND (1.00) UMercury 1631E UG/L 100 0.0188 0.0500 0.0556Nickel 1638 UG/L 20 0.260 20.0 93.7

### A-18J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.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).Table A-4. FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationSelenium 1638 UG/L 20 0.320 20.0 606Silver 1638 UG/L 20 0.0400 2.00 0.0695 JThallium 1638 UG/L 20 0.00800 0.400 15.8Zinc 1638 UG/L 20 4.18 10.0 15.2

### A-19J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical PollutantsAmmonia As Nitrogen (NH3-N)) 4500-NH3F MG/L 1 NP NP 0.230Nitrate/Nitrite (NO3-N + NO2-N) 353.2 MG/L 25 NP NP 36.0 RTotal Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 3.11Biochemical Oxygen Demand (BOD) 5210B MG/L 120 NP NP ND (120) UChloride 4500-CL-C MG/L 50 NP NP 11,500Sulfate D516-90 MG/L 100 NP NP 3,050Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 21,300Total Phosphorus 365.3 MG/L 1 NP NP 0.320Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 6.00Routine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 21.5Arsenic 200.7 UG/L 1 0.500 10.0 3.05 JBarium 200.7 UG/L 1 0.100 2.00 71.4Beryllium 200.7 UG/L 1 0.500 5.00 7.74Boron 200.7 UG/L 100 270 10,000 193,000Cadmium 200.7 UG/L 1 0.100 5.00 3.14 JCalcium 200.7 UG/L 100 510 5,000 2,070,000Chromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UCobalt 200.7 UG/L 1 0.600 50.0 6.25 JCopper 200.7 UG/L 1 0.200 10.0 12.0Iron 200.7 UG/L 1 5.40 100 86.6 J

### A-20J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLead 200.7 UG/L 1 0.700 50.0 1.79 JMagnesium 200.7 UG/L 100 890 20,000 2,650,000Manganese 200.7 UG/L 100 20.0 1,500 30,300Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 37.2Nickel 200.7 UG/L 1 1.10 50.0 33.5 JSelenium 200.7 UG/L 1 0.600 5.00 768Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,270,000Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 0.555 JTitanium 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 1.51 JZinc 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 14.2 JArsenic 200.7 UG/L 1 0.500 10.0 3.59 JBarium 200.7 UG/L 1 0.100 2.00 69.2Beryllium 200.7 UG/L 1 0.500 5.00 7.68Boron 200.7 UG/L 100 270 10,000 185,000Cadmium 200.7 UG/L 1 0.100 5.00 3.12 J

### A-21J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCalcium 200.7 UG/L 100 510 5,000 1,880,000Chromium 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 6.00 JCopper 200.7 UG/L 1 0.200 10.0 11.9Iron 200.7 UG/L 1 5.40 100 197Lead 200.7 UG/L 1 0.700 50.0 1.38 JMagnesium 200.7 UG/L 100 890 20,000 2,500,000Manganese 200.7 UG/L 100 20.0 1,500 29,000Mercury 245.1 UG/L 50 2.50 10.0 ND (10.0) UMolybdenum 200.7 UG/L 1 0.200 10.0 35.2Nickel 200.7 UG/L 1 1.10 50.0 31.8 JSelenium 200.7 UG/L 1 0.600 5.00 715Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 100 4,050 50,000 1,210,000Thallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 0.611 JTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 0.726 JYttrium 200.7 UG/L 1 0.200 5.00 1.22 JZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) ULow-Level Metals – TotalAntimony 1638 UG/L 20 0.140 0.400 ND (0.400) U

### A-22J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationArsenic 1638 UG/L 20 0.304 3.00 22.4Cadmium 1638 UG/L 20 0.0200 2.00 1.71 JChromium 1638 UG/L 20 1.66 16.0 11.7 JCopper 1638 UG/L 20 0.0800 4.00 9.90Lead 1638 UG/L 20 0.0200 1.00 0.0355 JMercury 1631E UG/L 100 0.0188 0.0500 0.117Nickel 1638 UG/L 20 0.260 20.0 92.2Selenium 1638 UG/L 20 0.320 20.0 605Silver 1638 UG/L 20 0.0400 2.00 0.0745 JThallium 1638 UG/L 20 0.00800 0.400 16.0Zinc 1638 UG/L 20 4.18 10.0 15.2Low-Level Metals - DissolvedAntimony 1638 UG/L 20 0.140 0.400 ND (0.400) UArsenic 1638 UG/L 20 0.304 3.00 22.4Cadmium 1638 UG/L 20 0.0200 2.00 1.68 JChromium 1638 UG/L 20 1.66 16.0 8.79 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 ND (2.50) UCopper 1638 UG/L 20 0.0800 4.00 9.52Lead 1638 UG/L 20 0.0200 1.00 0.0274 JMercury 1631E UG/L 100 0.0188 0.0500 0.0528Nickel 1638 UG/L 20 0.260 20.0 93.3Selenium 1638 UG/L 20 0.320 20.0 634Silver 1638 UG/L 20 0.0400 2.00 0.0891 J

### A-23J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.R – MS/MSD % Recovery outside method acceptance criteria.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-5. Duplicate of FGD Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationThallium 1638 UG/L 20 0.00800 0.400 15.8Zinc 1638 UG/L 20 4.18 10.0 16.2

### A-24J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-6. Bottom Ash Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical PollutantsAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 0.340Nitrate/Nitrite (NO3-N + NO2-N) 353.2 MG/L 10 NP NP 37.0Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 1.36Biochemical Oxygen Demand (BOD) 5210B MG/L 1 NP NP ND (2.00) UChloride 4500-CL-C MG/L 1 NP NP 90.0Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP ND (5.00) USulfate D516-90 MG/L 100 NP NP 1,290Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 1,250Total Phosphorus 365.3 MG/L 1 NP NP 1.09Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 5.00Routine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 323Antimony 200.7 UG/L 1 0.700 20.0 2.68 JArsenic 200.7 UG/L 1 0.500 10.0 6.50 JBarium 200.7 UG/L 1 0.100 2.00 101Beryllium 200.7 UG/L 1 0.500 5.00 0.569 JBoron 200.7 UG/L 1 2.70 100 396Cadmium 200.7 UG/L 1 0.100 5.00 0.117 JCalcium 200.7 UG/L 10 51.0 500 186,000Chromium 200.7 UG/L 1 0.200 10.0 0.549 JCobalt 200.7 UG/L 1 0.600 50.0 2.07 JCopper 200.7 UG/L 1 0.200 10.0 2.93 J

### A-25J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-6. Bottom Ash Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationIron 200.7 UG/L 1 5.40 100 355Lead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 31,800Manganese 200.7 UG/L 1 0.200 15.0 128Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 19.7Nickel 200.7 UG/L 1 1.10 50.0 7.36 JSelenium 200.7 UG/L 1 0.600 5.00 6.02Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 106,000Thallium 200.7 UG/L 1 0.500 10.0 1.10 JTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 6.78 JVanadium 200.7 UG/L 1 0.600 20.0 7.85 JYttrium 200.7 UG/L 1 0.200 5.00 0.314 JZinc 200.7 UG/L 1 0.200 10.0 21.6Routine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 231Antimony 200.7 UG/L 1 0.700 20.0 1.62 JArsenic 200.7 UG/L 1 0.500 10.0 4.88 JBarium 200.7 UG/L 1 0.100 2.00 106Beryllium 200.7 UG/L 1 0.500 5.00 0.576 JBoron 200.7 UG/L 1 2.70 100 397

