# Final Sampling Episode Report Buckeye Power Company’s
Cardinal Power Plant Brilliant, OH
Sampling Episode 6551

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 TABLE OF CONTENTS

Page

1. I NTRODUCTION 

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

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

2. P LANT 

### O VERVIEW 

### .............................................................................................................2-1 2.1 Particulate Control Systems.................................................................................2-2 2.2 Fly Ash Pond........................................................................................................2-3

3. S AMPLE 

### C OLLECTION 

### .......................................................................................................3-1 3.1 Sampling Points, Sample Collection Methods, and Field Measurements ...........3-1 3.1.1 Influent to Fly Ash Pond..........................................................................3-2 3.1.2 Effluent from Fly Ash Pond.....................................................................3-5 3.2 List of Analytes and Sample Preservation...........................................................3-7 3.3 Plant Operational Data.........................................................................................3-8 3.4 Deviations from the Sampling and Analysis Plan ...............................................3-8

4. L ABORATORY 

### A NALYTICAL 

### R ESULTS AND 

### D ISCUSSION 

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

4.1 Measured and Calculated Results fo r Fly Ash Pond Influent Samples ...............4-1 4.2 Fly Ash Pond........................................................................................................4-3

5. D ATA 

### Q UALITY 

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

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

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

6. R EFERENCES 

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

Appendix A: A NALYTICAL 

### R ESULTS



### Appendix B: A NALYTICAL 

### D ATA FOR 

### M ETALS



### , F LY 

### A SH 

### P OND



### Appendix C: D ATA 

### R EVIEW 

### N ARRATIVES



### Appendix D: P ICTURES 

### F ROM THE 

### S AMPLING 

### E PISODE

### ii LIST OF TABLES

Page

3-1 Sample Collection Information, Cardinal...................................................................... 3-10

3-2 Number of Samples Collected by Sampling Point, Cardinal......................................... 3-11

3-3 Field Measurements, Cardinal ....................................................................................... 3-12

3-4 Analytical Methods and Procedures for Samples Collected at Cardinal ....................... 3-13

3-5 Summary of Sample Containe r and Planned Preservation ............................................ 3-14

3-6 Sample Preservation Summary, Cardinal ...................................................................... 3-15

3-7 Generating Unit Operating Characteristics during Sample Collection, Cardinal.......... 3-16

3-8 Ash System Operating Characteristic s during Sample Collection, Cardinal................. 3-17

3-9 Fly Ash Pond Operating Ch aracteristics, Cardinal........................................................ 3-18

4-1 Biphasic Sample Results for Classica ls and Routine Total Metals Measured Above the Report Limit, Fly As h Pond Influent, Cardinal.............................................. 4-4

4-2 Classical Pollutants Measured Above the Report Limit for the Fly Ash Pond,

Cardinal....................................................................................................................... ..... 4-6

4-3 Metals Measured Above the Report Limit for the Fly Ash Pond, Cardinal .................... 4-7

5-1 Field Duplicate Results, Cardinal .................................................................................... 5-5

A-1 Fly Ash Pond Influent Anal ytical Data, Cardinal........................................................... A-1

A-2 ProChem Biphasic Filtration Blank Analytical Results, Cardinal................................ A-10

A-3 Fly Ash Pond Effluent Anal ytical Data, Cardinal ........................................................ A-11

A-4 Duplicate of Fly Ash Pond Efflue nt Analytical Data, Cardinal.................................... A-16

A-5 Bottle Blank and Equipment Blank Analytical Data, Cardinal .................................... A-21

A-6 Fly Ash Pond Influent Field Bla nk Analytical Data, Cardinal ..................................... A-27

A-7 Fly Ash Pond Effluent Field Bla nk Analytical Data, Cardinal..................................... A-31

B-1 Analytical Results for Metals in the Fly Ash Pond, Cardinal..........................................B-1

### iii LIST OF FIGURES

Page

2-1 Simplified Diagram of Ash Sluice Wast e Streams, Cardinal Power Plant...................... 2-4

2-2 Fly Ash Pond, Cardinal Power Plant ............................................................................... 2-5

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

D-2 Sample Location for the Infl uent to the Fly Ash Pond ................................................... D-2

D-3 Sample Collection Set-Up at the Influent to the Fly Ash Pond ...................................... D-3

D-4 “Shake and Pour” Set-Up for the Influent to the Fly Ash Pond ..................................... D-4

D-5 Waste Streams Entering the Fly Ash Pond at the Co mpletion of the Composite

Period ......................................................................................................................... ..... D-5

D-6 Waste Streams Entering th e Fly Ash Pond the Day before Sample Collection.............. D-6

D-7 Sample Collection Set-Up at the Effluent from the Fly Ash Pond................................. D-7

### 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 October 15 and 16, 2007, at Buckeye Power Company’s Cardinal Power Plant (Cardinal), located in Brilliant, Ohio (Sampli ng Episode 6551). The focus of Episode 6551 was to characterize the influent to and effluent from the fly ash pond at Cardinal.

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 flue gas desulfurization (F GD) scrubber system, including:

— Type of scrubber,

— Sorbent used,

— Year operation began,

— Chemical additives used,

— Forced oxidation process,

— Water cycling, and

— Solids removal process;

• 

### FGD wastewater treatment system;

• 

### Type of coal;

### 1-2 • 

### NO

x 

### controls;

• 

### Ash handling systems;

• 

### Ash treatment system; and

• 

### Mercury air controls.

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

• 

### The plant is a coal-fired power plant that burns east ern subbituminous coal; and

• 

### The plant operates an ash pond that re ceives fly ash sluice water almost exclusively.

1.3 Sampling Episode Overview

On May 15, 2007, EPA and its technical contra ctor, Eastern Research Group, Inc. (ERG),

conducted a site visit at Cardinal . The purpose of the site visit was to learn about the wastewater treatment operations regarding the fly ash pond, and to gather information in order to collect wastewater samples at Cardinal. The informati on collected during the si te visit was used to

create Sampling Plan, Buckeye Power Company’s Cardinal Power Plant (Sampling Plan) [1], which describes the sample collection pro cedures used during the sampling episode.

For this sampling episode, EPA arrived at Cardinal on Monday, October 15, 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 Tuesday, October 16, 2007. The following personnel participated in EPA’s samp le collection activities:

• 

### 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



### Cardinal operates three coal-fired steam el ectric generating units. Units 1 and 2 each have a capacity of approximately 600 megawatts (MW) and came on line in 1967. Unit 3 has a capacity of approximately 630 megawatts (MW) and came on line in 1977. The Cardinal Power Plant is located in Brilliant, Ohio near the Ohio River.

Units 1 and 2 use cold side electrostatic precipitators (ESPs) and have the following configuration:

• 

### Boiler → SCR → Air heater → ESP.

Unit 3 uses a hot side ESP and has the following configuration:

• 

### Boiler → ESP → SCR → Air heater.

Around the time of sampling, Cardinal wa s burning approximately 13,500 tons per day (tpd) of eastern subbituminous coal. Duri ng the sampling episode, Unit 1 was burning approximately 4,780 tpd of mid-sulfur s ubbituminous coal and Unit 3 was burning approximately 4,342 tpd of low-sulfur subbitumi nous coal. During the sa mpling episode, Unit 2 was shut down and therefore, was not burning any coal; however, plant pe rsonnel stated that the unit was typically burning 4,400 tpd of mid-sulfur subbituminous coal. Cardinal may begin to burn a blend of Powder River Basin (PRB) and eas tern subbituminous coal in Unit 3 in the near future. In addition to coal, all th ree units burn #2 fuel oil when the coal pulverizers go in and out of service. Thus, the amount of oil burned annua lly depends upon the number of coal pulverizer startups and shutdowns. Cardinal reported that in 2006, the plant burned the following volumes of fuel oil: 505,840 gallons in Unit 1; 391,210 gall ons in Unit 2; and 541,174 gallons in Unit 3.

In 2004, Cardinal retrofitted all three units with selective catalytic reduction (SCR) systems to control nitrogen oxide (NO

x 

### ) releases from the plant. Ca rdinal typically operates the SCR systems from May 1 through September 30; how ever, this year, Cardinal was still operating the Unit 3 SCR system during the sampling episode , with plans to operate it into November. Cardinal may at times temporarily suspend SCR operation during low-load operation (e.g., at night).

As the flue gas passes over the catalyst in th e SCR process, some of the sulfur dioxide is

oxidized to sulfur trioxide. Emissions of this sulf ur trioxide contribute to the formation of acid rain in the environment, as well as a blue plum e. To remove the sulfur trioxide, Cardinal was intermittently injecting ammonia into the flue gas at the time of sampling episode. However, since the sampling episode, Cardinal has built tr ona injectors. Cardinal will inject trona, a sodium-based carbonate (i.e., sodium carbonate and/ or sodium bicarbonate), into the flue gas to remove sulfur trioxide. Equation 2-1 shows th e reaction of sodium bicarbonate to sodium carbonate. Equation 2-2 shows the re action of sodium carbonate and sulfur trioxide to sodium

sulfate.

2 NaHCO 3 

### → Na 2 

### CO 3 

### + H 2 

### O + CO 2 

### (2-1)

Na 2 

### CO 3 

### + SO 3 

### → Na 2 

### SO 4 

### + CO 2 

### (2-2)

### 2-2 Cardinal uses ESPs to remove approximately 99.5 percent of the fly ash from the flue gas emitted from all three units. The fly ash and ot her particulates are collected in hoppers and sluiced to the fly ash pond. Section 2.1 discusses the particulate control systems and Section 2.2 discusses the fly ash pond.

At the time of the sampling episode, Cardin al was in the process of installing wet FGD systems on all three units to control sulfur dioxide emissions. Cardinal began operating the Unit 2 FGD system in December 2007 and the Unit 1 F GD system in March 2008. Cardinal plans to begin operating the Unit 3 FGD system in 2010. Th ese FGD systems are jet bubbler reactors that use limestone as a sorbent and forced oxidation to generate gypsum. The FGD reactors are designed to remove 98 per cent of the sulfur dioxide from the flue gas. Cardinal treats the wastewater generated from thes e FGD systems in a treatment system with the following operations: equalization, desaturation (lime a ddition), primary clarifi cation, ferric chloride addition, polymer addition, and secondary clarification.

2.1 Particulate Control Systems

As the coal is combusted in the boilers, so lid, noncombustible constituents of the coal, referred to as ash, are generated. The heavier ash particles collect on the bottom of the boiler and are referred to as bottom ash. The finer ash partic les are light enough to be transferred out of the boiler with the flue gas exhaust and are referred to as fly ash. The bottom ash is removed from the bottom of the boiler using a st ream of sluice water that transports the particles to a bottom ash pond.

Cardinal sluices the bottom ash from the bottoms of the Unit 1 and 2 boilers once per day. Cardinal sluices one boiler once per 12-hour shift (7:00 am to 7:00 pm) and alternates

between the Unit 1 and Unit 2 boiler each shift. Ca rdinal sluices the bottom ash from the bottom of the Unit 3 boiler twice per day, or once per 12 -hour shift. Each sluicing lasts two hours. The bottom ash sluice is transported to the bottom as h ponds where the bottom as h solids settle in the pond. Sluice water is only transferred to the bottom ash ponds when the bottom ash is being sluiced. The effluent from the bottom ash ponds is then transported to the bottom ash recirculation pond. Cardinal uses some of the wa ter in the bottom ash recirculation pond as the

bottom ash sluice water for all three units. Additio nally, water from the bottom ash recirculation pond can be reused for fly ash sluice and if ther e is excess water in the system, some of the

bottom ash recirculation water is transferred to the fly ash pond.

In Units 1 and 2, the fly ash flows with th e flue gas through the SCRs and is removed from the flue gas in the ESPs. In Unit 3, the fly ash flows with the flue gas through the ESP first, which removes the fly ash, and then the flue gas flows through the SCR. The ESP systems use high voltage to generate an electr ic charge on the particles containe d in the flue gas. The charged particles then collect on a metal plate with an opp osite electric charge. As the particles begin to layer on the metal plates, the plates are tapped/rapped to loosen the particles, which fall into collection hoppers. Each unit has multiple hoppers th at collect ash from different places in the ESP. The hoppers located closer to the inlet of the ESP collect the larger fly ash particles that are removed more easily and the hoppers located closer to the outlet of the ESP collect the finer fly ash particles that are more difficult to remove . The hoppers at the inlet of the ESP typically collect more fly ash than the hoppers at the outlet.

### 2-3 Cardinal continuously slui ces fly ash from Units 1 through 3 to the fly ash pond; however, the plant does not cont inuously sluice fly ash from each collection hopper within the units. In each unit, the plant automatically cycles through th e hoppers, sluicing from one hopper to the next, with no down time between hopper sluice s. It takes the plant 1 to 1.5 hours to sluice each hopper box. Units 1 and 2 contain two hopper boxes each. Unit 3 contains four hopper boxes, two of which are sluiced at a time. Therefore, the plant co mpletes one sluice cycle of the hopper boxes for each unit in two to three hours.

Figure 2-1 presents a simplified diagram of th e ash sluice streams at the Cardinal plant.

Cardinal uses service water a nd water recycled from the bottom ash recirculating pond as the source for bottom ash sluicing. The bottom ash sluice water is then transferred to the bottom ash ponds where the solids settle out of the wastew ater. From the bottom ash ponds, the wastewater

is transferred to the bottom ash recirculation pond. From the bottom ash recirculation pond, the

wastewater can be transferred to the following three operations:

1. Bottom ash sluice system;

2. Fly ash sluice system; and/or

3. Fly ash pond.

Section 2.2 describes the fly ash pond in more detail.

2.2 Fly Ash Pond

The fly ash pond at Cardinal receives fl y ash sluice water from Units 1 through 3 in separate pipes. The fly ash pond receives a comb ined average flow of 5.76 million gallons per day (MGD) of fly ash sluice water from Units 1 and 2, and an average flow of 3.17 MGD of fly ash sluice water from Unit 3. The fly ash pond o ccasionally receives wate r from the bottom ash recirculation pond and storm water. Based on 2006 data, the unlined fly ash pond had an open water area of 27.7 acres, a total water volume of 624,141 cubic yards, and a nominal retention time of about 10 days; however, the pond is fill ing up and the volume of the pond is decreasing. Cardinal began operating the fly ash pond in 1988 a nd expects to operate the pond in its current configuration until 2014 (i.e., until the pond reaches cap acity). The plant is currently considering

whether to raise the dam or conve rt to a dry fly ash handling syst em to handle the fly ash when the pond reaches capacity.

The fly ash sluice water enters the fly ash pond at one end of the pond. The opposite end of the pond is dammed. The plant does not dredge the fly ash pond, and fly ash has built up at the delta of the pond to a depth of approximately 20 feet. Wastewater is discharged from the dammed end of the pond through NPDES Outfall 019 to Blockhouse Hollow, a tributary of the Ohio River. Figure 2-2 presents a diagram of the fly ash pond. The effluent from the fly ash pond is not reused within the plant.

### 2-4 Figure 2-1. Simplified Diagram of Ash Sluice Waste Stream s, Cardinal Power Plant

### 2-5 Figure 2-2. Fly Ash Pond, Cardinal Power Plant

### 3-1 3. S AMPLE 

### C OLLECTION



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

During the sampling episode, Unit 2 was shut down due to a scheduled 13-week maintenance outage, which began in early Sept ember. Because of this outage, there was no Unit 2 fly ash sluice water entering th e fly ash pond during the sampling episode.

