# Sampling Episode Report

RRI Energy’s

Keystone Generating Station

Shelocta, PA

Sampling Episode 6563

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

13 April 2012

EPA Contract No. 68-C-02-095

Work Assignment 9-29

## i CONTENTS

Page

1. I NTRODUCTION 

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

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

1.2 Power Plant Site Selection...................................................................................1-1

1.3 Sampling Episode Overview................................................................................1-2

2. F ACILITY 

## O VERVIEW 

## ........................................................................................................2-1

2.1 FGD Scrubber System .........................................................................................2-1

2.2 FGD Wastewater Treatment System ...................................................................2-2

2.2.1 Physical/Chemical Separation .................................................................2-3

2.2.2 Sampling Points .......................................................................................2-4

3. S AMPLE 

## C OLLECTION 

## .......................................................................................................3-1

3.1 Sampling Points, Sample Collection Me thods, and Field Measurements ...........3-1

3.1.1 Influent to FGD Wastewat er Treatment System......................................3-2

3.1.2 Effluent from FGD Wastewat er Treatment System.................................3-3

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

3.3 Plant Operational Data.........................................................................................3-7

3.4 Deviations from the Sampling and Analysis Plan ...............................................3-8

4. L ABORATORY 

## A NALYTICAL 

## R ESULTS AND 

## D ISCUSSION 

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

4.1 Measured and Calculated Results for In fluent to FGD Wastewater Treatment

System Samples ...................................................................................................4-2

4.2 FGD Wastewater Treatment System ...................................................................4-4

5. D ATA 

## Q UALITY 

## .................................................................................................................5-1

5.1 Analytical Quality Control...................................................................................5-1

5.2 Field Quality Control ...........................................................................................5-1

5.2.1 Bottle Blanks............................................................................................5-1

5.2.2 Equipment Blanks....................................................................................5-2

5.2.3 Field Blanks .............................................................................................5-2

5.2.4 Field Duplicates .......................................................................................5-3

6. R EFERENCES 

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

Appendix A: A NALYTICAL 

## R ESULTS



## Appendix B: D ATA 

## R EVIEW 

## N ARRATIVES



## Appendix C: P ICTURES 

## F ROM THE 

## S AMPLING 

## E PISODE



## Appendix D: FGD ICP/MS SOP: I NDUCTIVELY 

## C OUPLED 

## P LASMA 

## M ASS 

## S PECTROMETRY FOR



## T RACE 

## E LEMENT 

## A NALYSIS IN 

## F LUE 

## G AS 

## D ESULFURIZATION 

## W ASTEWATERS

## ii LIST OF TABLES

Page

Table 3-1. Sample Collection Information, Keystone ................................................................. 3-9

Table 3-2. Sample Collection at Keystone ................................................................................ 3-11

Table 3-3. Field Measurements, Keystone ................................................................................ 3-12

Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Keystone .................... 3-13

Table 3-5. Analytical Methods, Keystone ................................................................................. 3-14

Table 3-6. Summary of Sample Container and Planned Preservation, Keystone...................... 3-15

Table 3-7. Sample Preservation Summary, Keystone ............................................................... 3-16

Table 3-8. Generating Unit Operating Characteris tics during Sample Collection, Keystone ... 3-18

Table 3-9. FGD Scrubber System Operat ing Characteristics, Keystone................................... 3-19

Table 3-10. Coal Usage during Sa mple Collection, Keystone .................................................. 3-20

Table 3-11. Scrubber Slurry Information duri ng Sample Collection, Keystone Creek............. 3-20

Table 3-12. FGD Wastewater Tr eatment System Operation Information, Keystone................ 3-21

Table 4-1. Influent to FGD Wastewat er Treatment System, Keystone ...................................... 4-6

Table 4-2. Effluent from FGD Wastewater Treatmen t System, Keystone............................... 4-11

Table 4-3. Classical Polluta nts 4-Day Average Data Summary for FGD Wastewater

Treatment System, Keystone ......................................................................................... 4-14

Table 4-4. Metals Pollutants 4-Day Aver age Data Summary fo r FGD Wastewater

Treatment System, Keystone ......................................................................................... 4-15

Table 5-1. Field Duplicate Re sults – Effluent fr om FGD Wastewater Treatment System,

Keystone ....................................................................................................................... ... 5-5

Table A-1. Biphasic Sample Results for Cla ssicals and Total Meta ls, Influent to FGD

Wastewater Treatment System, Day 1 Analytical Results, Keystone ............................ A-1

Table A-2. Biphasic Sample Results for Classi cals and Total Metals, Influent to FGD

Wastewater Treatment System, Day 2 Analytical Results, Keystone ............................ A-3

Table A-3. Biphasic Sample Results for Cla ssicals and Total Meta ls, Influent to FGD

Wastewater Treatment System, Day 3 Analytical Results, Keystone ............................ A-5

## LIST OF TABLES (Continued)

Page

iii Table A-4. Biphasic Sample Results for Cla ssicals and Total Meta ls, Influent to FGD

Wastewater Treatment System, Day 4 Analytical Results, Keystone ............................ A-7

Table A-5. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results,

Keystone ....................................................................................................................... .. A-9

Table A-6. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results,

Keystone ....................................................................................................................... A-16

Table A-7. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results,

Keystone ....................................................................................................................... A-22

Table A-8. Influent to FGD Wastewater Treatment System, Day 4 Analytical Results,

Keystone ....................................................................................................................... A-28

Table A-9. Effluent from FG D Wastewater Treatment System , Day 1 Analytical Results,

Keystone ....................................................................................................................... A-35

Table A-10. Effluent from FG D Wastewater Treatment System , Day 2 Analytical Results,

Keystone ....................................................................................................................... A-38

Table A-11. Effluent from FG D Wastewater Treatment System , Day 3 Analytical Results,

Keystone ....................................................................................................................... A-41

Table A-12. Effluent from FG D Wastewater Treatment System , Day 4 Analytical Results,

Keystone ....................................................................................................................... A-44

Table A-13. Duplicate of Effluent from Wast ewater Treatment System, Day 2 Analytical

Results, Keystone.......................................................................................................... A-47

Table A-14. Bottle Blank and Equipment Bl ank Analytical Data, Keystone........................... A-50

Table A-15. Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical

Results, Keystone.......................................................................................................... A-55

Table A-16. Effluent from FGD Wastewater Treatment System Field Blank, Day 1

Analytical Results, Keystone........................................................................................ A-58

Table A-17. Effluent from FG D Wastewater Treatment System , Day 2 Analytical Results,

Keystone ....................................................................................................................... A-61

Table A-18. Effluent from FG D Wastewater Treatment System , Day 3 Analytical Results,

Keystone ....................................................................................................................... A-62

Table A-19. Effluent from FG D Wastewater Treatment System , Day 4 Analytical Results,

Keystone ....................................................................................................................... A-63

## iv LIST OF FIGURES

Page

Figure 2-1. Simplified Diagram of the FGD Wa stewater Treatment System, Keystone ............ 2-6

Figure 2-2. Detailed Diagram of the FGD Wa stewater Treatment System, Keystone................ 2-7

Figure C-1. Sampler Working Inside a “Cleanbox” ....................................................................C-1

Figure C-2. Sample Tap and Tubing at the In fluent to the FGD Wastewater Treatment

System......................................................................................................................... .....C-2

Figure C-3. Sample Collection Set- Up at the Pump-Off Station.................................................C-3

Figure C-4. Sample Collection Set-Up at the E ffluent from the FGD Wastewater Treatment

System......................................................................................................................... .....C-4

## 1-1 1. I NTRODUCTION



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

Agency (EPA) is conducting a sampling program at steam electric power plants. The sampling

program will characterize raw wastewaters generate d by coal-fired steam electric power plants

and evaluate treatment technologi es and best management practic es used to reduce pollutant

discharges. This Sampling Episode Report (SER ) describes the sampling activities that took

place September 12-17, 2010, at RRI Energy’s Keyst one Generating Station (Keystone), located

in Shelocta, Pennsylvania (Sampling Episode 6563). The focus of Episode 6563 was to

characterize the purge stream entering the flue gas desulfurization (FGD) wastewater treatment

system and the effluent from the chemical precipitation system.

1.1 Background of Detailed Study

During EPA’s recently completed detailed study of the steam electric industry, EPA

identified metals and certain other constituents pr esent in the wastewater discharges from steam

electric power plants that substantially cont ribute to the toxic load ings for the industry.

Additionally, EPA determined that one of the wa ste streams contributing most of these toxic

loadings are associated with wet flue gas desu lfurization (FGD) systems present at coal-fired

power plants. Based on these findings, EPA ha s focused the sampling program on characterizing

the untreated FGD wastewaters a nd effluent quality from tec hnologies designed to treat the

wastewater.

1.2 Power Plant Site Selection

EPA selected steam electric plants for F GD wastewater sampling based on the process

configurations and characte ristics of the plants.

Keystone was selected by EPA for sampling ba sed on the following site characteristics:

 The plant is a coal-fired pow er plant that burns eastern bituminous coal in each of

its two generating units;

 The plant operates limestone forced oxidation wet FGD systems on both units;

 The plant operates a segregated FGD wastewater treatment system, which

includes the following steps:

— 

## Equalization,

— 

## Lime addition (pH adjustment/m etal hydroxide precipitation)

— 

## Organosulfide addition,

— 

## Ferric chloride addition,

— 

## Polymer addition,

— 

## Clarification,

— 

## Hydrochloric acid addition (pH adjustment),

— 

## Antiscalant addition,

— 

## Heat extraction (cooling), and

— 

## Filtration (sand filters and polishing filters); and

## 1-2  The plant operates selective catalytic reduction (SCR) systems on both generating

units.

1.3 Sampling Episode Overview

EPA and its technical contractor, Eastern Research Group, Inc. (ERG) conducted a oneday pre-sampling site visit at Keystone on Fe bruary 1, 2010 as part of the rulemaking. The

information collected during the pre- sampling site was used to create Sampling Plan, RRI

Energy’s Keystone Generating Station (Sampling Plan) [1], which describes the sample

collection procedures used during the sampling episode.

On Sunday, September 12, 2010, EPA arrived at Ke ystone to meet with plant personnel,

receive on-site safety training, review the sa mpling points, and determine the set-up for the

sample collection. EPA and ERG collected the samples specified in the Sampling Plan on

Monday through Friday (September 13–17, 2010). Th e following personnel participated in

EPA’s sample collection activities:

 Ron Jordan, EPA/EAD;

 Elizabeth Sabol, ERG;

 Becky Schwantes, ERG;

 Steve Strackbein, ERG;

 Kim Wagoner, ERG; and

 Jessica Wolford, ERG.

In addition, during the sample collection, EPA collected split sample s with the Utility

Water Act Group (UWAG). UWAG is a trade asso ciation for the electric power generating

industry. During the sampling episod e, UWAG acted as Keystone’s representative and collected

samples on behalf of the plant.

## 2-1 2. F ACILITY 

## O VERVIEW



## Keystone operates two steam el ectric units and each has a coal -fired boiler. Units 1 and 2,

which came on line in 1967 and 1968, respectively, each have a net capacity of 850 megawatts

(MW) (900 MW gross capacity). Both genera ting units burn eastern bituminous coal. The

Keystone plant and supporting facilities are located on approximately 1,000 acres in Shelocta,

Pennsylvania.

Keystone recently retrofitted both units with a wet FGD scr ubber system to control the

sulfur dioxide (SO 2 

## ) releases from the plant. The Unit 1 FGD system was installed in September

2009, and the Unit 2 FGD system was installed in November 2009. With the recent addition of

the FGD scrubber systems, Keystone also instal led an FGD wastewater treatment system to

control the discharges of the wastewater gene rated during the operation of the FGD scrubbers.

The FGD scrubber systems are discussed furthe r in Section 2.1 and the FGD wastewater

treatment system is discu ssed further in Section 2.2.

In 2003, Keystone retrofitted Units 1 and 2 with selective cata lytic reduction (SCR)

systems to control nitrogen oxide (NO

x 

## ) releases from the plant. In January 2009, Keystone

began operating the SCR systems year -round. Keystone also uses low NO

x 

## burners on Units 1

and 2, which were installed in 1994 and 1995 respectively, to control NO

x 

## releases from the

plant.

The electrostatic precipitators (ESPs) at Keys tone are particulate control devices that

remove the fly ash and other particulates from the flue gas. Keystone utilizes cold-side ESPs to

remove the fly ash from both units. The ESPs are designed to remove 99.5 percent of the fly ash

from the flue gas. The fly ash and other pa rticulates are collected in hoppers and are

pneumatically transferred to fly ash silos.

Units 1 and 2 have the following configuration:

 Boiler;

 SCR system;

 Air heater;

 ESP; and

 FGD scrubber system.

2.1 FGD Scrubber System

Keystone operates two forced oxidation we t FGD scrubber systems (one per unit) to

control the emission of sulfur dioxide from the unit. The plant uses limestone slurry as the

sorbent for sulfur dioxide absorption. Limestone and service water are fed to on-site ball mills,

which pulverize the limestone to create the slurry. From the ball mills, the slurry is transferred to

hydrocyclones to collect limestone particles that are too large for use in the FGD system. The

underflow from the hydrocyclones is sent back to the ball mills for processing. The overflow

from the hydrocyclones, which ranges from 25 to 35 percent solids (by weight ), is transferred to

the limestone slurry storage tank and then used as fresh limestone slurry in the absorber.

The fresh limestone slurry is fed to the reac tion tank of the FGD systems where the slurry

is pumped to the various levels of the FGD scr ubbers with the recycle pumps. Both absorbers

## 2-2 have five spray levels, but the plant does not alwa ys operate all of them at the same time. The

slurry is pressurized and sprayed downward into the scrubber vessel through spray nozzles. As

the slurry falls downward and the flue gas flows counter-current to the sl urry, the spray droplets

of the limestone slurry contact the flue gas and absorb the SO 2 

## , which reacts with the limestone

particles and produces calcium sulfite. The spray droplets flow downward until they settle on the

tray, forming a layer of slurry that the flue gas must pass through to exit the FGD system. The

tray has small holes in it that allow the flue gas to bubble throu gh the limestone slurry layered on

the tray, which provides additiona l contact between the limestone slurry and the flue gas. The

spray droplets continue to flow downward in the scrubber until it re aches the reaction tank.

Keystone bubbles air through the reaction tank to oxidize the calcium sulfite to calcium sulfate

(i.e., gypsum).

Keystone intermittently blows down the gypsum slurry from the reaction tank to control

the solids and chlorides concentration in each of the scrubbers. Blowdown from a scrubber

occurs when the chlorides concentration is between 18,000 and 20,000 ppm and/or when the

solids level is between 18 and 22 percent. Keys tone transfers the blow down from the scrubber

absorber to the gypsum dewatering operations.

The scrubber blowdown is pumped to the pr imary hydrocyclones where the solid gypsum

is separated from the water by centrifugal force. Th e solid gypsum is forced outward to the walls

of the hydrocyclones and falls downward, while the water exits the top of the hydrocyclones.

The underflow from the primary hydrocyclones is transferred to the vacuum filter belts. The

overflow from the primary hydrocyclones is mon itored. If the chloride concentration in the

primary hydrocyclone overflow is less than 16,000 pp m, then the waste stream is recycled back

to the absorber. Otherwise, the overflow is tran sferred to a holding tank, and then pumped to the

secondary hydrocyclones. The underflow from th e secondary hydrocyclones is returned to the

absorber. The overflow from the secondary hydroc yclones is sent to the purge tank and then

pumped to the FGD wastewater treatment sy stem. The secondary hydrocyclone overflow is

never recycled back to the absorber.

Keystone washes the gypsum sent to the vac uum filter belts with service water, as the

gypsum is poured onto the belts. The vacuum filter belts dry the gypsum to a moisture content of

less than 10 percent. The chlori de concentration in the dry gypsum is less than 120 ppm.

Keystone transfers the gypsum to an on-site ash landfill for disposal. Fly ash, bottom ash, and

dewatered sludge from the FGD wastewater treatment plant are also sent to this landfill. The

landfill is lined and has a leachate collection syst em. The leachate collection system produces a

continuous waste stream. Although Keystone is atte mpting to market gypsum, the plant currently

has no prospective clients. Ke ystone produces approximately 2,000 tons of gypsum every day.

2.2 FGD Wastewater Treatment System

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

FGD wastewater from the purge tank, which contains secondary hydrocyclone overflow. The

daily (24 hour) average flow rate is 260 gallons per minute (gpm). The plant attempts to keep the

flow rate constant by staggering the operation of the scrubbers. Ho wever, the flow rate can range

from no flow (if neither scrubbe r is purging wastewater) up to 400-450 gpm if both scrubbers are

operating and sending wastewater to treatment. Th e design maximum flow rate for the treatment

system is 450 gpm.

## 2-3 Keystone operates the FGD wastewater tr eatment system 24 hours per day, 7 days per

week. The wastewater treatment system was installed to treat the FGD scrubber purge

wastewater to meet the plant’s permit limits, which includes limits for total suspended solids

(TSS), total selenium, oil and grease, BOD 5 

## , beryllium, copper, lead, mercury, silver,

temperature, and pH. Keystone’s FGD wastewat er treatment system contains the following

treatment operations:

 Equalization;

 Lime addition (pH adjustment/m etal hydroxide precipitation);

 Organosulfide addition;

 Ferric chloride addition;

 Polymer addition;

 Clarification;

 Hydrochloric acid addition (pH adjustment);

 Antiscalant addition;

 Heat extraction (cooling);

 Filtration (sand filters and polishing filters); and

 Biocide addition.

Figures 2-1 and 2-2 located at the end of this section, presen t process flow diagrams of

the FGD wastewater treatment system, as well as the sampling locations for EPA’s sampling

episode. Figure 2-1 presents a simplified diag ram of the FGD wastewater treatment system.

Figure 2-2 presents a more complex diagram provi ding more detail on the chemical precipitation

treatment operations.

The secondary hydrocyclone overflow from the scrubbers is transfe rred to the purge tank

and then sent to the equalization tank at the start of the wastew ater treatment system. During the

sampling episode, the FGD influent wastewater was found to contain 2.0 to 5.5 percent solids,

had a pH between 6 and 7 S.U., and a temperat ure between 40 and 50 °C. The equalization tank

also receives wastewater from the wastewater treatment sump and e ffluent from the FGD

wastewater treatment system, which the plant recirculates to maintain a steady flow of

wastewater through the system.

2.2.1 Physical/Chemical Separation

From the equalization tank, the wastewater enters three reacti on tanks in series. First, the

wastewater flows into the desaturation tank, in which a lime slurry consisting of 10% lime is

added to encourage metal hydroxide precipitation a nd to increase the pH to between 8.0 and 8.5

S.U. The pH is optimal at this range because a higher pH would cause magnesium hydroxide to

precipitate. From the desaturati on tank, the wastewater flows to the heavy metals reaction tank

where organosulfide (TMT-15) is added. The wast ewater then flows to the flow splitter tank

where ferric chloride is added.

After the flow splitter tank, polym er is injected into the wa stewater as it flows to the

clarifiers. Keystone operates two solid contact clarifiers in para llel, which contain a sludge bed

that facilitates removal of the solids in the wa stewater. During the sampling episode, one of the

two clarifiers (clarifier B) had been draine d and was down for maintenance. On average,

approximately 65 percent of the sl udge from the clarifier is recy cled back to the desaturation

## 2-4 tank, while the remainder is transferred to a sl udge tank and then pumped to a filter press for

dewatering; however, the percent distribution varies throughout the day depending of the sludge

level in the clarifier. The dewatered sludge is sent to the on- site ash landfill. The filter press

filtrate is sent to the filtrate sump. All wastewater in the filtrate sump is recycled back to the

equalization tank.

The clarifier overflow is transferred to the heat exchanger feed tank. Hydrochloric acid

and an antiscalant are added to the wastewater as it is transferred to the heat exchangers. The

heat exchangers lower the temp erature of the wastewater from 120°F to 85-90°F. The internal

materials of construction for the heat exch anger are Hastelloy C- C276 stainless steel.

From the heat exchangers, the wastewater is transferred to three continuous backwash

sand filters operating in parallel. The sand filters reduce the level of total suspended solids in the

wastewater. During the sampling episode, one of the three sand filters (sand filter C) was not in

operation. Backwash from the sand filters is transf erred to the wastewater treatment sump. After

the sand filters, the wastewater flow s by gravity to the effluent tank.

From the effluent tank, the wastewater is se nt to the polishing filters, which contain a

Teflon® media. The polishing filters are continuous backwash filters. Backwash from the filters

is sent to the filtrate sump. Wast ewater in the filtrate sump fl ows back to the equalization tank.

The FGD wastewater treatment system was origin ally designed such th at the plant could bypass

the polishing filters if the TSS level after the sa nd filters met the plant’s permit limit. However,

Keystone has found that using the polishing filte rs full time is necessary to keep the TSS

concentration below their permit limit, which is 10 mg/L (monthly average) and 20 mg/L (daily

maximum). Therefore, Keystone plans to use th e polishing filters full ti me in accordance with

the revised system design. The hydraulic residence time of the FGD wastewat er treatment system

ranges from 16 to 18 hours.

During the sampling episode, the polishing fi lters were replaced beginning on Monday,

September 13, 2010 at 1200. The work on the polishi ng filters (cartridge filters) was being done

to address plugging of the filters due to biological growth that was occurring in the gravity sand

filter (sand filters A ). The problem was firs t identified on Monday, September 13, 2010, because

of an increase in the differential pressure across the filter leading to increased backflush

frequency. In order to eliminate the microbial growth in the sand filter, Keystone planned to

replace the polishing cartridge filters for the second time, bring sand filter C back into service,

and isolate and mechanically clean sand filters A and B, one at a time. Keystone personnel

believe that the final quality of the FGD wastewater treatment effluent samples were not affected

due to the availability of sand filters B and C.

2.2.2 Sampling Points

Figure 2-2 shows the sampling points for th e Keystone sampling episode; they are

summarized below:

 A sample of the purge stream entering the FGD wastewater treatment system

downstream of the purge tank and upstr eam of the equalization tank (i.e., the

sample was collected prior to any chem ical addition or mixing with recycle

streams); and

## 2-5  A sample of the effluent from the FGD wastewater treatment system after the

polishing filters, prior to discharge.

## 2-6Figure 2-1. Simplified Diagram of the FGD Wastewater Treatment System, Keystone

## 2-7Figure 2-2. Detailed Diagram of the FGDWastewater Treatment System, Keystone

## 3-1 3. S AMPLE 

## C OLLECTION



## During the Keystone sampling episode, th e sampling team followed the 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.

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

This section describes the sampling point s, sample collection methods, and field

measurements. Additional details are available in Section 3 of the Sampling Plan. Figures 2-1

and 2-2 of this report present flow diagrams of the plant’s wastewater treatment system,

including sampling point locations.

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

collection, and sample collection dates and times. Table 3-2 list s the sampling point numbers and

descriptions, the number of samples collected, and the pollutant parameters for which the

samples were analyzed. Table 3-3 presents th e field measurement data collected from each

sampling point. Table 3-4 presents a crosswalk be tween the sample numbers used for laboratory

sample identification and the sample points for each day.

The sampling points for this episode were:

 SP-1 Influent to FGD Wastewater Treatment System;

 SP-2 Effluent from FGD Wast ewater Treatment System:

 SP-3 Duplicate of Effluent from FGD Wastewater Treatment System (SP-2);

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

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

For all the sampling points, EPA collected spl it samples with Keystone’s representative

by inserting a “Y” splitte r into the sample tubing configurat ion at each sampling point to allow

for split sample collection. EPA collected all samples (other than mercury and cyanide) at all

sampling points as “true” splits (i.e., samp les for the same analyte were collected

simultaneously). The mercury and cyanide samples were collected directly from a sample tap;

therefore, for these samples, EPA and Keystone ’s representative collected duplicate samples,

with one filling the bottle im mediately after the other.

At each of the sampling points, EPA collected metals sample fractions following EPA

Method 1669 collection protocols. To collect these samples, EPA samplers donned Tyvek®

coveralls and dust masks (dust masks were worn until all mercury samples had been collected).

In addition, EPA set up a “cleanbox,” which consists of a portable plastic rectangular box with a

shallow lip and a flip-top lid th at secures itself ope n with clips. The “cleanbox” is double-bagged

with a clear inner bag, enclosed in a translu cent outer bag. The “cleanbo x” is handled using

“clean hands / dirty hands” techniques, where by the inner bag is ha ndled only by the “clean

hands” sampler. When the “cleanbox” is opened, the sampler is able to position his/her hands in

the box and pull the bag over the open ing of the box, but is still able to see the sample bottles and

## 3-2 tubing. The “cleanbox” minimizes potential at mospheric contamination during sample

collection. Figure C-1, in Appendix C, is a pictur e of a sampler working inside a “cleanbox.”

The metals sample bottles were also double-bagged. To collect the metals samples, EPA

placed the sample bottles (while still in its seal ed 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, then cl osed the sample bottle lid and sealed the inner

bag as quickly as possible with in the “cleanbox.” The bagged sample bottles were then removed

from the “cleanbox” and placed into the outer bag following the “clean hands / dirty hands”

protocols.

3.1.1 Influent to FGD Wastewater Treatment System

The influent to FGD wastewater treatment syst em (SP-1) was collected from a sample tap

located on the wastewater piping downstream of the purge tank and upstream of the equalization

tank. Figure 2-2 identifies the sampling location for SP-1. This sample was collected as a grab

sample because, according to plant representatives, the wastewater characteristics of the purge to

the wastewater treatment system are fairly cons istent during the purge. In addition, due to the

relatively high concentration of suspended solids , the FGD purge was not amenable to collecting

representative split samples using composite sa mpling techniques. The sample tap was located

inside the FGD wastewater treatment building (see Figure 2-2 for the sampling location for SP1). Because the sampling point was located inside , there were no wind or rain concerns during

the sample collection.

On Day 1 only, prior to collecting the sample s at the influent to the FGD wastewater

treatment system (SP-1), the sampling team collected field blanks (SP-4) for total mercury, total

and dissolved metals, and dissolved hexavalent chromium. See Section 5 .2.3 for a description of

the field blank sample collection procedures at the influent to the FGD wastewater treatment

system.

To collect the wastewater samples at the influent to the FGD wastewater treatment

system, the samplers attached a 10-foot length of silicone tubing to the sample tap on the

wastewater piping. The end of th e silicone tubing was fitted w ith a “Y” splitter, with two

additional lengths of silicone tubi ng attached to the “Y” splitter. Figure C-2, in Appendix C, is a

picture of the sample tap at the influent to th e FGD wastewater treatment system. The samplers

attached the silicone tubing to the sample tap, opened the valve, and al lowed sample to flow

through the tubing for two minutes before beginning to fill sample containers. The samplers did

not close the valve until all samples were collected (except the dissolved metals samples).

The samplers collected the following samples using a “cleanbox,” as described in Section

3.1:

 Total and dissolved mercury;

 Total metals by 200.8; and

 Total metals by 200.7.

Samplers then filled a 10-liter container with sample to be pumped off later for collection

of dissolved metals sample fractions. After all samples were collected at the sampling point for

## 3-3 the day, the filled 10-liter container was transported to the staging area, put on ice, and then left

untouched to allow the solids in the wastewater to settle.

The sampling team collected an aliquot of sample for field testing. Sample pH and

temperature were measured immediately at the sa mpling point using four-color pH paper, a pH

meter, and a thermometer. Table 3-3 presents the field measurement data for the influent to the

FGD wastewater treatment system.

The samplers then filled containe rs for biochemical oxygen demand (BOD 5 

## ), Group I,

Group II, and total cyanide samples directly fr om the tubing without using a “cleanbox.” See

Table 3-6 for a list of Group I and Group II analytes. BOD 5 

## , Group I, Group II, and total cyanide

samples were immediately placed on ice after sa mple collection.

The total cyanide sample was immediately preserved. Lead acetate test strips and

potassium-iodide starch test stri ps were used to measure for su lfides and oxidants, respectively.

No sulfides or oxidants were detected during th e sampling episode. The samplers then preserved

the total cyanide sample with sodium hydroxide to a pH >10 S.U. and placed it on ice.

Samples for the dissolved metals analyses we re pumped from the previously filled 10-

liter container. The pump-off station consisted of a length of Teflon® tubing attached to a length

of silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team

attached a capsule filter to th e silicone tubing, which was a s hort distance downstream of the

pump. They then attached another short length of silicone tubing to the capsule filter effluent,

which was attached to a “Y” spli tter and two lengths of silicone tubing. This set-up allowed EPA

to collect “true” split samples w ith Keystone’s representatives. Figure C-3, in Appendix C, is a

picture of the set-up at the pump-off station.

The sampling team placed the end of the Teflon® tubing into the 10-lit er container filled

with wastewater from the influent to the FGD wastewater treatment system. By this time, the

solids in the wastewater had b een settling for approximately 80 to 100 minutes. Approximately

1.0 - 1.5 liters 1 

## of sample were pumped through the tubi ng/filter to purge the line before

collecting samples.

Samplers collected the following dissolved sa mples using a “cleanbox,” as described in

Section 3.1:

 Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

Hexavalent chromium samples were immedi ately placed on ice after sample collection.