### A-26J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-6. Bottom Ash Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCadmium 200.7 UG/L 1 0.100 5.00 0.174 JCalcium 200.7 UG/L 10 51.0 500 192,000Chromium 200.7 UG/L 1 0.200 10.0 0.268 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 1.74 JCopper 200.7 UG/L 1 0.200 10.0 2.82 JIron 200.7 UG/L 1 5.40 100 106Lead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 32,600Manganese 200.7 UG/L 1 0.200 15.0 129Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 20.2Nickel 200.7 UG/L 1 1.10 50.0 7.06 JSelenium 200.7 UG/L 1 0.600 5.00 6.10 LSilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 106,000Thallium 200.7 UG/L 1 0.500 10.0 0.634 JTin 200.7 UG/L 1 0.400 30.0 1.22 JTitanium 200.7 UG/L 1 0.200 10.0 0.745 JVanadium 200.7 UG/L 1 0.600 20.0 6.98 JYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 35.2

### A-27J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-6. Bottom Ash Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLow-Level Metals – TotalAntimony 1638 UG/L 5 0.0350 0.100 1.09Arsenic 1638 UG/L 5 0.0760 0.750 6.52Cadmium 1638 UG/L 5 0.00500 0.500 0.0973 JChromium 1638 UG/L 5 0.415 4.00 2.67 JCopper 1638 UG/L 5 0.0200 1.00 2.37Lead 1638 UG/L 5 0.00500 0.250 0.231 JMercury 1631E UG/L 5 0.000940 0.00250 0.00511Nickel 1638 UG/L 5 0.0650 5.00 10.7Selenium 1638 UG/L 5 0.0800 5.00 5.74Silver 1638 UG/L 5 0.0100 0.500 0.0313 JThallium 1638 UG/L 5 0.00200 0.100 1.32Zinc 1638 UG/L 5 1.05 2.50 24.2Low-Level Metals - DissolvedAntimony 1638 UG/L 5 0.0350 0.100 0.990Arsenic 1638 UG/L 5 0.0760 0.750 5.00Cadmium 1638 UG/L 5 0.00500 0.500 0.117 JChromium 1638 UG/L 5 0.415 4.00 2.28 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 3.01Copper 1638 UG/L 5 0.0200 1.00 2.08Lead 1638 UG/L 5 0.00500 0.250 0.00830 JMercury 1631E UG/L 1 0.000188 0.000500 0.00141Nickel 1638 UG/L 5 0.0650 5.00 10.4

### A-28J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specificRL are 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 theanalyte was not detected above thereport limit, the report limit is presented inparentheses in the concentration column.U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-6. Bottom Ash Effluent Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationSelenium 1638 UG/L 5 0.0800 5.00 5.16Silver 1638 UG/L 5 0.0100 0.500 ND (0.500) UThallium 1638 UG/L 5 0.00200 0.100 1.31Zinc 1638 UG/L 5 1.05 2.50 15.0ND – Not detected (number in parenthesis is the report limit).



### A-29 Table A-7. Bottle Blank and Equipment Blank Analytical Data, Homer City

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-30 Table A-7. Bottle Blank and Equipment Blank Analytical Data, Homer City

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-31 Table A-7. Bottle Blank and Equipment Blank Analytical Data, Homer City

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)

LDPE 2000 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)ND – Not detected (number in parenthesis is the report limit).



### A-32 Table A-7. Bottle Blank and Equipment Blank Analytical Data, Homer City

Analyte Method Process Units Concentration

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)

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



### A-33 Table A-7. Bottle Blank and Equipment Blank Analytical Data, Homer City

Analyte Method Process Units Concentration

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

C-Flex Tubing Set – Equipment Blan k (#73 silicone tubing attached to #24 silicone tubing for sample

collection for low-level me rcury and metals from FGD influent sample tap)

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)

Tubing Set – Equipment Blank (25 feet of Teflon® tubi ng, 5 feet #24 silicone tubi ng, Y-splitter, two pieces of 5 feet #24 silicone tubing for sample collectio n for low-level mercury and metals from FGD primary clarifier effluent, efflue nt from FGD wastewater treatment syst em, and bottom ash pond effluent)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

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



### A-34 Table A-7. Bottle Blank and Equipment Blank Analytical Data, Homer City

Analyte Method Process Units Concentration

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Funnel Assembly Set – Equipment Blank (Plastic funnel attached to #73 silicone tubing for field blank sample collection for low-level to tal metals at the FGD influent)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

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

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

C-Flex Tubing Set – Equip ment Blank (10 feet #73 silic one tubing, Y-splitter, two pieces of 5 feet #24 silicone tubing for alternative sa mple collection approach for low- level mercury and metals from FGD influent sample tap)

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



### A-35 Table A-7. Bottle Blank and Equipment Blank Analytical Data, Homer City

Analyte Method Process Units Concentration

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

### A-36ND – 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-8. FGD Influent Field Blank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLow-Level Metals – TotalAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND (0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.129 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 ND (0.000500) UNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 ND (0.100) UThallium 1638 UG/L 1 0.000400 0.0200 ND (0.0200) UZinc 1638 UG/L 1 0.209 0.500 ND (0.500) ULow-Level Metals - DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND (0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.154 JCopper 1638 UG/L 1 0.00400 0.200 0.116 JLead 1638 UG/L 1 0.00100 0.0500 ND (0.0500) UNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 0.00260 JThallium 1638 UG/L 1 0.000400 0.0200 ND (0.0200) UZinc 1638 UG/L 1 0.209 0.500 ND (0.500) U

### A-37J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-9. FGD Second-Stage Clarifier OverflowField Blank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationRoutine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 ND (20.0) UArsenic 200.7 UG/L 1 0.500 10.0 ND (10.0) UBarium 200.7 UG/L 1 0.100 2.00 ND (2.00) UBeryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 3.93 JCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 17.4 JChromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND (10.0) UIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 14.6 JManganese 200.7 UG/L 1 0.200 15.0 0.347 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 ND (500) UThallium 200.7 UG/L 1 0.500 10.0 0.556 JTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) U

### A-38J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-9. FGD Second-Stage Clarifier OverflowField Blank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 0.634 JRoutine 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 0.425 JBeryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 4.13 JCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 41.3 JChromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 0.340 JIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 20.4 JManganese 200.7 UG/L 1 0.200 15.0 0.485 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 41.6 JThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) U

### A-39J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-9. FGD Second-Stage Clarifier OverflowField Blank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationTin 200.7 UG/L 1 0.400 30.0 0.533 JTitanium 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 1.78 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 0.140 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 ND (0.000500) UNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 ND (0.100) UThallium 1638 UG/L 1 0.000400 0.0200 ND (0.0200) UZinc 1638 UG/L 1 0.209 0.500 ND (0.500) ULow-Level Metals - DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND (0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.115 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 3.17Copper 1638 UG/L 1 0.00400 0.200 0.0770 JLead 1638 UG/L 1 0.00100 0.0500 ND (0.0500) U

### A-40J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-9. FGD Second-Stage Clarifier OverflowField Blank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 0.00240 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-41J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-10. FGD Effluent Field Blank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationRoutine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 ND (20.0) UArsenic 200.7 UG/L 1 0.500 10.0 ND (10.0) UBarium 200.7 UG/L 1 0.100 2.00 ND (2.00) UBeryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 51.0 JCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 141Chromium 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 8.90 200 157 JManganese 200.7 UG/L 1 0.200 15.0 1.91 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 ND (500) UThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) U