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

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

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

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

The sampling points for this episode were:

• 

### SP-1 Influent to Fly Ash Pond;

• 

### SP-2 Effluent from Fly Ash Pond;

• 

### SP-3 Duplicate of Effluent from Fly Ash Pond (SP-2);

• 

### SP-4 Influent to Fly Ash P ond (SP-1) Field Blank; and

• 

### SP-5 Effluent from Fly Ash Pond (SP-2) Field Blank.

For all the sampling points, EPA collected sp lit samples with Cardinal’s representative, the Utility Water Act Group (UWAG). EPA insert ed a “Y” splitter into the sample tubing configuration at each of the sampling points (ex cept SP-4) to allow for split sample collection. For this sampling episode, EPA collected all an alytes (other than HEM/SGT-HEM and several

field blanks collected at SP-4) as “true” splits (i.e., samples for the same analyte were collected simultaneously). The HEM/SGT-HEM samples were collected using a bottl e dipper; therefore, EPA and Cardinal’s representative collected duplicate samples, with one filling the bottle immediately after the other.

The low-level total mercury, low-level total metals, and routine total metal field blanks collected at SP-4 (influent to fl y ash pond) were not collected as “true” split samples. The field blanks for these samples were collected as “m ultipour” splits because the composite tubing did not have a splitter in its conf iguration. The “multipour ” splits were collected by the following procedure: one-third of the EPA sample bottle wa s filled and then one-third of the “split” bottle

### 3-2 was filled. The EPA sample bottle and the “split” bo ttle were each in turn then filled with an additional one-third sample. Finally, the EPA samp le bottle was filled completely and then the “split” bottle was filled completely. For a desc ription of the field blank sample collection procedures, see Section 5.2.3.

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

3.1.1 Influent to Fly Ash Pond

The influent to the fly ash pond (SP-1) was collected from the edge of a channel where fly ash sluice streams from Units 1, 2, and 3 commingle and enter the fly ash pond. During the sample collection period, the fl y ash pond did not receive fly ash sluice from Unit 2, as discussed in Section 3.0, but did receive water from the bottom ash recirculation pond. Figure 2-1 identifies the sampling location for SP-1. Figure D-2, in Appendi x D, is a picture of the influent ash sluice streams and the sample location. This sample wa s collected as a three-hour composite sample because the waste streams at the plant do not unde rgo equalization prior to flowing to the fly ash pond; therefore, EPA chose to collect a composite to account for some of the variability in the waste stream. EPA chose a three-hour compos ite because the plant completes one fly ash sluicing cycle for each unit in approximately three hours.

As discussed previously, the sampling point was located outside along the edge of the channel entering the pond. EPA did not set up a tent or tarps to c over the samplers/samples from

rain and/or wind. There were no rain or wind cond itions during the collection of the field blanks or the set-up of the sampling point. In additi on, it did not rain duri ng the composite period; therefore, there was no impact on the samples collected.

Prior to setting up the composite samplers at the influent to the fly ash pond (SP-1), the sampling team collected field bla nks (SP-4) for low-level total mercury, low-level total metals,

and routine total metals. See Section 5.2.3 for a de scription of the field blank sample collection at the influent to the fly ash pond. In addition, the samplers collected one set of HEM/SGT-HEM grab samples by dipping the bottles directly into the channel with the fly ash sluice streams with a bottle dipper. The HEM/SGT-HEM samples were not collected in the compositor because the oil and grease adheres to the sides of th e tubing and the composite containers.

### 3-3 EPA collected the wastewater samples of the influent to the fly ash pond by compositing 25 individual grab samples over a three-hour peri od. The individual grab samples were collected by automatically pumping samples from the fly as h sluice stream channe l into two composite containers, one each for the classical analytes and the metal analytes (see Section 3.2 for the analyte list). The samplers attached one end of a 25-foot length of Teflon® tubing to a piece of PVC pipe and inserted the pipe and tubing in to the sluice stream ch annel. The tubing was attached a couple feet above th e bottom of the PVC pipe because the pipe was pushed into the solids at the bottom of the channel to help keep the tubing in position during the entire composite period. In this position, the tubing was approximately at mid-depth in the channel; however, the channel was very shallow, only several inches deep. The other end of the Teflon® tubing was attached to a piece of silicone tubing, which wa s threaded through an ISCO peristaltic pump and attached to a vent cap on the 20-liter composite container. Because there were two composite containers, EPA had two tubing conf igurations and two ISCO perist altic pumps. The two ends of the Teflon® tubing were placed side by side on th e PVC pipe to ensure that nearly identical samples were collected. The one difference between the two set-ups for the composites was that, due to the difference in preservation requirements for these analytes, the composite container for the classicals was placed on ice and the composite container for the metals was not.

After they placed the PVC pipe and the ends of the Teflon® tubing in the channel and secured the PVC pipe so that it would not m ove during the composite period, the samplers purged the tubing for the metals composite for approximately three minutes. The samplers then programmed and calibrated the au tomatic compositor (ISCO perist altic pump) to collect 800 mL of sample every eight minutes for three hours, for a total of 20 liters of sample from 25 individual grabs. The samplers then attached the end of the silicone tubing to the vent cap on the

20-liter container.

After preparing the composite for the metals samples, the samplers followed the same procedures to prepare the composite for the classicals samples. The samplers programmed and calibrated the automatic compositor to collect 80 0 mL of sample every eight minutes for three hours and attached the end of the silicone tubing to the vent cap on a different 20-liter container. They then closed off the inner and outer bags surrounding the composite containers and placed each composite container in a separate trash ca n. The samplers then surrounded the classicals container with ice, to keep the grab samples cold, as required for preservation. The lid of the trash can was then placed on top of the composite c ontainers to protect the containers from rain; however, the lid was not shut down completely because it would kink the tubing. Figure D-3, in Appendix D, is a picture of the sampling set-up fo r the composite at the influent to the fly ash pond.

The samplers then started both of the automatic compositors at the same time and watched them to ensure that the samples were co llected in both containers. The samplers then

watched the collection of the s econd individual grab samples fo r each compositor. Because the two samples appeared to be collected successfull y, the samplers left the sampling point and did not return to the influent sampling point until the compositing time period was complete.

When the samplers returned to the samp ling point, the compositing period had already concluded. Upon retrieving the co mposite containers, EPA noticed that the metals composite container was not completely full; it had approxi mately 14 liters of samples while the classicals

container had a full 20 liters. Afte r removing the vent cap from th e metals composite container,

### 3-4 the sampling team operated the ISCO peristaltic pump to collect an additional manual composite, which the samplers estimated to be approximately 800 mL, into a spare 1-L container. Because this manual composite was approximately the same amount as each of the planned manual composite samples, EPA concluded that a full 20 liters of sample was not collected because the sample tubing configuration probably had a slight kink, which allowed it to collect samples, but limited the amount of sample collected. EPA beli eves that the compositor collected a similar amount of volume for each sample, but it was less than 800 mL; therefore, EPA believes that the metals composite sample collected is a representative sample.

The samplers then collected the second se t of HEM/SGT-HEM grab samples by dipping the bottles directly into the ash sluice channel with a bottle dipper. The two sets of HEM/SGTHEM grab samples were composited by the laboratory for a single sample result. The HEM/SGT-HEM samples were not collected in the compositor because the oil and grease

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

The samplers then transported the 20-liter co mposite containers back to the staging area to pour off and pump off. The samplers used a pour-off method, “shake a nd pour,” to collect the metals samples that did not require filtration and all of the classical samples, and then used a pump-off set-up to collect all of the dissolved metals samples.

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

bottom of the container. Once the solids were resuspended, the sampling team got in position to collect the samples. The shakers shook the 20-lit er container back and forth on its side for approximately 30 seconds, and then quickly placed the container on a table while another sampler removed the cap from the container. Once the cap was removed, the shakers slowly poured the sample into the funnel, which was being held by another sampler, and the sample flowed down the tubing, through the “Y” splitter, and into the EPA’s and the Cardinal’s representative’s sample bottles. Be cause the solids in this sample settled quickly to the bottom of the container, EPA performed the “shake and pour” for each individual bottle so that each bottle would contain approximately the sa me solids content. Figure D-4, in Appendix D, is a picture of the sample collection set-up for “shake and pour” method.

EPA first collected the low-level total metals, low-level total and dissolved mercury, routine total metals, and the arsenic/selenium speciation samples from the metals composite container, using the “shake and pour” method and filling the bottles in a “cleanbox,” as described in Section 3.1. The samplers th en placed the metals composite container near the pump-off station and began shaking the 20-liter classicals composite container. Afte r all the solids were resuspended in the classicals composite container, the samplers collected the BOD, Group I, and Group II samples, using the “shake and pour ” method and filling the bottles without a

“cleanbox.”

The sampling team then set up the pump-off station to collect the dissolved metals samples, which consisted of a length of Teflon® tubing attached to a length of silicone tubing, which was threaded through an ISCO peristalti c pump. The sampling team attached a capsule filter to the silicone tubing, which was a shor t distance downstream of the pump. The sampling

### 3-5 team attached another short length of silicone tubing to the capsule filter effluent, which was attached to a “Y” splitter and two lengths of si licone tubing. This set-up allowed EPA to collect “true” split samples with Cardinal’s representa tive. Prior to collecting any dissolved metals samples of the fly ash pond influent, the samplers collected a field blank sample (SP-4) for lowlevel dissolved metals, routine dissolved metals , and routine hexavalent chromium. See Section 5.2.3 for a description of the dissolved metals field blank sample collection at the influent to the fly ash pond.

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

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

that similar results were measured. The free and total residual chlorine measurements at this sampling point were not measured because the sa mpling schedule did not permit the samplers to analyze the field test aliquot in a reasonable amount of time af ter the aliquot was collected. Therefore, the samplers did not test/record the free and total chlorine measurements for the influent to the fly ash pond. Table 3-3 presents the field measuremen t data for the influent to the fly ash pond.

The sampling team observed that the plant wa s transferring a large quantity of bottom ash recirculation pond wastewater directly to th e fly ash pond during the three-hour composite sample collection at the influent to the fly as h pond. Figure D-2, in Appendix D, shows the waste streams entering the fly ash pond just prior to the sa mple collection at the in fluent to the fly ash pond. The fly ash sluice waste streams were a dark brown color, whereas the bottom ash

recirculation waste stream was clear. The wastewater in the influent channel was a grayish color. Figure D-5, in Appendix D, shows the waste streams entering the fly ash pond after the conclusion of the three-hour composite pe riod. For comparison purposes, Figure D-6, in Appendix D, shows the waste streams entering the fly ash pond the day before EPA collected the fly ash pond influent samples. At the time th e picture was taken, there was no bottom ash recirculation pond wastewater entering the fly ash pond.

3.1.2 Effluent from Fly Ash Pond

The effluent from the fly ash pond (SP-2) was collected from the channel that feeds Blockhouse Hollow, which is a tributary of the Ohio River. Figure 2-1 identifies the sampling location for SP-2. This sample was collected as a grab sample, because EPA believes the wastewater is equalized through the retention time within the fly ash pond; therefore, the

wastewater characteristics s hould be fairly homogeneous.

The samples were collected from a small wooden walkway protruding halfway over the channel. The sampling team, however, was lo cated on solid ground, along the side of the channel. The samplers did not set up a tent to cover the samplers /samples from rain. There were no rain or wind conditions during the sample collection.

### 3-6 Prior to collecting samples at the efflue nt from the fly ash pond (SP-2), the sampling team collected field blanks (SP-5) 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 e ffluent from the fly ash pond.

EPA collected the wastewater samples of the effluent from the fly ash pond by pumping samples from the channel into the sample contai ners. The sampling team attached one end of a 25-foot length of Teflon® tubing to a piece of PVC pipe, and inserted the PVC pipe and tubing into the channel. The sampling t eam attached the PVC pipe to a rail on the wooden walkway to secure the pipe and tubing in place for the duration of the sample collection. The samplers positioned the tubing to reach them at the sampling point set-up area and attached it to a piece of silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team attached a “Y” splitter to the other end of the silicone tubing, with two additional pieces of silicone tubing attached to the “Y” splitter. Th e length of silicone tubi ng between the pump and the “Y” splitter consisted of two pieces with a small connector, which allowed EPA to attach and detach a capsule filter inline with the tubing configuration. The “Y” splitter allowed EPA to collect “true” split samples with Cardinal’s re presentative. Figure D- 7, in Appendix D, is a picture of the sampling set-up for the effluent from the fly ash pond.

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

dissolved metals and low-level hexavalent chro mium samples, as well as the QC and duplicate samples for each analyte, because the capsule filter was already inline with the tubing configuration from the dissolved metals fiel d blank sample collection. The samplers then installed a new capsule filter and purged the tubing and filter for one minute. After purging the new filter, the sampling team collected the rou tine dissolved metals and routine hexavalent chromium samples, as well as the QC and dupli cate samples for each analyte. Each of these samples was collected in a “cleanbox ,” as described in Section 3.1.

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

The samplers used a bottle dipper to collect the HEM/SGT-HEM and HEM/SGT-HEM QC samples directly from the channel to preven t any oil and grease adheri ng to the sides of the tubing. Therefore, instead of collecting sp lit samples for HEM/SGT-HEM analysis with Cardinal’s representative, EPA collected duplicat e samples with Cardinal ’s representative. Two members of the sampling team collected th e HEM/SGT-HEM samples from the channel at approximately the same point within the channe l at which the other samples were collected.

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

### 3-7 the pH meter to ensure that similar results were measured. The free and total residual chlorine measurements at this sampling point were not measured becaus e the sampling schedule did not permit the samplers to analyze the field test a liquot in a reasonable amount of time after the aliquot was collected. Therefore, the samplers did not test/record the free and total chlorine measurements for the effluent from the fly as h pond. Table 3-3 presents the field measurement data for the effluent from the fly ash pond.

3.2 List of Analytes and Sample Preservation

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

• 

### Classicals:

— Biochemical oxygen demand, 5-day (BOD 5 

### ),

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus,

— Hexane extractable material (HEM), and

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

• 

### Metals:

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

— Routine dissolved metals (27 metals),

— Routine hexavalent chromium,

— Low-level total mercury,

— Low-level dissolved mercury,

— Low-level hexavalent chromium,

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

— Low-level dissolved metals (11 metals).

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

concentrations.

Table 3-5 lists the containe rs used for sample collection as well as the preservation requirements for each sample and Table 3-6 summa rizes the chemical preservation for each of the samples that were preserved on site. The sampling team preserved samples in accordance with procedures described in S ection 3.4 of the Sampling Plan. A ll samples except routine total and dissolved metals, low-level total and dissolv ed metals, and low-level hexavalent chromium

### 3-8 samples were placed on ice and cooled to <6°C immediately following collection. All dissolved metals samples, except low-level dissolved merc ury, were filtered in the field. The routine and low-level hexavalent chromium samples were pres erved in the field, but all other metals samples were acid-preserved prior to extraction at the laboratory. The routine hexavalent chromium samples were supposed to be preserved to a pH between 9.3 and 9.7 using an ammonium sulfate buffer solution; however, the sampling team disc ontinued preservation for some samples because 10 percent of the sample volume was added before the required pH was achieved (the pH of the preserved samples was approximately 9.0). The lo w-level hexavalent chromium sample bottles were prepreserved with 2 mL of 50-percen t NaOH. The Group II and HEM/SGT-HEM samples were preserved with sulfuric acid to a pH of <2 immediately afte r collection in the staging area, and the pH was confirmed with four-color pH strips.

3.3 Plant Operational Data

During the sampling episode at Cardinal, plant personnel provided the sampling team with operational data for each of the generating units and the as h collection system, as well as operational and flow data for the fly as h pond. Table 3-7 presents the unit operating characteristics, Table 3-8 presents the ash sy stem operating characteri stics, and Table 3-9 presents the fly ash pond operating charac teristics during the sampling episode.