3.1.2 Effluent from FGD Wastew ater Treatment System

The effluent from the FGD wastewater treatment system (SP-2) was collected

downstream of the polishing filters prior to discha rge. Keystone installed a three-way splitter on

the sample tap that had three separate taps to collect samples from the sampling point. The

1 

### On all sampling days, the filter/tubing was purged with 1.0 to 1.5 liters and there was no need to change the filter.

## 3-4 sample tap was located inside the FGD wastewat er treatment building (see Figure 2-2 for the

sampling location for SP-2). Because the sampling point was located inside, there were no wind

or rain concerns during the sample collection.

ERG collected the effluent from the FGD wastewater treatment system composite

samples using two automatic compositors which were programmed to collect individual sample

volumes into two 20-liter containers. The comp ositors were programmed to collect 830 mL

every hour during the 24-hour composite period. Following the composite period, ERG pumped

off the specific sample volumes into the individual sample containers.

ERG used one automatic compositor to collect sample volume for the metals analyses

(excluding mercury) and another automatic compos itor to collect sample volume for all classical

analytes (i.e., BOD 5 

## , Group I, and Group II, excluding cy anide). In addition to collecting

automatic composite samples for the analytes listed above, ERG collected total and dissolved

mercury grab samples every six hours during ea ch compositing period. ERG also collected one

grab sample for cyanide during each compositing period.

On day 1 only, ERG collected field blank samp les (SP-5) for hexavalent chromium, total

and dissolved metals by 200.7, and total and di ssolved metals by 200.8. See Section 5.2.3 for a

description of the field blank sample collection procedures at the effluent from the FGD

wastewater treatment system.

Samplers set up the compositors by attaching tw o T-splitter tubing sets to two of the taps

on the three-way splitter. The T-splitter tubing set consisted of three silicone tubes attached to a

T-splitter. The tubing configura tion was set up such that one e nd was connected to the sample

tap, one end was threaded through the automatic compositor, and connected to the large

composite container, and one end was placed next to a sump/drain near the sampling point. The

samplers attached the silicone tubing to the samp le tap, opened the valve, and allowed sample to

flow through both sets of tubing before calibrati ng either of the automatic compositors. This

ensured that the flow through the tubing during calibration would be the expected flow through

the tubing during sample collection. The automatic compositors were calibrated such that they

collected 830 mL every hour, so that the project ed complete volume would be 20 liters. After

calibration, the tubing was attached to a vented cap on a 20-liter composite container. The

sample tap was left open during the entire sample collection time period a nd flowed directly to

the sump/drain. The automatic compositor pulled sa mple from the flowing stream as dictated by

the sampling program and was capable of purging th e line back to the flowing stream between

each individual sample aliquot.

Both 20-liter composite containers were placed into plastic trash cans, and maintained on

ice for the entire 24-hour compositing period. A plas tic bag was placed on t op of the trash cans

to minimize contamination. Figure C-4, in Appendix C, is a picture of the composite sampling

set-up at the effluent from the F GD wastewater treatment system.

Immediately after setting up the compositors, ERG collected the first set of the total and

dissolved mercury grab samples. At the first gr ab sample every day, ERG collected field blanks

for total mercury samples. See Section 5.2.3 for a de scription of the field blank sample collection

procedures at the effluent from the FGD wastewater treatment system.

## 3-5 For mercury collection, samplers shrouded one of the three taps on the three-way splitter

(the other two taps were being used by the two compositors) with a clean plastic bag by

puncturing a hole in the bottom of the bag with the end of the tap and then securing it to the tap

with a ziptie. After purging the ta p for two minutes, the samples were collected directly from the

tap into the sample bottles. Becau se total mercury and dissolved mercury samples were collected

directly from the tap, ERG was not able to collec t split samples with Keystone’s representatives;

therefore, duplicate samples were collected. ER G collected another set of total and dissolved

mercury samples every six hours thereafter over the 24-hour period. The plastic shroud was

replaced for each set of mercury grab samples. After collecting each set of mercury grabs, ERG

filled a field test bottle and tested for pH and temperature using four-colored pH paper, a pH

meter, and a thermometer. Table 3-3 presents th e field measurement data for the effluent from

the FGD wastewater treatment system.

After the collection of the thir d set of mercury grabs, ERG collected a total cyanide grab

sample from the same tap on the three-way splitt er that was used for mercury sample collection.

Because total cyanide samples were collected directly from the ta p, ERG was not able to collect

split samples with Keystone’s representatives; therefore, duplicate samples were collected. The

total cyanide sample was immediately preserved with sodium hydroxide to a pH >10 S.U. and

placed on ice. Lead acetate test strips and potas sium-iodide starch test strips were used to

measure for sulfides and oxidants, respectively. No sulfides or oxidants were detected during this

sampling episode at the effluent from the FGD wastewater treatment system.

After the twenty-fourth aliquots were coll ected in the two composite containers, ERG

followed “clean hands / dirty hands” sampling tec hniques to disassemble the compositors from

the sampling set up. Closed caps were placed on th e two composite containers and the composite

containers were moved to the pump-off area wher e they remained on ice until individual sample

bottles were filled. The samplers then began setting up the compositors for the next day of

samples using new tubing sets and composite containers. The automatic compositor was

programmed to collect the same volum e on each day of sample collection.

After completing the set up for the next day of composite samples, the sampling team

transferred the wastewater coll ected in the 20-liter containe rs into the individual sample

containers at the pump-off area. For this samp ling point, ERG used a sample pump-off approach

to transfer the composite samples to the individual sample bottles. For this sample pump-off

procedure, the dissolved metals samples were collected before the total metals and classical

samples to prevent cross-contamination with in the tubing, which could lead to greater

concentrations in the dissolved metals fractions.

Samples for the dissolved and total metals analyses were pumped from one of the

previously filled 20-liter cont ainers. The pump-off station cons isted of a length of Teflon®

tubing attached to a length of silicone tubing, which was threaded throu gh an ISCO peristaltic

pump. The sampling team attached a capsule fi lter to the silicone t ubing, which was a short

distance downstream of the pump. They then attached another short length of silicone tubing to

the capsule filter effluent, which was attached to a “Y” splitter and two lengths of silicone

tubing. This set-up allowed EPA to collect “true” split samples with Keystone’s representatives.

Figure C-3, in Appendix C, is a picture of the set-up at the pump-off station.

On Day 1 only, prior to collec ting any samples of the efflue nt from the FGD wastewater

treatment system, the samplers collected a fiel d blank sample (SP-5) for dissolved and total

## 3-6 metals. See Section 5.2.3 for a description of the dissolved metals field blank sample collection

at the effluent from the FGD wastewater treatment system.

After collecting the field blank samples, the sampling team placed the end of the Teflon®

tubing into one of the 20-liter composite containers filled with wastewater from the effluent from

the FGD wastewater treatment system. After the tubing and filter were purged with 1-2 liters of

sample, samplers collected the following sample s using a “cleanbox,” as described in Section

3.1:

 Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

Hexavalent chromium samples were immedi ately placed on ice after sample collection.

After the dissolved metals had been collected, the filter was removed. Once the tubing was

purged with 1-2 liters of sample, samplers coll ected the following samples using a “cleanbox,” as

described in Section 3.1:

 Total metals by 200.8; and

 Total metals by 200.7.

After the metal samples had been collected, the sampling team placed the end of the

Teflon® tubing into the other prev iously filled 20-liter contai ner. After the tubing was purged

with 1-2 liters of sample, samplers fille d containers for biochemical oxygen demand (BOD 5 

## ),

Group I, and Group II samples directly from the tubing without using a “cleanbox.” See Table 3-

6 for a list of Group I and Group II analytes. BOD 5 

## , Group I, and Group II samples were

immediately placed on ice af ter sample collection.

For all analytes, ERG collected QC samples at the effluent from the FGD wastewater

treatment system (SP-2) on Day 3 of the sampli ng episode; however, the cyanide QC sample was

collected on Day 4 because the QC sample collected on Day 3 was not preserved in the specified

time limit. In addition, for all analytes, ERG collect ed a duplicate sample of the effluent from

FGD wastewater treatment system (SP- 3) on Day 2 of the sampling episode.

3.2 List of Analytes and Sample Preservation

Samples collected at Keystone were an alyzed for the following pollutants:

 Classicals:

— Biochemical oxygen demand, 5-day (BOD 5 

## ),

— Chemical oxygen demand (COD),

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

## 3-7 — Total phosphorus,

— Total cyanide;

 Total Metals 2 

## :

— 

## Aluminum, antimony, arsenic, barium, beryllium, boron, cadmium,

calcium, chromium, cobalt, copper , iron, lead, magnesium, manganese,

mercury, molybdenum, nickel, selenium, silver, sodium, thallium, tin,

titanium, vanadium, and zinc.

 Dissolved Metals:

— 

## Same parameters as listed for tota l metals, plus hexavalent chromium.

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

pollution control wastewaters, in cluding contributions from coal , scrubber sorb ents, treatment

chemicals, and other sources. Table 3-5 lists the analytical methods used to determine pollutant

concentrations.

Table 3-6 lists the containers used for sample collection as well as the preservation

requirements for each sample. Table 3-7 summarizes the chemical preservation for each of the

samples that were preserved on site. The sampli ng team preserved samples in accordance with

procedures described in Section 3.4 of the Sampling Plan. Immediately following sample

collection, the samplers placed the BOD 5 

## , Group I, Group II, dissolved hexavalent chromium,

and total cyanide samples on ice to cool the samp les to <6°C. The sampling team also placed the

total and dissolved metals on ice to ensure all samples shipped together would stay cold. The

total and dissolved mercury samples were put on ice because they were shipped with the

hexavalent chromium samples. All dissolved me tals samples, except for mercury, were filtered

in the field. The hexavalent chromium samples we re preserved in the field, but all other metals

samples were acid-preserved prior to extracti on at the laboratory. The hexavalent chromium

samples were preserved with ammonium sulfat e buffer solution and ammonium hydroxide to a

pH between 9.3 and 9.5 S.U. The Group II samples were preserved with sulfuric acid to a pH of

<2 S.U. in the staging area, and the pH was c onfirmed with four-color pH strips. Each total

cyanide sample was tested for sulfides and oxidants immediately af ter sample collection.

Because sulfides and oxidants were not dete cted at any of the sampling points during the

sampling episode, the samplers did not need to dilu te the samples or add sodium arsenite to the

samples. After testing for sulfides and oxidants, the total cyanide samples were preserved with

sodium hydroxide to a pH >10 S.U. and placed on ice. During the preservation of the cyanide

QC sample at the effluent from the FGD wastewater treatment sy stem (SP-2) collected on day 3,

the samplers ran out of sodium hydroxide at th e sample point. Because the sampling staff was

unable to preserve the sample in time, the cyanide QC sample was re-collected on day 4.

3.3 Plant Operational Data

During the EPA sampling episode, Keystone pl ant personnel provided the sampling team

with operational data for each of the generating units and the F GD scrubber system, as well as

operational and flow data for the FGD wastewater treatment system. Tabl e 3-8 presents the unit

operating characteristics, Table 3-9 presents th e FGD scrubber system operating characteristics,

2 

### In this report, EPA uses the terms “total meta ls” and “total recoverable metals” interchangeably.

## 3-8 Table 3-10 presents information on the coal burned during the sampling episode, Table 3-11

presents information on the FGD scrubber slu rry generation during th e sampling episode, and

Table 3-12 presents the FGD wastewater tr eatment system operating characteristics.

3.4 Deviations from the Sampling and Analysis Plan

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

described below:

 Preservation of hexavalent chromium: ERG planned to preserve the hexavalent

chromium samples to a pH between 9.3 and 9.7 S.U. using an ammonium sulfate

buffer solution; however, since the amm onium sulfate buffer solution was not

achieving the desired pH, the samplers added only 100 drops of ammonium

sulfate buffer solution, followed by as mu ch ammonium hydroxide as necessary

to reach the desired pH.

 Preservation of cyanide QC sample at SP-2 (Day 3): On day 3 of sample

collection at the effluent from the FG D wastewater treatment system (SP-2), ERG

planned to preserve the cyanide QC samp le to a pH greater than 10 S.U. using

sodium hydroxide; however, the sampling team ran out of sodium hydroxide at

the sample point and the sample was not preserved until one hour after collection.

EPA re-collected the cyanide QC sample on day 4.

 Cooling of total and dissolved meta ls sample at all sampling points: ERG had

not planned to cool the total and dissol ved metals samples on ice prior to the

shipping the samples to the laboratory; however, because some of the metals

samples were being shipped in the same coolers with the classicals samples,

which are required to be ke pt at <6°C, ERG iced the metals sample to prevent

them from raising the temperatur e in the cooler during shipment.

## 3-9 Table 3-1. Sample Collection Information, Keystone

Sampling

Point

Number Sampling Point Description Type of

Sample Sample Collection

Date Sample Collection Time

Influent to FGD Wastewater

Treatment System – Day 1 Grab 9/13/10 0935 a 

### and 1124 b



### Influent to FGD Wastewater

Treatment System – Day 2 Grab 9/14/10 0950 a 

### and 1123 b



### Influent to FGD Wastewater

Treatment System – Day 3 Grab 9/15/10 0910 a 

### and 1053 b 

### SP-1

Influent to FGD Wastewater

Treatment System – Day 4 Grab 9/16/10 0904 a 

### and 1053 b



### Composite 9/13/10

9/14/10 0700 c



### 0753 d 

### Effluent from FGD Wastewater

Treatment System – Day 1

Grab 9/13/10

9/14/10 0716 e 

### , 1316 f 

### , and 1915 g



### 0115 h



### Composite 9/14/10

9/15/10 0700 c



### 0748 d 

### Effluent from FGD Wastewater

Treatment System – Day 2

Grab 9/14/10

9/15/10 0715 e 

### , 1316 f 

### , and 1916 g



### 0114 h



### Composite 9/15/10

9/16/10 0700 c



### 0743 d 

### Effluent from FGD Wastewater

Treatment System – Day 3

Grab 9/15/10

9/16/10 0718 e 

### , 1315 f 

### , and 1914 g



### 0115 h



### Composite 9/16/10

9/17/10 0707 c



### 0641 d 

### SP-2

Effluent from FGD Wastewater

Treatment System – Day 4

Grab 9/16/10

9/17/10 0720 e 

### , 1316 f 

### , and 1915 g



### 0115 h



### Composite 9/14/10

9/15/10 0700 c



### 0748 d 

### SP-3 Duplicate of Effluent from FGD

Wastewater Treatment System –

Day 2 Grab 9/14/10

9/15/10 0716 e 

### , 1318 f 

### , and 1920 g



### 0116 h



### SP-4 Influent to FGD Wastewater

Treatment System Field Blank Grab 9/13/10 0916 i 

### and 1116 j



### Composite 9/13/10

9/14/10 0627 k



### 0740 l 

### Effluent from FGD Wastewater

Treatment System Field Blank –

Day 1

Grab 9/13/10 0710 m



### Effluent from FGD Wastewater

Treatment System Field Blank –

Day 2 Grab 9/14/10 0708 m



### Effluent from FGD Wastewater

Treatment System Field Blank –

Day 3 Grab 9/15/10 0712 m 

### SP-5

Effluent from FGD Wastewater

Treatment System Field Blank –

Day 4 Grab 9/16/10 0715 m

## 3-10 a 

### Start time for the collection of the total metals samples (total metals by 200.7, total metals by 200.8, total mercury,

and dissolved mercury) and classicals (BOD 5 

### , Group I, Group II, and total cyanide).

b 

### Start time for the collection of the dissolved metals samples (dissolved metals by 200.7, dissolved metals by 200.8,

and dissolved hexavalent chromium). Does not include dissolved mercury.

c 

### Started compositor.

d 

### Start time for the collection of dissolved metals samples (dissolved metals by 200.7, dissolved metals by 200.8,

and dissolved hexavalent chromium), total metals samples (total metals by 200.7 and total metals by 200.8), and

classicals (BOD 5 

### , Group I, and Group II).

e 

### Start time for the collection of the total and dissolved mercury Grab 1 samples.

f 

### Start time for the collection of the total and dissolved mercury Grab 2 samples.

g 

### Start time for the collection of the total and di ssolved mercury Grab 3 and total cyanide samples.

h 

### Start time for the collection of the total and dissolved mercury Grab 4 samples.

i 

### Start time for the collection of total and dissolved mercury and total metals by 200.7 and total metals by 200.8 field

blank samples.

j 

### Start time for the collection of dissolved metals by 200.7 and dissolved metals by 200.8, and hexavalent chromium

field blank samples.

k 

### Filled 20L field blank carboy

l 

### Start time for the collection of total metals by 200.7 and total metals by 200.8 field blank samples and collection of

dissolved hexavalent chromium, dissolved metals by 200.7, and dissolved metals by 200.8 field blank samples.

m



### Start time for the collection of total mercury field blank samples.

## 3-11Table 3-2. Sample Collection at KeystoneSamplingPointNumberSampling Point Name Total Metals (EPA Method 200.8 with collision cell) Total Metals (EPA Method 200.7) Dissolved Metals (EPA Method 200.8 with collision cell) Dissolved Metals (EPA Method 200.7) Total Mercury Dissolved Mercury Hexavalent Chromium BOD 5 Group I

a Group II

b Total CyanideSP-1 Influent to the FGD WastewaterTreatment System4 4 4 4 4 4 4 4 4 4 4SP-2 Effluent from the FGD WastewaterTreatment System4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-3 Field Duplicate of the Effluent fromFGD Wastewater Treatment System1 1 1 1 1 1 1 1 1 11SP-4 Influent to the FGD WastewaterTreatment System Field Blank1 1 1 1 1 1SP-5 Effluent from the FGD WastewaterTreatment System Field Blank1 1 1 1 4 1Total Number of Samples 11+1QC 11+1QC 11+1QC 11+1QC 14+1QC 9+1QC 11+1QC 9+1QC 9+1QC 9+1QC 9+1QCa – 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), chemical oxygen demand (COD), and total phosphorus.

## 3-12Table 3-3. Field Measurements, KeystoneTemperature (°C)pH(S.U.)SamplingPointNumberSampling Point DescriptionDateTimeThermometerProbeMeteraStripsWasteStreamFlow Rate(gpm)NotesInfluent to FGD WastewaterTreatment System – Day 19/13/2010 095446426.2 7 490Influent to FGD WastewaterTreatment System – Day 29/14/2010 10154640.86.06 7 493Influent to FGD WastewaterTreatment System – Day 39/15/2010 092439.5416.19 6.5 490SP-1Influent to FGD WastewaterTreatment System – Day 49/16/2010 091846426.2 6.5 497Samplers noted that thesamples appeared to behigh in solids. Nodetected sulfides oroxidants in total cyanidegrab.9/13/10 07192826.36.75 72479/13/10 13192926.56.54 72279/13/10 19232927.76.56 7 230Effluent from FGD WastewaterTreatment System – Day 19/14/10 01202625.76.50 7 2009/14/10 072128256.35 71999/14/10 132028276.40 71739/14/10 19162926.56.40 7 163Effluent from FGD WastewaterTreatment System – Day 29/15/10 01152825.86.47 7 1709/15/10 07202825.66.54 7 2099/15/10 13152826.16.67 6.5 1849/15/10 19142927.86.50 7 222Effluent from FGD WastewaterTreatment System – Day 39/16/10 01152826.76.57 7 2089/16/10 072329266.50 7 1689/16/10 13182926.46.50 7 2059/16/10 19282827.26.51 7 154SP-2Effluent from FGD WastewaterTreatment System – Day 49/17/10 01252827.76.53 7.5 212Samplers noted that plantpersonnel were unawareof the effects themaintenance work onpolishing filters andbiological growth in thesand filters would haveon the effluent samples.No detected sulfides oroxidants in total cyanidegrab.aThe pH meter was calibrated prior to the sampling episode and once every day during the sampling episode using prepackaged buffer solutions at pH 4.0, 7.0,and 10.0.

## 3-13 Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Keystone

Sample Number Sample Point Sample Description

71891 SP-1, Day 1 Influent to FGD Wastewater Treatment System - Day 1

71892 SP-1, Day 2 Influent to FGD Wastewater Treatment System - Day 2

71893 SP-1, Day 3 Influent to FGD Wastewater Treatment System - Day 3

71894 SP-1, Day 4 Influent to FGD Wastewater Treatment System - Day 4

71895 SP-2, Day 1 Effluent to FGD Wastewater Treatment System - Day 1

71896 SP-2, Day 2 Effluent to FGD Wastewater Treatment System - Day 2

71897 SP-2, Day 3 Effluent to FGD Wastewater Treatment System - Day 3

71898 SP-2, Day 4 Effluent to FGD Wastewater Treatment System - Day 4

71899 SP-3, Day 2 Duplicate of Effluent to FGD Wastewater Treatment System - Day 2

71900 SP-4, Day 1 Influent to FGD Wastewater Treatment System Field Blank - Day 1

71901 SP-5, Day 1 Effluent to FGD Wastewater Treatment System Field Blank - Day 1

71902 SP-5, Day 2 Effluent to FGD Wastewater Treatment System Field Blank - Day 2

71903 SP-5, Day 3 Effluent to FGD Wastewater Treatment System Field Blank - Day 3

71904 SP-5, Day 4 Effluent to FGD Wastewater Treatment System Field Blank - Day 4

## 3-14 Table 3-5. Analytical Methods, Keystone

Parameter Method Number Maximum Holding

Time a



### Classicals

Biochemical oxygen demand (BOD 5 

### ) SM 5210 B 48 hours

Chemical oxygen demand (COD) EPA 410.4 28 days

Total suspended solids (TSS) SM 2540 D 7 days

Total dissolved solids (TDS) SM 2540 C 7 days

Sulfate EPA 300.0 28 days

Chloride EPA 300.0 28 days

Ammonia as nitrogen EPA 350.1 28 days

Nitrate/nitrate as nitrogen EPA 353.2 28 days

Total Kjeldahl nitrogen (TKN) EPA 351.2 28 days

Total phosphorus EPA 365.1 28 days

Total cyanide SM 4500 CN E 14 days

Total and Dissolved Metals

Mercury EPA 1631E 90 days b



### Hexavalent chromium (dissolved only) EPA 218.6 28 days

Antimony, arsenic, cadmium, chromium, copper, lead,

nickel, selenium, silver, thallium, and vanadium EPA 200.8 with

collision cell c 

### 6 months

Aluminum, barium, beryllium, boron, calcium, cobalt,

iron, magnesium, manganese, molybdenum, sodium,

tin, titanium, and zinc EPA 200.7 6 months

a 

### The holding times are based on the on-site field preservation identified in Table 3-3.

b 

### The dissolved mercury samples must be filtered in the laboratory within 24 hours after sample collection.

Additionally, the samples must be preserved by the la boratory within 48 hours after sample collection.

c 

### EPA used an SOP developed specifically for analyzing FGD wastewater (see Appendix D).

## 3-15 Table 3-6. Summary of Sample Contain er and Planned Preservation, Keystone

Parameter Sample

Container and

Volume QC Sample

Container and

Volume On-Site Preservation

Classicals

BOD 5 

### One 1-L plastic

bottle One 1-L plastic

bottle ≤ 6  C

Group I a 

### One 1-L plastic

bottles One 1-L plastic

bottles ≤ 6  C

Group II b 

### Two 1-L plastic

bottles Two 1-L plastic

bottles H 2 

### SO 4 

### to pH <2 S.U., ≤ 6  C

Total cyanide One 1-L plastic

bottle One 1-L plastic

bottles Dilution until sulfide is not detected,

NaAsO 2 

### until total chlorine is not

present, NaOH to pH >10 S.U.,

≤ 6  C

Metals

Total metals (EPA Method 200.8 with

collision cell) One 500-mL

plastic bottle No additional

volume needed None

(acid preserve at laboratory)

Total metals (EPA Method 200.7) One 500-mL

plastic bottle No additional

volume needed None

(acid preserve at laboratory)

Dissolved metals (EPA Method 200.8

with collision cell) One 500-mL

plastic bottle No additional

volume needed 0.45-μm filter (performed in field)

(acid preserve at laboratory)

Dissolved metals (EPA Method 200.7) One 500-mL

plastic bottle No additional

volume needed 0.45-μm filter (performed in field)

(acid preserve at laboratory)

Total mercury:

Manual composite grab samples Four 125-mL

glass bottle No additional

volume needed

Influent samples and field blank

samples Two 250-mL

glass bottle No additional

volume needed None

(acid preserve at laboratory)

Dissolved mercury:

Manual composite grab samples Four 125-mL

glass bottle No additional

volume needed

Influent samples One 250-mL

glass bottle No additional

volume needed None

(filter and acid preserve at

laboratory)

Hexavalent chromium One 250-mL

plastic bottle No additional

volume needed 0.45-μm filter (performed in field)

Ammonium sulfate buffer to

pH 9.3 – 9.7 S.U., ≤ 6  C

(a) Group I includes TSS, TD S, sulfate, and chloride.

(b) Group II includes ammonia as nitrogen, COD, nitr ate/nitrite as nitrogen, TKN, and total phosphorus.

## 3-16 Table 3-7. Sample Preservation Summary, Keystone

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

71891 Group II Volume 1 9/13/10 H 2 

### SO 4 

### 7 2 45

71891 Group II Volume 2 9/13/10 H 2 

### SO 4 

### 7 2 45

(NH 4 

### ) 2 

### SO 4



### Buffer 8 100 71891 Hexavalent Chromium 9/13/10

NH 4 

### OH 7

9.3 23

(NH 4 

### ) 2 

### SO 4



### Buffer 9 100 71900 Hexavalent Chromium Field

Blank 9/13/10

NH 4 

### OH 5.5

9.3 3

71891 Total Cyanide 9/13/10 NaOH 7 11 225

71895 Total Cyanide 9/13/10 NaOH 7 11 55

71892 Group II Volume 1 9/14/10 H 2 

### SO 4 

### 6.5 2 55

71892 Group II Volume 2 9/14/10 H 2 

### SO 4 

### 6.5 2 55

71895 Group II Volume 1 9/14/10 H 2 

### SO 4 

### 7 2 45

71895 Group II Volume 2 9/14/10 H 2 

### SO 4 

### 7 2 45

(NH 4 

### ) 2 

### SO 4



### Buffer 7.7 50 71892 Hexavalent Chromium 9/14/10

NH 4 

### OH 6.5

9.3 25

(NH 4 

### ) 2 

### SO 4



### Buffer 8.0 100 71895 Hexavalent Chromium 9/14/10

NH 4 

### OH 7

9.3 18

(NH 4 

### ) 2 

### SO 4



### Buffer 8.7 100 71901 Hexavalent Chromium Field

Blank 9/14/10

NH 4 

### OH 7

9.3 4

71892 Total Cyanide 9/14/10 NaOH 6.5 11 150

71896 Total Cyanide 9/14/10 NaOH 7 10.5 70

71899 Total Cyanide 9/14/10 NaOH 7 10.5 70

71893 Group II Volume 1 9/15/10 H 2 

### SO 4 

### 7 2 55

71893 Group II Volume 2 9/15/10 H 2 

### SO 4 

### 7 2 55

71896 Group II Volume 1 9/15/10 H 2 

### SO 4 

### 6.5 2 45

71896 Group II Volume 2 9/15/10 H 2 

### SO 4 

### 6.5 2 45

71899 Group II Volume 1 9/15/10 H 2 

### SO 4 

### 6.5 2 45

71899 Group II Volume 2 9/15/10 H 2 

### SO 4 

### 6.5 2 45

(NH 4 

### ) 2 

### SO 4



### Buffer 8.1 100 71896 Hexavalent Chromium 9/15/10

NH 4 

### OH 6.5

9.3 18

(NH 4 

### ) 2 

### SO 4



### Buffer 8.1 100 71899 Hexavalent Chromium -

Duplicate 9/15/10

NH 4 

### OH 6.5

9.3 18

(NH 4 

### ) 2 

### SO 4



### Buffer 8.5 100 71893 Hexavalent Chromium 9/15/10

NH 4 

### OH 6.5

9.3 25

## 3-17 Table 3-7. Sample Preservation Summary, Keystone

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

71893 Total Cyanide 9/15/10 NaOH 6.5 11 210

71897 Total Cyanide 9/15/10 NaOH 7 11 70

71897 Total Cyanide – QC b 

### 9/15/10 NaOH 7 8 45

71897 Total Cyanide – QC (2) b 

### 9/15/10 NaOH 8 11 25

71894 Group II Volume 1 9/16/10 H 2 

### SO 4 

### 6.5 2 55

71894 Group II Volume 2 9/16/10 H 2 

### SO 4 

### 6.5 2 55

71897 Group II Volume 1 9/16/10 H 2 

### SO 4 

### 7 2 45

71897 Group II Volume 1 - QC 9/16/10 H 2 

### SO 4 

### 7 2 45

71897 Group II Volume 2 9/16/10 H 2 

### SO 4 

### 7 2 45

71897 Group II Volume 2 - QC 9/16/10 H 2 

### SO 4 

### 7 2 45

(NH 4 

### ) 2 

### SO 4



### Buffer 7 20 71894 Hexavalent Chromium 9/16/10

NH 4 

### OH 7

9.3 26

(NH 4 

### ) 2 

### SO 4



### Buffer 8 100 71897 Hexavalent Chromium 9/16/10

NH 4 

### OH 7

9.3 18

71894 Total Cyanide 9/16/10 NaOH 6.5 11 210

71898 Total Cyanide 9/16/10 NaOH 6.5 11 75

71898 Total Cyanide-QC b 

### 9/16/10 NaOH 6.5 11 75

71898 Group II Volume 1 9/17/10 H 2 

### SO 4 

### 7 2 45

71898 Group II Volume 2 9/17/10 H 2 

### SO 4 

### 7 2 45

(NH 4 

### ) 2 

### SO 4



### Buffer 7.7 100 71898 Hexavalent Chromium 9/17/10

NH 4 

### OH 7

9.3 18

a 

### Preservation of this sample was stopped because the bo ttle became too full and additional preservative could not be

added to the sample bottle.

b 

### The sampling team ran out of sodium hydroxide at SP-2 an d was unable to fully preserve the cyanide QC sample

(71897) until one hour after collection. The sampling team di d note the second preservation to achieve a pH of 10.