### A-42J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-10. FGD Effluent Field Blank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 0.517 JRoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 8.04 JArsenic 200.7 UG/L 1 0.500 10.0 ND (10.0) UBarium 200.7 UG/L 1 0.100 2.00 4.70Beryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 36.2 JCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 193Chromium 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 0.214 JIron 200.7 UG/L 1 5.40 100 6.21 JLead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 221Manganese 200.7 UG/L 1 0.200 15.0 2.83 JMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 55.8Nickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 15.1Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 ND (500) UThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) U

### A-43J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-10. FGD Effluent Field Blank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationTin 200.7 UG/L 1 0.400 30.0 0.971 JTitanium 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 0.427 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 0.132 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 ND (0.000500) UNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 ND (0.100) UThallium 1638 UG/L 1 0.000400 0.0200 ND (0.0200) UZinc 1638 UG/L 1 0.209 0.500 ND (0.500) ULow-Level Metals - DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 0.00190 JChromium 1638 UG/L 1 0.0830 0.800 0.115 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 2.56Copper 1638 UG/L 1 0.00400 0.200 ND (0.200) ULead 1638 UG/L 1 0.00100 0.0500 ND (0.0500) U

### A-44J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-10. FGD Effluent Field Blank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 ND (0.100) UThallium 1638 UG/L 1 0.000400 0.0200 0.000600 JZinc 1638 UG/L 1 0.209 0.500 ND (0.500) U

### A-45J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-11. Bottom Ash Effluent FieldBlank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationRoutine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 ND (50.0) UAntimony 200.7 UG/L 1 0.700 20.0 ND (20.0) UArsenic 200.7 UG/L 1 0.500 10.0 ND (10.0) UBarium 200.7 UG/L 1 0.100 2.00 ND (2.00) UBeryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 20.2 JCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 86.3Chromium 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 0.659 JIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 220Manganese 200.7 UG/L 1 0.200 15.0 3.98 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 40.5 500 128 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-46J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-11. Bottom Ash Effluent FieldBlank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 1.08 JRoutine 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 0.504 JBeryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 19.7 JCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 18.5 JChromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 1.01 JIron 200.7 UG/L 1 5.40 100 24.9 JLead 200.7 UG/L 1 0.700 50.0 1.57 JMagnesium 200.7 UG/L 1 8.90 200 ND (200) UManganese 200.7 UG/L 1 0.200 15.0 0.227 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 0.403 JSodium 200.7 UG/L 1 40.5 500 45.7 JThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) U

### A-47J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-11. Bottom Ash Effluent FieldBlank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) UYttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 0.636 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 0.00260 JChromium 1638 UG/L 1 0.0830 0.800 0.0868 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 ND (0.000500) UNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 ND (0.100) UThallium 1638 UG/L 1 0.000400 0.0200 ND (0.0200) UZinc 1638 UG/L 1 0.209 0.500 ND (0.500) ULow-Level Metals - DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 0.00130 JChromium 1638 UG/L 1 0.0830 0.800 ND (0.800) UHexavalent Chromium 1636 UG/L 5 1.75 2.50 4.36Copper 1638 UG/L 1 0.00400 0.200 0.240Lead 1638 UG/L 1 0.00100 0.0500 ND (0.0500) U

### A-48J – Result measured above the MDL, but less than the reporting limit.ND – Not detected (number in parenthesis is the report limit).U – Result below the MDL. (Number shown in parentheses is the reporting limit).Table A-11. Bottom Ash Effluent FieldBlank Analytical Data, Homer CityAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 ND (0.100) UThallium 1638 UG/L 1 0.000400 0.0200 0.000400 JZinc 1638 UG/L 1 0.209 0.500 ND (0.500) U

### Appendix B

ANALYTICAL DATA FOR METALS, FGD WASTEWATER AND BOTTOM ASH POND

### B-1J – 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).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Note: Results shown are not paired samples. See Section 4.2.Table B-1. Analytical Results for Metals in the FGD WastewaterTreatment System, Homer CityFGD Influent (SP-1)Second-Stage ClarifierOverflow Effluent (SP-2)Original FGD Effluent (SP-3)Duplicate FGD Effluent(SP-5)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedTotalDissolvedRoutine MetalsAluminum 200.7 UG/L 289,000 ND (50.0) UND (50.0) U ND (50.0) U ND (50.0) UND (50.0) U ND (50.0) U ND (50.0) UAntimony 200.7 UG/L 86.4 18.4 J 20.114.0 J 13.6 J 14.0 J 21.5 14.2 JArsenic 200.7 UG/L 1,590 7.51 J 3.81J 3.05 J 3.60 J 3.56 J 3.05 J 3.59 JBarium 200.7 UG/L 11,900 R 149 R 112116 71.1 R 71.9 R,T 71.4 69.2Beryllium 200.7 UG/L 28.8 10.5 7.697.90 7.61 7.74 7.74 7.68Boron 200.7 UG/L 224,000 254,000 191,000187,000 188,000 182,000 193,000 185,000Cadmium 200.7 UG/L 150 26.2 3.93 J3.58 J 3.24 J 3.30 J 3.14 J 3.12 JCalcium 200.7 UG/L 3,220,000 1,990,000 1,740,000 1,520,000 1,920,0001,970,000 2,070,000 1,880,000Chromium 200.7 UG/L 1,400 ND (10.0)U ND (10.0) U 2.46 J ND (10.0) U ND(10.0) U ND (10.0) U ND (10.0) UHexavalentChromiumD1687-92 UG/L NA ND (2.00) U NA ND (2.00)U NA ND (2.00) U NA ND (2.00) UCobalt 200.7 UG/L 369 201 10.8 J 10.7 J 6.36 J 6.27 J 6.25 J 6.00 JCopper 200.7 UG/L 811 14.5 12.312.0 13.0 11.6 12.0 11.9Iron 200.7 UG/L 824,000 ND (100) U 85.9 J 85.4 J 134 134 R 86.6 J 197Lead 200.7 UG/L 340 11.5 J 3.17 J ND (50.0) U 0.987 J 2.58 J 1.79 J 1.38 JMagnesium 200.7 UG/L 2,760,000 3,100,000 2,640,000 2,630,000 2,560,0002,520,000 2,650,000 2,500,000Manganese 200.7 UG/L 225,000173,000 47,700 47,000 29,800 29,200 30,300 29,000Mercury 245.1 UG/L 243 ND (10.0) U ND (10.0) U ND (10.0) U ND (10.0) U ND(10.0) U ND (10.0) U ND (10.0) UMolybdenum 200.7 UG/L 375 30.6 36.735.9 37.9 36.3 37.2 35.2Nickel 200.7 UG/L 2,560 R 1,350 56.956.9 34.0 J 31.7 J 33.5 J 31.8 JSelenium 200.7 UG/L 4,000 R 656 R 187 179 773 766 R 768 715Silver 200.7 UG/L 34.6 J 7.93 J 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-2J – 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).Exclude – Results were excluded because the MS/MSD samples had a zero percent recovery for total thallium.Note: Results shown are not paired samples. See Section 4.2.Table B-1. Analytical Results for Metals in the FGD WastewaterTreatment System, Homer CityFGD Influent (SP-1)Second-Stage ClarifierOverflow Effluent (SP-2)Original FGD Effluent (SP-3)Duplicate FGD Effluent(SP-5)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedTotalDissolvedSodium 200.7 UG/L 1,430,000 1,440,000 1,140,000 1,130,000 1,280,0001,250,000 1,270,000 1,210,000Thallium 200.7 UG/L Exclude 61.2 ND (10.0) U ND (10.0)U ND (10.0) U ND (10.0)U ND (10.0) U ND (10.0) UTin 200.7 UG/L 38.1 J ND (30.0) U 0.938J 1.88 J 3.41 J 4.41 J 0.555 J 0.611 JTitanium 200.7 UG/L 1,300 R ND (10.0) UND (10.0) U ND (10.0) U ND (10.0) UND (10.0) U ND (10.0) U ND (10.0) UVanadium 200.7 UG/L 766 ND (20.0) UND (20.0) U ND (20.0) U ND (20.0)U ND (20.0) U ND (20.0) U 0.726 JYttrium 200.7 UG/L 586 6.28 1.52 J1.62 J 1.46 J 1.53 J 1.51 J 1.22 JZinc 200.7 UG/L 1,900 ND (10.0) U ND(10.0) U ND (10.0) U ND (10.0)U 9.62 J ND (10.0) U ND (10.0) ULow-Level MetalsAntimony 1638 UG/L 31.1 ND (0.400) U ND (0.400) U ND(0.400)U ND (0.400) U ND(0.400)U ND (0.400) U ND (0.400) UArsenic 1638 UG/L 1,220 24.2 R 20.621.8 23.5 22.5 22.4 22.4Cadmium 1638 UG/L 52.8 R 24.5 1.74 J1.69 J 1.77 J 1.61 J 1.71 J 1.68 JChromium 1638 UG/L 1,270 ND (16.0) U 8.76 J 9.27 J 10.4 J 10.2 J 11.7 J 8.79 JHexavalentChromium1636 UG/L NA NA NA ND (2.50) U NAND (2.50) U NA ND (2.50) UCopper 1638 UG/L 747 11.3 10.9 9.22 9.44 9.26 9.90 9.52Lead 1638 UG/L 351 ND (1.00) U 0.0512 J 0.0485 J 0.0362 J ND (1.00) U 0.0355 J 0.0274 JMercury 1631E UG/L 533 0.0809 0.1250.0245 0.117 0.0556 0.117 0.0528Nickel 1638 UG/L 2,840 1,450 111116 92.0 93.7 92.2 93.3Selenium 1638 UG/L 3,530 584 238 241 621 606 605 634Silver 1638 UG/L ND (20.0) U ND (2.00) U 0.0413 J 0.0891 J 0.0672 J0.0695 J 0.0745 J 0.0891 JThallium 1638 UG/L 37.3 23.2 16.816.6 15.9 15.8 16.0 15.8Zinc 1638 UG/L 2,130 34.7 15.014.4 15.2 15.2 15.2 16.2J – Result measured above the MDL, but less than the reporting limit. L – Sample result between 5x and 10x blank result. ND – Not detected (number in parenthesis is the report limit). U – Result below the MDL. (Number shown in parentheses is the reporting limit).