As noted in Section 3.0, Unit 2 was shut down during the sampling episode due to a scheduled 13-week maintenance outage, which be gan in early September. Because of this outage, there was no Unit 2 fly ash sluice wate r entering the fly ash pond 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:

• 

### Total Metals Field Blank Sample Collect ion at the Influent to the Fly Ash Pond (SP-4). For the total metals field blank samples collected from the influent to fly ash pond (SP-4), EPA planned on co llecting the samples as duplicates with Cardinal’s representative. However, EPA collected the samples as “multipour” splits with Cardinal’s representative. In addition, because of the limited space along the ash sluice channel, the field bl ank samples were not collected at the same point where the composite samples were collected (as the Sampling Plan indicated may be the case). Instead, EPA fi rst collected the field blank samples at the top of the hill, above where the ash sluice streams enter the pond, and then the samplers moved the equipment down to the channel and set up the compositors for sample collection. See Section 5.2.3 fo r more details regarding the collection of the field blank samples.

### 3-9 • 

### Composite Collection Time at the In fluent to the Fly Ash Pond (SP-1). For the influent to the fly ash pond, EPA planned to set up the ISCO composite samplers to collect 25 individual grab sample s of 800 mL every 7.5 minutes for a threehour composite. Because the ISCO sampler could only be set up to collect samples by the minute, EPA set up the com positor to collect 25 individual grab samples of 800 mL every eight minutes. For this reason, the actual composite time period was three hours, 12 minutes.

• 

### Composite Sample Volume at the Influent to Fly Ash Pond (SP-1). EPA planned to fill two 20-liter composite containers with sample during the composite time period; however, as disc ussed in Section 3.3.1, EPA was only able to collect 14 liters of sample in the me tals composite container (the classicals composite container was filled completely ). As described in Section 3.3.1, EPA believes that the metals sample volume was representative and the reduced volume did not impact the sample collection.

• 

### Time for Sample Filtration at the In fluent to the Fly Ash Pond (SP-1). EPA planned to allow the solids in the metals composite container to settle for one hour after the samplers completed the “shake and pour” for the total metals sample collection and before they performed the filtration for the dissolved metals samples. However, EPA began the filtrati on of the dissolved metals samples after the composite container had settled for 45 minutes because the solids had appeared to settle sufficiently that the cartridge filters would not become clogged

with solids.

• 

### Sample Collection Point for the Effluent from the Fly Ash Pond (SP-2). EPA planned to collect the samples for the e ffluent from the fly ash pond from a steel bridge that was built over the effluent channel; however, due to contamination concerns from the steel, EPA collect ed the samples from a wooden walkway, located immediately downstream of the steel bridge, that protruded halfway across the channel. The steel bridge sp ans the entire effluent channel without contacting the water (supported on each e nd by concrete), ther efore collecting the sample downstream of the steel bridge introduces no contamination. As a precaution, the sampling team avoided walki ng on the steel bridge while samples were being collected to ensure contaminan ts were not dislodged from the bridge

into the effluent channel.

• 

### Chlorine Field Test Measurements. EPA planned to measure the free and total residual chlorine for each sampling point after returning to the staging area; however, due to the sampling schedule, th e samplers were unable to perform the

chlorine field test measurements in a r easonable time after the field test aliquot had been collected. Therefore, EPA did not test/record the free and total residual

chlorine measurements for either the infl uent to or effluent from the fly ash pond during the sampling episode.

### 3-10 • 

### 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).

Table 3-1. Sample Collection Information, Cardinal

Sampling

Point Number Sampling Point Description Type of Sample Sample Collection

Date and Time SCC Number

SP-1 Influent to Fly Ash Pond 3-Hour Composite 10/16/2007

0820 - 1130

1348 a 71120

SP-2 Effluent from Fly Ash Pond Grab 10/16/2007

1026 71121

SP-3 Duplicate of Effluent from Fly Ash Pond Grab 10/16/2007

1026 71122

SP-4 Influent to Fly Ash Pond Field Blank Grab 10/16/2007

0657 b and 1442 c 71123

SP-5 Effluent from Fly Ash Pond Field Blank Grab 10/16/2007

0955 71124

a – Collection of the pour-offs for total metals and classical s, as well as the pump-offs for the dissolved metals samples from the composite collection containers.

b – Collection of field blanks for total metals.

c – Collection of field blanks for dissolved metals.

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

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

cSP-1 Influent to Fly Ash Pond 1 1 1 1 1 1 1 1 1 1 1 1+dupSP-2 Effluent from Fly Ash Pond 1+QC1+QC 1+QC 1+QC 1+QC 1+QC 1+QC1+QC 1+QC 1+QC 1+QC 1+QC 1+dupSP-3 Duplicate of Effluent fromFly Ash Pond1 1 1 1 1 1 1 1 1 1 1SP-4 Influent to Fly Ash PondField Blank1 1 1 1 1 1SP-5 Effluent from Fly Ash PondField Blank1 1 1 1 1 1 1Total Number of Samples 5+1QC 5+1QC 5+1QC 3+1QC 3+1QC 5+1QC 5+1QC3+1QC 3+1QC 3+1QC 2+1QC 5+1QC 2+2dupa –Group I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate and chloride.b –Group II includes ammonia as nitrogen, nitrate/nitrite as nitrogen,total Kjeldahl nitrogen (TKN), and total phosphorus.c – The selenium/arsenic speciation results from the sampling episode were not available at thetime this report was finalizedand therefore are not included inthis report.

### 3-12Table 3-3. Field Measurements, CardinalTemp°CpH(S.U.)SamplingPointNumberSampling PointDescriptionTimeMeterThermometerMeteraStripsFreeChlorine(mg/L)TotalChlorine(mg/L)ManganeseInterferenceReading(mg/L)WasteStreamFlow Rate(MGD)Influent to Fly Ash Pond(beginning of composite)0800 19.4 20 7.02 7 NAbNAbNAbSP-1Influent to Fly Ash Pond(end of composite)1204 22.8 24 6.90 7 NAbNAbNAb6333cSP-2 Effluent from Fly AshPond1111 16.8 NA 7.97 8 NAbNAbNAb5416da – The pH meter was calibrated on the morning of October 16, 2007 using pre-packaged buffer solutions at pHs 4.0, 7.0, and 10.0.b – Due to sampling schedule limitations, the sampling team was unable to measure the free and total residual chlorine in a reasonable amount of time after thefield test aliquot was collected; therefore, EPA did not test/record the free and total residual chlorine from the sampling points.c – Based on the Cardinal’s water balance flow diagram, minusthe Unit 2 flow rates because Unit2 was not operational during the sampling episode. Note thatthe flow rate for the bottom ash recirculation pond was estimated for the actual sampling period.d – Based on three measurements recorded from the still well during the sampling period.NA – Not analyzed.

### 3-13 Table 3-4. Analytical Methods and Procedu res for Samples Collected at Cardinal

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.

### 3-14 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, 245.2) One 500-mL plastic bottle None (acid preserve at laboratory)

Routine dissolved metals, 27 element quantitation (Method 200.7, 200.8, 200.9, 245.2) One 500-mL plastic bottle 0.45 μm filter (performed in field) (acid preserve at laboratory)

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

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

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

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

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

Low-level hexavalent chromium (Method 1636) One 250-mL LDPE (ultraclean), fluoropolymer lined cap 0.45 μm filter (performed in field) 2 mL 50% NaOH per 250 mL sample (performed in field) c

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

a – Group I includes TSS, TDS, sulfate, and chloride.

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

### 3-15 Table 3-6. Sample Preservation Summary, Cardinal

Sampling

Point

Number Analysis Date Chemical Initial pH Final pH Amount Added

71120 Group II V1 10/16/07 H 2 SO 4 8 2 30 drops

71120 Group II V2 10/16/07 H 2 SO 4 8 2 30 drops

71120 HEM/SGT-HEM G1 V1 10/16/07 H 2 SO 4 7 2 30 drops

71120 HEM/SGT-HEM G1 V2 10/16/07 H 2 SO 4 7 2 30 drops

71120 HEM/SGT-HEM G2 V1 10/16/07 H 2 SO 4 7 2 30 drops

71120 HEM/SGT-HEM G2 V2 10/16/07 H 2 SO 4 7 2 30 drops

71120 Routine Hexavalent

Chromium 10/16/07 Ammonium

Sulfate Buffer 6.5 9 250 drops a

71120 Arsenic/Selenium Speciation (Duplicate) 10/16/07 HCl 8 2 15 drops

71121 Group II V1 10/16/07 H 2 SO 4 7 2 30 drops

71121 Group II V2 10/16/07 H 2 SO 4 7 2 30 drops

71121 Group II MS/MSD V1 10/16/07 H 2 SO 4 7 2 30 drops

71121 Group II MS/MSD V2 10/16/07 H 2 SO 4 7 2 30 drops

71121 HEM/SGT-HEM V1 10/16/07 H 2 SO 4 7 2 40 drops

71121 HEM/SGT-HEM V2 10/16/07 H 2 SO 4 7 2 40 drops

71121 HEM/SGT-HEM MS/MSD

V1 10/16/07 H 2 SO 4 7 2 40 drops

71121 HEM/SGT-HEM MS/MSD

V2 10/16/07 H 2 SO 4 7 2 40 drops

71121 Routine Hexavalent

Chromium 10/16/07 Ammonium

Sulfate Buffer 6.5 9 250 drops a

71121 Routine Hexavalent

Chromium MS/MSD 10/16/07 Ammonium

Sulfate Buffer 6.5 9 250 drops a

71122 Group II V1 10/16/07 H 2 SO 4 7 2 30 drops

71122 Group II V2 10/16/07 H 2 SO 4 7 2 30 drops

71122 Routine Hexavalent

Chromium 10/16/07 Ammonium

Sulfate Buffer 6.5 9 250 drops a

71123 Routine Hexavalent

Chromium 10/16/07 Ammonium

Sulfate Buffer 7 9.5 250 drops

71124 Routine Hexavalent

Chromium 10/16/07 Ammonium

Sulfate Buffer 7 9.5 250 drops

a – Preservation of this sample was stopped due to excessive buffering of the sample. The pH of the sample was not changing with the addition of the ammonium sulfate buff er solution; therefore, the preservation was stopped to prevent the sample from being diluted by the preservative.

### 3-16Table 3-7. Generating Unit Operating Characteristics during Sample Collection, CardinalUnitIDBoiler TypeCoal typeAmount ofCoal Used(tpd)Source ofCoal (coalregion and/orstate)SulfurContent ofthe Coala(lbs SO2/MBTU)Capacitya(MW)ElectricityProduction(or percentcapacity)SCR(No, On,Off)ParticulateControlSystem(HS/CS ESP,or BH)Wet FGDSystem(Yes/No)1 Babcock &Wilcoxsupercriticalwall fired drybottomEastern subbituminous:high sulfur4,780 West VirginiaSome Ohio3.98 600 581 (97 %) Off CS ESP No2bBabcock &Wilcoxsupercriticalwall fired drybottomEastern subbituminous:mid sulfurNA West VirginiaSome OhioNA 600 0 (0 %) Off CS ESP No3 Babcock &Wilcoxsupercriticalwall fired drybottomEastern subbituminous:low sulfur4,342 West VirginiaSome Ohio1.19 630 630 (100 %) On HS ESP Noa –Values reported as averages based on readings from 12 AM 10/15/07 to 12 PM 10/16/07.b –Unit 2 was not operating during sampling.HS ESP – Hot-side electrostatic precipitator.CS ESP – Cold-side electrostatic precipitator.BH – Baghouse.NA – Not applicable.

### 3-17Table 3-8. Ash System Operating Characteristics during Sample Collection, CardinalFly Ash SystemBottom Ash SystemUnitIDFly AshGeneration(tph)aFly Ash SluiceWater FlowRate (gph)Source of FlyAsh SluiceWaterSluice CycleDuration andFrequencyContinuousSluicing(Yes/No)Bottom AshGeneration(tph)aBottom AshSluice WaterFlow Rate(gph)Source ofBottom AshSluice WaterSluice CycleDuration andFrequencyContinuousSluicing(Yes/No)1 14.7 120,000bRecycledBottom AshsluiceContinuous Yes 3.7 96,000bRecirculatedIntake &cooling waterblowdown2 hrs.1x/dayNo2cNA NA NA NA NA NA NA NA NA NA3 18.9 132,000 RecycledBottom AshsluiceContinuous Yes 4.7 77,000 RecirculatedIntake &cooling waterblowdown2 hrs.2x/dayNoa – Ash generation was estimated based on the assumption that ash is 12% of the mass ofthe total coal burned per unit. Fly ashis assumed to be 80% of this amount and bottomash is assumed to be 20%.b –Flows for Unit 1 are based on Water Balance Diagram assuming 50%flow of the combined flow from Units 1 & 2.c –Unit 2 was not operating during sampling.NA – Not applicable.

### 3-18 Table 3-9. Fly Ash Pond Operating Characteristics, Cardinal

Ash Sluice Information

Total influent flow rate 9.12 MGD a

Unit 1 fly ash sluice 2.88 MGD

Unit 2 fly ash sluice 0.0 MGD b

Unit 3 fly ash sluice 3.17 MGD

Ash water recycle pond (Units 1&2) 0.0 MGD c

Ash water recycle pond (Unit 3) 3.0 MGD d

Stormwater 0.87 MGD

Influent duration Continuous

Influent percent solid 10–15% (average)

Fly Ash Pond Information

pH control system Sodium hydroxide at effluent

Chemicals added to pond system Sodium hydroxide

Drainage area routed to pond system 4,400 acres

Pond size 27.7 acres

Pond size 126,000,000 gallons

Pond retention time 10 days

Frequency of pond dredging NA

Sections of pond NA

Final discharge structure type Parshall flume

Effluent flow rate 7.8 MGD

Frequency of effluent discharge Continuous

a – Calculated assuming the flow is the sum of all aver age flows associated with Units 1 & 3, excluding

contributions associated with Unit 2.

b – Unit 2 was not operating during sampling; therefore, there was no fly ash sluice water from Unit 2.

c – There were no wastewater transfer s from the pond containing ash water recy cle from Units 1 & 2 to the fly ash pond during the sampling episode.

d – Estimated value to represent transfers during sampling episode. Cardinal personnel estimate that the average flow over the year (assuming continuous discharge) is 1.06 MGD. NA – Not applicable.

### 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 e ffluent from the fly ash pond.

Appendix A provides all analytical results for all samples collected at Cardinal, including all qualified results and all results that were measured above the method detection limit, but below the reporting limit (i.e., J-valu es). Appendix B presents the an alytical results in a format similar to that used for Section 4.2, but with the J-values shown (J-values are not included in the tables presented in Section 4.2).

4.1 Measured and Calculated Results for Fly Ash Pond Influent Samples

The samples of the influent to the fly ash pond (SP-1) were expected to contain significant amounts of readily settleable solids , mainly fly ash. Because of this, EPA was

concerned that there could be an alytical interferences for the metals analyses, since the acid digestion procedures used may not be sufficientl y rigorous for samples with high solids loads. Therefore, EPA directed its contract laboratories to separate the aqueous and solid phases of the sample prior to conducting certain analyses, wh ere allowed by the analytical method and if necessary to obtain acceptable an alytical results. This biphasic approach provides EPA with both measured and calculated pollutant concentra tions for the following 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.” [3] Because EPA expected the solids cont ent to be greater than one percent, ProChem developed an approach for the analysis of the fly ash pond influent samp les that consisted of filtering the solids from the sample and analyzing the solid and aqueous phases separately. To calculate the total sample concentration from th e solid and aqueous phase results, the laboratory also needed to measure the original sample vol ume, solid phase weight, and filtrate volume. EPA developed the following equation to calculate the individual metal total concentrations for the sample.

Sample Solid Solid Filtrate Filtrate 

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

= (4-1)

### 4-2 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, nitrate/nitrite, ch loride, sulfate, total Kjeldahl nitrogen (TKN), and total phosphorus.