However, because the sample was not preserved until one ho ur after collection, EPA re-collected the cyanide QC

sample at day 4; therefore, the Day 3 (71897) QC sample was not analyzed by the laboratory.

## 3-18 Table 3-8. Generating Unit Operating Charact eristics during Sample Collection, Keystone

Unit ID Boiler Type Capacity

(MW) Electricity Production

(MW)

(or Percent Capacity %) SCR

(No, On, Off) Particulate Control System

(HS/CS ESP, or BH)

1 Supercritical 850 net 96.6% ON CS ESP

2 Supercritical 850 net 96.6% ON CS ESP



### CS ESP – Cold-side elect rostatic precipitator.

## 3-19Table 3-9. FGD Scrubber System Operating Characteristics, KeystoneUnit IDWet FGDSystem (Yes/No)Type ofScrubberForcedOxidation(Yes/No)SorbentAdditives (DBA,formic acid,etc.)FGD Make-upWater SourceSO2RemovalPercentageType of SolidsSeparation1 Yes Wet FGD Yes Limeslurry None Plum Creek 98 Hydrocyclones2 Yes Wet FGD Yes Limeslurry None Plum Creek 98 Hydrocyclones

## 3-20 Table 3-10. Coal Usage during Sample Collection, Keystone

Day of

Sampling Unit

ID Coal Type Amount of Coal

Used During Day

of Sampling

(tpd) Source of

Coal (Coal

Region and/or

State) Percent

Sulfur in

Coal

(%) Chlorine Content

of Coal

(ppm)

1 Bituminous 7627 Western PA 2.56 995

1

2 Bituminous 7465 Western PA 2.56 995

1 Bituminous 7589 Western PA 2.63 1279

2

2 Bituminous 7705 Western PA 2.63 1279

1 Bituminous 7538 Western PA 2.37 949

3

2 Bituminous 7349 Western PA 2.37 949

1 Bituminous 7142 Western PA 2.59 939

4

2 Bituminous 7430 Western PA 2.59 939



## Table 3-11. Scrubber Slurry Information dur ing Sample Collection, Keystone Creek

Scrubber Slurry

Blowdown Flow Rate

Day of

Sampling FGD

System ID Associated

Unit IDs Flow Rate

(gpm) Duration 

### Scrubber

Slurry

Percent

Solids Time of

Dewatering

During

Sampling Day a 

### Percent

Filtrate

Recycled

Back to

Scrubber

FGD-1 1 242.5 9hr 12min 1.5 - 2.0 100%

1

FGD-2 2 242.5 9hr 12min 1.5 - 2.0 223 min

100%

FGD-1 1 243 12hr 18 min 1.5 - 2.0 100%

2

FGD-2 2 243 12hr 18min 1.5 - 2.0 516 min

100%

FGD-1 1 244 7hr 0min 1.5 - 2.0 100%

3

FGD-2 2 244 7hr 0min 1.5 - 2.0 410 min

100%

FGD-1 1 242.5 6hr 0min 1.5 - 2.0 100%

4

FGD-2 2 242.5 6hr 0min 1.5 - 2.0 297 min

100%

a 

### – Time of dewatering during sampling day represents the total time the plant was dewatering for the day. The

specific periods of time are not presented in this table.

## 3-21Table 3-12. FGD Wastewater Treatment System Operation Information, KeystoneScrubber PurgeChemical UsageDay ofSamplingFlow Rate(gpm)Duration(hr)Lime(lbs/day)Ferric Chloride(lbs/day)Organosulfide:TMT-15(lbs/day)Polymer:Scaletrol PDC9326(lbs/day)HCl(lbs/day)1 485 9hr 12min6728a(3,500 mg/L)815a(55 ppm)224a(14 ppm)19(3 ppm)5460a(147 ppm)2 486 12 hr 18 min6728a(3,500 mg/L)815a(55 ppm)224a(14 ppm)19(3 ppm)5460a(147 ppm)3 488 7 hr6728a(3,500 mg/L)815a(55 ppm)224a(14 ppm)19(3 ppm)5460a(147 ppm)4 485 1 hr6725a(3,500 mg/L)815a(55 ppm)224a(14 ppm)19(3 ppm)5460a(147 ppm)a– Estimated Values.Note: the values provided in parentheses are thesetpoint for the chemical in the reaction tanks.

## 4-1 4. L ABORATORY 

## A NALYTICAL 

## R ESULTS AND 

## D ISCUSSION



## This section summarizes the laboratory results of analyses of samples for the influent to

the FGD wastewater treatment system and the effluent from the FGD wastewater treatment

system. Section 4.1 discusses the methods used by the laboratories for th e biphasic analysis of

SP-1. Section 4.2 presents the laborat ory analytical data for the infl uent to and effluent from the

FGD wastewater treatment system.

The total and dissolved mercury samples we re analyzed by Frontier Global Sciences

(Frontier). The dissolved mercury samples were vacuum filtered through acid-cleaned cellulose

nitrate membrane filters contained in disposab le polystyrene filtration units at the Frontier

laboratory under clean room conditions on the day of sample receipt. Samples with elevated

solids were filtered through multiple filtration units until the entire sample was filtered. The

mercury samples were subjected to a room temp erature bromine monochlor ide digestion prior to

analysis using a method-compliant bubbler system.

For the total and dissolved mercury samples from SP-2, EPA collected four individual

grab samples that were composited by Frontier a nd analyzed as one sample. Frontier composited

these samples by combining the entire sample bo ttle for each of four i ndividual grab samples

prior to digestion and an alysis; however, if one or more of th e grab samples were received with

limited volume, equal volumes from each individual grab sample were combined for the

composite analysis.

The total and dissolved metals by EPA Method 200.7 were analyzed by TestAmerica

Laboratories – Denver (TestAmerica). As describe d in Section 3, the dissolved metals samples

were filtered in the field. The dissolved metals samples were preserved to a pH <2 at least 24

hours prior to being subjected to a heated ni tric acid digestion according to SW846 Method

3005A. The total metals samples were preserved to a pH <2 at least 24 hours prior to being

subjected to a heated nitric acid dige stion according to SW846 Method 3010A.

The total and dissolved metals by EPA Method 200.8 were also analyzed by

TestAmerica. Similar to the metals anal yzed by EPA Method 200.7, the dissolved metals

analyzed by EPA Method 200.8 were also filtered in the field. The total and dissolved metals

samples were preserved to a pH <2 at least 24 hou rs prior to being subjected to a closed vessel,

heated nitric acid and hydrochloric ac id digestion according to EPA Method 1638.

The classical analytes were analyzed by Te stAmerica and were di gested, prepared, and

analyzed according to the me thods specified in Table 3-5.

Appendix A provides all analytical results for all samples collected at Keystone,

including all qualified results a nd all results that were measur ed above the method detection

limit, but below the quantitation limit (i.e., J-values).

For EPA Method 200.7, some of the quantitat ion limits provided are TestAmerica’s

standard routine quantitation limits; these limits are used for most of TestAmerica’s projects and

were not optimized for FGD wastewater or the EPA sampling program. The quantitation limits

are established using not only the results of the MDL studies, but also are based on the results of

TestAmerica’s long term blank st udies. If the typical back ground blank levels for a given

element are variable or frequently elevated, th en the quantitation limit may be raised to prevent

## 4-2 the reporting of false positives. This resulted in some analytes (e.g., manganese, sodium) having

a QL/MDL ratio greater than five, where three to five is the normal range.

4.1 Measured and Calculated Results for In fluent to FGD Wastewater Treatment

System Samples

The samples of the influent to the FGD wast ewater treatment system were expected to

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

unreacted limestone, and fly ash. Because of th is, EPA was concerned that there could be

analytical interferences for the metals analyses, since the acid digestion procedures used may not

be sufficiently rigorous for samples with high solid s loads. Therefore, ERG directed its contract

laboratories to separate the aque ous and solid phases of the samp le prior to conducting certain

analyses, where allowed by the analytical method and if necessary to obtain acceptable analytical

results. This biphasic approach provides EPA with measured or calculated pollutant

concentrations for the follo wing phases of the sample:

 Aqueous phase;

 Solid phase; and

 Total sample.

The metals and classicals laboratory, Test America Laboratories - Denver (TestAmerica),

and the mercury laboratory, Frontier, used two different approaches for the biphasic analysis.

This section describes the approaches used by ea ch laboratory and presen ts the results of the

analyses.



## Metals and Classicals Analyses

TestAmerica used EPA Methods 200.7 and 200.8 to analyze the wastewater samples for

metals. Both EPA Methods 200.7 and 200.8 state, “Aqueous samples containing total suspended

solids ≥ 1% (w/v) should be extracted as a solid type sample.” [3, 4] Because EPA expected the

solids content to be greater than one percent, TestAmerica developed an approach for the

analysis of the FGD influent samples that consiste d of performing a pressure filtration to separate

the solids from the sample and analyzing the solid and aqueous phases separately.

Once the FGD influent samples were separa ted into solid and aqueous phases, the

aqueous portion was analyzed using EPA Method 200.7 or Method 200.8, depending on the

analyte. The solid portion of the samples asso ciated with the 200.7 analys is were prepared and

analyzed according to SW846 Method 6010B, while the solid portion of the samples associated

with the 200.8 analysis were prepared and analyzed according to SW846 Method 6020.

For solid phase analyses of n itrate/nitrite and ammonia, the analytical methods (i.e., EPA

Method 353.2 and EPA Method 350.1, respectively) do not include proce dures for analyzing

solid solids. Therefore, TestAmerica determin ed the concentration of nitrate/nitrite and

ammonia in the FGD influent solid samples by perf orming a deionized leach of the solid sample.

TestAmerica achieved this by placing a specified amount of the solid sample with an amount of

deionized water and shaking the mixture for one hour. TestAmerica than separated the leachate

from the solids using a centrifuge and then preser ved the leachate to a pH <2 S.U. and analyzed

the leachate according the specified methods.

## 4-3 TestAmerica also dried the solids prior to an alysis, so the solid c oncentration is on a dryweight basis. To calculate the total sample concentration from the solid and aqueous phase

results, the laboratory also needed to measure the original sample volum e, solid phase weight,

and filtrate volume. EPA developed the following e quation 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)

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.

TestAmerica used the same approach for the se ven classical pollutants that were analyzed

as biphasic samples: ammonia as nitrogen, chloride, sulfate, nitrate/nitrite, total cyanide, total

Kjeldahl nitrogen (TKN), and total phosphorus.



## Mercury Analyses

Frontier used EPA Method 1631E to analyze the wastewater samples for mercury. EPA

Method 1631E does not contain a ny language stating how wastewat er samples with high solid

concentrations should be analyzed ; therefore, Frontier developed an approach for the analysis of

the FGD influent samples that minimized potenti al contamination to the samples. Frontier’s

approach consisted of using a centr ifuge to separate the solids from the sample and analyzing the

solid and aqueous phases separately.

Once the FGD influent samples were separa ted into solid and aqueous phases, the

aqueous portion was analyzed using EPA Method 1631E , just like all the other mercury samples.

The solid portion was analyzed according to the Appendix to 1631: Total Mercury in Tissue,

Sludge, Sediment, and Soil by Acid Digestion and BrCl Oxidation , which was associated with

EPA Method 1631B. Frontier digested th e samples with aqua regia (HCl/HNO 3 

## ) and then

analyzed the samples using EPA Method 1631E.

Frontier did not dry the solids prior to analysis, so the solid concentration is on a wetweight basis. To calculate the total sample concentration from the solid and aqueous phase

results, the laboratory also needed to measure the original sample volum e, solid phase weight,

and filtrate volume. EPA used Equation 4-1 to calculate the individual total mercury

concentrations for the sample.

Appendix Tables A-1 through A-4 present th e results of the biphasic analysis for

ammonia as nitrogen, nitrate/nitrit e, chloride, sulfate, nitrate/nitrite, total cyanide, TKN, total

phosphorus, total metals, and total mercury for each of the four days of sampling. Results are

rounded to three significant figures.

## 4-4 4.2 FGD Wastewater Treatment System

Table 4-1 presents the analytical results for all classical and metal analytes for the four

days of sampling at the influent to the FGD wast ewater treatment system (SP-1), as well as the

calculated 4-day average result for each analyte for the sampling point. The total metal results

presented in Table 4-1 represent the calculated total result for all analytes for which biphasic

separation was performed. Table 4-2 presents the analytical results for all classical and metal

analytes for the four days of sampling at the e ffluent from the FGD wast ewater treatment system

(SP-2).

Tables 4-1 and 4-2 include the analytical results for all anal ytes for which EPA conducted

analyses. Results are rounded to three signifi cant digits. If an analyte was not detected in a

sample above the method detection limit, the resu lt is reported as “ND” followed by the samplespecific quantitation limit in parentheses. If an analyte was measured above the method

detection limit, but below the quantitation limit, the result is reported as “NQ” followed by the

sample-specific quantitation limit in parentheses.

For Table 4-2 (effluent from the FGD wastew ater treatment system), a duplicate sample

was collected on Day 2 of the sampling episode. The Day 2 results presented in Table 4-2

represent the averag e of the original and the duplicate samp le results. Table 5-1 presents the

analytical results for the original and duplicat e results and the calculated relative percent

difference (RPD).

When calculating the average concentrations for the duplicate samples or for the 4-day

averages, ERG used the following methodology:

 If all results were above the quantitati on limit, then all results were averaged

together;

 If at least one result was above the quan titation limit, then 1⁄2 the quantitation limit

was used in the average calculation for all results that were less than the

quantitation limit and the result is repo rted with a less than sign (“<”);

 If all results were below the quantitation limit, but at least one result was above

the method detection limit (i.e., J-value), then the sample-specific quantitation

limits for all results were averaged and the result is reported as “NQ” followed by

the average of the sample-specific quantitation limits; and

 If all results were below the method de tection limit, then the sample-specific

quantitation limits for all results were aver aged and the result is reported as “ND”

followed by the average of the sample-specific quantitation limits.

Table 4-3 presents the 4-day average results fo r all classical analytes for the influent to

the FGD wastewater treatment system (SP-1) and the efflue nt from the FGD wastewater

treatment system (SP-2). Table 4-4 presents th e 4-day average results for all metal analytes,

including total and dissolved analyses, for the in fluent to the FGD wastewater treatment system

(SP-1) and the effluent from th e FGD wastewater treatment system (SP-2). The results presented

in this report are not paired results, meaning that the sample collection across the treatment

system was not timed to reflect the amount of time it takes the wastewater to pass through the

system.

## 4-5 Appendix Tables A-1 through A-13 present all the analytical results from the influent to

the FGD wastewater treatment system (SP-1), th e effluent from the FGD wastewater treatment

system (SP-2), and the duplicate of the effluentfrom the FGD wastewater treatment system (SP3) sample analyses, including J-values.

## 4-6Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.P – Sample was not preserved immediately following collection.Table 4-1. Influent to FGD Wastewater Treatment System, KeystoneInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmonia mg/L 350.1 13.3F(P, Est) –S(P, Est) 14.1F(P, Est) – S(P,Est) 13.3F(P, Est) –S(P, Est) 11.8F(P, Est) –S(P, Est) 13.1Nitrate Nitrite asN mg/L 353.2 11.4F(P, Est) –S(P) 13.4F(P, Est) –S(P) 13.4F(P, Est) –S(P) 11.0F(P, Est) –S(P) 12.3Nitrogen, TotalKjeldahlmg/L 351.2 57.2F(B,L, P, Est) –S(P, Est)54.7F(B, L, P, Est) –S(P, Est)51.5F(B, L, P, Est)– S(P, Est)49.6F(B, L, P, Est)– S(P, Est)53.3BiochemicalOxygen Demand mg/L 5210B 10.0 S,Min 9.50 S,Min 13.0 S,Min 2.90 8.85ChemicalOxygen Demandmg/L 410.4 1,400 420 360 450 658Chloride mg/L 300.0, 9056 15,400 15,300 15,300 14,600 15,200Sulfate mg/L 300.0, 9056 1,920 2,020 2,040 1,950 1,980Cyanide, Total mg/L 4500 CN E 0.341F(H, P, Est) –S(H, P) 0.194F(H, P, Est)– S(H, P) 0.280F(H, P, Est)– S(H, P) 0.283F(H, P, Est) –S(H, P) 0.275Total DissolvedSolids mg/L 2540C 35,000 D,H,Est 35,000H,Est 37,000 H,Est 35,000 H,Est 35,500Total SuspendedSolidsmg/L 2540D 26,000 29,000 20,000 55,000 32,500Phosphorus,Total mg/L 365.1 1.12F(P) – S(P,Est) 11.0F(P) –S(P, Est)1.06F(P) –S(P, Est) 0.198F(P) –S(P, Est) 3.34

## 4-7Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.P – Sample was not preserved immediately following collection.Table 4-1. Influent to FGD Wastewater Treatment System, KeystoneInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageTotal MetalsAluminum ug/L 200.7, 6010B 1,000,000 F(^) 871,000 938,000 F (^) 922,000 F(^) 933,000Antimony ug/L 200.8, 6020 44.9 29.6 38.7 39.6 38.2Arsenic ug/L 200.8, 6020 3,080 2,470 2,720 2,560 2,710Barium ug/L 200.7, 6010B 19,600 11,900 10,300 10,300 13,000Beryllium ug/L 200.7, 6010B NQ (85.4) NQ(71.6) NQ (73.8) NQ (70.2)NQ(75.3)Boron ug/L 200.7, 6010B 411,000 F(B) 391,000 F(B) 403,000 F(B) 394,000 F(B) 400,000Cadmium ug/L 200.8, 6020 104 94.5 94.0 108 100Calcium ug/L 200.7, 6010B 6,780,000 6,670,000 7,200,000 6,710,000 6,840,000Chromium ug/L 200.8, 6020 3,010 S(B) 2,410 S(B) 2,630 S(B) 2,590 S(B) 2,660Cobalt ug/L 200.7, 6010B 968 891 913 861 908Copper ug/L 200.8, 6020 2,070 1,720 1,820 3,280 2,220Iron ug/L 200.7, 6010B 2,670,000 2,320,000 2,470,000 2,350,000 2,450,000Lead ug/L 200.8, 6020 1,140 904 1,000 981 1,010Magnesium ug/L 200.7, 6010B 2,880,000 2,780,000 2,790,000 2,750,000 2,800,000Manganese ug/L 200.7, 6010B 486,000 459,000 454,000 442,000 460,000Mercury ng/L1631E, FGS069533,000 515,000 559,000 622,000 557,000Molybdenum ug/L 200.7, 6010B 568 465 500 506 510Nickel ug/L 200.8, 6020 5,640 S(B) 4,990 S(B) 5,020 S(B) 6,560 S(B) 5,550

## 4-8Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.P – Sample was not preserved immediately following collection.Table 4-1. Influent to FGD Wastewater Treatment System, KeystoneInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageSelenium ug/L 200.8, 6020 4,200 3,740 4,380 4,000 4,080Silver ug/L 200.8, 6020 NQ (8.55) NQ (7.12) NQ (7.83) 387 < 99.7Sodium ug/L 200.7, 6010B 341,000 300,000 330,000 323,000 324,000Thallium ug/L 200.8, 6020 52.6 50.0 54.8 56.1 53.4Tin ug/L 200.7, 6010B ND (1,860) ND (1,610) ND (1,600) ND (1,520)ND(1,650)Titanium ug/L 200.7, 6010B 7,350 5,520 5,940 6,240 6,260Vanadium ug/L 200.8, 6020 4,010 3,190 3,440 3,270 3,480Zinc ug/L 200.7, 6010B 6,100 5,310 5,390 5,460 5,570Dissolved MetalsAluminum ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)ND(2.00)Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)NQ(4.00)Barium ug/L 200.7 400 380 370 360 378Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00)ND(2.00)Boron ug/L 200.7 410,000 B 380,000 B 400,000 B 390,000 B 395,000Cadmium ug/L 200.8 93.0 84.0 77.0 86.0 85.0Calcium ug/L 200.7 5,200,000 5,000,000 5,100,000 5,000,000 5,080,000

## 4-9Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.P – Sample was not preserved immediately following collection.Table 4-1. Influent to FGD Wastewater Treatment System, KeystoneInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageChromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.00)ND(8.00)Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10.0)ND(10.0)Cobalt ug/L 200.7 500 480 470 450 475Copper ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)NQ(4.00)Iron ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200) NQ (200)Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)ND(2.00)Magnesium ug/L 200.7 2,900,000 2,800,000 2,800,000 2,800,000 2,830,000Manganese ug/L 200.7 470,000 440,000 450,000 440,000 450,000Mercury ng/L 1631E 1,410 899 251 1,100 915Molybdenum ug/L 200.7 ND (40.0) ND (40.0) ND (40.0) ND (40.0)ND(40.0)Nickel ug/L 200.8 2,300 2,200 2,100 2,100 2,180Selenium ug/L 200.8 1,100 B 1,200 B 1,200 B 1,400 B 1,230Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)ND(2.00)Sodium ug/L 200.7 330,000 300,000 310,000 320,000 315,000Thallium ug/L 200.8 29.0 26.0 26.0 29.0 27.5

## 4-10Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.P – Sample was not preserved immediately following collection.Table 4-1. Influent to FGD Wastewater Treatment System, KeystoneInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageTin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0)NQ(20.0)Vanadium ug/L 200.8 NQ (10.0) ND (10.0) NQ (10.0) ND (10.0)NQ(10.0)Zinc ug/L 200.7 82.0 71.0 69.0 61.0 70.8

## 4-11Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.M – MS percent recovery outside themethod-specified criteria, but withinthe laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.Table 4-2. Effluent from FGD Wastewater Treatment System, KeystoneEffluent from FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmonia mg/L 350.1 13.0 12.0 11.0 12.0 12.0Nitrate Nitrite as N mg/L 353.2 9.70 M,Min 9.35 9.30 9.40 9.44Nitrogen, Total Kjeldahl mg/L 351.2 22.0 B 20.0 20.0 B,4 85.0 36.8Biochemical Oxygen Demand mg/L 5210B 8.50 S,Min 7.00 6.80 S,Min 3.50 S,Min 6.45Chemical Oxygen Demand mg/L 410.4 470 275 380 F,Min 320 361Chloride mg/L 300.0 15,000 15,000 14,000 13,000 14,300Sulfate mg/L 300.0 1,500 1,350 1,400 1,400 1,410Cyanide, Total mg/L 4500 CN E 0.120 B < 0.115 ND (0.100) 0.100 < 0.0963Total Dissolved Solids mg/L 2540C 35,000 B 30,500 29,000 29,000 30,900Total Suspended Solids mg/L 2540D 4.80 32.0 7.20 D,Est 9.60 13.4Phosphorus, Total mg/L 365.1 1.20 1.10 1.20 1.10 1.15Total MetalsAluminum ug/L 200.7 ND (200) NQ (200) ND (200) ND (200) NQ (200)Antimony ug/L 200.8 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.00)Arsenic ug/L 200.8 NQ (4.00) < 3.05 NQ (4.00) NQ (4.00) < 2.26Barium ug/L 200.7 320 300 290 280 298Beryllium ug/L 200.7 ND (2.00) ND (2.00)ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 300,000 B 300,000 280,000 B,4 290,000 B,4 293,000Cadmium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)Calcium ug/L 200.7 6,300,000 6,100,000 5,600,000 4 5,600,000 4 5,900,000Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.00) ND (8.00)Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) ND (20.0)

## 4-12Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.M – MS percent recovery outside themethod-specified criteria, but withinthe laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.Table 4-2. Effluent from FGD Wastewater Treatment System, KeystoneEffluent from FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageCopper ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00) ND (4.00)Iron ug/L 200.7 NQ (200) B NQ (200) NQ (200) B NQ (200) B NQ (200)Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) ND (2.00)Magnesium ug/L 200.7 1,900,000 B 2,000,000 1,900,000 B,4 1,900,000 B,4 1,930,000Manganese ug/L 200.7 24,000 B 23,000 19,000 B,4 23,000 B,4 22,300Mercury ng/L 1631E 119 108 78.6 31.2 84.1Molybdenum ug/L 200.7 42.0 43.5 42.0 43.0 42.6Nickel ug/L 200.8 6.80 7.50 8.60 7.00 7.48Selenium ug/L 200.8 300 350 300 320 F,4 318Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) F ND (2.00) F ND (2.00)Sodium ug/L 200.7 300,000 290,000 280,000 270,000 285,000Thallium ug/L 200.8 11.0 10.5 9.70 11.0 10.6Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0)Vanadium ug/L 200.8 NQ (10.0) B NQ (10.0) NQ (10.0) B NQ (10.0) B NQ (10.0)Zinc ug/L 200.7 ND (40.0) ND (40.0) NQ (40.0) ND (40.0) NQ (40.0)Dissolved MetalsAluminum ug/L 200.7 ND (200) ND (200) NQ (200) ND (200) NQ (200)Antimony ug/L 200.8 ND (2.00) NQ (2.00) NQ (2.00) NQ (5.00) NQ (2.75)Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (10.0) NQ (5.50)Barium ug/L 200.7 320 295 290 280 296Beryllium ug/L 200.7 ND (2.00) ND (2.00)ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 300,000 B 295,000 280,000 B,4 290,000 B,4 291,000

## 4-13Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.M – MS percent recovery outside themethod-specified criteria, but withinthe laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.Table 4-2. Effluent from FGD Wastewater Treatment System, KeystoneEffluent from FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageCadmium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)Calcium ug/L 200.7 6,300,000 6,000,000 5,700,000 4 5,800,000 4 5,950,000Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.00) ND (8.00)Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10.0) ND (10.0)Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) ND (20.0)Copper ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00) ND (4.00)Iron ug/L 200.7 ND (200) ND (200) NQ (200) ND (200) NQ (200)Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) ND (2.00)Magnesium ug/L 200.7 1,900,000 1,950,000 1,900,000 4 1,900,000 1,910,000Manganese ug/L 200.7 24,000 22,500 18,000 4 22,000 21,600Mercury ng/L 1631E 15.3 15.3 10.2 28.5 17.3Molybdenum ug/L 200.7 42.0 43.0 42.0 44.0 42.8Nickel ug/L 200.8 6.10 6.60 5.40 7.00 6.28Selenium ug/L 200.8 320 B 360 320 B,4 300 B,4 325Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) F ND (2.00) F ND (2.00)Sodium ug/L 200.7 300,000 290,000 280,000 280,000 288,000Thallium ug/L 200.8 11.0 10.5 11.0 10.0 10.6Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0)Vanadium ug/L 200.8 NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0)Zinc ug/L 200.7 ND (40.0) NQ (40.0) NQ (40.0) ND (40.0) NQ (40.0)

## 4-14< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).Table 4-3. Classical Pollutants 4-Day Average DataSummary for FGD Wastewater Treatment System, KeystoneAnalyteUnitsMethodSP-1SP-2ClassicalsAmmoniamg/L350.113.112.0Nitrate Nitrite as Nmg/L353.212.39.44Nitrogen, Total Kjeldahlmg/L351.253.336.8Biochemical Oxygen Demandmg/L5210B8.856.45Chemical Oxygen Demandmg/L410.4658361Chloridemg/L300.0, 905615,20014,300Sulfatemg/L300.0, 90561,9801,410Cyanide, Totalmg/L4500 CN E0.275< 0.0963Total Dissolved Solidsmg/L2540C35,50030,900Total Suspended Solidsmg/L2540D32,50013.4Phosphorus, Totalmg/L365.13.341.15

## 4-15< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-4. Metals Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, KeystoneInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent from FGDWastewater TreatmentSystem (SP-2)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedMetalsAluminumug/L200.7933,000ND (200)NQ (200)NQ (200)Antimonyug/L200.838.2ND (2.00)NQ (2.00)NQ (2.75)Arsenicug/L200.82,710NQ (4.00)< 2.26NQ (5.50)Bariumug/L200.713,000378298296Berylliumug/L200.7NQ (75.3)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7400,000395,000293,000291,000Cadmiumug/L200.810085.0NQ (4.00)NQ (4.00)Calciumug/L200.76,840,0005,080,0005,900,0005,950,000Chromiumug/L200.82,660ND (8.00)ND (8.00)ND (8.00)Chromium (VI)ug/L218.6NAND (10.0)NAND (10.0)Cobaltug/L200.7908475ND (20.0)ND (20.0)Copperug/L200.82,220NQ (4.00)ND (4.00)ND (4.00)Ironug/L200.72,450,000NQ (200)NQ (200)NQ (200)Leadug/L200.81,010ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.72,800,0002,830,0001,930,0001,910,000Manganeseug/L200.7460,000450,00022,30021,600Mercuryng/L1631E557,00091584.117.3Molybdenumug/L200.7510ND (40.0)42.642.8Nickelug/L200.85,5502,1807.486.28Seleniumug/L200.84,0801,230318325Silverug/L200.8< 99.7ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.7324,000315,000285,000288,000Thalliumug/L200.853.427.510.610.6

## 4-16< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-4. Metals Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, KeystoneInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent from FGDWastewater TreatmentSystem (SP-2)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTinug/L200.7ND (1,650)ND (200)ND (200)ND (200)Titaniumug/L200.76,260NQ (20.0)NQ (20.0)NQ (20.0)Vanadiumug/L200.83,480NQ (10.0)NQ (10.0)NQ (10.0)Zincug/L200.75,57070.8NQ (40.0)NQ (40.0)

## 5-1 5. D ATA 

## Q UALITY



## Quality assurance/quality control (QA/QC) procedures applicable to the Keystone

sampling episode are outlined in the Quality Assurance Project Plan for the Steam Electric

Rulemaking (QAPP) [2]. This section describes the QC pr ocedures used to assess the precision

and accuracy of the analytical data presented in Section 4 and Appendix A. 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

ERG contracted directly with analytical labor atories for the analysis of samples collected

during this episode. ERG verified that the pe rformance of the laboratories selected was

acceptable by conducting QC checks of the analytical data. Data review chemists at ERG

prepared written data review narr atives describing any qualifications of the analytical data from

this episode. The data review narrat ives are included in Appendix B.