### B-3 Table B-2. Analytical Result s for Metals in the Bottom Ash Pond Effluent, Homer City

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

Routine Metals

Aluminum 200.7 UG/L 323 231

Antimony 200.7 UG/L 2.68 J 1.62 J

Arsenic 200.7 UG/L 6.50 J 4.88 J

Barium 200.7 UG/L 101 106

Beryllium 200.7 UG/L 0.569 J 0.576 J

Boron 200.7 UG/L 396 397

Cadmium 200.7 UG/L 0.117 J 0.174 J

Calcium 200.7 UG/L 186,000 192,000

Chromium 200.7 UG/L 0.549 J 0.268 J

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

Cobalt 200.7 UG/L 2.07 J 1.74 J

Copper 200.7 UG/L 2.93 J 2.82 J

Iron 200.7 UG/L 355 106

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

Magnesium 200.7 UG/L 31,800 32,600

Manganese 200.7 UG/L 128 129

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

Molybdenum 200.7 UG/L 19.7 20.2

Nickel 200.7 UG/L 7.36 J 7.06 J

Selenium 200.7 UG/L 6.02 6.10 L

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

Sodium 200.7 UG/L 106,000 106,000

Thallium 200.7 UG/L 1.10 J 0.634 J

Tin 200.7 UG/L ND (30.0) U 1.22 J

Titanium 200.7 UG/L 6.78 J 0.745 J

Vanadium 200.7 UG/L 7.85 J 6.98 J

Yttrium 200.7 UG/L 0.314 J ND (5.00) U

Zinc 200.7 UG/L 21.6 35.2

Low-Level Metals – Total

Antimony 1638 UG/L 1.09 0.990

Arsenic 1638 UG/L 6.52 5.00

Cadmium 1638 UG/L 0.0973 J 0.117 J

Chromium 1638 UG/L 2.67 J 2.28 J

Hexavalent Chromium 1636 UG/L NA 3.01

Copper 1638 UG/L 2.37 2.08J – Result measured above the MDL, but less than the reporting limit. L – Sample result between 5x and 10x blank result. ND – Not detected (number in parenthesis is the report limit). U – Result below the MDL. (Number shown in parentheses is the reporting limit).



### B-4 Table B-2. Analytical Result s for Metals in the Bottom Ash Pond Effluent, Homer City

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

Lead 1638 UG/L 0.231 J 0.00830 J

Mercury 1631E UG/L 0.00511 0.00141

Nickel 1638 UG/L 10.7 10.4

Selenium 1638 UG/L 5.74 5.16

Silver 1638 UG/L 0.0313 J ND (0.500) U

Thallium 1638 UG/L 1.32 1.31

Zinc 1638 UG/L 24.2 15.0

### 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 7, 2007

TO: Ron Jordan, Project Officer

EPA EAD

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

SUBJECT: Data Review Narrative for Classical Analyses for the Steam Electric Study, Episode 6548

OVERVIEW

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

data for eight samples in Episode 6548 with the exception of Nitrate/Nitrite analysis. Six samples were analyzed for nitrate and nitrite by Analytical Laboratory Services, Inc., under EPA Contract Number 68- C-03-068. Sample 70420, identified as FGD influent, w as expected to contain a significant and variable particulate concentration. EPA and industry represent atives 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. Ther efore, 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 and 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 filtered 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

70420 Aqueous SP-1 – FGD Influent 8/22/07 NA BOD (SM 5210B),

Hexavalent Chromium (ASTM D1687-92), TSS (SM 2540D), TDS (SM 2540C), HEM (1664A), and SGT-HEM (1664A)

70420 Aqueous SP-1 – FGD Influent 8/22/07 Filtered Aqueous Chloride (SM 4500-Cl

- C), Total Phosphorus (365.3),

TKN (SM 4500-N C), Nitrate/Nitrite (353.2), Ammonia as nitrogen (SM 4500-NH3 F), and Sulfate (ASTM D516-90)2 Table 1 - Sample Identifiers, Descri ptions, Sampling Dates and Analytes

EPA Sample

# Matrix Sample Description Sampling

Date 

### Phase Analytes

70420 Aqueous SP-1 – FGD Influent 8/22/07 Filtered

Solid Chloride (SM 4500-Cl

- C), Total Phosphorus (365.3),

TKN (SM 4500-N C), Nitrate/Nitrite (1685), Ammonia as nitrogen (SM 4500-NH3 F), and Sulfate

(ASTM D516-90), and Total Solids (2540B)

70420 Aqueous SP-1 – FGD Influent NA Calculated

Total Chloride (SM 4500-Cl

- C), Total Phosphorus (365.3),

TKN (SM 4500-N C), Nitrate/Nitrite (353.2), Ammonia as nitrogen (SM 4500-NH3 F), and Sulfate (ASTM D516-90)