Table 4-1 presents the results of the bipha sic analysis for the ammonia as nitrogen, nitrate/nitrite, chloride, sulfate, TKN, total phosphorus, and routine to tal metals. Only those analytes that were detected at the influent to the fly ash pond (at levels above the report limit) are

included in the table. Results are rounded to three significant figures. Appendix Table A-1 presents all the analytical results from the infl uent to the fly ash pond (SP-1) sample analysis, including J-values.

ProChem performed a filtration blank associ ated with the biphasic sample separation process for the fly ash pond influent (SP-1) sa mple analysis. For the blank, ProChem poured blank water through the filter used for the separation and analyzed the filtered blank water for the routine metal analytes. No metals were measured in the filtration blank sa mple above the report limit, indicating that there was no contamination from the filtration process. Appendix Table A-2 presents all the analytical results from the filtration blank, including J-values.

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 fly ash pond influent samples that minimized potential contamination to th e samples. Battelle’s approach consisted of analyzing the total metals concentration and di ssolved metals concentration for each analyte directly from the sample bottles. By using this approach, the laboratory di d not have to perform an extra filtration step to determine the individual metals concentrations for the various phases in the sample. Battelle did not have any problems w ith the digestion of the solids during the total sample analyses for the Cardinal fly ash pond influent samples.

EPA decided that solid phase results for the fly ash pond influent samples were not necessary for the sampling program; therefore, th e laboratory did not calculate the solids phase concentrations for each of the metals. However, if EPA later decides to calculate the solid phase concentrations, EPA can use the following equati on 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;

### 4-3 C Total 

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

C Diss 

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

C TSS 

### = TSS concentration of the sample.

4.2 Fly Ash Pond

Table 4-2 presents the analytical results of th e classical pollutants at the influent to the fly ash pond (SP-1) and effluent from the fly ash pond (average of SP-2 and SP -3 results). Table 4-3 presents the analytical results of the routine and low-level metals for these same sampling points. Only those analytes that were detected in one or more samples (at le vels above the reporting limit) for the sampling episode are included in the table. Results are rounded to three significant digits. If an analyte was measured above the me thod detection limit, but below the report limit, “NQ” is reported followed by the sample-specific report limit in parenthese s. If an analyte was not detected in a sample above the method de tection limit, “ND” is reported followed by the sample-specific report limit in parentheses. Note that the results presente d in Tables 4-2 and 4-3 are not paired results, meaning that sample collection across the treatment system was not timed

to reflect the amount of time it takes the wast ewater to pass through th e ash pond (approximately 10 days).

Appendix Tables A-1, A-3, and A-4 present all th e analytical results from the influent to the fly ash pond (SP-1), effluent from the fly ash pond (SP-2), and duplicate of the effluent from the fly ash pond (SP-3) sample analyses, includi ng J-values. Appendix Table B-1 presents the analytical results for the metal an alytes in a format similar to Ta ble 4-3; however, Table B-1 also includes results where analytes were measured a bove the detection level, but below the reporting limit (i.e., J-values).E – Sample analyzed outside holding time. O – OPR %Recovery below cont ract-specified criteria. ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filt ered aqueous and/or the filtered solid analytical results, including J-values, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculate d result is presented in Appendix A with a CJ flag designation. NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appendix A with a J flag designation.



### 4-4 Table 4-1. Biphasic Sample Results for Clas sicals and Routine Total Metals Measured Above the Report Limit, Fly Ash Pond Influent, Cardinal

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

Classical Pollutants

Ammonia As Nitrogen (NH 3 -N) 0.170 ND (10.0) 0.170

Nitrate/Nitrite (NO 3 -N + NO 2 -N) 2.61 E 2.4 E 2.65

Total Kjeldahl Nitrogen (TKN) ND (0.100) 25.7 1.01

Chloride 60.0 100 56.8

Sulfate 4.52 31,100 1,110

Total Phosphorus 4.05 1.65 4.03

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

Routine Total Metals

Aluminum 65,000 6,350 O 320,000

Antimony NQ (20.0) NQ (2.00) NJ (81.2)

Arsenic 314 30.0 1,520

Barium 371 116 5,060

Beryllium 26.1 1.15 71.5

Boron 2,280 15.3 2,790

Cadmium 7.45 0.800 39.6

Calcium 164,000 1,180 204,000

Chromium 312 24.6 1,300

Cobalt 53.5 8.13 381

Copper 480 12.5 964

Iron 9,040 7,120 298,000

Lead 62.7 17.9 786

Magnesium 21,000 372 O 35,100

Manganese 425 17.7 1,120

Mercury ND (0.200) 0.0570 2.31

Molybdenum 203 3.44 333

Nickel 124 15.3 739

Selenium 17.5 ND (0.500) NJ (20.3)

Sodium 61,000 294 69,900

Thallium 33.2 ND (1.00) NJ (40.6)E – Sample analyzed outside holding time. O – OPR %Recovery below cont ract-specified criteria. ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filt ered aqueous and/or the filtered solid analytical results, including J-values, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculate d result is presented in Appendix A with a CJ flag designation. NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appendix A with a J flag designation.



### 4-5 Table 4-1. Biphasic Sample Results for Clas sicals and Routine Total Metals Measured Above the Report Limit, Fly Ash Pond Influent, Cardinal

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

Titanium 585 599 24,900

Vanadium 943 35.5 2,340

Yttrium 190 8.39 521

Zinc 343 22.1 1,220

### 4-6 Table 4-2. Classical Pollutants Measured Above the Report Limit for the Fly Ash Pond,

Cardinal

Analyte Method Unit Fly Ash Pond Influent (SP-1) Fly Ash Pond Effluent (SP-2/SP-3) a

Classical Pollutants

Ammonia As Nitrogen (NH 3 -N) 4500-NH 3 F MG/L 0.170 0.205

Nitrate/Nitrite (NO3-N + NO2 -N) 4500NO3H MG/L 2.65 4.73 E

Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1.01 <0.785 L

Chloride 4500-CL-C MG/L 56.8 60.0

Hexane Extractable Material (HEM) 1664A MG/L 7.00 10.0

Silica Gel Treated HEM (SGT-HEM) 1664A MG/L 6.00 ND (4.00)

Sulfate D516-90 MG/L 1,110 494

Total Dissolved Solids (TDS) 2540 C MG/L 662 673

Total Phosphorus 365.3 MG/L 4.03 0.0870

Total Suspended Solids (TSS) 2540 D MG/L 23,400 6.00

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



### 4-7 Table 4-3. Metals Measured Above the Report Limit for the Fly Ash Pond, Cardinal

Fly Ash Pond Influent (SP-1) Fly Ash Pond Effluent (SP-2/SP-3) a Analyte Method Unit Total Dissolved Total Dissolved

Routine Metals

Aluminum 200.7 UG/L 320,000 283 344 130 L

Antimony 200.7 UG/L NJ (81.2) NQ (20.0) 21.2 20.9

Arsenic 200.7 UG/L 1,520 86.8 77.6 74.6

Barium 200.7 UG/L 5,060 164 165 157

Beryllium 200.7 UG/L 71.5 ND (5.00) ND (5.00) ND (5.00)

Boron 200.7 UG/L 2,790 1,380 1,100 1,090

Cadmium 200.7 UG/L 39.6 NQ (5.00) NQ (5.00) NQ (5.00)

Calcium 200.7 UG/L 204,000 94,800 88,400 87,200

Chromium 200.7 UG/L 1,300 NQ (10.0) NQ (10.0) NQ (10.0)

Hexavalent Chromium D1687-92 UG/L NA 5.00 NA <3.50

Cobalt 200.7 UG/L 381 NQ (50.0) NQ (50.0) NQ (50.0)

Copper 200.7 UG/L 964 NQ (10.0) NQ (10.0) NQ (10.0)

Iron 200.7 UG/L 298,000 ND (100) NQ (100) ND (100)

Lead 200.7 UG/L 786 ND (50.0) ND (50.0) ND (50.0)

Magnesium 200.7 UG/L 35,100 15,200 17,900 17,700

Manganese 200.7 UG/L 1,120 40.3 64.7 42.9

Mercury 245.1 UG/L 2.31 ND (0.200) ND (0.200) ND (0.200)

Molybdenum 200.7 UG/L 333 243 361 352

Nickel 200.7 UG/L 739 NQ (50.0) NQ (50.0) NQ (50.0)

Selenium 200.7 UG/L NJ (20.3) 16.6 44.5 43.8

Sodium 200.7 UG/L 69,900 64,400 70,800 70,300

Thallium 200.7 UG/L NJ (40.6) NQ (10.0) NQ (10.0) NQ (10.0)

Titanium 200.7 UG/L 24,900 ND (10.0) 12.6 ND (10.0)

Vanadium 200.7 UG/L 2,340 70.7 104 99.9

Yttrium 200.7 UG/L 521 ND (5.00) NQ (5.00) ND (5.00)

Zinc 200.7 UG/L 1,220 ND (10.0) NQ (10.0) NQ (10.0)a – The fly ash pond effluent results represent the average of the fly ash pond effluent and the duplicate of the fly ash pond effluent analytical measurements. < – Average result includes at least one non-detect value. (Calculation uses detection limit for non-detected results). L – Sample result between 5x and 10x blank result. NA – Not Analyzed. ND – Not detected (number in parenthesis is the report limit). NJ – The analyte concentration was calculated using the filt ered aqueous and/or the filtered solid analytical results, including J-values, if applicable, and was determined to be less than the calculated sample-specific report limit (number in parenthesis is the report limit). The calculate d result is presented in Appendix A with a CJ flag designation. NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result is presented in Appe ndix A with a J flag designation. A “NQ” for the average fly ash pond effluent indicates that the original fly ash pond effluent and/or the duplicate of the fly ash pond effluent is a J-value. The analytical result for the original fly as h pond effluent and/or the duplicate of the fly ash pond effluent is presented in Appendix A with a J flag designation. Note: Results shown are not pair ed samples. See Section 4.2.



### 4-8 Table 4-3. Metals Measured Above the Report Limit for the Fly Ash Pond, Cardinal

Fly Ash Pond Influent (SP-1) Fly Ash Pond Effluent (SP-2/SP-3) a Analyte Method Unit Total Dissolved Total Dissolved

Low-Level Metals

Antimony 1638 UG/L 33.1 17.4 21.9 22.4

Arsenic 1638 UG/L 519 80.7 69.8 68.9

Cadmium 1638 UG/L 9.51 NQ (1.00) 1.14 1.11

Chromium 1638 UG/L 569 NQ (80.0) 4.64 L 4.49 L

Hexavalent Chromium 1636 UG/L NA NA NA 3.96

Copper 1638 UG/L 719 NQ (20.0) 2.98 2.27

Lead 1638 UG/L 260 NQ (0.500) 0.420 NQ (0.250)

Mercury 1631E UG/L 1.16 0.000550 0.00125 NQ (0.000500)

Nickel 1638 UG/L 291 NQ (100) 10.7 10.6

Selenium 1638 UG/L NQ (200) 21.2 45.8 45.0

Thallium 1638 UG/L 43.6 3.10 2.84 2.87

Zinc 1638 UG/L 720 NQ (50.0) 5.98 4.15

### 5-1 5. D ATA 

### Q UALITY



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

5.1 Analytical Quality Control

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

5.2 Field Quality Control

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

5.2.1 Bottle Blanks

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

Albion Environmental collected the bottle blanks for the low-level metals and low-level hexavalent chromium samples bottles (250 mL LDPE), the speciation sample bottles (125 mL amber glass bottles), and the 2-L blank water bottles by filling the pre-cleaned bottle to the neck with ASTM Type 1 water, preserving the sample with nitric acid to a pH <2, and allowing the sample to sit for at least 24 hours. Albion Envi ronmental 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 20-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 20-liter container and poured a representative sample into a pre-cleaned sample bottle (a LDPE bottle for low-level metals and a glass bottle for low-level mercury). The blank samples were then preserved and analyzed according to the analytical methods (i.e., EP A Method 1638 or 1631E), as described above for the other bottle blank samples.

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

5.2.2 Equipment Blanks

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

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

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

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

results.

No other metals were detected in the e quipment blanks, indicating that there was no contamination from the sampling equipment. Appe ndix Table A-5 presents all of the analytical

### 5-3 results from the bottle blank and equipment blank analyses for all of the equipment used for the collection of low-level samples. EPA assumed th e barium equipment blank concentration to be 0.490 ug/L for all tubing sets containing #73 silic one tubing because the tubing set may have been fabricated using #73 silicone from the cleani ng batch that had a detec tion for barium at that

concentration.

5.2.3 Field Blanks

The sampling team collected field blanks (SP-4 and SP-5) to evaluate possible contamination caused by sampling equipment, sa mpling equipment decontamination procedures, sample collection procedures, or atmospheric contamination. EPA analyzed the field blank samples for the low-level and routine metals an alyses, including both total and dissolved metals 1



### .

The low-level and routine total metals field blank samples for the influent to the fly ash pond (SP-4) were collected by pumping ASTM Type 1 water through the composite tubing consisting of 25 feet of Teflon® tubing attached to a length of silicone tubing. The container holding the ASTM Type 1 water was placed in a large plastic bag and the end of the Teflon® tubing was placed directly into the container. The large plastic bag was closed off as quickly as possible to minimize potential atmospheric depo sition. The sample bottles were placed in a “cleanbox” and the ASTM Type 1 water was pump ed through the tubing and poured into the sample bottles. EPA collected the field bla nk samples as “multipour” split samples with Cardinal’s representative, using the same pr ocedure discussed in the sample collection description (Section 3.1). The low-level and routine total metals field blank samples for the influent to the fly ash pond (SP- 4) were collected at a differe nt point from where the actual composite samples were collected because there was not enough space on the edge of the ash sluice channel to safely collect the field blanks. Therefore, the samplers collected the field blanks at the top of the hill above wh ere the influent ash sluice st reams enter the pond and then the sampling equipment was moved down to the channel to set up the composite sample collection.

The low-level and routine dissolved metals field blank samples for the influent to the fly ash pond (SP-4) were collected by pumping ASTM Type 1 water through the pump-off tubing used for the dissolved metals sample collecti on and a capsule filter. The container holding the ASTM Type 1 water was placed in a large plastic bag and the tubing was placed directly into the container. The large plastic bag was closed o ff as quickly as possible to minimize potential atmospheric deposition. The sample bottles were placed in a “cleanbox” and the ASTM Type 1 water was pumped through the tubing, capsule filter, “Y” splitter, and poured into the sample bottles. EPA collected the field blank samples as “true” split samples with Cardinal’s representative, using the same procedure disc ussed in the sample collection description (Section 3.1).

The low-level and routine total metals field blank samples for the effluent from the fly ash pond (SP-5) 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 cont ainer. The large plastic bag was closed off as

1 EPA did not collect a low-level dissolved mercury field blan k sample in the field because the sample filtration was performed at the laboratory to minimize potential mercury contamination. The laboratory performed a filtration blank prior to filtering the sample, which is assessed as th e field blank for the low-level dissolved mercury sample. Mercury was not detected above the method detectio n limit (0.000188 ug/L) in the filtration blank.

### 5-4 quickly as possible to minimize potential atmo spheric 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 sa mple bottles. The low-level and routine dissolved metals field blank samples for the effluent from the fly ash pond (SP-5) were collected by attaching a capsule filter inline with the sample tubing configuration and pumping ASTM Type 1 water through the tubing, “Y” splitter, and capsule fi lter, and into the sample bottles. EPA collected the field blank samples as “true” split samples with Cardinal ’s representative, using the same procedure discussed in the sample collec tion description (Section 3.1).

No metals were detected in the field bl ank samples above the reporting limit, indicating that there was no contamination from the samp le collection procedures. Appendix Tables A-6 and A-7 present all the analytical results for the field blanks from the influent to the fly ash pond (SP-4) and effluent from the fl y ash pond (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).