5.2 Field Quality Control

This subsection discusses the bottle blanks, equipment blanks, field blanks, and field

duplicate sample results. Section 3.8 of the Samp ling Plan discusses field QC specifications.

5.2.1 Bottle Blanks

ERG collects bottle blanks to evaluate possibl e contamination from the sample collection

bottles. Bottle blanks were collected and analyzed for metals (EPA Method 200.8, 200.7, and

1631E) by the supplier of the precleaned bottl es, Frontier Global Sciences (Frontier).

Frontier collected the bottle blanks for the meta ls sample bottles by filling the precleaned

bottle with reagent water, preserving the sample w ith nitric acid to a pH <2 S.U. Frontier then

analyzed the samples using EPA Method 1638.

Frontier collected the bottle blanks for the mercury sample bottles by filling the

precleaned bottle with reagent water, preserving the sample with bromine monochloride.

Frontier then analyzed the samples using EPA Method 1631E.

Albion Environmental collected the bottle bl anks for the 10- and 20-liter composite

containers by filling the container with approx imately two liters of ASTM Type 1 water and

allowing it to soak for approximately 24 hours. During this period, th e laboratory shook the

container periodically and changed its orientation to expose all surfaces of the container to the

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

poured a representative sample into a precleaned LDPE sample bottle. The blank samples were

then preserved and analyzed according to the analytical methods (i.e., EPA Method 1638).

No metals were detected in the bottle bl anks, except for aluminum in the 10-liter

composite containers. Aluminum was detected in the 10-L container at a concentration of 4.71

ug/L, which is well below the quantitation limit us ed for the sample analyses (i.e., 200 ug/L);

therefore, this contamination di d not affect the resu lts of the sampling episode. Appendix Table

## 5-2 A-14 presents all of the analytical results from the bottle blank an alyses for the bottles used to

collect the metals and mercury samples.

5.2.2 Equipment Blanks

EPA collects equipment blanks to evaluate possible contamination from the equipment

used for sample collection. The techniques used to collect field blanks (a s described in Section

5.2.3) include the sampling equipment and ther efore would identify whether the sampling

equipment was introducing contamination. In addition, Frontier collected and analyzed

equipment blanks for metals (EPA Met hod 1638 and 1631E) for each type of precleaned

equipment supplied for the episode.

Frontier collected the equipment blanks for th e capsule filters and fabricated tubing sets

by pumping reagent water through the cleaned and fully assemble d equipment sets (with the

filter attached) into a cleaned bottle (an HDPE bottl e for metals and a glass bottle for mercury).

The blank samples were then preserved and anal yzed according to the analytical methods (EPA

Method 1638 and 1631E), as described in Sectio n 5.2.1 for the bottle blank samples.

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

contamination from the sampling equipment. Appe ndix Table A-14 presents all of the analytical

results from the bottle blank and equipment blank analyses for all of the equipment used for the

collection of metals and mercury samples.

5.2.3 Field Blanks

The sampling team collected field blanks (SP-4 and SP-5) to evaluate possible

contamination from sampling equipment, samp ling equipment decontamination procedures,

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

samples for the total and dissolved metals and total and dissolved mercury samples 3



## .

The total mercury, total metals by 200.8, and total metals by 200.7 field blank samples

for the influent to the FGD wastewater treatm ent system (SP-6) were collected by pouring

ASTM Type 1 water through a precle aned funnel attached to the si licone tubing used for sample

collection. To prevent potential atmospheric deposition, the sampling team shrouded the blank

water and funnel with a plastic bag while pouring the blank water into the funnel and placed the

sample bottles in a “cleanbox.” Prior to filli ng the sample bottles, the tubing was purged with

approximately 1 liter of blank water. The ASTM Type 1 water flowed through the funnel, tubing,

and “Y” splitter, and was poured into the sample bottles. EPA collected the field blank samples

as “true” split samples with Keystone’s representa tive, using the same procedure discussed in the

sample collection description (Section 3.1).

3 

### EPA did not collect a dissolved mercury field blank samp le because the sample filtration was performed at the

laboratory to minimize potential mercury contamination. The laboratory performed a filtration blank prior to

filtering the sample, which is assessed as the field blank fo r the dissolved mercury sample. Mercury was detected at

a concentration of 0.46 ng/L in the filtration blank perf ormed for the fourth day of samples, which includes the

influent to the FGD wastewater treatment system (day 2), the third and fourth grab sample for the effluent from the

FGD wastewater treatment system (day 3), and the first and second grab samples for the effluent from the FGD

wastewater treatment system (day 4). Mercury was not detected above the method detection limit (0.24 ng/L) in the

filtration blanks performed for the first, second, third, or fifth day of samples.

## 5-3 The dissolved metals by 200.8, dissolved metals by 200.7, and dissolved hexavalent

chromium field blank samples for the influent to the FGD wastew ater treatment system (SP-4)

were collected by pouring ASTM Type 1 water th rough the funnel and tubi ng and into a 10-liter

composite container. After approximately 110 minutes, the sampling team began pumping off

the ASTM Type 1 water from the 10-liter composite container. Prior to filling the sample bottles,

the tubing was purged with approximately one liter of blank water. The sample bottles were

placed in a “cleanbox” and the ASTM Type 1 water was pumped through the tubing, capsule

filter, and “Y” splitter, and into the sample bo ttles. EPA collected the field blank samples as

“true” split samples with Keystone’s representa tive, using the same procedure discussed in the

sample collection description (Section 3.1).

The total mercury field blank sample for the effluent from the FGD wastewater treatment

system (SP-5) was collected by shrouding one of th e three taps on the sample tap splitter with a

clear plastic bag. Before purgi ng the sample tap, ASTM Type 1 water was poured directly into

the sample bottles under the clear plastic bag.

The total and dissolved metals by 200.7 and metals by 200.8 field blank samples for the

effluent from the FGD wastewater treatment sy stem (SP-5) were collected by filling a 20-liter

composite container with ASTM Ty pe 1 water. The same T-splitter tubing used to fill the metals

composite container was used with a pump to f ill the 20-liter field blank composite container.

Prior to attaching one end of the tubing to the sample tap, it was placed directly into the

container holding ASTM Type 1 water. The othe r end of the tubing was attached to the vented

cap on top of the 20-liter field blank composite container. After enough volume was pumped into

the 20-liter field blank composite container, the vented cap was replaced with a closed cap and

the container was placed on ice in a covered plastic trash can. Th e vented cap used for the field

blank collection was the same cap that was late r used for the metals composite container.

After 24 hours, the ASTM Type 1 water in th e 20-liter field bla nk composite container

was pumped off into the individual sample bottles. The sample bottles were placed in a

“cleanbox” and the ASTM Type 1 water was pump ed through the tubing and “Y” splitter, and

into the sample bottles. EPA collected the fiel d blank samples as “true” split samples with

Keystone’s representative, us ing the same procedure discu ssed in the sample collection

description (Section 3.1). Prior to filling the sample bot tles, the tubing was purged with

approximately one liter of ASTM Type 1 water. First the samplers collected the total metals by

200.8 and total metals by 200.7 field blank samples. Then the sampling team attached a filter to

the tubing set and purged the tubing with approximately one liter of ASTM Type 1 water. The

samplers then collected the dissolved metals by 200.8, dissolved metals by 200.7, and dissolved

hexavalent chromium field blank samples.

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

indicating that there was no cont amination from the sample collection procedures. Appendix

Tables A-15 through A-19 present al l the analytical results for the field blanks from each of the

sampling points, including all qua lified results and all results th at were measured above the

method detection limit, but below the quantitation limit (i.e., J-values).

5.2.4 Field Duplicates

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

precision for the episode. Field dupl icate samples are separate samp les collected from the same

## 5-4 location as the original sample. The duplicate is filled immediately after the original sample and

is stored and analyzed independently. The RPD be tween 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 du plicate samples for the effluent from the

FGD wastewater treatment system (SP-3) durin g day 2 of the sampling episode. The duplicate

samples were analyzed for all analytes. Table 5-1 presents analytical results and the RPD for SP3. Results are rounded to three significant digits . Appendix Tables A-10 a nd A-13 present all the

analytical results for the efflue nt from the FGD wastewater treat ment system (SP-2) Day 2 and

the duplicate of the effluent from the FGD wastew ater treatment system ( SP-3) sample analyses,

including all qualified results a nd all results that were measur ed above the method detection

limit, but below the quantitation limit (i.e., J-values).

## 5-5< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NC – Not calculated.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.B – Analyte was found in the blank and sample.Min – Minimum value.S – Seed correction blank recovery low.Table 5-1. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, KeystoneAnalyteMethodUnitsOriginal Effluent fromFGD WastewaterTreatment System, Day 2Concentration (SP-2)Duplicate Effluent fromFGD WastewaterTreatment SystemConcentration (SP-4)AverageResultRelativePercentDifferenceClassicalsAmmonia350.1mg/L12.012.012.00.00Nitrate Nitrite as N353.2mg/L9.409.309.351.07Nitrogen, Total Kjeldahl351.2mg/L19.0B21.0B20.010.0Biochemical Oxygen Demand5210Bmg/L7.10S,Min6.90S,Min7.002.86Chemical Oxygen Demand410.4mg/L31024027525.5Chloride300.0mg/L15,00015,00015,0000.00Sulfate300.0mg/L1,4001,3001,3507.41Cyanide, Total4500 CN Emg/LNQ (0.100)0.180< 0.115NCTotal Dissolved Solids2540Cmg/L31,00030,00030,5003.28Total Suspended Solids2540Dmg/L10.054.032.0138Phosphorus, Total365.1mg/L1.101.101.100.00Total MetalsAluminum200.7ug/LNQ (200)BND (200)NQ (200)NCAntimony200.8ug/LND (2.00)NQ (2.00)NQ (2.00)NCArsenic200.8ug/L4.10NQ (4.00)< 3.05NCBarium200.7ug/L3003003000.00Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L290,000B310,000B300,0006.67Cadmium200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCCalcium200.7ug/L6,000,0006,200,0006,100,0003.28

## 5-6< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NC – Not calculated.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.B – Analyte was found in the blank and sample.Min – Minimum value.S – Seed correction blank recovery low.Table 5-1. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, KeystoneAnalyteMethodUnitsOriginal Effluent fromFGD WastewaterTreatment System, Day 2Concentration (SP-2)Duplicate Effluent fromFGD WastewaterTreatment SystemConcentration (SP-4)AverageResultRelativePercentDifferenceChromium200.8ug/LND (8.00)ND (8.00)ND (8.00)NCCobalt200.7ug/LND (20.0)ND (20.0)ND (20.0)NCCopper200.8ug/LND (4.00)ND (4.00)ND (4.00)NCIron200.7ug/LNQ (200)BNQ (200)BNQ (200)NCLead200.8ug/LND (2.00)ND (2.00)ND (2.00)NCMagnesium200.7ug/L2,000,000B2,000,000B2,000,0000.00Manganese200.7ug/L23,000B23,000B23,0000.00Mercury1631Eng/L1101051084.65Molybdenum200.7ug/L44.043.043.52.30Nickel200.8ug/L7.507.507.500.00Selenium200.8ug/L3503503500.00Silver200.8ug/LND (2.00)ND (2.00)ND (2.00)NCSodium200.7ug/L290,000290,000290,0000.00Thallium200.8ug/L10.011.010.59.52Tin200.7ug/LND (200)ND (200)ND (200)NCTitanium200.7ug/LNQ (20.0)NQ (20.0)NQ (20.0)NCVanadium200.8ug/LNQ (10.0)BNQ (10.0)BNQ (10.0)NCZinc200.7ug/LND (40.0)ND (40.0)ND (40.0)NCDissolved MetalsAluminum200.7ug/LND (200)ND (200)ND (200)NCAntimony200.8ug/LNQ (2.00)ND (2.00)NQ (2.00)NCArsenic200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NC

## 5-7< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NC – Not calculated.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.B – Analyte was found in the blank and sample.Min – Minimum value.S – Seed correction blank recovery low.Table 5-1. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, KeystoneAnalyteMethodUnitsOriginal Effluent fromFGD WastewaterTreatment System, Day 2Concentration (SP-2)Duplicate Effluent fromFGD WastewaterTreatment SystemConcentration (SP-4)AverageResultRelativePercentDifferenceBarium200.7ug/L3002902953.39Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L300,000B290,000B295,0003.39Cadmium200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCCalcium200.7ug/L6,000,0006,000,0006,000,0000.00Chromium200.8ug/LND (8.00)ND (8.00)ND (8.00)NCChromium (VI)218.6ug/LND (10.0)ND (10.0)ND (10.0)NCCobalt200.7ug/LND (20.0)ND (20.0)ND (20.0)NCCopper200.8ug/LND (4.00)ND (4.00)ND (4.00)NCIron200.7ug/LND (200)ND (200)ND (200)NCLead200.8ug/LND (2.00)ND (2.00)ND (2.00)NCMagnesium200.7ug/L2,000,0001,900,0001,950,0005.13Manganese200.7ug/L23,00022,00022,5004.44Mercury1631Eng/L16.214.315.312.5Molybdenum200.7ug/L43.043.043.00.00Nickel200.8ug/L6.806.406.606.06Selenium200.8ug/L370B350B3605.56Silver200.8ug/LND (2.00)ND (2.00)ND (2.00)NCSodium200.7ug/L290,000290,000290,0000.00Thallium200.8ug/L10.011.010.59.52Tin200.7ug/LND (200)ND (200)ND (200)NCTitanium200.7ug/LNQ (20.0)NQ (20.0)NQ (20.0)NC

## 5-8< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NC – Not calculated.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.B – Analyte was found in the blank and sample.Min – Minimum value.S – Seed correction blank recovery low.Table 5-1. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, KeystoneAnalyteMethodUnitsOriginal Effluent fromFGD WastewaterTreatment System, Day 2Concentration (SP-2)Duplicate Effluent fromFGD WastewaterTreatment SystemConcentration (SP-4)AverageResultRelativePercentDifferenceVanadium200.8ug/LNQ (10.0)NQ (10.0)NQ (10.0)NCZinc200.7ug/LND (40.0)NQ (40.0)NQ (40.0)NC

## 6-1 6. R EFERENCES



## 1. Eastern Research Group, Inc., 2010. Sampling Plan, RRI Energy’s Keystone Generating

Station. September 3. DCN SE00504.

2. Eastern Research Group, Inc., 2010. Quality Assurance Project Plan for the Steam

Electric Effluent Guidelines Rulemaking . (October). DCN SE00058.

3. U.S. EPA. 2001. Method 200.7: Determination of Metals and Trace Elements in Water

and Wastes by Inductively C oupled Plasma – Atomic Emission Spectrometry. Revision

4.4.

4. U.S. EPA. 1994. Method 200.7: Determination of Trace Elements in Waters and Wastes

by Inductively Coupled Plasma - Mass Spectrometry. Revision 5.4.

## Appendix A

ANALYTICAL RESULTS

## A-1Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers associated withan ‘S( )’ are qualifiersassociated with the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteAqueous Phase Result(mg/L for Classicials;ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)ClassicalsAmmonia13P,Est34P,Est13.3F(P, Est) – S(P, Est)Nitrate Nitrite as N12P,Est6.6J,P11.4F(P, Est) – S(J,P)Nitrogen, Total Kjeldahl29B,L,P,Est900P,Est57.2F(B,L, P, Est) – S(P, Est)Chloride16,00013,00015,400Sulfate1,30021,0001,920Cyanide, Total0.36H,P,Est0.15J,H,P0.341F(H, P, Est) – S(J, H, P)Phosphorus, Total0.016J,P33P,Est1.12F(J, P) – S(P, Est)Total MetalsAluminumND (200)U,^30,0001,000,000F(U, ^)Antimony1.6J1.344.9F(J)Arsenic3.5J923,080F(J)Barium27058019,600BerylliumND (2)U2.2J73.5F(U) – S(U)Boron410,000B830411,000F(B)Cadmium860.7104Calcium5,000,00063,0006,780,000ChromiumND (8)U90B3,010F(U) – S(B)Cobalt50015968Copper32612,070

## A-2Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers associated withan ‘S( )’ are qualifiersassociated with the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteAqueous Phase Result(mg/L for Classicials;ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)IronND (200)U80,0002,670,000F(U)Lead7.5341,140Magnesium2,900,0005,2002,880,000Manganese470,0001,400486,000Mercury2,55017,500533,000MolybdenumND (40)U17568F(U)Nickel2,100110B5,640S(B)Selenium1,100954,200SilverND (2)U0.237.68F(U)Sodium340,000710J341,000S(J)Thallium171.152.6TinND (200)UND (50)UND (1,860)F(U) – S(U)TitaniumND (20)U2207,350F(U)VanadiumND (10)U1204,010F(U)Zinc931806,100

## A-3Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-2. Biphasic Sample Results for Classicals and TotalMetals, Influent to FGD Wastewater Treatment System, Day 2Analytical Results, KeystoneAnalyteAqueous Phase Result(mg/L for Clasicals;ug/L for Metals; and ng/Lfor Mercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)ClassicalsAmmonia14P,Est29P,Est14.1F(P, Est) – S(P, Est)Nitrate Nitrite as N14P,Est5J,P13.4F(P, Est) – S(J, P)Nitrogen, Total Kjeldahl32B,L,P,Est840P,Est54.7F(B, L, P, Est) – S(P, Est)Chloride16,0004,10015,300Sulfate1,30027,0002,020Cyanide, Total0.2H,P,Est0.15J,H,P0.194F(H, P, Est) – S(J, H, P)Phosphorus, TotalND (0.05)U,P380P,Est11F(U, P) – S(P, Est)Total MetalsAluminumND (200)U30,000871,000F(U)Antimony1.2J0.9829.6F(J)Arsenic2.2J852,470F(J)Barium27040011,900BerylliumND (2)U2.1J61F(U) – S(J)Boron390,000B730391,000F(B)Cadmium770.7494.5Calcium4,800,00073,0006,670,000ChromiumND (8)U83B2,410F(U) – S(B)Cobalt48015891Copper7.1591,720Iron47J80,0002,320,000F(J)

## A-4Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-2. Biphasic Sample Results for Classicals and TotalMetals, Influent to FGD Wastewater Treatment System, Day 2Analytical Results, KeystoneAnalyteAqueous Phase Result(mg/L for Clasicals;ug/L for Metals; and ng/Lfor Mercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)Lead3.531904Magnesium2,800,0004,3002,780,000Manganese450,0001,100459,000Mercury3,83017,800515,000MolybdenumND (40)U16465F(U)Nickel2,200100B4,990S(B)Selenium1,000963,740SilverND (2)U0.25.81F(U)Sodium300,000550J300,000S(J)Thallium161.250TinND (200)UND (49)UND (1,610)F(U) – S(U)TitaniumND (20)U1905,520F(U)VanadiumND (10)U1103,190F(U)Zinc881805,310

## A-5Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-3. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, KeystoneAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/g forMercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)ClassicalsAmmonia13P,Est32P,Est13.3F(P, Est) – S(P, Est)Nitrate Nitrite as N14P,Est4.3J,P13.4F(P, Est) – S(J, P)Nitrogen, Total Kjeldahl31B,L,P,Est710P,Est51.5F(B, L, P, Est) – S(P, Est)Chloride16,0004,50015,300Sulfate1,30026,0002,040Cyanide, Total0.29H,P,Est0.19J,H,P0.28F(H, P, Est) – S(J, H, P)Phosphorus, TotalND (0.05)U,P34P,Est1.06F(U, P) – S(P, Est)Total MetalsAluminumND (200)U,^30,000938,000F(U, ^)Antimony1.3J1.238.7F(J)Arsenic1.8J872,720F(J)Barium28032010,300BerylliumND (2)U2.2J68.8F(U) – S(J)Boron400,000B780403,000F(B)Cadmium730.894Calcium5,000,00079,0007,200,000ChromiumND (8)U84B2,630F(U) – S(B)Cobalt47015913Copper9.8581,820

## A-6Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-3. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, KeystoneAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/g forMercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)IronND (200)U79,0002,470,000F(U)LeadND (2)U321,000F(U)Magnesium2,800,0004,6002,790,000Manganese440,0001,200454,000Mercury3,51017,500559,000MolybdenumND (40)U16500F(U)Nickel2,000100B5,020S(B)Selenium1,0001104,380SilverND (2)U0.195.94F(U)Sodium330,000570J330,000S(J)Thallium151.354.8TinND (200)UND (45)UND (1,600)F(U) – S(U)TitaniumND (20)U1905,940F(U)VanadiumND (10)U1103,440F(U)Zinc841705,390

## A-7Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-4. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatment System,Day 4 Analytical Results, KeystoneAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated TotalSample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)ClassicalsAmmonia12P,Est32P,Est11.8F(P, Est) – S(P, Est)Nitrate Nitrite as N12P,Est5.1J,P11F(P, Est) – S(J, P)Nitrogen, Total Kjeldahl26B,L,P,Est880P,Est49.6F(B, L, P, Est) – S(P, Est)Chloride16,0004,90014,600Sulfate1,30026,0001,950Cyanide, Total0.31H,P,Est0.12J,H,P0.283F(H, P, Est) – S(J, H, P)Phosphorus, Total0.005J,P6.5P,Est0.198F(J, P) – S(P, Est)Total MetalsAluminum15J,^31,000922,000F(J, ^)Antimony1J1.339.6F(J)Arsenic2.3J862,560F(J)Barium26034010,300BerylliumND (2)U2.2J65.4F(U) – S(J)Boron410,000B800394,000F(B)Cadmium831.1108Calcium5,000,00074,0006,710,000ChromiumND (8)U87B2,590F(U) – S(B)Cobalt46015861Copper6.71103,280

## A-8Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-4. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatment System,Day 4 Analytical Results, KeystoneAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated TotalSample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)IronND (200)U79,0002,350,000F(U)LeadND (2)U33981F(U)Magnesium2,900,0004,5002,750,000Manganese450,0001,200442,000Mercury3,75020,100622,000MolybdenumND (40)U17506F(U)Nickel2,000160B6,560S(B)Selenium1,200984,000SilverND (2)U13387F(U)Sodium340,000550J323,000S(J)Thallium161.456.1TinND (200)UND (45)UND (1,520)F(U) – S(U)TitaniumND (20)U2106,240F(U)VanadiumND (10)U1103,270F(U)Zinc1201805,460

## A-9NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery lowU – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5. Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassical Pollutants - TotalAmmonia350.1mg/LNA0.3434.0713.3Nitrate Nitrite as N353.2mg/LNA0.05960.85511.4Nitrogen, Total Kjeldahl351.2mg/LNA2.4313.457.2Biochemical Oxygen Demand5210Bmg/L10.32.510S,MinChemical Oxygen Demand410.4mg/L401608001,400Chloride300.0, 9056mg/LNA1251,45015,400Sulfate300.0, 9056mg/LNA14.13171,920Cyanide, Total4500 CN Emg/LNA0.0220.110.341Total Dissolved Solids2540Cmg/L116033035,000D,H,EstTotal Suspended Solids2540Dmg/L19233026,000Phosphorus, Total365.1mg/LNA0.03170.211.12Classicals Pollutants - Solid (dry weight)Ammonia350.1mg/Kg14.11034P,EstNitrate Nitrite as N353.2mg/Kg10.72206.6J,PNitrogen, Total Kjeldahl351.2mg/Kg562260900P,EstChloride9056mg/Kg50971,50013,000Sulfate9056mg/Kg50852,50021,000Cyanide, Total4500 CN Emg/Kg10.10.50.15J,H,PPhosphorus, Total365.1mg/Kg10.814.933P,EstClassicals Pollutants -Filtered AqueousAmmonia350.1mg/L10.22413P,Est

## A-10NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery lowU – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5. Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationNitrate Nitrite as N353.2mg/L20.0380.212P,EstNitrogen, Total Kjeldahl351.2mg/L50.38529B,L,P,EstChloride300.0mg/L5001301,50016,000Sulfate300.0mg/L50122501,300Cyanide, Total4500 CN Emg/L10.020.10.36H,P,EstPhosphorus, Total365.1mg/L10.0050.050.016J,PMetals - Calculated TotalAluminum200.7, 6010Bug/LNA2661,8601,000,000Antimony200.8, 6020ug/LNA1.6115.244.9Arsenic200.8, 6020ug/LNA84.61,0103,080Barium200.7, 6010Bug/LNA1518619,600Beryllium200.7, 6010Bug/LNA6.0185.473.5Boron200.7, 6010Bug/LNA3236,340411,000Cadmium200.8, 6020ug/LNA6.1525.4104Calcium200.7, 6010Bug/LNA3,93017,7006,780,000Chromium200.8, 6020ug/LNA8.0920.83,010Cobalt200.7, 6010Bug/LNA17.7186968Copper200.8, 6020ug/LNA24.387.22,070Iron200.7, 6010Bug/LNA6642,6602,670,000Lead200.8, 6020ug/LNA1.8811.91,140Magnesium200.7, 6010Bug/LNA1,11012,7002,880,000

## A-11NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery lowU – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5. Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese200.7, 6010Bug/LNA28.8634486,000Mercury1631E, FGS-069ng/LNA21,50059,000533,000Molybdenum200.7, 6010Bug/LNA44.9368568Nickel200.8, 6020ug/LNA5.8828.75,640Selenium200.8, 6020ug/LNA11.651.84,200Silver200.8, 6020ug/LNA1.898.557.68Sodium200.7, 6010Bug/LNA9,85092,800341,000Thallium200.8, 6020ug/LNA0.6738.5552.6Tin200.7, 6010Bug/LNA1551,860ND (1,860)Titanium200.7, 6010Bug/LNA24.51867,350Vanadium200.8, 6020ug/LNA4.1342.44,010Zinc200.7, 6010Bug/LNA75.35386,100Metals - DissolvedAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.242.8JBarium200.7ug/L22.520400Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000410,000BCadmium200.8ug/L21.2493Calcium200.7ug/L501,70010,0005,200,000

## A-12NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery lowU – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5. Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.120500Copper200.8ug/L20.9643.4JIron200.7ug/L23220044JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0002,900,000Manganese200.7ug/L5013500470,000Mercury1631Eng/L10024.150.51,410Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.8942,300Selenium200.8ug/L51.6101,100BSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000330,000Thallium200.8ug/L20.47229Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.4JVanadium200.8ug/L21.7101.7JZinc200.7ug/L29.14082Metals - Filtered AqueousAluminum200.7ug/L29.4200ND (200)U,^Antimony200.8ug/L20.7221.6J

## A-13NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery lowU – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5. Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationArsenic200.8ug/L21.243.5JBarium200.7ug/L22.520270Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000410,000BCadmium200.8ug/L105.92086Calcium200.7ug/L501,70010,0005,000,000Chromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120500Copper200.8ug/L20.96432Iron200.7ug/L232200ND (200)ULead200.8ug/L20.7327.5Magnesium200.7ug/L5054010,0002,900,000Manganese200.7ug/L5013500470,000Mercury1631Eng/L5001222552,550Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L104.5202,100Selenium200.8ug/L103.1201,100Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000340,000Thallium200.8ug/L20.47217Tin200.7ug/L24.8200ND (200)U