70421 Aqueous SP-2 – 2 nd Stage

Clarifier 8/23/07 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 (353.2), Ammonia as nitrogen (SM 4500-NH3 F), and Sulfate (ASTM D516-90), HEM (1664A), and SGT-HEM (1664A)

70422 Aqueous SP-3 – FGD

Effluent 8/22/07-

8/23/07 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 (353.2), Ammonia as nitrogen (SM

4500-NH3 F), Sulfate (ASTM D516-90), HEM (1664A), and SGT-HEM (1664A)3 Table 1 - Sample Identifiers, Descri ptions, Sampling Dates and Analytes

EPA Sample

# Matrix Sample Description Sampling

Date 

### Phase Analytes

70423 Aqueous SP-4 – Bottom Ash

Effluent 8/23/07 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 (353.2), Ammonia as nitrogen (SM

4500-NH3 F), Sulfate (ASTM D516-90), HEM (1664A), and SGT-HEM (1664A)

70424 Aqueous SP-5 – FGD Effluent Duplicate 8/22/07 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 (353.2), Ammonia as nitrogen (SM 4500-NH3 F), and Sulfate (ASTM D516-90)

70426 Aqueous SP-7 – 2 nd Stage

Clarifier Field Blank 8/23/07 NA Hexavalent Chromium (ASTM D1687-92)

70427 Aqueous SP-8 – FGD

Effluent Field Blank 8/22/07 NA Hexavalent Chromium (ASTM D1687-92)

70428 Aqueous SP-9 – Bottom Ash

Effluent Field Blank 8/23/07 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 specified in the sampling and analysis plan. The calibration and continuing calibration standards were successfully analyzed. Laboratory bla nks were performed for each analysis, and there was no contamination detected above the laboratory re porting limit. Field blanks were analyzed for

hexavalent chromium and were f ound to contain no hexavalent chromium above the ML. The quality control samples (QC), including the ongoing preci sion and recovery sample (OPR) and matrix spike/matrix spike duplicate (MS/MSD) samples, demonstrated that laboratory performance for these4 

### analyses was acceptable with the excepti on of the samples described below. 

### The MS/MSDs analyses were performed on numerous samples and are detailed below.

DATA ISSUES

Nitrate and Nitrite

The matrix spike (MS) recovery for sample 70424 (9 6%) was within the contr act specified acceptance criteria (75-125%). The related matrix spike dupli cate (MSD) recovery (73%) was outside the acceptance criteria. The relative percent difference (RPD) ( 14%) between the MS and MSD in sample 70424 was within the acceptance criteria of 20%. CSC considers th e nitrate/nitrite results in sample 70424 to be of acceptable quality, but may be a minimum value.

Ammonia as Nitrogen, Total Phosphorus, and TSS

The relative percent difference (RPD) between fi eld duplicate samples 70422 (FGD effluent) and 70424 (FGD effluent duplicate) for the following analytes were: ammonia as nitrogen (44%), total phosphorus (78%) and TSS (100%). CSC does not routinely qualify results based on field duplicate RPD.

TECHNICAL NOTES

BOD (Biochemical Oxygen Demand)

Samples 70420, 70421, 70422, and 70424 did not meet the contract-specified minimum dissolved oxygen depletion of 2.0 mg/L, indicating that less dilute samp le aliquots should have been analyzed. The samples were re-prepared using less dilute aliquots, however, the 48-hour holding time had expired. Therefore, CSC recommends reporting the original results for th ese samples in the database as not detected at the lower limit of the measurement range, adjusted for dilution.

HEM/SGT-HEM

Although HEM/SGT-HEM analyses were requested for samples 70420, 70421 , 70422, and 70423, SGTHEM analysis was not required because HE M was not detected in these samples.

Nitrate/Nitrite

The ICV, CCV, ICB, and CCB analyses were not pe rformed in the proper sequence (blanks were run before verification samples) for the nitrate/nitrite analytes. All calibration verification standards and blanks, however, met contract specifications. Therefore, CSC considers the sample data acceptable without qualification.

QC Samples

The laboratory performed QC sample analyses on the following:

• 70420: chloride, sulfate, ammonia as nitrogen, TKN, and total phosphorus

• 70422: BOD, hexavalent chromium, TSS, Hem, chloride, sulfate, TDS, ammonia as nitrogen, TKN, and total phosphorus

• 70423: BOD, hexavalent chromium, TSS, Hem, chloride, sulfate, TDS, ammonia as nitrogen, TKN, and total phosphorus.

• 70424: nitrate/nitrite5 

### 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

Some of these variables were required for used to cal culate a total result; there should be one set of these records for each of Group I and Group II analyses. Th e laboratory failed to provide those items listed in

bold above for Group 1 analyses and all of the required elements for the Group II analyses.

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

For Group I, several variables were not recorded by the laboratory as requested—most importantly, the original sample volume and filtrate volume. In discu ssion with the lab, CSC was able to calculate the missing variables based on other information that the la boratory was able to provide including the original sample density, original sample weight, and the so lid phase weight. 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)

For Group II, because none of the required elements were recorded, Group I volumes and weights were used to generate the “Calculated Total”. CSC be lieves because there was a equalization tank at the FGD influent sampling point, Group I and II sample bottles should be very similar in particulate content; the Group I volumes and weights therefore may be applie d to Group II results. However, because this still involves some level of uncertainty, calculated to tal data for Group II analyses will be qualified as estimated for sample 70420.

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”.

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. 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 × +

=6 

### Percent Solids

The percent solid result is provided in Table 3, if d esired, to convert 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 Beverly Randolph, EPA Nelson Andrews, EPA Brian Englert, EPA Deb Bartram, ERG TJ Finseth, ERG Lynn Walters, CSC Barbara Beard, CSC

Table 2 Data Review Summary Table

Episode: 6548 Analysis: Classicals

Industry: Steam Electric Study Reviewer: Maria A. Vargas

Sample Analyte Action Reason CSC Qual Level

70420 Ammonia as nitrogen, Nitrate/Nitrite,

TKN, Total Phosphorus Estimated value Estimated value used

in calculation of total NA See database

70424 Nitrate/Nitrite Minimum value MSD Recovery below the contract-specified

criteria NA 36 mg/L

NA= Not Applicable7 

### Table 3 Phase Separation Data Elements

Episode: 6548 Analysis: Classicals

Industry: Steam Electric Study Reviewer: Maria A. Vargas

Group number I II

Sample number 70420 70420

Original sample vol (mL) 997.01 a 997.01 b

Net weight of solid phase on the filter (g) 24.73 24.73 b

Density (g/mL) 1.004 1.004 b

Original sample weight (g) 1001 1001 b

Filtrate weight (g) 976.27 a 976.27 b

Filtrate volume (mL) 972.38 a 972.38 b

Percent Solid (of solid phase) (%) 61 62

a 

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

b 

### Volumes and weights from Group I bottle because measur ements were not performed on the Group II

bottle.C o m put er Sci e nces C o r p orat i on

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### MEMORANDUM

DATE: December 7, 2007

TO: Ron Jordan, Work Assignment Manager

EPA EAD

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

SUBJECT: Revised D a ta Review Nar r a tive for Total and Di ssolved Metals An aly ses for the Stea m Electric Study, Episode 65 48

Under EPA contract num ber 68-C-03-044, ProChem Anal y tical subm itted data for the anal y s is of total

and dissolved metals by EP A Method 20 0.7 and m e rc ur y b y Metho d 24 5.1 i n Ep isode 654 8. Eight

aqueous sa mples in this episode were an aly zed for total and dissolved metals.