5.2.4 Field Duplicates

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

100

2 D S D S (%) RPD × ⎟ ⎠ ⎞ ⎜ ⎝ ⎛ + −

= 

### (5-1)

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

result.

During this sampling episode, EPA collected a duplicate sample (SP-3) for all analytes (except HEM/SGT-HEM) from the effluent from the fly ash pond (SP-2). Table 5-1 presents analytical results and the RPD for SP-2 and SP-3 and includes analytical results for only those analytes that were detected in one or more samples for the sampling episode. Appendix Tables A-3 and A-4 present all the analytical results fo r the effluent from the fly ash pond (SP-2) and duplicate of the effluent from the fly ash pond (S P-3) sample analyses, including all qualified

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

### 5-5< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, CardinalAnalyteOriginal Fly Ash PondEffluent Concentration (SP-2)Duplicate Fly Ash PondEffluent Concentration (SP-3)Average ResultRelative PercentDifference (%)UnitsClassical PollutantsAmmonia As Nitrogen (NH3-N) 0.220 0.190 0.205 15 MG/LNitrate/Nitrite (NO3-N + NO2-N) 5.43 E 4.02 E 4.73 30 MG/LTotal Kjeldahl Nitrogen (TKN) 1.47 L ND (0.100) < 0.785 NC MG/LChloride 50.0 70.0 60.0 33 MG/LHexane Extractable Material (HEM) 10.0 NA 10.0 NC MG/LSilica Gel Treated HEM (SGT-HEM) ND (4.00) NA ND (4.00) NC MG/LSulfate 655 333 494 65 MG/LTotal Dissolved Solids (TDS) 676 670 673 0.89 MG/LTotal Phosphorus 0.0880 0.0860 0.0870 2.3 MG/LTotal Suspended Solids (TSS) 7.00 5.00 6.00 33 MG/LRoutine Total MetalsAluminum 362 326 344 10 UG/LAntimony 21.5 20.8 21.2 3.3 UG/LArsenic 78.1 77.1 77.6 1.3 UG/LBarium 166 163 165 1.8 UG/LBeryllium ND (5.00) ND (5.00) ND (5.00) NC UG/LBoron 1,110 1,080 1,100 2.7 UG/LCadmium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LCalcium 88,900 87,800 88,400 1.2 UG/LChromium NQ (10.0) NQ (10.0) ND (10.0) NC UG/LCobalt NQ (50.0) NQ (50.0) ND (50.0) NC UG/L

### 5-6< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, CardinalAnalyteOriginal Fly Ash PondEffluent Concentration (SP-2)Duplicate Fly Ash PondEffluent Concentration (SP-3)Average ResultRelative PercentDifference (%)UnitsCopper NQ (10.0) NQ (10.0) ND (10.0) NC UG/LIron NQ (100) NQ (100) ND (100) NC UG/LLead ND (50.0) ND (50.0) ND (50.0) NC UG/LMagnesium 18,100 17,700 17,900 2.2 UG/LManganese 65.1 64.3 64.7 1.2 UG/LMercury ND (0.200) ND (0.200) ND (0.200) NC UG/LMolybdenum 365 357 361 2.2 UG/LNickel NQ (50.0) NQ (50.0) ND (50.0) NC UG/LSelenium 44.5 44.4 44.5 0.22 UG/LSodium 71,000 70,500 70,800 0.71 UG/LThallium NQ (10.0) NQ (10.0) ND (10.0) NC UG/LTitanium 13.8 11.4 12.6 19 UG/LVanadium 105 103 104 1.9 UG/LYttrium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LZinc NQ (10.0) NQ (10.0) ND (10.0) NC UG/LRoutine Dissolved MetalsAluminum 132 L 128 L 130 3.1 UG/LAntimony 20.9 20.9 20.9 0.0 UG/LArsenic 75.1 74.1 74.6 1.3 UG/LBarium 159 155 157 2.5 UG/LBeryllium ND (5.00) ND (5.00) ND (5.00) NC UG/LBoron 1,090 1,080 1,090 0.92 UG/L

### 5-7< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, CardinalAnalyteOriginal Fly Ash PondEffluent Concentration (SP-2)Duplicate Fly Ash PondEffluent Concentration (SP-3)Average ResultRelative PercentDifference (%)UnitsCadmium NQ (5.00) NQ (5.00) ND (5.00) NC UG/LCalcium 87,600 86,800 87,200 0.92 UG/LChromium NQ (10.0) NQ (10.0) ND (10.0) NC UG/LHexavalent Chromium 5.00 ND (2.00) < 3.50 NC UG/LCobalt NQ (50.0) NQ (50.0) ND (50.0) NC UG/LCopper NQ (10.0) NQ (10.0) ND (10.0) NC UG/LIron ND (100) ND (100) ND (100) NC UG/LLead ND (50.0) ND (50.0) ND (50.0) NC UG/LMagnesium 17,700 17,700 17,700 0.0 UG/LManganese 43.1 42.7 42.9 0.93 UG/LMercury ND (0.200) ND (0.200) ND (0.200) NC UG/LMolybdenum 356 348 352 2.3 UG/LNickel NQ (50.0) NQ (50.0) ND (50.0) NC UG/LSelenium 43.9 43.6 43.8 0.69 UG/LSodium 70,600 69,900 70,300 1.00 UG/LThallium NQ (10.0) NQ (10.0) ND (10.0) NC UG/LTitanium ND (10.0) ND (10.0) ND (10.0) NC UG/LVanadium 100 99.8 99.9 0.20 UG/LYttrium ND (5.00) ND (5.00) ND (5.00) NC UG/LZinc NQ (10.0) NQ (10.0) ND (10.0) NC UG/LLow-Level Total MetalsAntimony 21.7 22.1 21.9 1.8 UG/L

### 5-8< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, CardinalAnalyteOriginal Fly Ash PondEffluent Concentration (SP-2)Duplicate Fly Ash PondEffluent Concentration (SP-3)Average ResultRelative PercentDifference (%)UnitsArsenic 69.0 70.5 69.8 2.2 UG/LCadmium 1.17 1.10 1.14 6.2 UG/LChromium 4.88 L 4.40 L 4.64 10 UG/LCopper 2.84 3.12 2.98 9.4 UG/LLead 0.400 0.440 0.420 9.5 UG/LMercury 0.00125 0.00124 0.00125 0.80 UG/LNickel 10.5 10.9 10.7 3.7 UG/LSelenium 45.6 45.9 45.8 0.66 UG/LThallium 2.82 2.85 2.84 1.1 UG/LZinc 5.64 6.32 5.98 11 UG/LLow-Level Dissolved MetalsAntimony 22.5 22.3 22.4 0.89 UG/LArsenic 69.6 68.2 68.9 2.0 UG/LCadmium 1.11 1.11 1.11 0.0 UG/LChromium 4.41 L 4.57 L 4.49 3.6 UG/LHexavalent Chromium 3.81 4.10 3.96 7.3 UG/LCopper 2.29 2.25 2.27 1.8 UG/LLead NQ (0.250) NQ (0.250) ND (0.250) NC UG/LMercury NQ (0.000500) NQ (0.000500) ND (0.000500) NC UG/LNickel 10.5 10.6 10.6 0.95 UG/L

### 5-9< – Average result includes atleast one non-detect value. (Calculation usesdetection limit for non-detected results).E – Sample analyzed outside holding time.L – Sample result between 5x and 10x blank result.NA – Not analyzed.NC – Not calculated.ND – Not detected (number in parenthesis is the report limit).NQ – Analyte was measured above the method detection limit, but below the report limit (number in parenthesis is the report limit). The analytical result ispresented in Appendix A with a J flag designation.Table 5-1. Field Duplicate Results, CardinalAnalyteOriginal Fly Ash PondEffluent Concentration (SP-2)Duplicate Fly Ash PondEffluent Concentration (SP-3)Average ResultRelative PercentDifference (%)UnitsSelenium 45.1 44.9 45.0 0.44 UG/LThallium 2.89 2.85 2.87 1.4 UG/LZinc 4.21 4.08 4.15 3.1 UG/L

### 6-1 6. R EFERENCES



### 1. Eastern Research Group, Inc., 2007. Sampling Plan, Buckeye Power Company’s Cardinal

Power Plant. October 9. DCN 05917A1.

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

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

### Appendix A

ANALYTICAL RESULTS

### A-1CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.O – OPR %Recovery below contract-specified criteria.U – Result below the MDL. Number shown in parentheses is the reporting limit).NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. Fly Ash Pond InfluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical Pollutants – TotalAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L NA NP NP 0.170Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L NA NP NP 2.65Total Kjeldahl Nitrogen (TKN) 4500-N,C MG/L NA NP NP 1.01Biochemical Oxygen Demand (BOD) 5210B MG/L 1 NP NP ND (2.00) UChloride 4500-CL-C MG/L NA NP NP 56.8Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP 7.00Silica Gel Treated HEM (SGT-HEM) 1664A MG/L 1 NP NP 6.00Sulfate D516-90 MG/L NA NP NP 1,110Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 662Total Phosphorus 365.3 MG/L NA NP NP 4.03Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 23,400Classical Pollutants – Solid (wet weight)Ammonia As Nitrogen (NH3-N) 4500-NH3F MG/KG 1 NP NP ND (10.0) UNitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/KG 1 NP NP 2.40 ETotal Kjeldahl Nitrogen (TKN) 4500-N,C MG/KG 1 NP NP 25.7Chloride 4500-CL-C MG/KG 1 NP NP 100Sulfate D516-90 MG/KG 10 NP NP 31,100Total Phosphorus 365.3 MG/KG 1 NP NP 1.65

### A-2CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.O – OPR %Recovery below contract-specified criteria.U – Result below the MDL. Number shown in parentheses is the reporting limit).NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. Fly Ash Pond InfluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical Pollutants – Filtered AqueousAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 0.170Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 20 NP NP 2.61 ETotal Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP ND (0.100) UChloride 4500-CL-C MG/L 1 NP NP 60.0Sulfate D516-90 MG/L 1 NP NP 4.52Total Phosphorus 365.3 MG/L 5 NP NP 4.05Routine Metals – TotalAluminum 200.7 UG/L NA NC 203 320,000Antimony 200.7 UG/L NA NC 81.2 35.1 CJArsenic 200.7 UG/L NA NC 40.6 1,520Barium 200.7 UG/L NA NC 8.12 5,060Beryllium 200.7 UG/L NA NC 20.3 71.5Boron 200.7 UG/L NA NC 406 2,790Cadmium 200.7 UG/L NA NC 20.3 39.6Calcium 200.7 UG/L NA NC 500 204,000Chromium 200.7 UG/L NA NC 40.6 1,300Cobalt 200.7 UG/L NA NC 203 381Copper 200.7 UG/L NA NC 40.6 964

### A-3CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.O – OPR %Recovery below contract-specified criteria.U – Result below the MDL. Number shown in parentheses is the reporting limit).NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. Fly Ash Pond InfluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationIron 200.7 UG/L NA NC 406 298,000Lead 200.7 UG/L NA NC 203 786Magnesium 200.7 UG/L NA NC 812 35,100Manganese 200.7 UG/L NA NC 60.9 1,120Mercury 245.1 UG/L NA NC 1.01 2.31Molybdenum 200.7 UG/L NA NC 40.6 333Nickel 200.7 UG/L NA NC 203 739Selenium 200.7 UG/L NA NC 20.3 16.6 CJSilver 200.7 UG/L NA NC 81.2 7.81 CJSodium 200.7 UG/L NA NC 2,030 69,900Thallium 200.7 UG/L NA NC 40.6 31.6 CJTin 200.7 UG/L NA NC 122 61.2 CJTitanium 200.7 UG/L NA NC 40.6 24,900Vanadium 200.7 UG/L NA NC 81.2 2,340Yttrium 200.7 UG/L NA NC 20.3 521Zinc 200.7 UG/L NA NC 40.6 1,220Routine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 283Antimony 200.7 UG/L 1 0.700 20.0 15.1 J

### A-4CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.O – OPR %Recovery below contract-specified criteria.U – Result below the MDL. Number shown in parentheses is the reporting limit).NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. Fly Ash Pond InfluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationArsenic 200.7 UG/L 1 0.500 10.0 86.8Barium 200.7 UG/L 1 0.100 2.00 164Beryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 1,380Cadmium 200.7 UG/L 1 0.100 5.00 0.103 JCalcium 200.7 UG/L 1 5.10 50.0 94,800Chromium 200.7 UG/L 1 0.200 10.0 6.68 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 5.00Cobalt 200.7 UG/L 1 0.600 50.0 2.45 JCopper 200.7 UG/L 1 0.200 10.0 3.21 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 15,200Manganese 200.7 UG/L 1 0.200 15.0 40.3Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 243Nickel 200.7 UG/L 1 1.10 50.0 11.8 JSelenium 200.7 UG/L 1 0.600 5.00 16.6Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) U

### A-5CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.O – OPR %Recovery below contract-specified criteria.U – Result below the MDL. Number shown in parentheses is the reporting limit).NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. Fly Ash Pond InfluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationSodium 200.7 UG/L 1 40.5 500 64,400Thallium 200.7 UG/L 1 0.500 10.0 1.69 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 70.7Yttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 ND (10.0) URoutine Metals – Filtered AqueousAluminum 200.7 UG/L 1 10.6 50.0 65,000Antimony 200.7 UG/L 1 0.700 20.0 12.5 JArsenic 200.7 UG/L 1 0.500 10.0 314Barium 200.7 UG/L 1 0.100 2.00 371Beryllium 200.7 UG/L 1 0.500 5.00 26.1Boron 200.7 UG/L 1 2.70 100 2,280Cadmium 200.7 UG/L 1 0.100 5.00 7.45Calcium 200.7 UG/L 10 51.0 500 164,000Chromium 200.7 UG/L 1 0.200 10.0 312Cobalt 200.7 UG/L 1 0.600 50.0 53.5Copper 200.7 UG/L 1 0.200 10.0 480

### A-6CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.O – OPR %Recovery below contract-specified criteria.U – Result below the MDL. Number shown in parentheses is the reporting limit).NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. Fly Ash Pond InfluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationIron 200.7 UG/L 1 5.40 100 9,040Lead 200.7 UG/L 1 0.700 50.0 62.7Magnesium 200.7 UG/L 1 8.90 200 21,000Manganese 200.7 UG/L 1 0.200 15.0 425Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 203Nickel 200.7 UG/L 1 1.10 50.0 124Selenium 200.7 UG/L 1 0.600 5.00 17.5Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 61,000Thallium 200.7 UG/L 1 0.500 10.0 33.2Tin 200.7 UG/L 1 0.400 30.0 0.426 JTitanium 200.7 UG/L 1 0.200 10.0 585Vanadium 200.7 UG/L 1 0.600 20.0 943Yttrium 200.7 UG/L 1 0.200 5.00 190Zinc 200.7 UG/L 1 0.200 10.0 343Routine Metals – Solid (wet weight)Aluminum 200.7 MG/KG 1 1.75 5.00 6,350 OAntimony 200.7 MG/KG 1 0.110 2.00 0.572 J