## A-14NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery lowU – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5. Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.7ug/L29.14093Metals - Solid (dry weight)Aluminum6010Bmg/kg57.75030,000Antimony6020mg/kg20.0280.41.3Arsenic6020mg/kg502.53092Barium6010Bmg/kg50.385580Beryllium6010Bmg/kg50.162.52.2JBoron6010Bmg/kg54.950830Cadmium6020mg/kg20.0190.20.7Calcium6010Bmg/kg57025063,000Chromium6020mg/kg20.150.490BCobalt6010Bmg/kg50.5515Copper6020mg/kg100.72.561Iron6010Bmg/kg5197480,000Lead6020mg/kg20.0360.334Magnesium6010Bmg/kg518995,200Manganese6010Bmg/kg50.551,400MercuryFGS-069ng/g40,0007041,94017,500Molybdenum6010Bmg/kg51.39.917

## A-15NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery lowU – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5. Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationNickel6020mg/kg20.050.3110BSelenium6020mg/kg20.260.9995Silver6020mg/kg20.040.20.23Sodium6010Bmg/kg52902,500710JThallium6020mg/kg20.0070.21.1Tin6010Bmg/kg54.550ND (50)UTitanium6010Bmg/kg50.695220Vanadium6020mg/kg20.0760.99120Zinc6010Bmg/kg5215180

## A-16NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassical Pollutants - TotalAmmonia350.1mg/lNA0.3284.0814.1Nitrate Nitrite as N353.2mg/lNA0.05670.77113.4Nitrogen, Total Kjeldahl351.2mg/lNA2.11254.7Biochemical Oxygen Demand5210Bmg/L10.32.59.5S,MinChemical Oxygen Demand410.4mg/L1041200420Chloride300.0, 9056mg/lNA1241,44015,300Sulfate300.0, 9056mg/lNA16.33792,020Cyanide, Total4500 CN Emg/lNA0.02190.1090.194Total Dissolved Solids2540Cmg/L116033035,000H,EstTotal Suspended Solids2540Dmg/L114050029,000Phosphorus, Total365.1mg/lNA0.241.4711Classicals Pollutants - Solid (dry weight)Ammonia350.1mg/Kg14.11029P,EstNitrate Nitrite as N353.2mg/Kg10.71205J,PNitrogen, Total Kjeldahl351.2mg/Kg560250840P,EstChloride9056mg/Kg20385804,100Sulfate9056mg/Kg1001704,90027,000Cyanide, Total4500 CN Emg/Kg10.10.50.15J,H,PPhosphorus, Total365.1mg/Kg108.149380P,EstClassicals Pollutants -Filtered AqueousAmmonia350.1mg/L10.22414P,EstNitrate Nitrite as N353.2mg/L20.0380.214P,Est

## A-17NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationNitrogen, Total Kjeldahl351.2mg/L50.38532B,L,P,EstChloride300.0mg/L5001301,50016,000Sulfate300.0mg/L50122501,300Cyanide, Total4500 CN Emg/L10.020.10.2H,P,EstPhosphorus, Total365.1mg/L10.0050.05ND (0.05)U,PMetals - Calculated TotalAluminum200.7, 6010Bug/LNA2271,610871,000Antimony200.8, 6020ug/LNA1.4112.129.6Arsenic200.8, 6020ug/LNA14.21582,470Barium200.7, 6010Bug/LNA13.116111,900Beryllium200.7, 6010Bug/LNA5.3271.661Boron200.7, 6010Bug/LNA3016,170391,000Cadmium200.8, 6020ug/LNA6.0924.294.5Calcium200.7, 6010Bug/LNA3,59016,5006,670,000Chromium200.8, 6020ug/LNA6.9117.82,410Cobalt200.7, 6010Bug/LNA15.3161891Copper200.8, 6020ug/LNA19.267.71,720Iron200.7, 6010Bug/LNA5532,3102,320,000Lead200.8, 6020ug/LNA1.629.74904Magnesium200.7, 6010Bug/LNA1,03012,3002,780,000Manganese200.7, 6010Bug/LNA26.6617459,000Mercury1631E, FGS-069ng/LNA20,00054,900515,000

## A-18NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMolybdenum200.7, 6010Bug/LNA39.3320465Nickel200.8, 6020ug/LNA5.5726.84,990Selenium200.8, 6020ug/LNA9.9144.53,740Silver200.8, 6020ug/LNA1.617.125.81Sodium200.7, 6010Bug/LNA9,290117,000300,000Thallium200.8, 6020ug/LNA0.6267.1250Tin200.7, 6010Bug/LNA1321,610ND (1,610)Titanium200.7, 6010Bug/LNA21.31615,520Vanadium200.8, 6020ug/LNA3.59353,190Zinc200.7, 6010Bug/LNA63.84745,310Metals - DissolvedAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.243.1JBarium200.7ug/L22.520380Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000380,000BCadmium200.8ug/L21.2484Calcium200.7ug/L501,70010,0005,000,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.120480Copper200.8ug/L20.9642.4J

## A-19NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationIron200.7ug/L23220069JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0002,800,000Manganese200.7ug/L5013500440,000Mercury1631Eng/L10024.150.5899Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.8942,200Selenium200.8ug/L51.6101,200BSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000300,000Thallium200.8ug/L20.47226Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.5JVanadium200.8ug/L21.710ND (10)UZinc200.7ug/L29.14071Metals - Filtered AqueousAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7221.2JArsenic200.8ug/L21.242.2JBarium200.7ug/L22.520270Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000390,000BCadmium200.8ug/L105.92077

## A-20NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCalcium200.7ug/L501,70010,0004,800,000Chromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120480Copper200.8ug/L20.9647.1Iron200.7ug/L23220047JLead200.8ug/L20.7323.5Magnesium200.7ug/L5054010,0002,800,000Manganese200.7ug/L5013500450,000Mercury1631Eng/L5001222553,830Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L104.5202,200Selenium200.8ug/L103.1201,000Silver200.8ug/L20.592ND (2)USodium200.7ug/L1092050,000300,000Thallium200.8ug/L20.47216Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.7ug/L29.14088Metals - Solid (dry weight)Aluminum6010Bmg/kg57.54930,000Antimony6020mg/kg20.0250.350.98Arsenic6020mg/kg100.455.385

## A-21NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationBarium6010Bmg/kg50.374.9400Beryllium6010Bmg/kg50.162.42.1JBoron6010Bmg/kg54.849730Cadmium6020mg/kg20.0170.180.74Calcium6010Bmg/kg56824073,000Chromium6020mg/kg20.130.3583BCobalt6010Bmg/kg50.494.915Copper6020mg/kg100.632.259Iron6010Bmg/kg5187380,000Lead6020mg/kg20.0320.2731Magnesium6010Bmg/kg518974,300Manganese6010Bmg/kg50.494.91,100MercuryFGS-069ng/g40,0006911,90017,800Molybdenum6010Bmg/kg51.39.716Nickel6020mg/kg20.0450.27100BSelenium6020mg/kg20.240.8896Silver6020mg/kg20.0360.180.2Sodium6010Bmg/kg52902,400550JThallium6020mg/kg20.00620.181.2Tin6010Bmg/kg54.449ND (49)UTitanium6010Bmg/kg50.684.9190Vanadium6020mg/kg20.0680.88110Zinc6010Bmg/kg51.915180

## A-22NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassical Pollutants - TotalAmmonia 350.1 mg/l NA 0.336 4.1 13.3Nitrate Nitrite as N 353.2 mg/l NA 0.0581 0.814 13.4Nitrogen, Total Kjeldahl 351.2 mg/l NA 2.27 12.9 51.5Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 13 S,MinChemical Oxygen Demand 410.4 mg/L 5 20 100 360Chloride 300.0, 9056 mg/l NA 124 1,440 15,300Sulfate 300.0, 9056 mg/l NA 16.7 390 2,040Cyanide, Total 4500 CN E mg/l NA 0.022 0.11 0.28Total Dissolved Solids 2540C mg/L 1 160 330 37,000 H,EstTotal Suspended Solids 2540D mg/L 1 92 330 20,000Phosphorus, Total 365.1 mg/l NA 0.0294 0.197 1.06Classicals Pollutants - Solid (dry weight)Ammonia 350.1 mg/Kg 1 4.1 10 32 P,EstNitrate Nitrite as N 353.2 mg/Kg 1 0.71 20 4.3 J,PNitrogen, Total Kjeldahl 351.2 mg/Kg 5 61 260 710 P,EstChloride 9056 mg/Kg 20 38 580 4,500Sulfate 9056 mg/Kg 100 170 4,900 26,000Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.5 0.19 J,H,PPhosphorus, Total 365.1 mg/Kg 1 0.79 4.8 34 P,EstClassicals Pollutants -Filtered AqueousAmmonia 350.1 mg/L 1 0.22 4 13 P,EstNitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 14 P,EstNitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 31 B,L,P,EstChloride 300.0 mg/L 500 130 1,500 16,000Sulfate 300.0 mg/L 50 12 250 1,300

## A-23NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.29 H,P,EstPhosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) U,PMetals - Calculated TotalAluminum 200.7, 6010B ug/L NA 228 1,600 938,000Antimony 200.8, 6020 ug/L NA 1.49 13.8 38.7Arsenic 200.8, 6020 ug/L NA 16.1 182 2,720Barium 200.7, 6010B ug/L NA 13.3 160 10,300Beryllium 200.7, 6010B ug/L NA 5.36 73.8 68.8Boron 200.7, 6010B ug/L NA 301 6,130 403,000Cadmium 200.8, 6020 ug/L NA 6.14 24.9 94Calcium 200.7, 6010B ug/L NA 3,610 16,600 7,200,000Chromium 200.8, 6020 ug/L NA 7.5 19.4 2,630Cobalt 200.7, 6010B ug/L NA 15.1 160 913Copper 200.8, 6020 ug/L NA 21.9 78.8 1,820Iron 200.7, 6010B ug/L NA 562 2,310 2,470,000Lead 200.8, 6020 ug/L NA 1.75 10.6 1,000Magnesium 200.7, 6010B ug/L NA 1,040 12,300 2,790,000Manganese 200.7, 6010B ug/L NA 26.4 613 454,000Mercury 1631E, FGS-069 ng/L NA 22,600 62,200 559,000Molybdenum 200.7, 6010B ug/L NA 39 322 500Nickel 200.8, 6020 ug/L NA 11.8 62.7 5,020Selenium 200.8, 6020 ug/L NA 10.7 48.3 4,380Silver 200.8, 6020 ug/L NA 1.75 7.83 5.94Sodium 200.7, 6010B ug/L NA 8,610 81,400 330,000Thallium 200.8, 6020 ug/L NA 0.651 7.83 54.8Tin 200.7, 6010B ug/L NA 133 1,600 ND (1,600)

## A-24NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTitanium 200.7, 6010B ug/L NA 21.5 160 5,940Vanadium 200.8, 6020 ug/L NA 3.89 38.8 3,440Zinc 200.7, 6010B ug/L NA 64.9 475 5,390Metals - DissolvedAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 2.7 JBarium 200.7 ug/L 2 2.5 20 370Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 400,000 BCadmium 200.8 ug/L 2 1.2 4 77Calcium 200.7 ug/L 50 1,700 10,000 5,100,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) UCobalt 200.7 ug/L 2 1.1 20 470Copper 200.8 ug/L 2 0.96 4 1.9 JIron 200.7 ug/L 2 32 200 33 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,800,000Manganese 200.7 ug/L 50 13 500 450,000Mercury 1631E ng/L 100 24.1 50.5 251Molybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 2,100Selenium 200.8 ug/L 5 1.6 10 1,200 BSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 310,000

## A-25NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationThallium 200.8 ug/L 2 0.47 2 26Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 4.7 JVanadium 200.8 ug/L 2 1.7 10 1.9 JZinc 200.7 ug/L 2 9.1 40 69Metals - Filtered AqueousAluminum 200.7 ug/L 2 9.4 200 ND (200) U,^Antimony 200.8 ug/L 2 0.72 2 1.3 JArsenic 200.8 ug/L 2 1.2 4 1.8 JBarium 200.7 ug/L 2 2.5 20 280Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 400,000 BCadmium 200.8 ug/L 10 5.9 20 73Calcium 200.7 ug/L 50 1,700 10,000 5,000,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 470Copper 200.8 ug/L 2 0.96 4 9.8Iron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,800,000Manganese 200.7 ug/L 50 13 500 440,000Mercury 1631E ng/L 500 122 255 3,510Molybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 10 4.5 20 2,000Selenium 200.8 ug/L 10 3.1 20 1,000Silver 200.8 ug/L 2 0.59 2 ND (2) U

## A-26NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationSodium 200.7 ug/L 2 180 10,000 330,000Thallium 200.8 ug/L 2 0.47 2 15Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 84Metals - Solid (dry weight)Aluminum 6010B mg/kg 5 7 45 30,000Antimony 6020 mg/kg 2 0.026 0.38 1.2Arsenic 6020 mg/kg 10 0.48 5.7 87Barium 6010B mg/kg 5 0.35 4.5 320Beryllium 6010B mg/kg 5 0.15 2.3 2.2 JBoron 6010B mg/kg 5 4.5 45 780Cadmium 6020 mg/kg 2 0.018 0.19 0.8Calcium 6010B mg/kg 5 64 230 79,000Chromium 6020 mg/kg 2 0.14 0.38 84 BCobalt 6010B mg/kg 5 0.45 4.5 15Copper 6020 mg/kg 10 0.67 2.4 58Iron 6010B mg/kg 5 17 68 79,000Lead 6020 mg/kg 2 0.034 0.28 32Magnesium 6010B mg/kg 5 17 91 4,600Manganese 6010B mg/kg 5 0.45 4.5 1,200Mercury FGS-069 ng/g 40,000 707 1,950 17,500Molybdenum 6010B mg/kg 5 1.2 9.1 16Nickel 6020 mg/kg 10 0.24 1.4 100 BSelenium 6020 mg/kg 2 0.25 0.94 110

## A-27NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Min – Minimum value.P – Sample was not preserved immediately following collection.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationSilver 6020 mg/kg 2 0.038 0.19 0.19Sodium 6010B mg/kg 5 270 2,300 570 JThallium 6020 mg/kg 2 0.0066 0.19 1.3Tin 6010B mg/kg 5 4.1 45 ND (45) UTitanium 6010B mg/kg 5 0.64 4.5 190Vanadium 6020 mg/kg 2 0.073 0.94 110Zinc 6010B mg/kg 5 1.8 14 170

## A-28NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8. Influent to FGD Wastewater TreatmentSystem, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSampleSpecific QLConcentrationClassical Pollutants - TotalAmmonia 350.1 mg/l NA 0.32 3.91 11.8Nitrate Nitrite as N 353.2 mg/l NA 0.0554 0.775 11Nitrogen, Total Kjeldahl 351.2 mg/l NA 2.13 11.9 49.6Biochemical OxygenDemand 5210B mg/L 1 0.3 2.5 2.9Chemical Oxygen Demand 410.4 mg/L 5 20 100 450Chloride 300.0, 9056 mg/l NA 118 1,370 14,600Sulfate 300.0, 9056 mg/l NA 15.9 371 1,950Cyanide, Total 4500 CN E mg/l NA 0.021 0.105 0.283Total Dissolved Solids 2540C mg/L 1 160 330 35,000 H,EstTotal Suspended Solids 2540D mg/L 1 280 1,000 55,000Phosphorus, Total 365.1 mg/l NA 0.0286 0.191 0.198Classicals Pollutants - Solid (dry weight)Ammonia 350.1 mg/Kg 1 4.1 10 32 P,EstNitrate Nitrite as N 353.2 mg/Kg 1 0.71 20 5.1 J,PNitrogen, Total Kjeldahl 351.2 mg/Kg 5 60 250 880 P,EstChloride 9056 mg/Kg 20 38 580 4,900Sulfate 9056 mg/Kg 100 170 4,900 26,000Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.5 0.12 J,H,PPhosphorus, Total 365.1 mg/Kg 1 0.81 4.9 6.5 P,Est

## A-29NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8. Influent to FGD Wastewater TreatmentSystem, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSampleSpecific QLConcentrationClassicals Pollutants -Filtered AqueousAmmonia 350.1 mg/L 1 0.22 4 12 P,EstNitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 12 P,EstNitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 26 B,L,P,EstChloride 300.0 mg/L 500 130 1,500 16,000Sulfate 300.0 mg/L 50 12 250 1,300Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.31 H,P,EstPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.005 J,PMetals - Calculated TotalAluminum 200.7, 6010B ug/L NA 217 1,520 922,000Antimony 200.8, 6020 ug/L NA 1.42 12.8 39.6Arsenic 200.8, 6020 ug/L NA 69.5 836 2,560Barium 200.7, 6010B ug/L NA 12.4 152 10,300Beryllium 200.7, 6010B ug/L NA 5.1 70.2 65.4Boron 200.7, 6010B ug/L NA 284 5,850 394,000Cadmium 200.8, 6020 ug/L NA 5.83 23.4 108Calcium 200.7, 6010B ug/L NA 3,440 15,900 6,710,000Chromium 200.8, 6020 ug/L NA 7.14 18.2 2,590Cobalt 200.7, 6010B ug/L NA 14.4 152 861Copper 200.8, 6020 ug/L NA 20.2 72 3,280Iron 200.7, 6010B ug/L NA 534 2,200 2,350,000Lead 200.8, 6020 ug/L NA 1.64 10.1 981

## A-30NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8. Influent to FGD Wastewater TreatmentSystem, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSampleSpecific QLConcentrationMagnesium 200.7, 6010B ug/L NA 993 11,700 2,750,000Manganese 200.7, 6010B ug/L NA 25.1 585 442,000Mercury1631E, FGS069 ng/L NA 22,000 60,600 622,000Molybdenum 200.7, 6010B ug/L NA 37.1 304 506Nickel 200.8, 6020 ug/L NA 10.9 59.7 6,560Selenium 200.8, 6020 ug/L NA 9.93 45.4 4,000Silver 200.8, 6020 ug/L NA 6.18 29.2 387Sodium 200.7, 6010B ug/L NA 8,190 77,400 323,000Thallium 200.8, 6020 ug/L NA 0.614 7.16 56.1Tin 200.7, 6010B ug/L NA 126 1,520ND(1,520)Titanium 200.7, 6010B ug/L NA 20.2 152 6,240Vanadium 200.8, 6020 ug/L NA 3.64 36.4 3,270Zinc 200.7, 6010B ug/L NA 61.7 452 5,460Metals - DissolvedAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 2 JBarium 200.7 ug/L 2 2.5 20 360Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 390,000 B

## A-31NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8. Influent to FGD Wastewater TreatmentSystem, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSampleSpecific QLConcentrationCadmium 200.8 ug/L 2 1.2 4 86Calcium 200.7 ug/L 50 1,700 10,000 5,000,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) UCobalt 200.7 ug/L 2 1.1 20 450Copper 200.8 ug/L 2 0.96 4 2.5 JIron 200.7 ug/L 2 32 200 54 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,800,000Manganese 200.7 ug/L 50 13 500 440,000Mercury 1631E ng/L 100 24.1 50.5 1,100Molybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 2,100Selenium 200.8 ug/L 5 1.6 10 1,400 BSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 320,000Thallium 200.8 ug/L 2 0.47 2 29Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 4.4 JVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 61Metals - Filtered Aqueous

## A-32NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8. Influent to FGD Wastewater TreatmentSystem, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSampleSpecific QLConcentrationAluminum 200.7 ug/L 2 9.4 200 15 J,^Antimony 200.8 ug/L 2 0.72 2 1 JArsenic 200.8 ug/L 2 1.2 4 2.3 JBarium 200.7 ug/L 2 2.5 20 260Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 410,000 BCadmium 200.8 ug/L 10 5.9 20 83Calcium 200.7 ug/L 50 1,700 10,000 5,000,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 460Copper 200.8 ug/L 2 0.96 4 6.7Iron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,900,000Manganese 200.7 ug/L 50 13 500 450,000Mercury 1631E ng/L 500 122 255 3,750Molybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 10 4.5 20 2,000Selenium 200.8 ug/L 10 3.1 20 1,200Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 340,000Thallium 200.8 ug/L 2 0.47 2 16

## A-33NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8. Influent to FGD Wastewater TreatmentSystem, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSampleSpecific QLConcentrationTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 120Metals - Solid (dry weight)Aluminum 6010B mg/kg 5 7 45 31,000Antimony 6020 mg/kg 2 0.026 0.37 1.3Arsenic 6020 mg/kg 50 2.3 28 86Barium 6010B mg/kg 5 0.34 4.5 340Beryllium 6010B mg/kg 5 0.15 2.3 2.2 JBoron 6010B mg/kg 5 4.4 45 800Cadmium 6020 mg/kg 2 0.017 0.18 1.1Calcium 6010B mg/kg 5 64 230 74,000Chromium 6020 mg/kg 2 0.14 0.37 87 BCobalt 6010B mg/kg 5 0.45 4.5 15Copper 6020 mg/kg 10 0.65 2.3 110Iron 6010B mg/kg 5 17 68 79,000Lead 6020 mg/kg 2 0.033 0.28 33Magnesium 6010B mg/kg 5 17 90 4,500Manganese 6010B mg/kg 5 0.45 4.5 1,200Mercury FGS-069 ng/g 40,000 712 1,960 20,100Molybdenum 6010B mg/kg 5 1.2 9 17

## A-34NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8. Influent to FGD Wastewater TreatmentSystem, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSampleSpecific QLConcentrationNickel 6020 mg/kg 10 0.23 1.4 160 BSelenium 6020 mg/kg 2 0.24 0.92 98Silver 6020 mg/kg 10 0.19 0.92 13Sodium 6010B mg/kg 5 270 2,300 550 JThallium 6020 mg/kg 2 0.0064 0.18 1.4Tin 6010B mg/kg 5 4.1 45 ND (45) UTitanium 6010B mg/kg 5 0.63 4.5 210Vanadium 6020 mg/kg 2 0.071 0.92 110Zinc 6010B mg/kg 5 1.8 14 180

## A-35ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.M – MS percent recovery outside themethod-specified criteria, but withinthe laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-9. Effluent from FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 2 0.11 2 13Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 9.7 M,MinNitrogen, TotalKjeldahl 351.2 mg/L 5 0.38 5 22 BBiochemical OxygenDemand 5210B mg/L 1 0.3 2.5 8.5 S,MinChemical OxygenDemand 410.4 mg/L 5 20 100 470Chloride 300.0 mg/L 500 130 1,500 15,000Sulfate 300.0 mg/L 50 12 250 1,500Cyanide, Total4500 CNE mg/L 1 0.02 0.1 0.12 BTotal Dissolved Solids 2540C mg/L 1 47 100 35,000 BTotal SuspendedSolids 2540D mg/L 1 1.1 4 4.8Phosphorus, Total 365.1 mg/L 5 0.025 0.25 1.2Total MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 0.92 JArsenic 200.8 ug/L 2 1.2 4 3.9 JBarium 200.7 ug/L 2 2.5 20 320Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 300,000 BCadmium 200.8 ug/L 2 1.2 4 2.2 JCalcium 200.7 ug/L 50 1,700 10,000 6,300,000

## A-36ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.M – MS percent recovery outside themethod-specified criteria, but withinthe laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-9. Effluent from FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 66 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 1,900,000 BManganese 200.7 ug/L 50 13 500 24,000 BMercury 1631E ng/L 20 4.83 10.1 119Molybdenum 200.7 ug/L 2 1.6 40 42Nickel 200.8 ug/L 2 0.89 4 6.8Selenium 200.8 ug/L 10 3.1 20 300Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 300,000Thallium 200.8 ug/L 2 0.47 2 11Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 18 JVanadium 200.8 ug/L 2 1.7 10 3.3 J,BZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 2 JBarium 200.7 ug/L 2 2.5 20 320Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 300,000 BCadmium 200.8 ug/L 2 1.2 4 2.1 J

## A-37ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.M – MS percent recovery outside themethod-specified criteria, but withinthe laboratory-specified criteria.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-9. Effluent from FGD Wastewater TreatmentSystem, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationCalcium 200.7 ug/L 50 1,700 10,000 6,300,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 1,900,000Manganese 200.7 ug/L 50 13 500 24,000Mercury 1631E ng/L 10 2.41 5.05 15.3Molybdenum 200.7 ug/L 2 1.6 40 42Nickel 200.8 ug/L 2 0.89 4 6.1Selenium 200.8 ug/L 5 1.6 10 320 BSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 300,000Thallium 200.8 ug/L 2 0.47 2 11Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 16 JVanadium 200.8 ug/L 2 1.7 10 3.8 JZinc 200.7 ug/L 2 9.1 40 ND (40) U

## A-38ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-10. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 2 0.11 2 12Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 9.4Nitrogen, TotalKjeldahl 351.2 mg/L 5 0.38 5 19 BBiochemical OxygenDemand 5210B mg/L 1 0.3 2.5 7.1 S,MinChemical OxygenDemand 410.4 mg/L 5 20 100 310Chloride 300.0 mg/L 500 130 1,500 15,000Sulfate 300.0 mg/L 50 12 250 1,400Cyanide, Total4500 CNE mg/L 1 0.02 0.1 0.035 JTotal Dissolved Solids 2540C mg/L 1 47 100 31,000Total Suspended Solids 2540D mg/L 1 1.1 4 10Phosphorus, Total 365.1 mg/L 5 0.025 0.25 1.1Total MetalsAluminum 200.7 ug/L 2 9.4 200 21 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 4.1Barium 200.7 ug/L 2 2.5 20 300Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 290,000 BCadmium 200.8 ug/L 2 1.2 4 2.9 JCalcium 200.7 ug/L 50 1,700 10,000 6,000,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) U

## A-39ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-10. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 63 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,000,000 BManganese 200.7 ug/L 50 13 500 23,000 BMercury 1631E ng/L 10 2.41 5.05 110Molybdenum 200.7 ug/L 2 1.6 40 44Nickel 200.8 ug/L 2 0.89 4 7.5Selenium 200.8 ug/L 5 1.6 10 350Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 290,000Thallium 200.8 ug/L 2 0.47 2 10Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 18 JVanadium 200.8 ug/L 2 1.7 10 3.3 J,BZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 0.88 JArsenic 200.8 ug/L 2 1.2 4 3.3 JBarium 200.7 ug/L 2 2.5 20 300Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 300,000 BCadmium 200.8 ug/L 2 1.2 4 2.6 JCalcium 200.7 ug/L 50 1,700 10,000 6,000,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) U

## A-40ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-10. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,000,000Manganese 200.7 ug/L 50 13 500 23,000Mercury 1631E ng/L 5 1.21 2.52 16.2Molybdenum 200.7 ug/L 2 1.6 40 43Nickel 200.8 ug/L 2 0.89 4 6.8Selenium 200.8 ug/L 5 1.6 10 370 BSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 290,000Thallium 200.8 ug/L 2 0.47 2 10Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 16 JVanadium 200.8 ug/L 2 1.7 10 3.8 JZinc 200.7 ug/L 2 9.1 40 ND (40) U

## A-41ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-11. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 2 0.11 2 11Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 9.3Nitrogen, TotalKjeldahl 351.2 mg/L 5 0.38 5 20 B,4Biochemical OxygenDemand 5210B mg/L 1 0.3 2.5 6.8 S,MinChemical OxygenDemand 410.4 mg/L 5 20 100 380 F,MinChloride 300.0 mg/L 500 130 1,500 14,000Sulfate 300.0 mg/L 50 12 250 1,400Cyanide, Total4500 CNE mg/L 1 0.02 0.1 ND (0.1) UTotal Dissolved Solids 2540C mg/L 1 47 100 29,000Total Suspended Solids 2540D mg/L 1 1.1 4 7.2 D,EstPhosphorus, Total 365.1 mg/L 5 0.025 0.25 1.2Total MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 1.2 JArsenic 200.8 ug/L 2 1.2 4 3.6 JBarium 200.7 ug/L 2 2.5 20 290Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 280,000 B,4Cadmium 200.8 ug/L 2 1.2 4 3.4 JCalcium 200.7 ug/L 50 1,700 10,000 5,600,000 4

## A-42ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-11. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 110 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 1,900,000 B,4Manganese 200.7 ug/L 50 13 500 19,000 B,4Mercury 1631E ng/L 10 2.41 5.05 78.6Molybdenum 200.7 ug/L 2 1.6 40 42Nickel 200.8 ug/L 2 0.89 4 8.6Selenium 200.8 ug/L 5 1.6 10 300Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 280,000Thallium 200.8 ug/L 2 0.47 2 9.7Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 15 JVanadium 200.8 ug/L 2 1.7 10 1.9 J,BZinc 200.7 ug/L 2 9.1 40 9.9 JDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 37 JAntimony 200.8 ug/L 2 0.72 2 0.79 JArsenic 200.8 ug/L 2 1.2 4 3.9 JBarium 200.7 ug/L 2 2.5 20 290Beryllium 200.7 ug/L 2 0.71 2 ND (2) U

## A-43ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-11. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationBoron 200.7 ug/L 50 170 5,000 280,000 B,4Cadmium 200.8 ug/L 2 1.2 4 3.3 JCalcium 200.7 ug/L 50 1,700 10,000 5,700,000 4Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 75 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 1,900,000 4Manganese 200.7 ug/L 2 0.51 20 18,000 4Mercury 1631E ng/L 5 1.21 2.52 10.2Molybdenum 200.7 ug/L 2 1.6 40 42Nickel 200.8 ug/L 2 0.89 4 5.4Selenium 200.8 ug/L 5 1.6 10 320 B,4Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 280,000Thallium 200.8 ug/L 5 1.2 5 11Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 15 JVanadium 200.8 ug/L 2 1.7 10 4.1 JZinc 200.7 ug/L 2 9.1 40 9.6 J