Sam p le 7042 0, identified a s FGD Influent, was expected to contain a significant and variable particulate concentration. EPA and Industry re presentatives wer e concerned that the variable nature of the sa m p le would 1) com p licate the collection of a r e presentative sam p le for both EPA and I ndustr y anal yses and 2) lead to analy t ical interferen ces. Therefor e, the laboratory was direc t ed by EPA to separate the FGD

Influent sam p l e into an aqueous phase and a solid ph ase, and analy z e each for m e rcury

. The two sets of results (filtered aqueous and filtered solid phases) are provided in the analy tical database, incl uding the calculated total result (derived by com b ining filte red aqueous and filtered solid phase results). Please

note that the t o tal metals results for the F GD Influe nt sam p le will be delivered under a separat e Data

Review N a rra tive.

Table 1 provides a list of sa m p les, matri ces, desc riptions, 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 # Ma trix Sample Descri ption Sa mpling

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

D i ssol v e d 20 0. 7, 2 4 5

. 1

8 / 22 /07 F i l t e r e d So lid Ph a s e

F i l t e r e d Aqu e ou s Ph a s e 70 4 20 Aq ue o u s S P

- 1 F G D In fl uent

N A C a l c u l ated To t a l 24 5. 1

To tal 70 4 21 Aq ue o u s S P

- 2 2 nd Stage Clarifier 8/23/07 Dissol v ed 20 0. 7, 2 4 5

. 1

To tal 70 4 22 Aq ue ous SP- 3 F G D E ffl uent 8/ 2 2 / 0 7 Dissol v ed 20 0. 7, 2 4 5

. 1

To tal 70 4 23 Aq ue ous SP- 4 B o t t o m Ash Ef fl ue nt 8/ 2 3 / 0 7 Dissol v ed 20 0. 7, 2 4 5

. 1

To tal 70 4 24 Aq ue ous SP- 5 F G D E ffl uent D upl i cat e 8/ 2 2 / 0 7 Dissol v ed 20 0. 7, 2 4 5

. 1

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

7 0 3

. 46 1.200 0 Fax 703 .4 61 .20 2 0Table 1 - Sam p le Identifiers , Des criptions , Sa mpling Da tes, a nd A n a l ysis M e thods

EPA Sample # Ma trix Sample Descri ption Sa mpling

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

To tal 70 4 26 Aq ue ous SP-7 2 nd Stage Clarifier Field

B l ank 8/ 2 3 / 0 7 Dissol v ed 20 0. 7, 2 4 5

. 1

To tal 70 4 27 Aq ue ous SP- 8 F G D E ffl uent Fi el d

B l ank 8/ 2 2 / 0 7 Dissol v ed 20 0. 7, 2 4 5

. 1

To tal 70 4 28 Aq ue ous SP- 9 B o t t o m Ash Ef fl ue nt
Field Blank 8/ 2 3 / 0 7 Dissol v ed 20 0. 7, 2 4 5

. 1

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 eci fications listed in EPA Methods 20 0

. 7 (Rev. 5.0)

, and 245.1 (03/83). All data are of accept a ble quality with the qualifiers describe d below and detailed in

the data review su mmary table (Table 2).

SUMMARY

All sam p les were successf ull y anal y zed within the method-specified holdi ng ti mes, with the exceptions

noted below f o r mercury

. The method d e tection lim it (MDL) studies were performed and m e t the contract-specified criteria. The aqueous initial preci sion and recovery (IPR) analy s is was performed and met the contract-specifi ed criteria. The solid phase initial precision and recovery (IPR) analy s is was al so performed and m e t the con t ract-specifi e d criteria.

Calibration curves, calibration standards

, and calibra tion blanks were succe ssfull y analy zed, with the exceptions noted below. Preparation blanks perform e d for each analy s is detected no contam i n ation above the laboratory’ s reporting li mits. Field and filter blank analy ses de tected no analy t es above the ML, with the exception s noted below

. QC sam p les, includi n g o ngoin g precision and recov e ry (OPR) sam ples, 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

issues des c ribed below and su mmarized i n Table 2. The MS/MSD analy ses were performed on sa m p les

7042 0, 7 042 2

, and 70 423

.

DATA ISSU ES

Method and Analytical Blanks

Several analy t es wer e dete cted in the preparation bl anks (PBs), ini tial calibration blanks (IC Bs), and continuing calibration blanks (CCBs) asso ciated with the sam p les i n this episode at concentrations greater than the respective MDLs, but less than t h e method- specified MLs. The data qualit y is affected as

follows:

• Sa m p le Re sults Great er than Five Tim es but Less than Ten Times Bl ank Results : CSC considers

these results t o be of acceptable quality

, but the y m a y be maxi m u m values. The affected sa mpl es and analytes are as follows: dissolved s e leniu m in sam p le 70423.

• Sa m p le Re sults Great er than Ten Tim e s Blank Results or Analy t e Not Detect ed in Sam p le : CSC

does not cons ider the presence of the analy t e in th e bla nk to adversely affect the data in case s where the sa m p l e results a r e greater tha n ten tim es th e associ ated blank results or where the

23 

### 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.

Holding Times - Mercury

Due to severe matrix interferences in the original analyses for mercury, the la boratory redigested and reanalyzed several samples one day past the contract-s pecified holding time. The affected sample results are as follows: filtered aqueous phase and dissolved mercury for sample 70420; total and dissolved mercury for samples 70422 and 70424. In all cases, me rcury was not detected in the sample. CSC does not qualify results for holding time failures when the a ffected analytes are not detected in the samples.

Matrix Performance

MS/MSD and Serial Dilution analyses were perfo rmed on samples 70420, 70422, and 70423.

70420

The percent recoveries for dissolved barium in the ma trix spike (MS) and matrix spike duplicate (MSD) for sample 70420 were below contract-specified criteria of 75% (48% and 51% respectively). CSC

recommends that the result for dissolved barium in sample 70420 be considered of acceptable quality but may be a minimum value.

The percent recovery for dissolved selenium ( 133%) in the MSD for sample 70420 was above the contract-specified criteria of 125%. In addition, the serial diluti on percent difference for dissolved selenium (29%) in dissolved sample 70420 was above the contract-specified criteria of 10%. The combination of spike recovery failure and serial dilu tion failure indicates severe matrix interferences. Therefore, CSC recommends that the result for disso lved selenium in sample 70420 be considered an

estimated value.

The percent recoveries for dissolved antimony (1 35% and 139%) in the MS and MSD for sample 70420 were above the contract-specified criteria of 125%. In addition, the serial dilution percent difference (130%) was above the contract-specified criteria of 10%. Because antimony was not detected in dissolved sample 70420, CSC recommends that the result for antimony be included in the database without qualification.

The percent recoveries for dissolved arsenic (129%) and silver (127%) in the MSD for sample 70420 were above the contract-specified criteria of 125%. Because arsenic and silver were not detected in dissolved sample 70420, CSC recommends that the resu lts for arsenic and silver be included in the database without qualification.

The serial dilution percent differences for several analytes were above the contract-specified criteria of 10% in sample 70420. These instances are as follo ws: dissolved cadmium (14%), copper (47%), molybdenum (43%), and thallium (100%) in sample 70420. In these cases, MS/MSD percent recoveries were within acceptable criteria. CSC recommends that the results for these an alytes be included in the database without qualification.