### A-7CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.O – OPR %Recovery below contract-specified criteria.U – Result below the MDL. Number shown in parentheses is the reporting limit).NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. Fly Ash Pond InfluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationArsenic 200.7 MG/KG 1 0.110 1.00 30.0Barium 200.7 MG/KG 1 0.0200 0.200 116Beryllium 200.7 MG/KG 1 0.0100 0.500 1.15Boron 200.7 MG/KG 1 0.200 10.0 15.3Cadmium 200.7 MG/KG 1 0.0200 0.500 0.800Calcium 200.7 MG/KG 1 0.400 5.00 1,180Chromium 200.7 MG/KG 1 0.0200 1.00 24.6Cobalt 200.7 MG/KG 1 0.360 5.00 8.13Copper 200.7 MG/KG 1 0.0300 1.00 12.5Iron 200.7 MG/KG 1 1.06 10.0 7,120Lead 200.7 MG/KG 1 0.100 5.00 17.9Magnesium 200.7 MG/KG 1 2.18 20.0 372 OManganese 200.7 MG/KG 1 0.0200 1.50 17.7Mercury 245.5 MG/KG 1 0.00600 0.0250 0.0570Molybdenum 200.7 MG/KG 1 0.0600 1.00 3.44Nickel 200.7 MG/KG 1 0.0800 5.00 15.3Selenium 200.7 MG/KG 1 0.170 0.500 ND (0.500) USilver 200.7 MG/KG 1 0.100 2.00 0.192 JSodium 200.7 MG/KG 1 6.23 50.0 294

### A-8CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.O – OPR %Recovery below contract-specified criteria.U – Result below the MDL. Number shown in parentheses is the reporting limit).NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. Fly Ash Pond InfluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationThallium 200.7 MG/KG 1 0.110 1.00 ND (1.00) UTin 200.7 MG/KG 1 0.100 3.00 1.50 JTitanium 200.7 MG/KG 1 0.120 1.00 599Vanadium 200.7 MG/KG 1 0.0800 2.00 35.5Yttrium 200.7 MG/KG 1 0.0300 0.500 8.39Zinc 200.7 MG/KG 1 0.200 1.00 22.1Low-Level Metals – TotalAntimony 1638 UG/L 50 0.350 1.00 33.1Arsenic 1638 UG/L 200 3.04 30.0 519Cadmium 1638 UG/L 50 0.0500 5.00 9.51Chromium 1638 UG/L 200 16.6 160 569Copper 1638 UG/L 200 0.800 40.0 719Lead 1638 UG/L 50 0.0500 2.50 260Mercury 1631E UG/L 19 0.00357 0.00950 1.16Nickel 1638 UG/L 200 2.60 200 291Selenium 1638 UG/L 200 3.20 200 22.1 JSilver 1638 UG/L 50 0.100 5.00 0.682 JThallium 1638 UG/L 200 0.0800 4.00 43.6Zinc 1638 UG/L 200 41.8 100 720

### A-9CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.O – OPR %Recovery below contract-specified criteria.U – Result below the MDL. Number shown in parentheses is the reporting limit).NA – Not applicable. Calculated value.NC – A sample-specific MDL was not calculated for the analyte.ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-1. Fly Ash Pond InfluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLow-Level Metals - DissolvedAntimony 1638 UG/L 10 0.0700 0.200 17.4Arsenic 1638 UG/L 100 1.52 15.0 80.7Cadmium 1638 UG/L 10 0.0100 1.00 0.722 JChromium 1638 UG/L 100 8.30 80.0 35.8 JCopper 1638 UG/L 100 0.400 20.0 3.34 JLead 1638 UG/L 10 0.0100 0.500 0.0217 JMercury 1631E UG/L 1 0.000188 0.000500 0.000550Nickel 1638 UG/L 100 1.30 100 14.9 JSelenium 1638 UG/L 10 0.160 10.0 21.2Silver 1638 UG/L 10 0.0200 1.00 ND (1.00) UThallium 1638 UG/L 10 0.00400 0.200 3.10Zinc 1638 UG/L 100 20.9 50.0 44.5 J

### A-10 Table A-2. ProChem Biphasic Filtration Blank Analytical Results, Cardinal

Analyte Method Unit Dilution

Factor SampleSpecific MDL Sample-Specific

RL Concentration

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

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

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

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

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

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

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

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

Chromium 200.7 UG/L 1 0.200 10.0 0.200 J

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Zinc 200.7 UG/L 1 0.200 10.0 0.400 J

ND – Not detected (number in parenthesis is the report limit). U – Result below the MDL. (Number shown in parentheses is the reporting limit). J – Result measured above the MDL, but less than the reporting limit.

### A-11E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-3. Fly Ash Pond EffluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationClassical PollutantsAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 0.220Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 20 NP NP 5.43 ETotal Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP 1.47 LBiochemical Oxygen Demand (BOD) 5210B MG/L 1 NP NP ND (2.00) UChloride 4500-CL-C MG/L 1 NP NP 50.0Hexane Extractable Material (HEM) 1664A MG/L 1 NP NP 10.0Silica Gel Treated HEM (SGT-HEM) 1664A MG/L 1 NP NP ND (4.00) USulfate D516-90 MG/L 50 NP NP 655Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 676Total Phosphorus 365.3 MG/L 1 NP NP 0.0880Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 7.00Routine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 362Antimony 200.7 UG/L 1 0.700 20.0 21.5Arsenic 200.7 UG/L 1 0.500 10.0 78.1Barium 200.7 UG/L 1 0.100 2.00 166Beryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 1,110Cadmium 200.7 UG/L 1 0.100 5.00 0.171 JCalcium 200.7 UG/L 1 5.10 50.0 88,900Chromium 200.7 UG/L 1 0.200 10.0 3.13 J

### A-12E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-3. Fly Ash Pond EffluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationCobalt 200.7 UG/L 1 0.600 50.0 1.58 JCopper 200.7 UG/L 1 0.200 10.0 4.34 JIron 200.7 UG/L 1 5.40 100 83.0 JLead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 18,100Manganese 200.7 UG/L 1 0.200 15.0 65.1Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 365Nickel 200.7 UG/L 1 1.10 50.0 9.34 JSelenium 200.7 UG/L 1 0.600 5.00 44.5Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 71,000Thallium 200.7 UG/L 1 0.500 10.0 1.40 JTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 13.8Vanadium 200.7 UG/L 1 0.600 20.0 105Yttrium 200.7 UG/L 1 0.200 5.00 0.206 JZinc 200.7 UG/L 1 0.200 10.0 1.95 JRoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 132 LAntimony 200.7 UG/L 1 0.700 20.0 20.9Arsenic 200.7 UG/L 1 0.500 10.0 75.1

### A-13E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-3. Fly Ash Pond EffluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationBarium 200.7 UG/L 1 0.100 2.00 159Beryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 1,090Cadmium 200.7 UG/L 1 0.100 5.00 0.104 JCalcium 200.7 UG/L 1 5.10 50.0 87,600Chromium 200.7 UG/L 1 0.200 10.0 2.44 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 5.00Cobalt 200.7 UG/L 1 0.600 50.0 1.02 JCopper 200.7 UG/L 1 0.200 10.0 3.00 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 17,700Manganese 200.7 UG/L 1 0.200 15.0 43.1Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 356Nickel 200.7 UG/L 1 1.10 50.0 8.38 JSelenium 200.7 UG/L 1 0.600 5.00 43.9Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 70,600Thallium 200.7 UG/L 1 0.500 10.0 1.06 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) U

### A-14E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-3. Fly Ash Pond EffluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationVanadium 200.7 UG/L 1 0.600 20.0 100Yttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 0.535 JLow-Level Metals – TotalAntimony 1638 UG/L 5 0.0350 0.100 21.7Arsenic 1638 UG/L 5 0.0760 0.750 69.0Cadmium 1638 UG/L 5 0.00500 0.500 1.17Chromium 1638 UG/L 5 0.415 4.00 4.88 LCopper 1638 UG/L 5 0.0200 1.00 2.84Lead 1638 UG/L 5 0.00500 0.250 0.400Mercury 1631E UG/L 1 0.000188 0.000500 0.00125Nickel 1638 UG/L 5 0.0650 5.00 10.5Selenium 1638 UG/L 5 0.0800 5.00 45.6Silver 1638 UG/L 5 0.0100 0.500 0.0171 JThallium 1638 UG/L 5 0.00200 0.100 2.82Zinc 1638 UG/L 5 1.05 2.50 5.64Low-Level Metals - DissolvedAntimony 1638 UG/L 5 0.0350 0.100 22.5Arsenic 1638 UG/L 5 0.0760 0.750 69.6Cadmium 1638 UG/L 5 0.00500 0.500 1.11Chromium 1638 UG/L 5 0.415 4.00 4.41 LHexavalent Chromium 1636 UG/L 5 1.75 2.50 3.81

### A-15E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-3. Fly Ash Pond EffluentAnalytical Data, CardinalAnalyteMethodUnitDilution FactorSample-SpecificMDLSample-SpecificRLConcentrationCopper 1638 UG/L 5 0.0200 1.00 2.29Lead 1638 UG/L 5 0.00500 0.250 0.00730 JMercury 1631E UG/L 1 0.000188 0.000500 0.000468 JNickel 1638 UG/L 5 0.0650 5.00 10.5Selenium 1638 UG/L 5 0.0800 5.00 45.1Silver 1638 UG/L 5 0.0100 0.500 0.0217 JThallium 1638 UG/L 5 0.00200 0.100 2.89Zinc 1638 UG/L 5 1.05 2.50 4.21

### A-16E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. Duplicate of Fly Ash Pond Effluent Analytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationClassical PollutantsAmmonia As Nitrogen (NH3-N) 4500-NH3F MG/L 1 NP NP 0.190Nitrate/Nitrite (NO3-N + NO2-N) 4500NO3H MG/L 20 NP NP 4.02 ETotal Kjeldahl Nitrogen (TKN) 4500-N,C MG/L 1 NP NP ND (0.100) UBiochemical Oxygen Demand (BOD) 5210B MG/L 1 NP NP ND (2.00) UChloride 4500-CL-C MG/L 1 NP NP 70.0Sulfate D516-90 MG/L 10 NP NP 333Total Dissolved Solids (TDS) 2540 C MG/L 1 NP NP 670Total Phosphorus 365.3 MG/L 1 NP NP 0.0860Total Suspended Solids (TSS) 2540 D MG/L 1 NP NP 5.00Routine Metals – TotalAluminum 200.7 UG/L 1 10.6 50.0 326Antimony 200.7 UG/L 1 0.700 20.0 20.8Arsenic 200.7 UG/L 1 0.500 10.0 77.1Barium 200.7 UG/L 1 0.100 2.00 163Beryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 1,080Cadmium 200.7 UG/L 1 0.100 5.00 0.179 JCalcium 200.7 UG/L 1 5.10 50.0 87,800Chromium 200.7 UG/L 1 0.200 10.0 3.02 JCobalt 200.7 UG/L 1 0.600 50.0 1.59 JCopper 200.7 UG/L 1 0.200 10.0 4.01 JIron 200.7 UG/L 1 5.40 100 72.7 J

### A-17E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. Duplicate of Fly Ash Pond Effluent Analytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationLead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 17,700Manganese 200.7 UG/L 1 0.200 15.0 64.3Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 357Nickel 200.7 UG/L 1 1.10 50.0 9.26 JSelenium 200.7 UG/L 1 0.600 5.00 44.4Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 70,500Thallium 200.7 UG/L 1 0.500 10.0 1.53 JTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 11.4Vanadium 200.7 UG/L 1 0.600 20.0 103Yttrium 200.7 UG/L 1 0.200 5.00 0.237 JZinc 200.7 UG/L 1 0.200 10.0 1.82 JRoutine Metals – DissolvedAluminum 200.7 UG/L 1 10.6 50.0 128 LAntimony 200.7 UG/L 1 0.700 20.0 20.9Arsenic 200.7 UG/L 1 0.500 10.0 74.1Barium 200.7 UG/L 1 0.100 2.00 155Beryllium 200.7 UG/L 1 0.500 5.00 ND (5.00) UBoron 200.7 UG/L 1 2.70 100 1,080Cadmium 200.7 UG/L 1 0.100 5.00 0.149 J

### A-18E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. Duplicate of Fly Ash Pond Effluent Analytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationCalcium 200.7 UG/L 1 5.10 50.0 86,800Chromium 200.7 UG/L 1 0.200 10.0 2.41 JHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 1.17 JCopper 200.7 UG/L 1 0.200 10.0 2.85 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 17,700Manganese 200.7 UG/L 1 0.200 15.0 42.7Mercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 348Nickel 200.7 UG/L 1 1.10 50.0 8.06 JSelenium 200.7 UG/L 1 0.600 5.00 43.6Silver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 69,900Thallium 200.7 UG/L 1 0.500 10.0 1.67 JTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 99.8Yttrium 200.7 UG/L 1 0.200 5.00 ND (5.00) UZinc 200.7 UG/L 1 0.200 10.0 0.878 JLow-Level Metals – TotalAntimony 1638 UG/L 5 0.0350 0.100 22.1

### A-19E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. Duplicate of Fly Ash Pond Effluent Analytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationArsenic 1638 UG/L 5 0.0760 0.750 70.5Cadmium 1638 UG/L 5 0.00500 0.500 1.10Chromium 1638 UG/L 5 0.415 4.00 4.40 LCopper 1638 UG/L 5 0.0200 1.00 3.12Lead 1638 UG/L 5 0.00500 0.250 0.440Mercury 1631E UG/L 1 0.000188 0.000500 0.00124Nickel 1638 UG/L 5 0.0650 5.00 10.9Selenium 1638 UG/L 5 0.0800 5.00 45.9Silver 1638 UG/L 5 0.0100 0.500 0.0480 JThallium 1638 UG/L 5 0.00200 0.100 2.85Zinc 1638 UG/L 5 1.05 2.50 6.32Low-Level Metals - DissolvedAntimony 1638 UG/L 5 0.0350 0.100 22.3Arsenic 1638 UG/L 5 0.0760 0.750 68.2Cadmium 1638 UG/L 5 0.00500 0.500 1.11Chromium 1638 UG/L 5 0.415 4.00 4.57 LHexavalent Chromium 1636 UG/L 5 1.75 2.50 4.10Copper 1638 UG/L 5 0.0200 1.00 2.25Lead 1638 UG/L 5 0.00500 0.250 0.0191 JMercury 1631E UG/L 1 0.000188 0.000500 0.000364 JNickel 1638 UG/L 5 0.0650 5.00 10.6Selenium 1638 UG/L 5 0.0800 5.00 44.9Silver 1638 UG/L 5 0.0100 0.500 0.0368 J

### A-20E – Sample analyzed outside holding time.J – Result measured above the MDL, but less than the reporting limit.L – Sample result between 5x and 10x blank result.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).NP – Not provided. The sample-specific MDL and sample-specific RLare only provided for the metal analytes because EPA is presenting analytical values formetals that are quantified below the report limit. For this analyte, only values above the report limit are presented. If the analyte was not detected above the reportlimit, the report limit is presented in parentheses in the concentration column.Table A-4. Duplicate of Fly Ash Pond Effluent Analytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationThallium 1638 UG/L 5 0.00200 0.100 2.85Zinc 1638 UG/L 5 1.05 2.50 4.08a – Barium was detected in two equipment blanks for #73 silicone tubing at 0.490 ug/L and 0. 476 ug/L. Because #73 silicone tubing was used in this fabricated tubing set, the barium concentration is assumed to be 0.490 ug/L. ND – Not detected (number in parenthesis is the report limit).