## A-44ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-12. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 2 0.11 2 12Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 9.4Nitrogen, TotalKjeldahl 351.2 mg/L 5 1.9 25 85Biochemical OxygenDemand 5210B mg/L 1 0.3 2.5 3.5 S,MinChemical OxygenDemand 410.4 mg/L 5 20 100 320Chloride 300.0 mg/L 500 130 1,500 13,000Sulfate 300.0 mg/L 50 12 250 1,400Cyanide, Total4500 CNE mg/L 1 0.02 0.1 0.1Total Dissolved Solids 2540C mg/L 1 47 100 29,000Total Suspended Solids 2540D mg/L 1 1.1 4 9.6Phosphorus, Total 365.1 mg/L 5 0.025 0.25 1.1Total MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 0.82 JArsenic 200.8 ug/L 2 1.2 4 3.2 JBarium 200.7 ug/L 2 2.5 20 280Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 290,000 B,4Cadmium 200.8 ug/L 2 1.2 4 3.5 JCalcium 200.7 ug/L 50 1,700 10,000 5,600,000 4

## A-45ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-12. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 91 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 1,900,000 B,4Manganese 200.7 ug/L 50 13 500 23,000 B,4Mercury 1631E ng/L 10 2.41 5.05 31.2Molybdenum 200.7 ug/L 2 1.6 40 43Nickel 200.8 ug/L 2 0.89 4 7Selenium 200.8 ug/L 100 31 200 320 F,4Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 270,000Thallium 200.8 ug/L 2 0.47 2 11Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 17 JVanadium 200.8 ug/L 2 1.7 10 3.6 J,BZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 5 1.8 5 1.8 JArsenic 200.8 ug/L 5 3.1 10 3.5 JBarium 200.7 ug/L 2 2.5 20 280Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 290,000 B,4

## A-46ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-12. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationCadmium 200.8 ug/L 2 1.2 4 3.1 JCalcium 200.7 ug/L 50 1,700 10,000 5,800,000 4Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 1,900,000Manganese 200.7 ug/L 50 13 500 22,000Mercury 1631E ng/L 20 4.83 10.1 28.5Molybdenum 200.7 ug/L 2 1.6 40 44Nickel 200.8 ug/L 2 0.89 4 7Selenium 200.8 ug/L 5 1.6 10 300 B,4Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 280,000Thallium 200.8 ug/L 5 1.2 5 10Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 16 JVanadium 200.8 ug/L 2 1.7 10 5.5 JZinc 200.7 ug/L 2 9.1 40 ND (40) U

## A-47ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-13. Duplicate of Effluentfrom Wastewater Treatment System, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 2 0.11 2 12Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 9.3Nitrogen, TotalKjeldahl 351.2 mg/L 5 0.38 5 21 BBiochemical OxygenDemand 5210B mg/L 1 0.3 2.5 6.9 S,MinChemical OxygenDemand 410.4 mg/L 5 20 100 240Chloride 300.0 mg/L 500 130 1,500 15,000Sulfate 300.0 mg/L 50 12 250 1,300Cyanide, Total4500 CNE mg/L 1 0.02 0.1 0.18Total Dissolved Solids 2540C mg/L 1 47 100 30,000Total Suspended Solids 2540D mg/L 1 1.1 4 54Phosphorus, Total 365.1 mg/L 5 0.025 0.25 1.1Total MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 0.76 JArsenic 200.8 ug/L 2 1.2 4 3.5 JBarium 200.7 ug/L 2 2.5 20 300Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 310,000 BCadmium 200.8 ug/L 2 1.2 4 2.9 JCalcium 200.7 ug/L 50 1,700 10,000 6,200,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) U

## A-48ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-13. Duplicate of Effluentfrom Wastewater Treatment System, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 52 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,000,000 BManganese 200.7 ug/L 50 13 500 23,000 BMercury 1631E ng/L 10 2.41 5.05 105Molybdenum 200.7 ug/L 2 1.6 40 43Nickel 200.8 ug/L 2 0.89 4 7.5Selenium 200.8 ug/L 5 1.6 10 350Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 290,000Thallium 200.8 ug/L 2 0.47 2 11Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 17 JVanadium 200.8 ug/L 2 1.7 10 3.9 J,BZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 3.4 JBarium 200.7 ug/L 2 2.5 20 290Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 290,000 BCadmium 200.8 ug/L 2 1.2 4 3.1 JCalcium 200.7 ug/L 50 1,700 10,000 6,000,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) U

## A-49ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-13. Duplicate of Effluentfrom Wastewater Treatment System, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 1,900,000Manganese 200.7 ug/L 50 13 500 22,000Mercury 1631E ng/L 5 1.21 2.52 14.3Molybdenum 200.7 ug/L 2 1.6 40 43Nickel 200.8 ug/L 2 0.89 4 6.4Selenium 200.8 ug/L 5 1.6 10 350 BSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 290,000Thallium 200.8 ug/L 2 0.47 2 11Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 16 JVanadium 200.8 ug/L 2 1.7 10 4.8 JZinc 200.7 ug/L 2 9.1 40 12 Ja 

### Aluminum was detected in two equipment blanks for the 10 -liter composite container at 2.53 ug/L and 4.71 ug/L.

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



## A-50 Table A-14. Bottle Blank and Equipmen t Blank Analytical Data, Keystone

Analyte Method Process Units Concentration

HDPE 250 ml Plastic Bottles – Bottle Blank (for metals and hexavalent chromium samples)

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)

Lead EPA 1638 Total Reco verable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)

HDPE 500 ml Plastic Bottles – Bottle Blank (for metals samples)

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)a 

### Aluminum was detected in two equipment blanks for the 10 -liter composite container at 2.53 ug/L and 4.71 ug/L.

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



## A-51 Table A-14. Bottle Blank and Equipmen t Blank Analytical Data, Keystone

Analyte Method Process Units Concentration

Lead EPA 1638 Total Reco verable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)

125 ml Glass Bottles – Bottle Blank (for mercury composite samples)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

250 ml Glass Bottles – Bottle Bl ank (for mercury grab samples)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

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

Aluminum a 

### EPA 1638 Dissolved ug/L 4.71

Antimony EPA 1638 Dissolved ug/L ND (0.50)

Arsenic EPA 1638 Dissolved ug/L ND (0.50)

Barium EPA 1638 Dissolved ug/L ND (0.10)

Beryllium EPA 1638 Dissolved ug/L ND (0.10)

Cadmium EPA 1638 Dissolved ug/L ND (0.10)

Chromium EPA 1638 Dissolved ug/L ND (1.0)

Cobalt EPA 1638 Dissolved ug/L ND (0.10)

Copper EPA 1638 Dissolved ug/L ND (0.30)

Lead EPA 1638 Dissolved ug/L ND (0.050)

Manganese EPA 1638 Dissolved ug/L ND (0.50)

Molybdenum EPA 1638 Dissolved ug/L ND (0.50)

Nickel EPA 1638 Dissolved ug/L ND (0.50)

Selenium EPA 1638 Dissolved ug/L ND (2.0)

Silver EPA 1638 Dissolved ug/L ND (0.10)

Thallium EPA 1638 Dissolved ug/L ND (0.050)

Vanadium EPA 1638 Dissolved ug/L ND (1.0)

Zinc EPA 1638 Dissolved ug/L ND (0.50)

LDPE 20 L Composite Bottles – Bottle Blank (sample composite bottle for dissolved/filtration pump-off)

Aluminum EPA 1638 Dissolved ug/L ND (2.0)

Antimony EPA 1638 Dissolved ug/L ND (0.50)a 

### Aluminum was detected in two equipment blanks for the 10 -liter composite container at 2.53 ug/L and 4.71 ug/L.

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



## A-52 Table A-14. Bottle Blank and Equipmen t Blank Analytical Data, Keystone

Analyte Method Process Units Concentration

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)

Sample Tap Tubing Set – Equipment Blank (seven feet of #73 silicone tubing, Y-sp litter, and two pieces of 5

feet of #24 silicone tubing for sample collect ion for mercury and metals from sample taps)

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)

Lead EPA 1638 Total Reco verable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)a 

### Aluminum was detected in two equipment blanks for the 10 -liter composite container at 2.53 ug/L and 4.71 ug/L.

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



## A-53 Table A-14. Bottle Blank and Equipmen t Blank Analytical Data, Keystone

Analyte Method Process Units Concentration

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)

Pump-Off Tubing Set – Equipment Blan k (Three feet of Teflon® tubing, 10 feet of #73 silicone tubing, Ysplitter, and two pieces of 5 feet of #24 silicone tubing for total and di ssolved sample collection for metals)

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)

Lead EPA 1638 Total Reco verable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)

T-Splitter Tubing Set – Equipment Blank (Ten feet of #7 3 silicone tubing, T-splitter, six feet of #73 silicone

tubing, and 15 feet of #73 silicone tubing for total and dissolved sample collect ion for metal composites)

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)a 

### Aluminum was detected in two equipment blanks for the 10 -liter composite container at 2.53 ug/L and 4.71 ug/L.

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



## A-54 Table A-14. Bottle Blank and Equipmen t Blank Analytical Data, Keystone

Analyte Method Process Units Concentration

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)

Lead EPA 1638 Total Reco verable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)

## A-55ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-15. Influent to FGD Wastewater Treatment SystemField Blank, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 12 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 61 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 79 JChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 32 J,BManganese 200.7 ug/L 2 0.51 20 4.7 J,BMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000ND(10,000)UThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) U

## A-56ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-15. Influent to FGD Wastewater Treatment SystemField Blank, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 38 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 1 0.39 2 ND (2) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 1.2 JMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 1.1 J,BSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000ND(10,000) UThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) U

## A-57ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-15. Influent to FGD Wastewater Treatment SystemField Blank, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 ND (40) U

## A-58ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-16. Effluent from FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecific QLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 67 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 83 JChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 30 J,BManganese 200.7 ug/L 2 0.51 20 3.6 J,BMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000ND(10,000) UThallium 200.8 ug/L 2 0.47 2 ND (2) U

## A-59ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-16. Effluent from FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecific QLConcentrationTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 2.9 J,BZinc 200.7 ug/L 2 9.1 40 11 JDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 49 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 1 0.39 2 ND (2) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 0.6 JMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 0.72 J,B

## A-60ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-16. Effluent from FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, KeystoneAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecific QLConcentrationSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000ND(10,000) UThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 2.1 JZinc 200.7 ug/L 2 9.1 40 ND (40) U

## A-61ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-17. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

## A-62ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-18. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, KeystoneAnalyteMethodUnitDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

## A-63ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-19. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, KeystoneAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

## Appendix B

DATA REVIEW NARRATIVES

## 1 

# MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram, ERG

TJ Finseth, ERG

From: Donna Tedder, ERG

Laura Aviles

- Alvarez , ERG

Date: 9 / 1 /2011

Subject: FGS Data R eview Narrative for Total and Dissolved Mercury

– Episode 65 6 3

Frontier Global Sciences (FGS) generated analytical data for total and dissolved mercury.

FGS analyzed t he samples according to EPA Method 1631E for mercury by Cold Vapor

Atomic Fluorescence Spectrometry (CVAFS) analysis.

Table 1 summarizes the 23 s amples ( ex cluding laboratory filter blanks) FG S extracted

and analyzed for total and dissolved mercury

.

Table 1. 

## EPA Episode 6563 Total & Dissolved Mercury

– Sample Identification

EPA

Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

71891 1009100

- 03 Aqueous FGD Influent Day 1 9/13/2010

71891 1009100

- 04 Aqueous Dissolved FGD Influent, Day 1 9/13/2010

71892 1009111

- 08 Aqueous FGD Influent, Day 2 9/14/2010

71892 1009111

- 09 Aqueous Dissolved FGD Influent, Day 2 9/14/2010

71893 1009128

- 04 Aqueous FGD Influent, Day 3 9/15/2010

71893 1009128

- 05 Aqueous Dissolved FGD Influent, Day 3 9/15/2010

71894 1009134

- 03 Aqueous FGD Influent, Day 4 9/16/2010

71894 1009134

- 04 Aqueous Dissolved FGD Influent, Day 4 9/16/2010

71895 1009111

- 10 Aqueous FGD Effluent Day 1 9/14/2010

71895 1009111

- 11 Aqueous Dissolved FGD Effluent, Day 1 9/14/2010

71896 1009128

- 06 Aqueous FGD Effluent, Day 2 9/15/2010

71896 1009128

- 07 Aqueous Dissolved FGD Effluent, Day 2 9/15/2010

71897 1009134

- 05 Aqueous FGD Effluent, Day 3 9/16/2010

71897 1009134

- 06 Aqueous Dissolved FGD Effluent, Day 3 9/16/2010

71898 1009141

- 02 Aqueous FGD Effluent, Day 4 9/17/2010

71898 1009141

- 03 Aqueous Dissolved FGD Effluent, Day 4 9/17/2010

71899 1009128

- 08 Aqueous FGD Effluent Duplicate, Day 2 9/15/2010

71899 1009128

- 09 Aqueous Dissolved FGD Effluent Duplicate, Day 2 9/15/2010

71900 1009100

- 05 Aqueous FGD Influent Field Blank, Day 1 9/13/2010

## 2 Table 1. 

## EPA Episode 6563 Total & Dissolved Mercury

– Sample Identification

EPA

Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

71901 1009100

- 08 Aqueous FGD Effluent Field Blank, Day 1 9/13/2010

71902 1009111

- 12 Aqueous FGD Effluent Field Blank, Day 2 9/14/2010

71903 1009128

- 12 Aqueous FGD Effluent Field Blank, Day 3 9/15/2010

71904 1009134

- 07 Aqueous FGD Effluent Field Blank, Day 4 9/16/2010



## SUMMARY

The samples were prepared according to EPA Method 1631E to be analyzed by CVAFS

.

There were no findings from the data review that required additional qualifiers in this

dataset.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no s ample receipt issues in this data package

.

I NITIAL CAL IBRATION

FGS performed the initial calibrations on each analysis day. The i nitial calibration for

the CVAFS analysis consisted of a blank and five calibration standards with a correlation

coefficient ≥0.995

. All method

- specified criteria were met.

INITIAL AND C ONTINUING C ALIBRATION V ERIFICATION S

All initial and c ontinuing c alib ration v erifications ( ICVs, CCVs ) met method

- specified

criteria

.

BLANK S

All the preparation blanks or laboratory reagent blanks (LRBs) and the continuing

calibration blanks (CCBs) met method

- specified criteria. Preparation Blanks F0 10073

-

BLK 5, F0 10073

- BLK 6, F0 10122

- BLK 6, F0 10122

– BLK 7, and F0 10123

- BLK 5 had

mercury level s of 0. 45, 0.29, 0.16, 0.13, and 0. 09 ng/L

, r espectively . These blank results

were greater than the MDL ( 0.08 ng/L), but less than the RL ( 0.50 ng/L). Because all of

the blank results were less than the RL, no samples were qualified based on these

prepara tion blank results.

DUPLICATES

A f ield duplicate , Sample 71899, was collected on the Sample 71896 . The total mercury

relative percent difference ( RPD ) was 4.65% and the dissolved mercury RPD was

12.46%. The method

- suggested RPD criteria between field duplicates is 20%.

## 3 L aboratory duplicate s w ere performed in this episode on samples 71891 and 71896 . All

RPDs were less than 20% (the method

- suggested RPD criterion between field duplicates;

the method does not require the analysis of laboratory duplicates )

.

LABORATORY CONTROL SAMPLES

All laboratory control samples were within Frontier’s control limits of 80

- 120% recovery

and 24% RPD, except F010073

- BS3 (blank spike (BS)), which had a recovery of 121%

recovery

. Because this recovery does meet the ongoing precision and recovery ( OPR )

criteria, and because the other BS samples and all initial and continuing calibration

verification samples in this batch met method criteria, there was no need to qualify any

data based on this BS failure.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on samples

71891

, 71896, and 71 897 for the total mercury analyse s . MS and MSDs were performed

on sample 71897 for the dissolved mercury analyses. All aqu eous MS/MSD recoveries

were within method specifications of 71

- 125%. All RPDs met method

- specified criteria

.

D ETECTION LIMITS

The laboratory MDL in the synthetic matrix was 0.239 ng/L. Results below this MDL

were reported as not detected (ND).

## 1 

# MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram

, ERG

TJ Finseth

, ERG

From: Randy Mercurio, ERG

Date: 9 / 1 /2011

Subject: TestAmerica Data R eview Narrative for Total and Dissolved Metals by 200.8

– Episode 65 63

TestAmerica generated analytical data for total and dissolved metals ( a ntimony, a rsenic,

c admium, c hromium, c opper, l ead, n ickel, s elenium, s ilver, t hallium

, and v anadium ) for

Sample Episode 6563

. T he samples were analyzed according to EPA Method 200.8

.

Table 1 summarizes the samples TestAmerica extracted and analyzed for total and

dissolved metals by EPA Method 200.8

.

Table 1. 

## EPA Episode 6563 Total & Dissolved Metals

– Sample Identification

EPA

Sample

# EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71891 FGD Influent, Day 1 280

- 7312

- 1 Aqueous 9/13/2010 9/14/2010

71891 FGD Influent, Day 1

– Solid 280

- 7312

- 3 Solid 9/13/2010 9/14/2010

71891 FGD Influent, Day 1

- Filtrate 280

- 7312

- 4 Aqueous 9/13/2010 9/14/2010

71892 FGD Influent, Day 2 280

- 7362

- 1 Aqueous 9/14/2010 9/15/2010

71892 FGD Influent, Day 2

– Solid 280

- 7362

- 4 Solid 9/14/2010 9/15/2010

71892 FGD Influent, Day 2

– Filtrate 280

- 7362

- 5 Aqueous 9/14/2010 9/15/2010

71893 FGD Influent, Day 3 280

- 7401

- 1 Aqueous 9/15/2010 9/16/2010

71893 FGD Influent, Day 3

– Solid 280

- 7401

- 4 Solid 9/15/2010 9/16/2010

71893 FGD Influent, Day 3

– Filtrate 280

- 7401

- 5 Aqueous 9/15/2010 9/16/2010

71894 FGD Influent, Day 4 280

- 7482

- 1 Aqueous 9/16/2010 9/17/2010

71894 FGD Influent, Day 4

– Solid 280

- 7482

- 3 Solid 9/16/2010 9/17/2010

71894 FGD Influent, Day 4

- Filtrate 280

- 7482

- 4 Aqueous 9/16/2010 9/17/2010

71895 FGD Effluent, Day 1 280

- 7362

- 2 Aqueous 9/14/2010 9/15/2010

71896 FGD Effluent, Day 2 280

- 7401

- 2 Aqueous 9/15/2010 9/16/2010

71897 FGD Effluent, Day 3 280

- 7482

- 2 Aqueous 9/16/2010 9/17/2010

71898 FGD Effluent, Day 4 280

- 7536

- 1 Aqueous 9/17/2010 9/18/2010

71899 FGD Effluent, Day 2

- Duplicate 280

- 7401

- 3 Aqueous 9/15/2010 9/16/2010

## 2 Table 1. 

## EPA Episode 6563 Total & Dissolved Metals

– Sample Identification

EPA

Sample

# EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71900 FGD Influent Field Blank,

Day 1 280

- 7312

- 2 Aqueous 9/13/2010 9/14/2010

71901 FGD Effluent Field Blank,

Day 1 280

- 7362

- 3 Aqueous 9/14/2010 9/15/2010



## SUMMARY

T he sample s were prepared for total and dissolved metals analysis according

TestAmerica’s “FGD ICP/MS SOP: Inductively Coupled Plasma Mass Spectrometry for

Trace Element Analysis in Flue Gas Desulfurization Wastewaters,” dated October 6,

2010, based on EPA Method 200.8, by ICP/MS analysis. Any significant findings are

s ummarized below. No additional data qualifiers were required

.

• The serial dilution analysis for thallium in the solid phase of sample 71891 did not

meet TestAmerica’s requirement of ± 10% difference

.

• The serial dilution analysis for total nickel in the filtrate phase of sample 71891

did not meet TestAmerica’s requirement of ± 10% difference

.

• All matrix spike ( M S ) / matrix spike duplicates ( MSD ) for total and dissolved

s ilver failed the 70

– 130% control limits , except for dissolved silver in the MS for

sample 71897

.

• All the MS/MSD RPDs for silver failed TestAmerica’s SOP control limits of

±20%.

• The MS/MSD RPD for total selenium for sample 71898 failed TestAmerica’s

SOP control limits of ±20%

.

• The post digestion spikes (PDS) for selenium in the solid phase for sample 71891

failed the method criteria of 85

– 115%.

• The PDS for silver failed the method criteria of 85

- 115% for several samples.

INTERNAL STANDARDIZA TION

All internal standards used by TestAme rica were within the method criteria.

## 3 INITIAL CALIBRATION

Test America performed the initial calibrations on each analysis day or before each

analysis if more than one analysis was performed in one day

. The initial calibration for

the ICP

- MS analysis consisted of a blank and four calibration standards

.

I NITIAL AND CONTINUING CALIBRATION VERIFICATION (ICV/CCV)

The initial calibration verifications (ICV) and continuing calibration verifications (CCV)

performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANK S

All the method b lanks were less than the r eporting l imit ; however, some elements were

above the MDL and flagged with a “J” qualifier

. No additional quali fiers were required

for method b lanks.

All i nstrument b lanks ( ICB and CCB) were less tha n the r eporting l imit ; however, some

elements were above the MDL and flagged with a “J” qualifier. No additional qua lifiers

were required for i nstrument b lanks.

REPORTING LIMIT VERIFICATION STANDARD ( CRI )

A ll C RI samples passed Test America’s SOP control limits of 50

– 150%.

LABORATORY CONTROL SAMPLE S (LCS)

All LCS samples passed the method limits of 85

– 115% , with the exception of s elenium

in the solid sample LCS 280

- 34676/2

- A at 84% ; however, TestAmerica had a control

limit set at 78

– 108%

. No data was qualified based on this LCS.

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION

Based on TestAmerica’s SOP, all interference check sample A (ICSA) results had

analytes of interest with concentrations less than the RL or less than five times the RL

when known inherent contaminants are present in the stock solution used to make the

ICS.

All interference check sample B (ICSAB) synthetic s pikes recovered within

TestAmerica’s SOP criteria of 70

– 130% of the true value.

SERIAL DILUTION (SRD)

The s erial dilution performed for solid sample 71 89 1 FGD Influent, Day 1

- Solid (280

-

7312

- 3) failed Test America’s requirement of ±10% difference for t hallium and was

flagged “W”

. The serial dilution performed for sample 71891 FGD Influent, Day 1

-

## 4 Filtrate (280

- 7312

- 4) failed Test America’s requirement of ±10% difference for n ickel

and was flagged “W”. All other elements passed Test America’s requirement of ±10%

difference in the serial dilutions and required no further qualifiers.

FIELD DUPLICATES

The relative percent difference ( RPD ) of the field duplicates (71896/71899 ) were less

than ±20% for all values equal to or greater than the reporting limit

.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

MS and MSD were performed on Sa mple s 71897 and 71898. Many spike recoveries were

outside the method control limits of 70

– 130% when sample concentrations exceeded the

spike concentration by a factor of four or more, which have been flagged “4”

. All

M S/MSDs for total and dissolved s ilver failed the 70

– 130% method control limits with

the exception of the dissolved silver in sample 71897 FGD Effluent, Day 3 MS

. All the

MS/MSD RPDs for s ilver failed TestAmerica’s SOP control limits of ±20 %

. Th e poor

recoveries and RPD of s ilver ar e probably due to high sulfates in this episode’s samples

t hat could form insoluble silver sulfide and/or silver s ulfate. All other RPD results were

less than the method required 20% with the exception of selenium for MSD sample

71898 FGD Effluent, Day 4 (280

- 7536

- 1 MSD) , which was 25%.

POST DIGESITON SPIKE S

The PDS performed on solid sample 7189 1 FGD In fluent, Day 1

- Solid (280

- 7312

- 3

PDS ) fail ed Test America’s 7 5

– 12 5% control limits for s elenium , which was flagged

“W”

. S ilver failed Test America’s 85

- 115% control limits for the following samples:

• T otal silver for 71891 FGD Influent, Day 1

– Filtrate (280

- 7312

- 4 PDS) ;

• T otal silver for 71897 FGD Effluent, Day 3 (280

- 7482

- 2 PDS);

• D issolved silver for 71897 FGD Effluent, Day 3 (280

- 7482

- 2 PDS); and

• D issolved silver for 71898 FGD Effluent, Day 4 (280

- 7536

- 1 PDS)

.

Each of these samples were flagged “W”

. The poor recoveries of s ilver ar e probably due

to high sulfates in this episode’s samples that could form insolu ble s ilver s ulfide and/or

s ilver s ulfate. Sample 71897 FGD Effluent, Day 3 (280

- 7482

- 2 PDS) also failed Test

America’s 85

- 115% control limits for total s elenium, and dissolved v anadium which

w ere both flagged “W”. No additional qualifiers were required for PDS samples.

D ETECTION LIMITS

The laboratory performed an MDL study in the synthetic FGD wastewater matrix, instead

of reagent water.

## 1 

# MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram

, ERG

TJ Finseth

, ERG

From: Randy Mercurio, ERG

Date: 9 / 1 /2011

Subject: TestAmerica Data R eview Narrative for Total and Dissolved Metals by 200.7

– Episode 65 63

Test America generated analytical data for total and dissolved metals ( a l u minum, b oron,

b arium, b eryllium, c alcium, c obalt, i ron, m agnesium, m anganese, m olybdenum, s odium,

t in, t itanium

, and z inc ) for Sample Episode 6563

. T he samples were analyzed according

to EPA Method 200. 7

.

Table 1 summarizes the s ample s Test America extracted and analy zed for total and

dissolved metals by EPA Method 200.7

.

Table 1. 

## EPA Episode 6563 Total & Dissolved Metals

– Sample Identification

EPA

Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71891 FGD Influent, Day 1 280

- 7312

- 1 Aqueous 9/13 /2010 9/14 /2010

71 891 FGD Influent, Day 1

- Solids 280

- 7312

- 3 Solid 9/13 /2010 9/14 /2010

71 891 FGD Influent, Day 1

- Filtrate 280

- 7312

- 4 Aqueous 9/13 /2010 9/14 /2010

71 892 FGD In fluent , Day 2 280

- 7362

- 1 Aqueous 9/14 /2010 9/15 /2010

71 892 FGD Influent, Day 2

– Solids 280

- 7362

- 4 Solid 9/14 /2010 9/15 /2010

71 892 FGD Influent, Day 2

– Filtrate 280

- 7362

- 5 Aqueous 9/14 /2010 9/15 /2010

71 893 FGD Influent, Day 3 280

- 7401

- 1 Aqueous 9/15 /2010 9/16 /2010

71 893 FGD In fluent, Day 3

– Solids 280

- 7401

- 4 Solid 9/15 /2010 9/16 /2010

71 893 FGD In fluent, Day 3

– Filtrate 280

- 7401

- 5 Aqueous 9/15 /2010 9/16 /2010

71 894 FGD Influent, Day 4 280

- 7482

- 1 Aqueous 9/16 /2010 9/17 /2010

71 894 FGD Influent, Day 4

– Solids 280

- 7482

- 3 Solid 9/16 /2010 9/17 /2010

71894 FGD Influent, Day 4

- Filtrate 280

- 7482

- 4 Aqueous 9/16 /2010 9/17 /2010

71 895 FGD Ef fluent

, Day 1 280

- 7362

- 2 Aqueous 9/14 /2010 9/15 /2010

71 896 FGD Effluent, Day 2 280

- 7401

- 2 Aqueous 9/15 /2010 9/16 /2010

71897 FGD Effluent, Day 3 280

- 7482

- 2 Aqueous 9/16 /2010 9/17 /2010

71898 FGD Effluent, Day 4 280

- 7536

- 1 Aqueous 9/17 /2010 9/18 /2010

71899 FGD Effluent, Day 2

- Duplicate 280

- 7401

- 3 Aqueous 9/15 /2010 9/16 /2010

## 2 Table 1. 

## EPA Episode 6563 Total & Dissolved Metals

– Sample Identification

EPA

Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71 900 FGD Influent Field Blank, Day 1 280

- 7312

- 2 Aqueous 9/13 /2010 9/14 /2010

71 901 FGD Effluent Field Blank , Day 1 280

- 7362

- 3 Aqueous 9/14 /2010 9/15 /2010



## SUMMARY

The sample s were prepared for total and dissolved metals analysis according to

Test America’s SOP for ECP Analysis for Trace Metals by Method 200.7

. Any significant

findings are summarized below. No additional qualifiers were required.

The post digestion spikes (PDS) for total barium, total calcium, and total zinc in the

filtrate phase for sample 71891 failed the method criteria of 85

– 115%.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were n o s ample receipt issues i n this data package

.

INTERNAL STANDARDIZA TION

Whil e the internal standard (ISTD) y ttrium was used for these analyses, no checks for the

ISTD recoveries within the ±30% criterion of the calibration blank as per Section 9.11 of

the SOP were seen. All ISTD were within the control limits.

I NITIAL CAL IBRATION

Test America performed the initial calibrations on each analysis day. The initial

calibration for the ICP analysis consisted of a blank and one calibration standard.