70422

The percent recoveries for dissolved barium in the ma trix spike (MS) and matrix spike duplicate (MSD) for sample 70422 were below contract-specified criteria of 75% (21% and 64% resp ectively). In addition,4 

### the relative percent difference (RPD) between the matrix spike and matrix spik e duplicate for dissolved barium in sample 70422 (87%) was above contract-speci fied criteria of 20%. CSC recommends that the result for dissolved barium in sample 70422 be considered an estimated value.

The percent recoveries for total barium in the MS and MSD for sample 70422 (44% and 50% respectively) were below contract-specified criteri a of 75%. CSC recommends that the result for total barium in sample 70422 be considered of acceptable quality but may be a minimum value.

The percent recovery for dissolved iron in the MS for sample 70422 (68%) was below the contractspecified criteria of 75%. CSC recommends that the result for dissolved iron in sample 70422 be considered of acceptable quality but may be a minimum value.

The percent recovery for dissolved selenium ( 130%) in the MSD for sample 70422 was above the contract-specified criteria of 125%. In addition, th e serial dilution percent difference for selenium (20%) was above the contract-specified criteria of 10%. Th e combination of spike recovery failure and serial

dilution failure indicates severe matrix interferences . Therefore, CSC recommends that the result for dissolved selenium in sample 70422 be considered an estimated value.

The percent recoveries for dissolved arsenic (138%), silver (126%), and yttrium (127%) in the MSD for sample 70422 were above the contract-specified crite ria of 125%. In addition, the RPD between the MS and MSD for dissolved arsenic (36%) was above the c ontract-specified criteria of 20%. Because arsenic, silver, and yttrium were not detected in dissolved sample 70422, CSC recommends that the results be included in the database without qualification.

The percent recovery for dissolved tin (25%) in the MS for sample 70422 was below the contractspecified criteria of 75%. In addition, the RPD between the MS and MSD for dissolved tin (119%) was above the contract-specified criteria of 20%. Becau se tin was not detected in dissolved sample 70422,

CSC recommends that the result for tin be in cluded in the database without qualification.

The relative percent differences between the MS and MSD for dissolved lead (21%) and titanium (21%) were above the contract-specified criteria of 20%. Because these analytes were not detected in dissolved sample 70422, CSC recommends that the results be included in the database without qualification.

The serial dilution percent differences for several analytes were above the contract-specified criteria of 10% in sample 70422. These instances are as follows:

• Dissolved cadmium (21%), copper (43%), and zinc (100%) in sample 70422;

• Total cadmium (19%), copper (18%), and selenium (18%) in sample 70422.

In these cases, MS/MSD percent recoveries were with in acceptable criteria. CSC recommends that the results for these analytes be included in the database without qualification.

70423

The serial dilution percent differences for total al uminum (37%) and titanium (19%) were above the contract-specified criteria of 10% in sample 70423. In these cases, MS/MSD percent recoveries were within acceptable criteria. CSC recommends that the results for these analytes be included in the database without qualification.5 

### Field Duplicates

The relative percent difference (RPD) between th e dissolved iron re sults for samples 7042 2 (F GD effluent) and 7042 4 (FGD effluent dupli cate) was 38% . For sam p le 7042 2 (FGD effluent), antim ony was detected at a level below the ML, but was detected slightl y ab ove t h e ML for tot a l sam p le 70424 (FGD effluent dupli cate). CSC d o es not routi n ely qualif y re sults based on field duplicate RPD.

Field Blanks/Filter Blanks

Several analy t es wer e dete cted at conce n trations above the contract-specified mini m u m lev e ls. These

instances ar e su mmarized a s follows:

• Bariu m , cal ci um
, magnesi um
, m o ly bde num , and sele n ium wer e de tected in the dissolved field

blank sam ple 7042 7;

• Calciu m was detected in the total field bl ank sam p le 70427;

• Calciu m and magnesiu m were detected in the total fiel d blank sam p l e 7042 8.

Per EPA request, CSC does not qualify sam p le r esu lts based on field and filter blanks results.

TECHNICAL NOT E S

Phase Separation and Calculations

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

• Original sample weight

• Original sample volume

• Net weight of solid phase on the filter

• Filtrate weig ht

• Filtrate volume

The laboratory failed to pr ovide th ose item s listed in bold above.

CSC calculated the total mercury result for sam p le 70420 (FGD Inf l uent) using t h e following form ula:

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 

### × +

=



### Phase separ at ion Data Elements ar e summa rized in Table 3.

In the generation of t h e Calculated Total result, CSC included value s reported b y the laborator y that were greater than the MDL but less than the ML. Ho wever, if any conc entration was affected by

conta m ination in an associated blank at less than 5 times the a ssoc i ated blank result, it was changed to a zero, per CSC's data review protocols before going t h rough the calculation. Negative values subm itted by the laboratory were not used in the calculations.

Becaus e the laboratory provided on ly the solid phase weight, CSC esti m ated the original sam p l e volum e to be 500 m L , based on the bottle size, and because th e laboratory reported that the bottles were full upon6 

### receipt. The filtrate volume was calculated using this estimated original volume, solid phase weight, and the density of the original sample measured by th e laboratory. This series of calculations follows:

• 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)

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.

• 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 6548 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 6548, the 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%).

As a result, all calculated total data for mercur y will be qualified as estimated for sample 70420.

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

TOTAL”.

Minimum Levels

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

Due to severe matrix interferences, the laboratory an alyzed several samples at 50-fold dilutions for mercury. The affected sample results are as follo ws: filtered aqueous phase and dissolved mercury for sample 70420; total and dissolved mercury for sampl es 70421, 70422 and 70424. Reporting limits for these results have been adjusted for dilution.

Percent Solids

For sample 70420, a percent solid evaluation was perform ed and is summarized in Table 3. The percent solid result is provided only for the use by EPA to convert solid phase wet weight basis values to dry weight results. The percent solid was not used in the generation of the “CALCULATED TOTAL”.

If you have any questions regarding the analyses of these samples or the review of these data, please contact Barbara Beard by telephone at (703) 461-2154 , by facsimile at (703) 461-8056, or by email at

bbeard2@csc.com.

cc: Brian D’Amico, EPA Beverly Randolph, EPA7 

### Marla Smith, EPA Nelson Andrews, EPA Brian Englert, EPA Deb Bartram, ERG TJ Finseth, ERG Lynn Walters, CSC Barbara Beard, CSC8 Table 2 Data Review Summary Table

Episode: 6548 Analysis: Metals

Industry: Steam Electric Study Reviewer: Lisa White

Sample Analyte Action Reason CSC Qual Level

70420 dissolved Ba Minimum Value MS and MSD %R below contract-specified criteria NA See Database

70420 dissolved Se Estimated Value Serial Dilution %D above contract-specified criteria;

MSD %R above contractspecified criteria NA See Database

70420

calculated total Hg Estimated Value Estimated value used in

calculation of total NA See Database

70422 dissolved Ba Estimated Value MS/MSD %R below contract-specified criteria;

RPD between MS and

MSD above contractspecified criteria NA See Database

70422 total Ba Minimum Value MS/MSD %R below contract-specified criteria NA See Database

70422 dissolved Fe Minimum Value MS %R below contractspecified criteria NA See Database

70422 dissolved Se Estimated Value Serial Dilution %D above contract-specified criteria;