### A-21 Table A-5. Bottle Blank and Equipment Blank Analytical Data, Cardinal

Analyte Method Process Units Concentration

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

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

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

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

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



### A-22 Table A-5. Bottle Blank and Equipment Blank Analytical Data, Cardinal

Analyte Method Process Units Concentration

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

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

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

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

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

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

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



### A-23 Table A-5. Bottle Blank and Equipment Blank Analytical Data, Cardinal

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)

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

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

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

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

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

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

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

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



### A-24 Table A-5. Bottle Blank and Equipment Blank Analytical Data, Cardinal

Analyte Method Process Units Concentration

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 #24 silicone tubing for dissolved sample collection for low-level metals)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium EPA 1638 Dissolved UG/L ND (0.10)

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

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

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

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

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium a EPA 1638 Dissolved UG/L 0.490

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

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



### A-25 Table A-5. Bottle Blank and Equipment Blank Analytical Data, Cardinal

Analyte Method Process Units Concentration

Manganese EPA 1638 Dissolved UG/L ND (0.50)

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

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Tubing Set – Equipment Blank (25 feet of Teflon® tubing, 10 feet #73 silic one tubing, Y-splitter, two pieces of 5 feet #24 silicone tubing for sample collectio n for low-level mercury and metals from fly ash pond effluent)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium a EPA 1638 Dissolved UG/L 0.490

Beryllium EPA 1638 Dissolved UG/L ND (0.10)

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

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

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

Funnel Assembly Set – Equipment Blank (Plastic funnel attached to #73 silicone tubing, Y-splitter, and 2 pieces of 5 feet of #24 silicone tubi ng for sample collection for low-leve l total metals at the fly ash pond influent)

Aluminum EPA 1638 Dissolved UG/L ND (2.0)

Antimony EPA 1638 Dissolved UG/L ND (0.50)

Arsenic EPA 1638 Dissolved UG/L ND (0.50)

Barium a EPA 1638 Dissolved UG/L 0.490

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



### A-26 Table A-5. Bottle Blank and Equipment Blank Analytical Data, Cardinal

Analyte Method Process Units Concentration

Cadmium EPA 1638 Dissolved UG/L ND (0.10)

Chromium EPA 1638 Dissolved UG/L ND (1.0)

Cobalt EPA 1638 Dissolved UG/L ND (0.10)

Copper EPA 1638 Dissolved UG/L ND (0.30)

Lead EPA 1638 Dissolved UG/L ND (0.050)

Manganese EPA 1638 Dissolved UG/L ND (0.50)

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

Molybdenum EPA 1638 Dissolved UG/L ND (0.50)

Nickel EPA 1638 Dissolved UG/L ND (0.50)

Selenium EPA 1638 Dissolved UG/L ND (2.0)

Silver EPA 1638 Dissolved UG/L ND (0.10)

Thallium EPA 1638 Dissolved UG/L ND (0.050)

Vanadium EPA 1638 Dissolved UG/L ND (1.0)

Zinc EPA 1638 Dissolved UG/L ND (0.50)

### A-27J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-6. Fly Ash Pond Influent Field Blank Analytical Data, CardinalAnalyteMethodUnitDilution 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 ND (100) UCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 ND (50.0) UChromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND (10.0) UIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 ND (200) UManganese 200.7 UG/L 1 0.200 15.0 ND (15.0) UMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 ND (10.0) UNickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND (5.00) USilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 ND (500) UThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) U

### A-28J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-6. Fly Ash Pond Influent Field Blank Analytical Data, CardinalAnalyteMethodUnitDilution 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 0.347 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 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 ND (100) UCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 ND (50.0) UChromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND (10.0) UIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 ND (200) UManganese 200.7 UG/L 1 0.200 15.0 ND (15.0) UMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 ND (10.0) UNickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND (5.00) USilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 ND (500) UThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) U

### A-29J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-6. Fly Ash Pond Influent Field Blank Analytical Data, CardinalAnalyteMethodUnitDilution 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 0.314 JLow-Level Metals – TotalAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 0.0163 JCadmium 1638 UG/L 1 0.00100 0.100 ND (0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.169 JCopper 1638 UG/L 1 0.00400 0.200 ND (0.200) ULead 1638 UG/L 1 0.00100 0.0500 0.00130 JMercury 1631E UG/L 1 0.000188 0.000500 ND (0.000500) UNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 0.00360 JThallium 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 0.135 JCopper 1638 UG/L 1 0.00400 0.200 0.0111 JLead 1638 UG/L 1 0.00100 0.0500 0.00460 JNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) U

### A-30J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-6. Fly Ash Pond Influent Field Blank Analytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationSelenium 1638 UG/L 1 0.0160 1.00 ND (1.00) USilver 1638 UG/L 1 0.00200 0.100 0.00290 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-31J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-7. Fly Ash Pond Effluent Field Blank Analytical Data, CardinalAnalyteMethodUnitDilution 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 ND (100) UCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 ND (50.0) UChromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND (10.0) UIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 ND (200) UManganese 200.7 UG/L 1 0.200 15.0 ND (15.0) UMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 ND (10.0) UNickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND (5.00) USilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 ND (500) UThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) UTin 200.7 UG/L 1 0.400 30.0 ND (30.0) UTitanium 200.7 UG/L 1 0.200 10.0 ND (10.0) UVanadium 200.7 UG/L 1 0.600 20.0 ND (20.0) U

### A-32J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-7. Fly Ash Pond Effluent Field Blank Analytical Data, CardinalAnalyteMethodUnitDilution 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 0.464 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 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 ND (100) UCadmium 200.7 UG/L 1 0.100 5.00 ND (5.00) UCalcium 200.7 UG/L 1 5.10 50.0 ND (50.0) UChromium 200.7 UG/L 1 0.200 10.0 ND (10.0) UHexavalent Chromium D1687-92 UG/L 1 1.00 2.00 ND (2.00) UCobalt 200.7 UG/L 1 0.600 50.0 ND (50.0) UCopper 200.7 UG/L 1 0.200 10.0 ND (10.0) UIron 200.7 UG/L 1 5.40 100 ND (100) ULead 200.7 UG/L 1 0.700 50.0 ND (50.0) UMagnesium 200.7 UG/L 1 8.90 200 ND (200) UManganese 200.7 UG/L 1 0.200 15.0 ND (15.0) UMercury 245.1 UG/L 1 0.0500 0.200 ND (0.200) UMolybdenum 200.7 UG/L 1 0.200 10.0 ND (10.0) UNickel 200.7 UG/L 1 1.10 50.0 ND (50.0) USelenium 200.7 UG/L 1 0.600 5.00 ND (5.00) USilver 200.7 UG/L 1 0.400 20.0 ND (20.0) USodium 200.7 UG/L 1 40.5 500 ND (500) UThallium 200.7 UG/L 1 0.500 10.0 ND (10.0) U

### A-33J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-7. Fly Ash Pond Effluent Field Blank Analytical Data, CardinalAnalyteMethodUnitDilution 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 0.328 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 0.110 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 0.00420 JThallium 1638 UG/L 1 0.000400 0.0200 0.00170 JZinc 1638 UG/L 1 0.209 0.500 ND (0.500) ULow-Level Metals - DissolvedAntimony 1638 UG/L 1 0.00700 0.0200 ND (0.0200) UArsenic 1638 UG/L 1 0.0152 0.150 ND (0.150) UCadmium 1638 UG/L 1 0.00100 0.100 ND (0.100) UChromium 1638 UG/L 1 0.0830 0.800 0.150 JHexavalent Chromium 1636 UG/L 5 1.75 2.50 1.84 JCopper 1638 UG/L 1 0.00400 0.200 0.0668 JLead 1638 UG/L 1 0.00100 0.0500 0.00350 J

### A-34J – Result measured above the MDL, but less than the reporting limit.U – Result below the MDL. Number shown in parentheses is the reporting limit).ND – Not detected (number in parenthesis is the report limit).Table A-7. Fly Ash Pond Effluent Field Blank Analytical Data, CardinalAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific RLConcentrationNickel 1638 UG/L 1 0.0130 1.00 ND (1.00) USelenium 1638 UG/L 1 0.0160 1.00 0.0463 JSilver 1638 UG/L 1 0.00200 0.100 0.00470 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

### Appendix B

ANALYTICAL DATA FOR METALS, FLY ASH POND

### B-1CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.L – Sample result between 5x and 10x blank result.J - Result measured above the MDL, but less than the reporting limit.U - Result below the MDL. Number shownin parentheses is the reporting limit).NA – Not analyzed.ND – Not detected (number in parenthesis is the report limit).Note: Results shown are not paired samples. See Section 4.2.Table B-1. Analytical Results for Metals in the Fly Ash Pond, CardinalFly Ash Pond Influent (SP-1)Original Fly Ash Pond Effluent (SP-2)Duplicate Fly Ash Pond Effluent (SP-3)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedRoutine MetalsAluminum 200.7 UG/L320,000 283 362 132 L 326 128 LAntimony 200.7 UG/L35.1 CJ 15.1 J 21.5 20.9 20.8 20.9Arsenic 200.7 UG/L1,520 86.8 78.1 75.1 77.1 74.1Barium 200.7 UG/L5,060 164 166 159 163 155Beryllium 200.7 UG/L71.5 ND (5.00) U ND (5.00) U ND(5.00) U ND (5.00) U ND (5.00) UBoron 200.7 UG/L2,790 1,380 1,110 1,090 1,080 1,080Cadmium 200.7 UG/L39.6 0.103 J 0.171 J 0.104 J 0.179 J 0.149 JCalcium 200.7 UG/L204,000 94,800 88,900 87,600 87,800 86,800Chromium 200.7 UG/L1,300 6.68 J 3.13 J 2.44 J 3.02 J 2.41 JHexavalentChromiumD1687-92 UG/L NA5.00NA5.00NAND (2.00) UCobalt 200.7 UG/L381 2.45 J 1.58 J 1.02 J 1.59 J 1.17 JCopper 200.7 UG/L964 3.21 J 4.34 J 3.00 J 4.01 J 2.85 JIron 200.7 UG/L298,000 ND (100) U 83.0 J ND (100) U 72.7 J ND (100) ULead 200.7 UG/L786 ND (50.0) U ND (50.0) U ND (50.0) U ND (50.0) U ND (50.0) UMagnesium 200.7 UG/L35,100 15,200 18,10017,700 17,700 17,700Manganese 200.7 UG/L1,120 40.3 65.1 43.1 64.3 42.7Mercury 245.1 UG/L2.31 ND (0.200) U ND (0.200) U ND (0.200) U ND (0.200) U ND (0.200) UMolybdenum 200.7 UG/L333 243 365 356 357 348Nickel 200.7 UG/L739 11.8 J 9.34 J 8.38 J 9.26 J 8.06 JSelenium 200.7 UG/L16.6 CJ 16.6 44.5 43.9 44.4 43.6

### B-2CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.L – Sample result between 5x and 10x blank result.J - Result measured above the MDL, but less than the reporting limit.U - Result below the MDL. Number shownin parentheses is the reporting limit).NA – Not analyzed.ND – Not detected (number in parenthesis is the report limit).Note: Results shown are not paired samples. See Section 4.2.Table B-1. Analytical Results for Metals in the Fly Ash Pond, CardinalFly Ash Pond Influent (SP-1)Original Fly Ash Pond Effluent (SP-2)Duplicate Fly Ash Pond Effluent (SP-3)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedSilver 200.7 UG/L7.81 CJ ND (20.0) U ND (20.0) U ND (20.0) U ND (20.0) U ND (20.0) USodium 200.7 UG/L69,900 64,400 71,00070,600 70,500 69,900Thallium 200.7 UG/L31.6 CJ 1.69 J 1.40 J 1.06 J 1.53 J 1.67 JTin 200.7 UG/L61.2 CJ ND (30.0) U ND (30.0) U ND (30.0) U ND (30.0) U ND (30.0) UTitanium 200.7 UG/L24,900 ND (10.0) U 13.8 ND (10.0) U 11.4 ND (10.0) UVanadium 200.7 UG/L2,340 70.7 105 100 103 99.8Yttrium 200.7 UG/L521 ND (5.00) U 0.206 J ND (5.00) U 0.237 J ND (5.00) UZinc 200.7 UG/L1,220 ND (10.0) U 1.95 J 0.535 J 1.82 J 0.878 JLow-Level MetalsAntimony 1638 UG/L33.1 17.4 21.7 22.5 22.1 22.3Arsenic 1638 UG/L519 80.7 69.0 69.6 70.5 68.2Cadmium 1638 UG/L9.51 0.722 J 1.17 1.11 1.10 1.11Chromium 1638 UG/L569 35.8 J 4.88 L 4.41 L 4.40 L 4.57 LHexavalentChromium1636 UG/L NANA NA 3.81NA4.10Copper 1638 UG/L719 3.34 J 2.84 2.29 3.12 2.25Lead 1638 UG/L260 0.0217 J 0.400 0.00730 J 0.440 0.0191 JMercury 1631E UG/L1.16 0.000550 0.00125 0.000468 J 0.00124 0.000364 JNickel 1638 UG/L291 14.9 J 10.5 10.5 10.9 10.6Selenium 1638 UG/L22.1 J 21.2 45.6 45.1 45.9 44.9

### B-3CJ – Calculated J-value. The J-value was calculated using thefiltered aqueous and/or the filtered solid analytical results, including J-values, if applicable. At leastone of the sample fraction analytical results (i.e., filtered aqueous and/or filtered solid concentration) was measured above the method detection limit, and thecalculated total sample concentration is less than the calculated sample-specific report limit.L – Sample result between 5x and 10x blank result.J - Result measured above the MDL, but less than the reporting limit.U - Result below the MDL. Number shownin parentheses is the reporting limit).NA – Not analyzed.ND – Not detected (number in parenthesis is the report limit).Note: Results shown are not paired samples. See Section 4.2.Table B-1. Analytical Results for Metals in the Fly Ash Pond, CardinalFly Ash Pond Influent (SP-1)Original Fly Ash Pond Effluent (SP-2)Duplicate Fly Ash Pond Effluent (SP-3)AnalyteMethodUnitTotalDissolvedTotalDissolvedTotalDissolvedSilver 1638 UG/L0.682 J ND (1.00) U 0.0171 J 0.0217 J 0.0480 J 0.0368 JThallium 1638 UG/L43.6 3.10 2.82 2.89 2.85 2.85Zinc 1638 UG/L720 44.5 J 5.64 4.21 6.32 4.08

### Appendix C

DATA REVIEW NARRATIVES1 

### MEMORANDUM

DATE: December 31, 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 6551

OVERVIEW

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

data for five samples in Episode 6551. Sample 71120, identified as SP – 1 Influent to Fly Ash Pond, was expected to contain a significant and variable partic ulate concentration. EPA and industry representatives were concerned that the variable nature of the sample would 1) complicate the collection of a representative sample for both EPA and industry anal yses and 2) lead to analytical interferences. Therefore, for some classical analyses (those with a phase listed in Table 1), the laboratory was directed by EPA to separate the influent to fly ash pond sample into an aqueous-phase and a solid-phase and analyze each. The two sets of results (filtered aque ous and filtered solid phases) are provided in the analytical database, as are calculated total results (derived by combining f iltered 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

71120 Aqueous SP-1 – Influent to Fly Ash Pond 10/16/07 NA BOD (SM 5210B),

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

71120 Aqueous SP-1 – Influent to Fly Ash Pond 10/16/07 Filtered Aqueous Chloride (SM 4500-Cl

- C), Total Phosphorus (365.3),

TKN (SM 4500-N C), Nitrate/Nitrite (SM 4500-

NO3 H), 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

71120 Aqueous SP-1 – Influent to Fly Ash Pond 10/16/07 Filtered

Solid Chloride (SM 4500-Cl

- C), Total Phosphorus (365.3),

TKN (SM 4500-N C), Nitrate/Nitrite (SM 4500-

NO3 H), Ammonia as nitrogen (SM 4500-NH3 F), and Sulfate (ASTM D516-90)

71120 Aqueous SP-1 – Influent to Fly Ash Pond NA Calculated

Total Chloride (SM 4500-Cl

- C), Total Phosphorus (365.3),

TKN (SM 4500-N C), Nitrate/Nitrite (SM 4500-

NO3 H), Ammonia as nitrogen (SM 4500-NH3 F), and Sulfate (ASTM D516-90)

71121 Aqueous SP-2 – Effluent from Fly Ash Pond 10/16/07 NA BOD (SM 5210B),

Hexavalent Chromium (ASTM D1687-92), TSS (SM 2540D), TDS (SM 2540C), Chloride (SM

4500-Cl

- C), Total Phosphorus (365.3), TKN (SM 4500-N C), Nitrate/Nitrite (SM 4500-

NO3 H), Ammonia as nitrogen (SM 4500-NH3 F), Sulfate (ASTM D516- 90), HEM (1664A), and

SGT-HEM (1664A)

71122 Aqueous SP-3 – Duplicate of Effluent from Fly

Ash Pond 10/16/07 NA BOD (SM 5210B),

Hexavalent Chromium (ASTM D1687-92), TSS (SM 2540D), TDS (SM 2540C), Chloride (SM

4500-Cl

- C), Total Phosphorus (365.3), TKN (SM 4500-N C), Nitrate/Nitrite (SM 4500-

NO3 H), Ammonia as nitrogen (SM 4500-NH3 F), and Sulfate (ASTM D516-90)

71123 Aqueous SP-4 – Influent to Fly Ash Pond Field

Blank 10/16/07 NA Hexavalent Chromium (ASTM D1687-92)

71124 Aqueous SP-5 – Effluent from Fly Ash Pond Field

Blank 10/16/07 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.3 

### These data have been reviewed in accordance with CSC’s Data Review Guidelines for Classical Wet Chemistry Analyses (DR-02 Revision 2, September 1, 2007) and with the specifications listed in the contract. A summary of the results of the data re view process is provided below, followed by detailed descriptions of data issues identified with these samples. Based on this review, all data in this episode are considered of acceptable quality with the qualifications described below and detailed in the attached data review summary table (Table 2).