I NITIAL AND CONTINUING CALIBRATION VERIFICATION S

The initial c alibration v erifications (ICV) and c ontinuing c alibration v erifications (CCV)

performed by Test America all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANKS

All the m ethod b lanks were less than the r eporting l imit; however, some had levels above

the MDL and were flagged with the “J” qualifier.

All i nstrument b lanks (ICB and CCB) were less than the r eporting l imit; however, some

elements were above the MDL and were flagged with the “J” qualifier.

## 3 LABORATORY CONTROL SAMPLES (LCS)

All LCSs passed the method control limits of 85

– 115%.

INTERFERENCE CHECK SOLUTION S

Interference checks were performed using the synthetic matrix as the check solution. All

data quality objectives met TestAmerica’s SOP criteria.

REPORTING LIMIT VERIFICATION STANDARD ( CRI )

A ll CRI samples passed Test America’s SOP control limits of 50

– 150%.

FIELD DUPLICATES

The total and dissolved relative percent differences ( RPD s ) of the field duplicate (71899 )

to parent sample ( 71896 ) were less than 2 0% for values greater than the reporting limit

.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on the total and

dissolved sample s of 71897 and 71898

. Some elements with high concentrations

frequently failed the EPA 200.7 Method spike recovery control limits of 70

– 130% but

were flagged with a “4” qualifier indicating that the concentration in the parent sample

was greater than 4 times the spike and could not be reliab ly calculated

. No MS/MSD

spike reco veries failed the EPA 200.7 Method control limits of 70

– 130%

, except those

already qualified with a “4” as mentioned above, and therefore no additional data

qualifiers were needed

. In addition, all RPDs of the MS/MSDs were within

TestAmerica’s ± 20% requirements

.

SERIAL DILUTION (SRD)

Serial dilutions were performed for each batch of total and dissolved samples. A ll serial

dilution percent differences were less than 10% as require d by Test America’s SOP

.

POST DIGESTION SPIKE

Both t otal and dissolved PDS sample s performed passed the method criteria of 85

– 115%

, with the exception of barium, calcium and z inc in the filtrate for sample 71891 FGD

Influent, Day 1 (280

- 7312

- 4 PDS)

.

D ETECTION LIMITS

The laboratory performed an MDL study in the synthetic FGD wastewater matrix, instead

of reagent water.

## 1 

# MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram

, ERG

TJ Finseth

, ERG

From: Donna Tedder, ERG

Laura Aviles

- Alvarez, ERG

Date: 9 / 1 /201 1

Subject: FGS Data R eview Narrative for Dissolved Hexavalent Chromium

– Episode

65 6 3

Frontier Global Sciences (FGS) generated analytical data for dissolved hexavalent

chromium for Sample Episode 6563

. FGS analyzed t he samples according to a m odified

EPA Method 2 18. 6 for dis solved hexavalent chromium by Liquid Chromatography

– Inductively Coupled Plasma Mass Spectrometry (LC

- ICP

- MS)

.

Table 1 summarizes the s amples FG S extracted and analyzed for dissolved hexavalent

chromium

.

Table 1. 

## EPA Episode 6563 Dissolved Hexavalent Chromium

– Sample Identification

EPA

Sample

# Sample

Matrix Sample Description Sampling

Date Analysis Date

71 8 9 1 Aqueous FGD Influent Day 1 9 / 13/ 10 10/11 /10

71 8 9 2 Aqueous FGD Influent Day 2 9 / 14 /10 10/11/10

71 8 9 3 Aqueous FGD Influent Day 3 9 / 15 /10 10/12/10

71894 Aqueous FGD Influent Day 4 9/16/10 10/12/10

71895 Aqueous FGD Effluent Day 1 9/14/10 10/12/10

71896 Aqueous FGD Effluent Day 2 9/15/10 10/12/10

71897 Aqueous FGD Effluent Day 3 9/16/10 10/12/10

71898 Aqueous FGD Effluent Day 4 9/17/10 10/12/10

71899 Aqueous FGD Effluent Dup Day 2 9/15/10 10/12/10

71900 Aqueous FGD Influent F ield B lank Day 1 9/13/10 10/11/10

71 90 1 Aqueous FGD Effluent F ield B lank Day 1 9 / 14 /10 10/11/10



## SUMMARY

The samples were prepared for dissolved hexavalent chromium analysis according to

FGS

- 129.01 Standard Operating Procedure ( SOP ) , a modified EPA Method 218. 6

.

## 2 Several s amples ( 718 9 1, 718 9 2, 718 9 3, 718 9 4, 718 95 , 718 9 6, 718 9 7, 718 9 8, and 718 9 9 )

were diluted prior to analysis due to the presence of high levels of nontarget chloride

interferences

.

T here were no issues requiring additional data qualifiers for the hexavalent chromium

data in this episode.

SAMPLE REC E IPT, HANDLING, AND STORAGE ISSUES

There were no s ample receipt issues in this data package

.

I NITIAL P RECISION AND ACCURACY/ R ECOVERY

The initial precision and recovery ( IPR ) performed by F GS had recoveries within the

method criteria.

O N

- GOING P RECISION AND ACCURACY/ R ECOVERY

The analytical method did not require the analysis of an on

- going precision and recovery

( OPR )

.

I NITIAL CAL IBRATION

FGS performed the initial calibrations on each analysis day. The i nitial calibration for

the LC

- ICP

- MS analysis consisted of a blank and eight calibration standards with a

correlation factor ≥ 0.995 as required by the method

.

A secondary source initial calibration verification (ICV) was within the ± 10 % of true

value required by the method

.

C ONTINUING C ALIBRATION V ERIFICATION

All CCVs me t method

- specified criteria

, ± 10% of true value with recoveries ranging

from 9 4.9 to 95.5 %.

BLANK

All of the prep aration blanks /laboratory reagent blanks (LRBs) and the continuing

calibration blanks (CCBs) met method

- specified requirements

.

OTHER CHECKS

The l aboratory c ontrol s ample /duplicate (LCS /LCSD ) or laboratory fortified

blank /duplicate (LFB /LFBD ) passed method criteria of ± 10% of true value with

recoveries of 101 % and 102%

. The method suggested that a second source quality

## 3 control sample (QCS) must be analyzed by the laboratory at least once a quarter. The

second source ICV meets this recommendation

.

D ETECTION LIMITS

The laboratory method detection limit (MDL) in the synthetic matrix was 0.392 ug/L.

Results below this MDL were reported as not detected.

DUPLICATES

There were no laboratory duplicates performed in this episode other than a duplicate of

the LCSD and a duplicate of the matrix spike ( MS ).

One field duplicate w as collected and analyzed. Sample 71899 was a du plicate of

effluent sample 71896

. These samples were nondetects ( NDs ) , indicating the analyte was

not detected at or above the method detection limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The M S and matrix spike duplicate ( MSD ) were performed using a secondary source

spike on sample s 71891 and 718 97

. All MS/MSD recoveries with within 75%

- 125%,

with RPD s of 2.63 % and 1.88 % , respectively

.

## 1 

# MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram

, ERG

TJ Finseth, ERG

From: Donna Tedder

, ERG

Date: 9 / 1 /201 1

Subject: TestAmerica Data Review Narrative for C lassicals Analyses

– Episode 6563

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry

analyses for Sample Episode 65 63

. All samples were tested for the following analytes:

• Ammonia by EPA M ethod 350.1,

• Biochemical Oxygen Demand

– 5 day (BOD 5 

## ) by SM 5210B,

• Chloride and S ulfate by EPA Method 300.0,

• Chemical Oxygen Demand (COD) by EPA Method 410.4,

• Cyanide by SM 4500 CN

- 

## E,

• Nitrate / Nitrite by EPA Method 353.2

,

• Phosphorus by EPA Method 365.1,

• Total D issolved S olids (TDS) by SM 2540C,

• Total K jeldah l N itrogen (TKN) by EPA Method 351 .2

, and

• Total S uspended S olids (TSS) by SM 2540D

.

The TSS concentration of the influent samples was greater than one percent, so as

requested, the laboratory separated the solid and liquid port ions of the samples and

analyzed both portions separately for the following analytes :

• Ammonia,

• Chloride,

• Cyanide,

• Nitrate/Nitrite,

• Phosphorus,

• Sulfate, and

• TKN.

Table 1 summarizes the nine field samples analyzed by TestAmerica and particularly

highlights how the laboratory split and analyzed the influent samples.

## 2 Table 1. EPA Episode 65 63 Classical Analytes

– Sample Identification

EPA

Sample # Sample Description Sampling

Date Sample

Matrix Portion of

Sample Analytes

71 891 FGD Influent, Day 1 9/13 /10 Water Entire

Fraction BOD 5 

## , COD, TDS, and

TSS

Water Filtrate Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Sulfate, Phosphorus, and

TKN

Solids Solids Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Sulfate, Phosphorus, and

TKN

71 892 FGD Influent, Day 2 9/14 /10 Water Entire

Fraction BOD 5 

## , COD, TDS, and

TSS

Water Filtrate Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Sulfate, Phosphorus, and

TKN

Solids Solids Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Sulfate, Phosphorus, and

TKN

71 893 FGD Influent, Day 3 9/15 /10 Water Entire

Fraction BOD 5 

## , COD, TDS, and

TSS

Water Filtrate Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Sulfate, Phosphorus, and

TKN

Solids Solids Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Sulfate, Phosphorus, and

TKN

71 894 FGD Influent, Day 4 9/16 /10 Water Entire

Fraction BOD 5 

## , COD, TDS, and

TSS

Water Filtrate Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Sulfate, Phosphorus, and

TKN

Solids Solids Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Sulfate, Phosphorus, and

TKN

71 895 FGD Effluent, Day 1 9/14 /10 Water Entire

Fraction All analytes

## 3 Table 1. EPA Episode 65 63 Classical Analytes

– Sample Identification

EPA

Sample # Sample Description Sampling

Date Sample

Matrix Portion of

Sample Analytes

71 896 FGD Effluent, Day 2 9/15/ 10 Water Entire

Fraction All analytes

71 897 FGD Effluent, Day 3 9/16 /10 Water Entire

Fraction All analytes

71 898 FGD Effluent, Day 4 9/17 /10 Water Entire

Fraction All analytes

71 899 FGD Effluent

- Duplicate 9/15 /10 Water Entire

Fraction All analytes

SUMMARY

Unless otherwise noted below, all samples were analyzed within the holding time

specified in 40 CFR 136 Table II

.

TestAmerica could not use a preserved sample volume for phase separation. Therefore,

they combined two of the unpreserved 25 0 mL metal sample volumes and phase

separated this volume. After phase separation, TestAmerica preserved the samples

accordingly. Because of this process, ammonia, nitrate/nitrite, TKN, phosphorus, and

cyanide influent samples were not preserved immediately fo llowing sample collection as

required by the method.

One field duplicate sample w as collected and analyzed for each analyte. The r elative

p ercent d ifference (RPD) between the sample and its duplicate was less than 20% unless

otherwise noted below.

If applicab le, the appropriate number of standards was used to create a calibration curve.

If sample results were above the highest standard used to create the curve, the sample was

diluted and reanalyzed. All sample results were between t he lowest and highes t standards

unless noted below. Additionally, all calibration blanks and calibration verification

samples met the criteria specified in the method.

If required by the method, the quality control sample (QCS), a secondary source standard

used to verify cal ibration, was always within the control limits specified by the method.

As described below, the analyte of interest was detected above the method detection limit

(MDL) in some laboratory reagent blanks (LRB). However, the analyte of interest was

never de tected above the reporting limit (RL) in the LRBs . If required by the method, all

laboratory fortified blanks (LFB) met the criteria specified in the method unless noted

below

.

## 4 If required by the method, a matrix spike (M S) sample was a nalyzed on sample 7 1 897

(FGD effluent ) for each analyte to check for matrix interferences

. For some analytes,

TestAmerica spiked more samples than required. All MS samples analyzed met the

criteria specified in the method unless described below.

DATA NOTES /ISSUES

Ammonia

As stated above, f iltrate and solid aliquots of samples 71 89 1

- 71 89 4 were not preserved

immediately after sample collection. Instead

, TestAmerica preserved the sample after

phase separation. Because these samples were not preserved immediately following

s ample collection, they were qualified as estimated values.

The data reviewer identified n o other issues. All QC samples met the criteria specified in

EPA Method 3 50.1.

BOD 5



## All glucose

- glutamic acid standards and water blanks we re analyzed appropriately and

met the criteria specified in SM 5210B

.

The RPD between sample 71897 and its laboratory duplicate was 23%, which is above

both the method and laboratory criteria of 20%. S ample 71897 was qualified as an

estimated value.

Three of the four batches had seed correction factors lower than 0.6 mg/L. The seed

correction factors were 0.5373 mg/L, 0.552 mg/L, 0.6147 mg/L, and 0.576 mg/L for

batches 31398, 31731, 31878, and 32012, respectively. TestAmerica did not flag these

sample s with an “s” to indicat e the seed correction blank (SCB) recovery was low

. A low

seed correction factor indicates that samples may be bi ased low. Thus, samples 71891,

71892, 71893, 71895, 71896, 71898, and 71899 were qualified as minimum values and

for co nsistency were also flagged with an “s

. ” Due to the short holding time, the samples

could not be reanalyzed.

Chloride and Sulfate

The analyzed results for the MS and matrix spike duplicate ( MSD ) samples associated

with sample 71897 for both chloride and sulfate were above the calibration range.

TestAmerica did not rerun the samples with a greater dilution factor because the MS and

MSD percent recoveries were within the method control criteria. If reported, the MS and

MSD results will be qualified as estim ated values.

## 5 COD

The percent recoveries for the MS and MSD analyse s for sample 71 897 ( F GD effluent )

were below the control limits of 90

- 110% required by EPA Method 410.4. The percent

recoveries for the MS and MSD analys e s were 8 9 % and 8 2 %

, respectively. The low

percent recovery could indicate that results for samples with the same matrix (FGD

effluent ) could be biased low. Sample 71 897 was flagged as a minimum value. The LFBs

associated with all samples met the method criteria.

The RPD between sample 71 896 and its field duplicate 71899 was 25.5 %. Even though

the RPD w as greater than 20%, the sample w as not qualified because there are no specific

control limits for field duplicates specified in EPA Method 410.4

.

Cyanide

As stated above, filtrate and solid aliquots of samples 71891

- 71894 were not preserved

immediately after sample collection. Instead

, TestAmerica preserved the sample after

performing the phase separation. The solid aliquot results of samples 71891

- 71894 were

already qualified by Te stAmerica with a “J” meaning the results were estimated values

because they were less than the RL, so no further qualification was necessary. Because

the filtrate aliquots of samples 71891

- 71894 were not preserved immediately after

sample collection, the y were qualified as estimated values.

Both solid and filtrate volumes of s ample s 71891

- 71894 were analyzed 10, 9, 8, and 7

days outside of the 14

- day holding time. All of these samples were qualified by the lab

with an “ H

, ” meaning the samples were anal yzed beyond the method

- specified hold time

. Because all of these samples were either qualified with a “J” meaning that the results

were estimated values because they were less than the RL or they were qualified as

estimated values because they were not pre served immediately after sample collection, no

further qualification was necessary.

The analyzed results for s ample 71896 and s olid s ample s 71891

- 71894 were lower than

the lowest calibration standard. Since all th e samples were already qualified by

TestAmerica with a “ J ” indicating that the results were estimated values because they

were less than the RL , the se samples did not need to be further qualified.

The RPD between sample 71896 and its field duplicate 71899 was 135%. The r esult for

71896 was below the RL and flagged with a “ J ” , but the result for 71899 was above the

RL. The low amount of cyanide present in these samples was likely the cause for the high

RPD. Even though the RPD was greater than 20%, the sample was not qualified because

there are no specific control limits for field duplicates specified in SM 4500 CN

- 

## E

.

Cyanide was detected in the laboratory reagent blank associated with sample 71895 at

0.00415 mg/L , which was greater than the MDL, but less than the RL. Since the blank

result was less than the RL, no samples were qualified.

## 6 Nitrate / Nitrite

As stated above, filtrate and solid aliquots of samples 71891

- 71894 were not preserved

immediately after sample collection. Instead

, TestAmerica preserved the sample after

phase separation. The solid aliquot results of samples 71891

- 71894 were already

qualified by TestAmerica with a “J” meaning the results were estimated values because

they were less than the RL, so no further qualification was necessary. Because the filtrate

aliquots of samples 71891

- 71894 were not preserved immediately after sample

collection, they were qualified as estimated values.

The percent recoveries for the MS analysis for sample 71 895 and the MS and MSD

analys e s for sample 71 897 (FGD effluent) were below the control limits of 90

- 110%

required by EPA Method 353.2 but within the laboratory control limits of 72

- 113%. T he

percent recover ies for the MS and MSD samples w ere 89% and 92% respectively for

sample 71895 and were both 84% for sample 71897. The MS and MSD results for

sample 71897 were above the calibration curve, but not reanalyzed using a higher

dilution factor. Because the MS and MSD results for sample 71897 at 12.7 mg/L were

more than ±10% greater than the highest calibration level (10.0 mg/L), the MS and MSD

recoveries were considered unreliable. Because it wa s not possible to tell whether the low

percent recovery was caused by matrix interferences or the MS and MSD results being

above the calibration curve, sample 71897 was not qualified. Sample 71895 was qualified

as a minimum value. The LFBs associated with all samples met the method criteria.

Phosphorus

As stated above, filtrate and solid aliquots of samples 71891

- 71894 were not preserved

immed iately after sample collection. Instead

, TestAmerica preserved the sample after

phase separation. The filtrate a liquot results of samples 71891 and 71894 were already

qualified by TestAmerica with a “J” meaning the results were estimated values because

the y were less than the RL, so no further qualification was necessary. Phosphorus was not

detected in the filtrate aliquots of samples 71892 and 71893, so these samples also did not

need to be qualified. Because the solid aliquots of samples 71891

- 71894 wer e not

preserved immediately after sample collection, they were qualified as estimated values.

Results for the filtrate volumes of s amples 71891 and 71894 were below the lowest

calibration standard. These samples were al ready qualified with a “ J ” meaning the results

were estimated values because they were less than the RL, so no further qualification was

necessary.

## 7 TDS

Samples 71891

- 71894 were analyzed 14, 13, 12, and 11 days, respectively , past the 7

- day hold time due to laboratory error

. Tes tAmerica only qualified these samples with an

“H”, so they were additionally qualified as estimated values.

All 14 samples analyzed for TDS did not achieve a constant weight after three drying

cycles. T he weight increased from the first weighing to the se cond weighing for samples

71895, 71896, 71898, and 71899. SM 2540C warns that samples that contain high levels

of calcium, magnesium, chloride, and sulfate may be hygroscopic, meaning they absorb

moisture from the air. FGD wastewater contains high concentr ations of all of these

species, so this was likely the cause for the inconsistent weight calculations. The samples

were not qualified, but results may be biased high.

The RPD between sample 71 897 and its laboratory duplicate w as less than 10 % as

required by SM 2540C

. T he RPD between sample 71 891 and its laboratory duplicate was

1 1 %. Because the RPD was greater than the method control limits, sample 71 891 was

qualified as an estimated value

.

TDS was detected at 8.0 mg/L, which is above the MDL (4.7 mg/L) , but below the RL

(10 mg/L) , in the LRB associated with sample 71895

. Because the blank result was less

than the RL, no samples needed to be qualified based on the LRB result

.

TKN

As stated above, filtrate and solid aliquots of samples 71891

- 71894 we re not preserved

immediately after sample collection. Instead

, TestAmerica preserved the sample after

phase separation. Because these samples were not preserved immediately after sample

collection, they were qualified as estimated values.

TKN was detected in the LRB associated with filtrate sample s 71891

- 71894 at 0.133

mg/L and also detected in the LRB associated with samples 71895

- 71897 and 71899 at

0.219 mg/L

. The blank result s w ere greater than the MDL (0.077 mg/L ), but less than the

RL (1.0 mg/L )

. Because the blank result s w ere less than the RL, no samples were

qualified based on the LRB result s

.

The LFB and LFBD percent recoveries associated with filtrate samples 71891

- 71894

were not within the method criteria of 90

- 110%, but were within the lab oratory criteria of

77

- 115%. The percent recoveries of the LFB and LFBD were 84% and 86%,

respectively. Filtrate samples 71891

- 71894 were already qualified as estimated values

because the samples were not preserved immediately after sample collection, so there

was no need to further qualify these samples as minimum values

.

The percent recoveries for the MS and MSD analys e s for sample 71 897 (FGD effluent )

did not meet the control limits (90

- 110%) specified in EPA Method 351.2 and did not

meet the laboratory criteria of 54

- 131%. The MS and MSD percent recoveries were

## 8 137% and 175%. TestAmerica flagged the MS/MSD samples with a “ 4 ” because the

sample result was more than 4 times the spike amount indicating the control limits are not

reliable. Thus, s ample 71897 was not additionally qualified because of the high MS/MSD

percent recoveries. The LFB associated with sample 71897 met the method criteria.

TSS

The laboratory duplicate RPDs for samples 71 891 , 71 893 , and 71 895 were less than 10%

as required by SM 2540D. However, the RPD for sample 71 897 and its laboratory

duplicate w as 1 2%

. Because this RPD w as above the method criteria, sample 71897 was

qualified as an estima ted value

.

The RPD between sample 71896 and its field duplicate 71899 was 138%. Even though

the RPD was greater than 20%, the sample was not qualified because there are no specific

control limits for field duplicates specified in SM 2540D.

Constant weight was not achieved after three drying cycles for sample 71899. SM 2540D

warns tha t samples that contain high levels of calcium, magnesium, chloride, and sulfate

may be hygroscopic, meaning they absorb moisture from the air. FGD wastewater

contains high concentrations of all of these species, so this was likely the cause for the

inconsi stent weight calculations. The sample was not qualified, but results may be biased

high.

## 9 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detected

71891

(filtrate) Ammonia Estimate Value Sample not preserved

immediately following

collection. 13 mg/L

71892

(filtrate) Ammonia Estimate Value Sample not preserved

immediately following

collection. 14 mg/L

71893

(filtrate) Ammonia Estimate Value Sample not preserved

immediately following

collection. 13 mg/L

71894

(filtrate) Ammonia Estimate Value Sample not preserved

immediately following

collection. 12 mg/L

71891

(solids) Ammonia Estimate Value Sample not preserved

immediately following

collection. 34 mg/Kg

71892

(solids) Ammonia Estimate Value Sample not preserved

immediately following

collection. 29 mg/Kg

71893

(solids) Ammonia Estimate Value Sample not preserved

immediately following

collection. 32 mg/Kg

71894

(solids) Ammonia Estimate Value Sample not preserved

immediately following

collection. 32 mg/Kg

71891 BOD Minimum Value,

s SCB Recovery Low 10 mg/L

71892 BOD Minimum Value,

s SCB Recovery Low 9.5 mg/L

71893 BOD Minimum Value,

s SCB Recovery Low 13 mg/L

71895 BOD Minimum Value,

s SCB Recovery Low 8.5 mg/L

71896 BOD Minimum Value,

s SCB Recovery Low 7.1 mg/L

71897 BOD Estimated Value Lab duplicate RPD >

method

- specified

criteria 6.8 mg/L

71898 BOD Minimum Value,

s SCB Recovery Low 3.5 mg/L

71899 BOD Minimum Value,

s SCB Recovery Low 6.9 mg/L

## 10 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detected

71897 COD Minimum Value MS % recovery <

method

- specified

criteria 380 mg/L

71891

(filtrate) Cyanide H, Estimated

Value Sample not preserved

immediately following

collection. Analyzed 10

days past hold time 0.36 mg/L

71892

(filtrate) Cyanide H, Estimated

Value Sample not preserved

immediately following

collection. Analyzed 9

days past hold time 0.20 mg/L

71893

(filtrate) Cyanide H, Estimated

Value Sample not preserved

immediately following

collection. Analyzed 8

days past hold time 0.29 mg/L

71894

(filtrate) Cyanide H, Estimated

Value Sample not preserved

immediately following

collection. Analyzed 7

days past hold time 0.31 mg/L

71891

(filtrate) Nitrate/Nitrite Estimated Value Sample not preserved

immediately following

collection. 12 mg/L

71892

(filtrate) Nitrate/Nitrite Estimated Value Sample not preserved

immediately following

collection. 14 mg/L

71893

(filtrate) Nitrate/Nitrite Estimated Value Sample not preserved

immediately following

collection. 14 mg/L

71894

(filtrate) Nitrate/Nitrite Estimated Value Sample not preserved

immediately following

collection. 12 mg/L

71895 Nitrate/Nitrite Minimum Value MS % recovery <

method

- specified

criteria 9.7 mg/L

71891

(solids) Phosphorus Estimated Value Sample not preserved

immediately following

collection. 33 mg/Kg

71892

(solids) Phosphorus Estimated Value Sample not preserved

immediately following

collection. 380 mg/Kg

## 11 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detected

71893

(solids) Phosphorus Estimated Value Sample not preserved

immediately following

collection. 34 mg/Kg

71894

(solids) Phosphorus Estimated Value Sample not preserved

immediately following

collection. 6.5 mg/Kg

71891 TDS H, Estimated

Value Analyzed 14 days past

hold time, Lab duplicate

RPD > method

specified criteria 35,000

mg/L

71892 TDS H, Estimated

Value Analyzed 13 days past

hold time 35,000

mg/L

71893 TDS H, Estimated

Value Analyzed 12 days past

hold time 37,000

mg/L

71894 TDS H, Estimated

Value Analyzed 11 days past

hold time 35,000

mg/L

71897 TSS Estimated Value Lab duplicate RPD >

method

- specified

criteria 7.2 mg/L

71891

(filtrate) TKN Estimated Value Sample not preserved

immediately following

collection. LFB %

recovery < method

specified criteria 29 mg/L

71892

(filtrate) TKN Estimated Value Sample not preserved

immediately following

collection. LFB %

recovery < method

specified criteria 32 mg/L

71893

(filtrate) TKN Estimated Value Sample not preserved

immediately following

collection. LFB %

recovery < method

specified criteria 31 mg/L

71894

(filtrate) TKN Estimated Value Sample not preserved

immediately following

collection. LFB %

recovery < method

specified criteria 26 mg/L

71891

(solids) TKN Estimated Value Sample not preserved

immediately following

collection. 900 mg/Kg

## 12 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detected

7189 2

(solids) TKN Estimated Value Sample not preserved

immediately following

collection. 840 mg/Kg

7189 3

(solids) TKN Estimated Value Sample not preserved

immediately following

collection. 710 mg/Kg

7189 4

(solids) TKN Estimated Value Sample not preserved

immediately following

collection. 880 mg/Kg

## Appendix C

PICTURES FROM THE SAMPLING EPISODE

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

## C-2

Figure C-2. Sample Tap at the Influent to the FGD Wastewate r Treatment System

## C-3 Figure C-3. Sample Collection Set Up at the Pump-Off Stati on

## C-4

Figure C-4. Composite Sample Collection Set Up at the Efflu ent from the FGD Wastewater

Treatment System

## Appendix D

FGD ICP/MS SOP: I NDUCTIVELY 

## C OUPLED 

## P LASMA 

## M ASS 

## S PECTROMETRY FOR 

## T RACE



## E LEMENT 

## A NALYSIS IN 

## F LUE 

## G AS 

## D ESULFURIZATION 

## W ASTEWATERS

## D-1 

# FGD ICP/MS SOP: Inductively Co upled Plasma Mass Spectrometry for

Trace Element Analysis in Flue Gas Desulfurization Wastewaters

1.0 Scope and Application

1.1 This document describes procedures used to measure elements in Flue Gas

Desulfurization, FGD, wastewaters. Inductively coupled plasma-mass

spectrometry (ICP/MS), as described in EPA Methods 200.8 and 1638, was used

with a collision cell to mitigate the effects of interferences in the samples. These

procedures are intended for use by analysts experienced with applying ICP/MS

to complex wastewater samples.

1.2 These procedures are applicable to the analysis of acid digested FGD

wastewater, and have been evaluated for the analysis of 13 elements of interest.

These are Al, As, Cd, Cr, Cu, Pb, Mn, Ni, Se, Ag, Tl, V and Zn. Additional

elements may be included provided that the performance criteria presented in

Sections 9 and 12 are met.

1.3 Flue Gas Desulfurization wastewaters frequently have very high levels of

calcium, sodium, magnesium, manganese, chloride and sulfate (up to thousands

of ppm). The use of instrument configurations and/or accessories designed to

accommodate samples with high dissolved solids levels is highly recommended.

2.0 Summary

2.1 Aqueous samples, digestates, or leachates are nebulized into a spray chamber

where a stream of argon carries the sample aerosol through the quartz torch and

injects it into an RF plasma. There the sample is decomposed and desolvated.

2.2 The ions produced are entrained in the plasma gas and by means of a watercooled, differentially pumped interface, introduced into a high-vacuum chamber

that houses a quadrupole mass spectrometer capable of providing a resolution

better than or equal to 0.9 amu peak width at 10% of the peak height. The ions

are separated according to their mass-to-charge ratio and measured with a

detector, such as an electron multiplier.