MSD %R above contractspecified criteria NA See Database

70423 dissolved Se Maximum Value Sample result >5x but

<10x blank result NA See Database

NA= Not applicable

ND= Not detected9 

### Table 3 Phase Separation Data Elements

Episode: 6548 Analysis: Metals

Industry: Steam Electric Study Reviewer: Lisa White

Sample number 70420

Original sample vol (mL) 500 a

Net weight of solid phase on the filter (g) 8.39

Density (g/mL) 1.004

Original sample weight (g) 502

Filtrate weight (g) 494

Filtrate volume (mL) 492

Percent Solid (of solid phase) (%) 63

a 

### Derived value. Calculated using lab measured results (if available), or otherwise estimatedC o m put er Sci e nces C o r p orat i on

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### 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 20, 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

6548

Under EPA contract number 68-C-03- 046, Battelle Marine Sciences submitted data for the analyses of trace metals. All nine aqueous samples in this epis ode were analyzed for total mercury (Hg) by Method 1631E and total metals including antimony (Sb), ar senic (As), cadmium (Cd), copper (Cu), chromium (Cr), lead (Pb), nickel (Ni), selenium (Se), silver (A g), thallium (Tl), and zinc (Zn) by Method 1638 (ICPMS). Seven of the nine (FGD and Bottom Ash effluents; Clarifier; FGD effluent duplicate; FGD effluent, Bottom Ash effluent, and Clarifier fi eld blanks) were analyzed for hexavalent chromium by Method 1636. Several samples were analyzed for dissolved metals as well as total. Because influent samples for this study were expected to be highly variable in solids content, EPA chose to obtai n results for this phase as well. The solid-phase results for sample 70420 were not directly analyzed, but rather calculated from total, dissolved, and TSS results.

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

EPA Sample

# Matrix Sample Description Sampling

Date Phase Methods

Total 1631E,

1638 8/22/07

Dissolved 1631E,

1638 70420 Aqueous SP-1 FGD influent

NA Calculated

Solid 1631E,

1638

Total 1631E,

1638

Dissolved 1631E,

1638 70421 Aqueous SP-2 2 nd Stage Clarifier 8/23/07

NA 1636

Total 1631E,

1638

Dissolved 1631E,

1638 70422 Aqueous SP-3 FGD Effluent 8/22/07

NA 16362 Table 1 - Sample Identifiers, Descriptions , Sampling Dates, and Analysis Methods

EPA Sample

# Matrix Sample Description Sampling

Date Phase Methods

Total 1631E,

1638

Dissolved 1631E,

1638 70423 Aqueous SP-4 Bottom Ash Effluent 8/23/07

NA 1636

Total 1631E,

1638

Dissolved 1631E,

1638 70424 Aqueous SP-5 FGD Effluent Duplicate 8/22/07

NA 1636

Total 1631E,

1638 70425 Aqueous SP-6 FGD Influent Field Blank 8/22/07

Dissolved 1638

Total 1631E,

1638

Dissolved 1638 70426 Aqueous SP-7 2 nd Stage Clarifier Field Blank 8/23/07

NA 1636

Total 1631E,

1638

Dissolved 1638 70427 Aqueous SP-8 FGD Effluent Field Blank 8/22/07

NA 1636

Total 1631E,

1638

Dissolved 1638 70428 Aqueous SP-9 Bottom Ash Effluent Field

Blank 8/23/07

NA 1636

NA = Not applicable



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

described below and detailed in the da ta review summary table (Table 2).

SUMMARY

All nine samples were successfully analyzed with in the method-specified holding times, and initial precision and recovery (IPR) analyses and met hod detection limit (MDL) studies were acceptably performed. All QC samples, including ongoing precisi on and recovery samples (OPR), matrix spike and matrix spike duplicate (MS/MSD) samples, and qua lity control samples (QCS) were within method specified criteria, with the exceptions described below. The MS/MSD analyses were performed on samples 70420, 70422, and 70423. Calibration curv es and calibration verification standards were successfully analyzed.3 

### All calibration and preparation blanks were free of contamination above the report limit (minimum level or ML). No analytes were detected at levels a bove the reporting limit in the field blanks, with the exceptions described 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 Less than Five Times Blank Results : When the sample result is less than five times the blank result, there are no means by which to ascertain whether or not the presence of the analyte may be attributed to contamination. Therefore, CSC recommends that the data be reported in the database as a not detected at the ML, adjusted for sample size, dilution, and matrices. The affected sampl es and analytes are as follows: 70420 dissolved Sb; 70421 dissolved and total Sb; 70422 dissolved and tota l Sb; 70424 dissolved and total Sb.

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

Field Blanks

CSC reviewed results from four field blanks. All fiel d blanks exhibited no results above the ML with the following exceptions: hexavalent chromium in sample 70426, 70427, and 70428; dissolved copper in sample 70428. Per EPA request, CSC does not qualify results based on field blank contamination.

MS/MSD

The recovery for total cadmium (116%) in the MS performed on sample 70420 was marginally above Method 1638 limits (84 – 113%). CSC recommends that the total cadmium result for the unspiked sample 70420 be considered of acceptable quality, but may be a maximum value.

The RPD for dissolved chromium (21%) for the MS /MSD set performed on sample 70420 was just above laboratory limits (20%). Recoveries for both the MS and MSD were acceptable. Because dissolved chromium was not detected in the unspiked sample, CSC recommends that the results be included in the database without qualification.

The recovery for dissolved arsenic (74%) in th e MSD performed on sample 70420 was slightly below laboratory limits (75 – 125%). CSC recommends that the total cadmium result for the unspiked sample 70420 be considered of acceptable quality, but may be a minimum value.4 

### 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

In order to alleviate interference caused by high leve ls of dissolved solids, the laboratory performed various dilutions on several samples on which Method 1636 and 1638 were performed. MLs are adjusted appropriately.

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)”.

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

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

The TSS result for the sample 70420 bottle analyzed for mercury is 10490 mg/L. The TSS result for the sample 70420 bottle analyzed for Me thod 1638 metals is 11635 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 Deb Bartram, ERG Beverly Randolph, EPA TJ Finseth, ERG Marla Smith, EPA Lynn Walters, CSC Nelson Andrews, EPA Barbara Beard, CSC Brian Englert, EPA sample original Dissolved Total


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

/ ) /

. /

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

=5 Table 2 Data Review Summary Table

Episode: 6548 Analysis: Trace Metals

Industry: STELEC Study Reviewer: Cris Robinson

Sample Analyte Action Reason SCC Qual Level

70420

Dissolved

70421

Dissolved

70421 Total

70422

Dissolved

70422 Total

70424

Dissolved

70424 Total Sb Report in database

as non-detect Sample result <5x blank

result NA

70420 Total Cd Maximum value MS % recovery above contract-specified criteria NA

70420

Dissolved As Minimum value MS % recovery below contract -specified criteria NA

70420

Calculated Solid Cd Maximum value Associated total result is a

maximum NA See Database

NA = Not applicable

### Appendix D

PICTURES FROM THE SAMPLING EPISODE

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

### D-2 Figure D-2. Sample Tap Splitter at the Influent to FGD Wastewater Treatment System

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

### D-4 Figure D-4. Sample Collection Point for the 2 nd 

### Stage Clarifier Overflow

### D-5 Figure D-5. Sampling Set Up for the 2 nd 

### Stage Clarifier Overflow (SP-2)

### D-6 Figure D-6. Sample Collection Point for the E ffluent from the FGD Wastewater Treatment System

### D-7 Figure D-7. Sampling Set Up at Effluent from FGD Wastewater Treatment System (SP-3)

### D-8 Figure D-8. Sampling Set Up at Efflue nt from the Bottom Ash Pond (SP-4)