SUMMARY

All samples were analyzed within the contract-sp ecified holding times for all classical wet chemistry parameters specified in the sampling and analysis pl an with the exception of n itrate/nitrite, as described below. The calibration and continuing calibration st andards were successfully analyzed. Laboratory blanks were performed for each analysis, and there was no contamination detected above the laboratory reporting limit with the exception of the samples descr ibed below. Field blanks were analyzed for

hexavalent chromium and were f ound to contain no hexavalent ch romium above the minimum level (ML). The quality control samples (QC), including the ongoing precision and recovery sample (OPR) and matrix spike/matrix spike duplicate (MS/MSD) sa mples, demonstrated that laboratory performance for these analyses was acceptable with the exception of the samples described below. 

### The MS/MSDs analyses were performed on sample 71121.

DATA ISSUES

SGT-HEM

The relative percent difference (47%) between th e MS/MSD for sample 71121 was greater than the method-specified limit (34%). The MS recovery (76% ) and MSD recovery (123%) were both within the method-specified criteria (64-132%). Because the sample result was not detected in sample 71121 respectively, CSC recommends that the result be included in the database without qualification.

TKN

TKN was detected in the laboratory preparation bla nk (PB) at a concentration of 0.24 mg/L, which is greater than the ML of 0.1 mg/L. The data quality is affected as follows:

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

matrices. These instances are detailed below and in the attached data review summary table. a) sample 71120 filtered aqueous b) sample 71122

• Sample Results Greater than Five Times but Less than Ten Times Blank Results : CSC considers these results to be of acceptable quality, but th ey may be maximum values. These instances are detailed below and in the attached data review summary table. a) sample 71121

• 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 associ ated samples. Sample 71120 filtered solid falls into this category,4 

### but because CSC considers such data to be accep table without qualification, these cases do not

merit further detail.

Nitrate and Nitrite

Nitrate and nitrite analyses were performed beyond the 28-day hold time by several hours. CSC recommends that the nitrate/nitrite results in samp les 71120 filtered aqueous an d filtered solid; 71121 and

71122 be considered estimated values.

BOD (Biochemical Oxygen Demand)

One of the GGA standard recoveries (79%) was below the method-specified acceptance criteria of 84-

116%. Because the BOD results for the associated samples (71120, 71121, and 71122) were notdetected, CSC recommends the sample results to be acceptable without qualification.

Hexavalent chromium, Chloride, Sulfate, Nitrate/Nitrite, TKN and TSS

The relative percent difference (R PD) between field duplicate samples 71121 (effluent from fly ash pond) and 71122 (duplicate of effluent from fly ash pond) for the following analytes were: hexavalent chromium (200%), chloride (33%), sulfate (65%), n itrate/nitrite (30%), TKN (51%), and TSS (33%). CSC does not routinely qualify results based on field duplicate RPD.

TECHNICAL NOTES

Phase Separation and Calculations

As described in the phase separation document, EPA’s contract laboratory was asked to measure and record the following data as part of the phase separation process:

• Original sample weight

• Original sample volume

• Net weight of solid phase on the filter

• Filtrate weight

• Filtrate volume

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. All values are provided in Table 3.

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

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

sample original phase solid phase solid Filtrate Filtrate × +

=5 

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

TOTAL”.

Minimum Levels

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

Percent Solids

The percent solid 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, CSC6 

### Table 2 Data Review Summary Table

Episode: 6551 Analysis: Classicals

Industry: Steam Electric Study Reviewer: Maria A. Vargas

Sample Analyte Action Reason CSC Qual Level

71120 filtered

aqueous ND

71122 TKN Report in

database as not

detected Sample result <5x

blank result NA

ND

71121 TKN Maximum

value Sample result >5x but

<10x blank result NA 1.47 mg/L

71120 filtered

aqueous 2.61 mg/L

71120 filtered

solid Samples analyzed outside holding time 2.4 mg/kg

71120

calculated

total Nitrate/Nitrite Estimated value

Associated filtered aqueous and filtered

solid results are

estimated values 2.65 mg/L

71121 5.43 mg/L

71122 Nitrate/Nitrite Estimated value Samples analyzed outside holding time NA

4.02 mg/L

NA= Not Applicable

ND= Not Detected7 

### Table 3 Phase Separation Data Elements

Episode: 6551 Analysis: Classicals

Industry: Steam Electric Study Reviewer: Maria A. Vargas

Group number I II

Sample number 71120 71120

Original sample vol (mL) 970 940

Net weight of solid phase on the filter (g) 34.5 36.9

Original sample weight (g) 945 957

Filtrate weight (g) 850 899

Filtrate volume (mL) 860 920

Percent Solid (of solid phase) (%) 76.6% 73.1%Computer Sciences Corporation

www.csc.com

6101 Stevenson Avenue Alexandria, Virginia 22304

703.461.2000 Fax 703.461.2020 

### MEMORANDUM

DATE: January 7, 2008

TO: Ron Jordan, Work Assignment Manager

EPA EAD

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

SUBJECT: Data Review Narrative for Total and Dissolv ed Metals Analyses for the Steam Electric Study, Episode 6551

Under EPA contract number 68-C-03-0 44, ProChem Analytical submitted da ta for the analysis of metals by EPA Method 200.7 and mercury by Method 245.1. Five aqueous samples in this episode were analyzed for total and dissolved metals. Sample 71120, identified as SP – 1 Influent to Fly Ash Pond, was expected to contain a significant and variable particulate concentration. EPA and industry representatives were concerned that the variable nature of the sample would 1) complicate the collection of a representative sample for both EPA and industry an alyses and 2) lead to analytical interferences. Therefore the laboratory was directed by EPA to separate the SP – 1 Influent to Fly Ash Pond sample into an aqueous-phase and a solid-phase, and analyze each fo r metals and mercury. The two sets of results (filtered aqueous and filtered solid phases) are provided in the analytical database, including the calculated total result (derived by combining f iltered aqueous and filtere d solid phase results).

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

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

EPA Sample

# Matrix Sample Description Sampling

Date Phase Methods

10/16/2007 Dissolved

10/16/2007 Filtered

Solid

10/16/2007 Filtered Aqueous 71120 Aqueous SP – 1 Influent to Fly Ash Pond

NA Calculated

Total

Dissolved 71121 Aqueous SP – 2 Effluent from Fly Ash Pond 10/16/2007 Total

Dissolved
71122 Aqueous SP – 3 Effluent from Fly Ash Pond Duplicate 10/16/2007 Total

Dissolved 71123 Aqueous SP – 4 Influent to Fly Ash Pond Field

Blank 10/16/2007 Total

Dissolved 71124 Aqueous SP – 5 Effluent from Fly Ash Pond Field

Blank 10/16/2007 Total 200.7,

245.1

NA= Not applicable2 

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

SUMMARY

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

criteria.

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

issues described below and summarized in Table 2. Th e field filter blanks and the laboratory filter blank detected no analytes above the contract-specified MLs. The MS/MSD analyses were performed on the total and dissolved fractions of sample 71121.

DATA ISSUES

Method and Analytical Blanks

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

follows:

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

matrices. These instances are detailed below and in the attached data review summary table. a) filtered solid phase selenium in sample 71120

• Sample Results Greater than Five Times but Less than Ten Times Blank Results : CSC considers these results to be of acceptable quality, but th ey may be maximum values. These instances are detailed below and in the attached data review summary table. a) dissolved aluminum in samples 71121 and 71122

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

detail.3 

### Ongoing Precision and Recovery (OPR)

The solid OPR recoveries for aluminum (69%) and ma gnesium (74%) were below the contract acceptance criteria (80%). Because aluminum and magnesium we re detected in the filtered solid phase sample 71120, CSC considers the results of acceptabl e quality but they may be minimum values.

Serial Dilutions

The serial dilution percent differences for total alum inum in sample 71121 (3 3%) and total antimony (32%) were above the contract-specified criteria of 10%. The serial dilution percent difference for dissolved antimony in sample 71121 (31%) was also above the criteria. However, the MS/MSD

recoveries were within the criteria for total aluminum, total antimony and dissolved antimony. CSC does not qualify sample data based on serial dilution resu lts alone and believes that no further action is required

.



### TECHNICAL NOTE

Phase Separation and Calculations

As described in the phase separation document, EPA’s contract laboratory was asked to measure and record the following data as part of the phase separation process:

• Original sample weight

• Original sample volume

• Net weight of solid phase on the filter

• Filtrate weight

• Filtrate volume

CSC calculated the total result for the SP – 1 Influent to Fly Ash Pond sample using the following

formula:

In the generation of the routine metals “Calcula ted Total” results, at EPA's request, CSC included concentrations that were greater th an the MDL but less than the ML unless both factors in the calculations were less than the ML. However, if any concentra tion was affected by contamination in an associated blank at less than 5 times the associated blank result, it was changed to a zero before going through the calculation, per CSC's data review protocols. Ne gative values submitted by the laboratory were not used

in the calculations.

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

TOTAL”. 

### 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 

### × +

=4 

### Minimum Levels



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

Percent Solids



### Percent solid evaluation was performed for sample 71120 and is summarized in Table 3. The percent solids results is provided to convert if desired, solid phase wet weight basis values to dry weight results; percent solids results were not used to ge nerate the “Calculated Total” results.

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

bbeard2@csc.com.

cc: Brian D’Amico, EPA Deb Bartram, ERG Beverly Randolph, EPA TJ Finseth, ERG Marla Smith, EPA Lynn Walters, CSC Nelson Andrews, EPA Barbara Beard, CSC Brian Englert, EPA5 

### Table 2 Data Review Summary Table

Episode: 

### 6551 Analysis: 

### Metals

Industry: 

### Steam Electric Study Reviewer: 

### Maria A. Vargas

Sample Analyte Action Reason CSC Qual Level

71120 solid phase Se Report in database

as not detected Sample result < 5x blank

result NA ND

71120 solid phase OPR %R below contractspecified criteria 6350 mg/kg

71120

calculated total Al Minimum value Associated solid phase

result is a minimum NA

320000 ug/L

71120 solid phase OPR %R below contractspecified criteria 372 mg/kg

71120

calculated total Mg Minimum value Associated solid phase

result is a minimum NA

35100 ug/L

71121 dissolved 132 ug/L

71122 dissolved Al Maximum value Sample result between 5x

and 10x blank result NA 128 ug/L

NA= Not Applicable

ND= Not detected6 

### Table 3 Phase Separation Data Elements

Episode: 

### 6551 Analysis: 

### Metals

Industry: 

### Steam Electric Study Reviewer: 

### Maria A. Vargas

Sample number 71120

Original sample vol (mL) 510

Net weight of solid phase on the filter (g) 20.7

Original sample weight (g) 509.8

Filtrate weight (g) 481

Filtrate volume (mL) 485

Percent Solid (of solid phase) (%) 76.9Computer 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

6551

Under EPA contract number 68-C-03- 046, Battelle Marine Sciences submitted data for the analyses of trace metals. All five aqueous samples in this epis ode were analyzed for total mercury (Hg) by Method 1631E 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). Three of the five (Fly Ash Pond Effluent, Fly Ash Pond Effluent Duplicate, and Fly Ash Pond Effluent Field Blank) were analyzed for hexavalent chromium by Method 1636. Several samples were analyzed for dissolved metals as well as total.

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

EPA Sample

# Matrix Sample Description Sampling

Date Phase Methods

Total 1631E, 1638 71120 Aqueous SP-1 Fly Ash Pond Influent 10/16/07 Dissolved 1631E, 1638

Total 1631E, 1638

Dissolved 1631E, 1638 71121 Aqueous SP-2 Fly Ash Pond Effluent 10/16/07

NA 1636

Total 1631E, 1638

Dissolved 1631E, 1638 71122 Aqueous SP-3 Fly Ash Pond Effluent Duplicate 10/16/07

NA 1636

Total 1631E, 1638 71123 Aqueous SP-4 Fly Ash Pond Influent Field Blank 10/16/07 Dissolved 1638

Total 1631E, 1638

Dissolved 1638 71124 Aqueous SP-5 Fly Ash Pond Effluent Field

Blank 10/16/07

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).2 

### SUMMARY

All five samples were successfu lly analyzed within 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 be low. The MS/MSD analyses were performed on total and dissolved 71121 samples. Calibration curves and ca libration verification standards were successfully analyzed, with the excepti ons described below.

All calibration and preparation blanks were free of contamination above the report limit (minimum level or ML), with the exceptions describ ed below. No analytes were detected at levels above the reporting

limit in the field blanks.

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-sp ecified MLs. Antimony was detected in one ICB and zinc was detected in one CCB at levels marginal ly above their respective MLs. The data quality is

affected as follows:

• Sample Results Greater than Five Times but Less than Ten Times Blank Results : CSC considers these results to be of acceptable quality, but they may be maximum values. The affected samples and analytes are as follows: 71121 total chromium, 71121 dissolved chromium, 71122 total chromium, and 71122 dissolved chromium.

• 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.

CCV

The recoveries of silver (108% and 109%) in two continuing calibration verification samples (CCV) were slightly above the method-specified upper limit of 107% . The affected result is total silver for sample 71120. However, because silver was not detected in this sample, CSC recommends that the result be included in the database without qualification.

TECHNICAL NOTES

Sample Temperature

Trace metals samples were not chille d during shipment for this study.3 

### 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.

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

Table 2 Data Review Summary Table

Episode: 6551 Analysis: Trace Metals

Industry: STELEC Study Reviewer: Cris Robinson

Sample Analyte Action Reason SCC Qual Level

71121 Total

71121 Dissolved

71122 Total

71122 Dissolved Cr Maximum value Sample result >5x and

<10x blank result NA See Database

NA = Not applicable

### Appendix D

PICTURES FROM THE SAMPLING EPISODE

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

### D-2 Figure D-2. Sample Location for th e Influent to the Fly Ash Pond

### D-3 Figure D-3. Sample Collection Set-Up at the Influent to the Fly Ash Pond

### D-4 Figure D-4. “Shake and Pour” Set-Up fo r the Influent to the Fly Ash Pond

### D-5 Figure D-5. Waste Streams Entering the Fly As h Pond at the Completion of the Composite

Period

### D-6 Figure D-6. Waste Streams Entering the Fly Ash Pond the Day before Sample Collection

### D-7 Figure D-7. Sample Collection Set-Up at the Effluent from the Fly Ash Pond