2.3 A collision/reaction cell utilizing He and (optionally) H 2 

### gases is used to remove

molecular interferences.

2.4 Interferences not eliminated by the collision/reaction cell must be assessed and

valid corrections applied, or the data flagged to indicate problems. Interference

correction must include compensation for interferences not removed by the

collision / reaction cell. Recommended elemental equations are listed in

Attachment 1. Use of the internal standard technique is required to compensate

for suppressions and enhancements caused by sample matrices.

3.0 Definitions

3.1 Batch – A group of samples which behave similarly with respect to the sampling

or the testing procedures being employed and which are processed as a unit.

For QC purposes, if the number of samples in a group is greater than 20, then

each group of 20 samples or less will all be handled as a separate batch

## D-2 3.2 Dissolved Metals - Those elements which pass through a 0.45-  m membrane

filter (sample is acidified after filtration).

3.3 Suspended Metals - Those elements which are retained by a 0.45-  m

membrane filter.

3.4 Total Recoverable Metals - The concentration determined on an unfiltered

sample following treatment with hot, diluted mineral acids, as described in this

procedure

3.5 Instrument Detection Limit (IDL) - See Section 12.2

3.6 Sensitivity - The slope of the analytical curve (i.e., the functional relationship

between raw instrument signal and the concentration).

3.7 Tuning Solution - This is a multi-element solution containing analytes which are

representative of the entire mass range capable of being scanned by the

instrument. It is used to optimize the sensitivity of the instrument and to verify

the mass resolution meets method criteria.

3.8 Initial Calibration Verification / Quality Control Standard (ICV/QCS) - A multielement standard of known concentrations prepared to verify instrument

calibration. This solution must be an independent standard prepared near the

mid-point of the calibration curve, and at a concentration other than that used for

instrument calibration.

3.9 Continuing Calibration Verification (CCV) - A multi-element standard of known

concentrations prepared to monitor and verify the instrument daily continuing

performance.

3.10 Laboratory Control Sample / Laboratory Fortified Blank (LCS/LFB) - A multielement standard of known concentrations that is carried through the entire

sample preparation and analysis procedure. This solution is used to verify

method performance in an ideal sample matrix.

3.11 Reagent Blank - High purity (> 18 megohm-cm) water containing the same acid

matrix as the calibration standards that is carried through the entire digestion

process. The reagent blank is used to determine the concentrations of trace

metals in the reagents used to prepare and analyze the samples.

3.12 Calibration Blank - High purity (> 18 megohm- cm) water acidified with the

same acid concentrations present in the standards and samples. Also referred to

as the Initial Calibration Blank (ICB) and Continuing Calibration Blank (CCB).

3.13 Method Detection Limit (MDL) – Refers to the instructions in Appendix B to 40

CFR Part 136. Also see Section 12.1 of this document. The MDL is determined

from analysis of a sample in a given matrix containing the analyte.

3.14 Individual FGD Interference Check solutions – Single element solutions at

concentrations similar to those found in flue gas desulfurization wastewaters.

3.15 Synthetic FGD wastewater – A mixed solution of elements at typical

concentrations found in flue gas desulfurization wastewaters.

4.0 Interferences

4.1 Isobaric Interferences

Isobaric interferences in the ICP/MS are caused by isotopes of different elements

forming ions with the same nominal mass-to-charge ratio (m/z). The

## D-3 recommended ions used for the elements in this procedure do not have

elemental isobaric interferences, except for a very small interference from

krypton on 78 

### Se, which can be avoided by using argon free of krypton.

4.2 Isobaric Molecular

Isobaric molecular interferences are caused by ions consisting of more than one

atom. These molecular interferences are minimized by use of the collision cell

utilizing He and/or H 2 

### gases. Common examples are potential interferences from

40 

### Ar 35 

### Cl or 40 

### Ca 35 

### Cl on 75 

### As, or 35 

### Cl 16 

### O on 51 

### V, or 40 

### Ar 12 

### C on 52 

### Cr. Collision cell

interference removal works both by causing the interfering molecular ion to

dissociate and by reducing the kinetic energy of the ion. The latter is termed

Kinetic Energy Discrimination (KED), and is the primary mechanism for

interference removal. Polyatomic ions are larger than elemental ions and so

collide with the helium atoms in the collision cell more frequently than the smaller

elemental ions. Each collision reduces the energy of the ion, so the molecular

ions lose energy more quickly. At the end of the collision cell a positive voltage

plate prevents passage of the now low energy molecular ions. Thus, the

interference is eliminated because the molecular ions do not reach the detector.

4.3 Doubly Charged Ion Interferences

Doubly charged elemental ions are possible in cases where the second

ionization potential of the element is significantly below the fist ionization

potential for argon (15.7eV). If a doubly charged ion is formed, it will cause a

response at half of its elemental mass, potentially causing an interference.

Fortunately, most elements have high enough second ionization potentials that

formation of doubly charged ions is not an issue. For the target analytes in this

procedure, a significant potential for interference is from 150 

### Nd and 150 

### Dy

(potential interference on 75 

### As and from 156 

### Gd (potential interference on 78 

### Se). To

check for these potential interferences, monitor the response for mass 150 and

156. If the cps for these masses is > 5 times the cps for the quantitation limit for

arsenic (in the case of mass 150) or selenium (in the case of mass 156) an

interference is possible. In this case analyze a 100ppb standard of Nd and Dy (if

mass 150 is observed) or Gd (if mass 156 is observed) and measure the

response at 150 and 75 (or 156 and 78). This ratio can then be used to create an

interference correction equation. For example, if the response for a 100ppb Gd

standard at mass 156 is 10,000 cps, and the observed response for the same

standard at mass 78 is 1,000 counts, then the equation for 78 

### Se would be:

78 

### Se = 78 

### Se – ( 156 

### Gd/10)

4.4 Physical Interferences

 Physical interferences are associated with the transport and nebulization

process. Internal standards are used to compensate for these types of

interferences.

 Internal standards should be added at a level to give approximately

50,000 - 800,000 counts of raw signal intensity. The mass of the internal

standard should ideally be within 50 amu of the mass of the measured

analyte. Consideration should also be given to matching internal

standards to analytes with similar ionization potentials.

 Matrix effects are monitored by comparing the internal standard intensity

in the sample to the internal standard intensity of the calibration blank.

The internal standards must be between 60% and 125% of the calibration

## D-4 blank. If they are outside this window the sample is diluted by a factor of

2 (1:1) and is reanalyzed.

 Memory effects are dependent on the relative concentration differences

between samples and/or standards which are analyzed sequentially. The

rinse period between samples must be long enough to eliminate

significant memory interference (see section 10.3.6).

5.0 Safety

This procedure may involve hazardous material, operations and equipment. This

procedure does not purport to address all of the safety problems associated with its use.

It is the responsibility of the user of the method to follow appropriate safety, waste

disposal and health practices under the assumption that all samples and reagents are

potentially hazardous. Safety glasses, gloves, lab coats and closed-toe, nonabsorbent

shoes are required.

5.1 Specific Safety Concerns or Requirements

5.1.1 Eye protection that satisfies ANSI Z87.1, laboratory coat, and

nonpowdered nitrile or latex gloves must be worn while handling

samples, standards, solvents, and reagents. Disposable gloves that

have been contaminated must be removed and discarded; nondisposable gloves must be cleaned immediately.

5.1.2 The ICP plasma emits strong UV light and is harmful to vision. All

analysts must avoid looking directly at the plasma. The RF Generator

produces strong radio frequency waves, most of which are unshielded.

People with pacemakers should not go near the instrument while in

operation.

5.2 Primary Materials Used

The following is a list of the materials used in this method, which have a serious

or significant hazard rating. Note: This list does not include all materials

used in the method. The table contains a summary of the primary hazards

listed in the MSDS for each of the materials listed in the table.

## D-5 Material (1) Hazards Exposure

Limit (2) Signs and Symptoms of Exposure

Nitric Acid Corrosive

Oxidizer

Poison 2 ppmTWA

4 ppmSTEL Nitric acid is extremely hazardou s; it is corrosive, reactive,

an oxidizer, and a poison. I nhalation of vapors can cause

breathing difficulties and lead to pneumonia and pulmonary

edema, which may be fatal. Other symptoms may include

coughing, choking, and irritation of the nose, throat, and

respiratory tract. Can cause redness, pain, and severe skin

burns. Concentrated solutions cause deep ulcers and stain

skin a yellow or yellow-brown color. Vapors are irritating and

may cause damage to the eyes. Contact may cause severe

burns and permanent eye damage.

Material (1)

Hazards Exposure

Limit (2) Signs and Symptoms of Exposure

Hydrochloric

Acid Corrosive

Poison 5 ppmCeiling Inhalation of vapors can cause coughing, choking,

inflammation of the nose, thr oat, and upper respiratory tract,

and in severe cases, pulmonary edema, circulatory failure,

and death. Can cause redness, pain, and severe skin burns.

Vapors are irritating and may cause damage to the eyes.

Contact may cause severe burns and permanent eye

damage.

1 – Always add acid to water to prevent violent reactions.

2 – Exposure limit refers to the OSHA regulatory exposure limit.



### 6.0 Equipment and Supplies

6.1 Instrumentation

 

### Inductively Coupled Plasma Mass Spectrometer (ICP/MS) capable of providing

resolution, less than or equal to 0.9 amu at 10% peak height from 6-253 amu

and 1.0 amu at 5% peak height from 6-253 amu with a data system that allows

corrections for isobaric interferences and the application of the internal standard

technique. The ICP/MS must be equipped with a collisio n cell for the removal of

molecular interferences. This procedure was developed using an Agilent 7500

or 7700 instrument equipped with a high matrix interface. The interface extends

the amounts of total dissolved solids that may be measured into the percent

concentration range. Any collision cell instrumentation that meets the

specifications in this procedure may be used.

 

### A discrete sample introduction system enables the use of only the exact amount

of sample volume required for data acquisition.

 

### Accessories and configuration that are designed to accommodate samples with

high levels of dissolved solids should be used.

 

### This sampling system results in less matrix being deposited in the system

during analysis and minimizes the rinse times normally needed for difficult

matrices.

 

### Autosampler with autosampler tubes.

 

### Appropriate water cooling device.

 

### Block digester with tubes.

## D-6 6.2 Supplies

 

### Argon gas: High purity grade (99.99%).

 

### Helium gas: High purity grade (99.99%).

 

### Hydrogen gas: High purity grade (99.99%).

 

### Calibrated automatic pipettes or Class A glass volumetric pipettes.

7.0 Reagents and Standards

7.1 Storage and Shelf-Life

7.1.1 All standards must be stored in glass, FEP fluorocarbon or previously

unused polyethylene or polypropylene bottles. Standards stored at

concentrations as received from the vendor and mid-level dilutions must

be replaced prior to the expiration date assigned by the vendor. If no

expiration date is provided, the stocks and mid-level standards may be

stored for up to one year. They must be replaced sooner if verification

from an independent source indicates a problem (See section 10.3.5 for

initial calibration verification acceptance criteria).

7.1.2 Working standards, i.e., all standards at concentrations ready to

analyze on the ICP/MS (all except tuning mixes, ICSA and ICSAB

mixes, which are received at ready-to-use concentrations), are prepared

fresh daily.

7.2 Standards

7.2.1 Tuning Solution, 10 ppb

The tuning solution stock is purchased as a custom multi-element mix.

The concentrations of the constituents are shown in Attachment 5.

Prepare the Tuning Solution as detailed below.

 Obtain a clean 100 mL volumetric flask.

 Place 50 mL of reagent water and 2 mL of conc. HNO 3 

### and 0.5

mL of conc. HCl in the flask.

 Swirl to mix.

 Pipet 0.1mL of the Tuning Solution Stock into the flask.

 Dilute to volume with reagent water. Stopper and mix.

7.2.2 PA Tuning Solution

The dual detector solution may be commercially purchased as a custom

multi-element mix.

Prepare the PA Tuning Solution as detailed below.

 Add approximately 50 mL of the 2% HNO 3 

### / 0.5% HCl to a 100

mL volumetric flask.

 Prepare at a concentration recommended by the instrument

manufacturer.

7.2.3 Calibration Standards

Stock calibration standards are purchased as custom multi-element

mixes or as single element solutions. Each day of analysis, the

standards are diluted to working levels using 2% nitric acid and 0.5%

## D-7 HCl acid matrix. Suggested concentrations are given in Attachment 8,

but the laboratory may adjust calibration standard concentrations as

appropriate for the instrument and samples. At a minimum, a 3 point

curve must be used.

7.2.4 Individual FGD Interference check solutions.

7.2.4.1 All individual FGD interference check solutions should be

made up in the same acid matrix as the calibration standards.

7.2.4.2 Chloride, 10,000 mg/L

7.2.4.3 Calcium, 5,000 mg/L

7.2.4.4 Sulfate, 4,000 mg/L

7.2.4.5 Magnesium, 3,000 mg/L

7.2.4.6 Sodium, 2,000 mg/L

7.2.4.7 Boron, 500 mg/L

7.2.4.8 Iron, 500 mg/L

7.2.4.9 Nitrate, 250 mg/L

7.2.4.10 Manganese, 200 mg/L

7.2.4.11 Bromide, 100 mg/L

7.2.4.12 Fluoride, 100 mg/L

7.2.4.13 Selenium, 20 mg/L

7.2.4.14 Vanadium, 10 mg/L

7.2.4.15 Zinc, 2 mg/L

7.2.4.16 Chromium, 1 mg/L

7.2.4.17 Copper, 1 mg/L

7.2.5 Mixed Interference Check Solution (Synthetic FGD Wastewater)

7.2.5.1 Chloride, 5,000 mg/L

7.2.5.2 Calcium, 2,000 mg/L

7.2.5.3 Magnesium, 1,000 mg/L

7.2.5.4 Sulfate, 2,000 mg/L

7.2.5.5 Sodium, 1,000 mg/L

7.2.5.6 Butanol, 2000ppm

7.2.6 Initial Calibration Verification (ICV) Standard

The ICV stock is from a source different than the source for the

calibration standards. Each day of analysis, the ICV standard is

prepared in 2% HNO 3 

### and 0.5 % HCl acid to the concentrations shown

in Attachment 8.

## D-8 7.2.7 Continuing Calibration Verification (CCV) Standard

The CCV is prepared from the same source as the calibration

standards. The CCV standards are prepared fresh each day of analysis

in 2% HNO 3 

### /0.5% HCl. The concentrations are shown in Attachment 8.

Prepare the Working CCV as detailed below.

 Dilute by 2X a known volume of the Working Calibration

Standard in the 2% HNO 3 

### / 0.5% HCl acid matrix.

7.2.8 Spiking Stock Solution

The spike stock solution is prepared from the same stocks as the

calibration standards using the 2% HNO 3 

### / 0.5% HCl acid matrix. Spike

concentrations are listed in Attachment 8.

7.3 Reagents

7.3.1 Reagent Water - ASTM Type I or equivalent for the elements of

interest, generated using an ion-exchange water polishing system

capable of achieving 18.0 megohm-cm.

7.3.2 Blank Matrix 2% HNO 3 

### and 0.5% HCl.

8.0 Sample Collection, Preservation, Shipment and Storage

Sample container, preservation techniques and holding times may vary and are

dependent on sample matrix, method of choice, regulatory compliance, and/or specific

contract or client requests. Listed below are the holding times and the references that

include preservation requirements.



## Matrix Sample

Containe

r Min.

Sample

Size Preservation Holding Time Reference

Waters 

## HDPE 50 mLs HNO 3 

## , pH < 2 180 Days 40 CFR Part

136.3

Soils Glass or

HDPE 4 oz Cool 4 + 2 o 

## C 180 Days N/A

9.0 Quality Control

9.1 Quality control requirements are also summarized in Attachment 7.

9.2 Ongoing data quality checks are compared with established performance criteria

to determine if the results of analyses meet the performance characteristics of

the method. Any QC result that fails to meet control criteria must be

documented.

9.3 Individual interference check solutions

The individual interference check solutions listed in section 7.2.6 are analyzed

prior to initiating sample analysis, and at least once per quarter while FGD

## D-9 wastewaters are being analyzed, and after any major changes to instrument

operating conditions. Concentrations of target elements observed should be less

than their reporting limits. In some cases it may not be possible to obtain

interference check solutions that are completely free of contamination. In this

case, results up to 5X the reporting limit are acceptable if it is possible to

demonstrate that the isotopic ratios correspond to natural abundances. For

example, the natural abundances of zinc isotopes are Zn 64 

### 48.6%; Zn 66 

### 27.9%;

Zn 67 

### 4.1%; Zn 68 

### 18.8%; Zn 70 

### 0.6%. The measured ratios are not expected to be

exact, especially for low abundance isotopes, and some isotope may be masked

by other elements in the solution, (for example Zn 70 

### in the above example will be

masked by Ge 70 

### ) but it must be possible to explain the observed ratios.

Because Arsenic, Manganese and Aluminum are monoisotopic, this

demonstration is not possible and the level of interference observed must be less

than the reporting limit

.

9.4 Synthetic FGD interference check solution

The synthetic FGD matrix solution listed in section 7.2.7 is analyzed prior to

initiating sample analysis, and at least once per day (immediately after

calibration) while FGD wastewaters are being analyzed, and after any major

changes to instrument operating conditions. Internal standard recovery must

meet method criteria (Section 9.9) and concentrations of target elements

observed should be less than their reporting limits. In some cases it may not be

possible to obtain interference check solutions that are completely free of

contamination. In this case, results up to 5X the reporting limit are acceptable if it

is possible to demonstrate that the isotopic ratios correspond to natural

abundances. For example, the natural abundances of zinc isotopes are Zn 64



### 48.6%; Zn 66 

### 27.9%; Zn 67 

### 4.1%; Zn 68 

### 18.8%; Zn 70 

### 0.6%. The measured ratios are

not expected to be exact, and some isotopes may be masked by other elements

in the solution, (for example Zn 70 

### in the above example will be masked by Ge 70 

### )

but it must be possible to explain the observed ratios. Because Arsenic,

Manganese and Aluminum are monoisotopic, this demonstration is not possible,

and the level of interference observed must be less than the reporting limit.

If the Synthetic FGD solution has to be diluted in order to analyze it

effectively on the ICP/MS, then all samples and QC (including the MDL

replicates) must be diluted by at least the same factor.

9.4.1 Laboratory fortified Synthetic FGD solution

The synthetic FGD solution is spiked with 40ppb of each of the target

elements (400ppb for zinc and 4000ppb for aluminum) and analyzed

once per day, immediately after the synthetic FGD check in section 9.4.

All target elements must be recovered within 70-130% of the true value.

If the Laboratory Fortified Synthetic FGD solution has to be diluted

in order to analyze it effectively on the ICP/MS, then all samples

and QC (including the MDL replicates) must be diluted by at least

the same factor.

9.5 Linear range determination

The linear range for each element is determined prior to initiating sample

analysis and at least once per year thereafter. The linear range must also be

determined subsequent to changes that will have a major effect on instrument

sensitivity, such as changing the detector. The linear range is established using a

single element standard at the desired linear range. The result of the analysis

must be within 10% of the true value.

## D-10 9.6 Method Blank / Laboratory Reagent Blank (MB/LRB)

The method blank consists of reagent water that has been processed in

the same manner as the samples. One method blank must be processed with

each preparation batch.

Acceptance Criteria: Method blank results are acceptable if the concentration

for each analyte of interest is less than the reporting limit.

Corrective Action: If the method blank does not meet the acceptance

criteria, the source of contamination should be

investigated to determine if the problem can be

minimized or eliminated. Samples associated with the

contaminated blank shall be reprocessed for analysis, or

under the following circumstances, may be reported as

qualified (qualifier flags or narrative comments must be

included on report):

 The same analyte was not detected in the

associated samples;

 The method blank concentration is less than 1/10 of

the measured concentration of any sample in the

batch;

 The method blank concentration is less than 1/10

the specified regulatory limit; or

 The analyte is a common laboratory contaminant

(copper, iron, lead, calcium, magnesium,

potassium, sodium, or zinc) less than 2 times the

RL. Note that some programs do not recognize

common lab contaminants.

If the above criteria are not met and reanalysis is not

possible, then the sample data must be qualified. This

anomaly must be addressed in the project narrative

and the client must be notified.

9.7 Laboratory Control Sample / Laboratory Fortified Blank (LCS/LFB)

The LCS consists of reagent water that is spiked with the analytes of

interest as summarized in Attachment 8. One LCS must be processed (digestion

and analysis) for each preparation batch.

Acceptance Criteria: LCS control limits are based on three standard

deviations of past laboratory results. These limits are not

to exceed 85-115% recovery. The control limits are

maintained in a LIMS or other appropriate system.

Corrective Action: If the LCS % recovery falls outside of the control limits for

any analyte, that analyte is judged to be out of control.

All associated samples must be reprocessed for

analysis. One possible exception is a recovery for a

given element above the upper control limit with no

detection for the same element in the samples.

9.8 Matrix Spike / Matrix Spike Duplicate / Laboratory Fortified Sample Matrix /

Laboratory Fortified Matrix Duplicate (MS/MSD/LFSM/LFMD)

MS is prepared by taking a second aliquot of a selected sample and spiking it

with the analytes of interest as summarized in Attachment 8. An MSD is

## D-11 prepared by taking a third aliquot of a selected sample and spiking it with the

analytes of interest as summarized in Attachment 8. The MS and MSD are

processed in the same manner as the samples. One MS/MSD pair must be

processed every 10 samples.

Acceptance Criteria: Control limits are based on three standard deviations of

past laboratory results. These limits are not to exceed

70-130% recovery, and 20% relative percent difference

(RPD). The control limits are maintained in the LIMS

system. If the sample concentration for a specific analyte

in the sample selected for spiking is greater than the

concentration added by the spike, then recovery

accuracy will be reduced. In this case a dilution test may

be performed. A 1:5 dilution should agree within 20% of

the original determination. If not, a physical or chemical

interference is suspected, and must be discussed in the

sample narrative.

Corrective Action: If MS/MSD results and any applicable dilution tests do

not meet the acceptance criteria and all other quality

control criteria have been met, then a matrix interference

is suspected. Failed matrix spikes are flagged, and are

discussed in the final report case narrative.

9.9 Internal Standards Evaluation for Samples

The internal standards in samples must be between 60 and 125% of the intensity

in the calibration blank. If the sample intensities fall outside this range, the

calibration blank is reanalyzed to confirm the instrument has not drifted out of

control. If the criteria is met, the sample is diluted by a factor of 2 (1:1) and

reanalyzed. IS limits and corrective actions for standards and blanks are

described in Section 10.

10.0 Procedure

10.1 One-time procedural variations are allowed only if deemed necessary in the

professional judgment of the supervisor to accommodate variation in sample

matrix, radioactivity, chemistry, sample size, or other parameters. Any variation

in procedure shall be completely documented. Any unauthorized deviations from

this procedure must also be documented as a nonconformance, with a cause

and corrective action described.

10.2 Sample Preparation

10.2.1 EPA Method 1638 was used as the reference for the digestion of the

samples in which Section 12.2.8 describes Closed Vessel digestion.

10.2.2 Transfer a 50mL (+/- 0.5mL) aliquot from a well mixed acid preserved

sample to a 50mL digestion tube.

10.2.3 Add 0.5mL of concentrated nitric acid and 0.25 mL hydrochloric acid.

10.2.4 Spike the LCS and MS/MSD samples per spiking protocols.

## D-12 10.2.5 The total volume of the solution in the tube is now greater than 50 mLs.

The final volume will be 50 ml following the procedure to eliminate the

discrepancy in the initial and final volumes.

10.2.6 Tightly cap each digestion vessel.

10.2.7 Place the digestion tube into a block digester adjusted to achieve a

temperature of approximately 85 o 

### C.

10.2.8 Heat for 2 hours after 85 o 

### C is obtained.

10.2.9 Remove from the block and allow to cool.

10.3 Calibration

10.3.1 Instrument Start Up

Set up the instrument according to manufacturer’s operating instructions.

Allow the instrument to become thermally stable for at least 30 minutes

before tuning.

10.3.2 Instrument Tuning / Mass Calibration

Tune the instrument with a solution containing elements representing all

of the mass regions of interest. The relative standard deviations must be

less than 5% for a minimum of 4 integrations of the solution. Mass

calibration and resolution checks using the tuning solution must be

completed at the beginning of every day.

Mass Calibration Check – The mass calibration results must be within

0.1 amu from the true value. If this criterion

is not met, the mass calibration must be

adjusted before running samples.

Mass Resolution Check - The resolution must be verified to be less

than 0.9 amu full width at 10% peak height.

10.3.3 Mass 75 interference check

The concentration determined for arsenic (mass 75) must be less than

0.25 x the reporting limit when the blank matrix (2% nitric acid / 0.5%

hydrochloric acid) is infused (using the collision gas mode used for

arsenic).

10.3.4 Initial Calibration

The ICP/MS is calibrated each day of operation using a blank and at

least 3 standards (see Section 7.2.3). Report the average of at least

three integrations.

The validity of the calibration is determined by the subsequent

calibration verifications, which are performed at concentrations as

described in the next sections.

10.3.5 Second-Source Initial Calibration Verification (ICV)

A 40  g/L / 4,000 ug/L ICV standard (see Section 7.2.8) is analyzed

immediately after the initial calibration. This is a standard obtained from

a different vendor than the standard used for calibration. This analysis

also satisfies the Method 200.8 requirement for a Quality Check

Standard (QCS).

Acceptance Criteria: The ICV recovery must be within 90-110%.

Additionally, the internal standard recoveries for

## D-13 200.8 must fall between 60 and 125% of true

values. The ICV can be reanalyzed, but must

be successful twice in succession or corrective

action must be taken.

Corrective Action: If the ICV results are outside of the acceptance

limits, investigate the accuracy of the

standards, correct as necessary, and

recalibrate.

10.3.6 Calibration Blank

Checks for the memory effects described at Section 4.4 may be

accomplished by analysis of an initial calibration blank (ICB) after the

ICV. Continuing calibration blanks (CCBs) are analyzed after each

continuing calibration verification.

Acceptance Criteria: Results for the calibration blanks must be less

than the RL.

Corrective Action: If the calibration blank exceeds acceptance

limits, then the possibility of instrument

contamination should be examined, particularly

the possibility of carry-over from high level

samples. The blank can be reanalyzed, and if

successful, analysis can continue. However,

samples tested after high-level samples should

be retested. If the reanalysis is not successful,

then the analysis should be terminated. After

the problem is corrected, recalibrate and

reanalyze all samples tested since the last

acceptable CCB.

10.3.7 Reporting Limit (RL) Verification Standard

An independent standard is analyzed after the ICV to monitor the lab’s

ability to produce reliable results at RL-level concentrations. The RL

verification standard is analyzed after the daily ICB.

Acceptance Criteria: For project reporting limits at or above two

times the MDL, the results should be within

50% of the expected value. Some programs

may require tighter control, in which case the

RLs will need to be three or more times the

MDL concentration.

Corrective Action: If the RL verification fails to meet acceptance

limits, data for the associated samples must be

assessed. For example, if the results are high,

consider blank contamination, and if the results

are low, consider MDL verifications. At a

minimum, sample results must be qualified in

the final report.

10.3.8 Continuing Calibration Verification (CCV) Standard

A 50  g/L CCV standard is analyzed after every set of ten samples and

at the end of the analytical sequence.

## D-14 Acceptance Criteria: The CCV recovery must be within 85-115%. In

addition, the IS recovery must be within 60-

125%. If CCV results are not within these

limits, the CCV can be reanalyzed, but it must

be successful twice in succession or further

corrective action must be taken.

Corrective Action: If the CCV fails acceptance criteria, then the

analysis should be terminated. Recalibrate and

reanalyze all samples tested since the last

acceptable CCB.

10.4 Sample Analysis

10.4.1 Report the average of at least three integrations for all field and QC

samples analyzed.

10.4.2 Flush the system with the rinse blank for at least 30 seconds between

samples and standards during the analytical run. Evaluate the

effectiveness of this time and increase the flush time, if needed.

10.4.3 It may be valuable to monitor additional isotopes for elements that are

potentially susceptible to interferences. In particular, monitoring

additional isotopes for selenium may help data analysis.

10.4.4 Dilute and reanalyze samples that are more concentrated than the

highest calibration standard for an analyte or specific isotope of interest.

No analyte may be reported from an analysis of a diluted sample in

which the analyte concentration is less than 5 times the RL.

The analytical run sequence should be performed as follows to meet all

quality control criteria:

Instrument initialization

Warm-up

Tune instrument

Perform mass calibration

Perform resolution check

Validate tuning criteria

Calibration blank

Calibration standard 1

Calibration standard 2

Calibration standard 3

ICV

ICB

RL verification standard

Synthetic FGD matrix

Spiked synthetic FGD matrix

Carryover check

CCV

CCB

10 Samples (which can include all sample types)

CCV

CCB

## D-15 11.0 Calculations / Data Reduction

11.1 LCS percent recoveries are calculated according to the equation:

11.2 ICV percent recoveries are calculated according to the equation:

11.3 CCV percent recoveries are calculated according to the equation:

11.4 Matrix Spike Recoveries are calculated according to the following equation:



## Where:

SSR = Spike Sample Result

SR = Sample Result

SA = Spike Added

NOTE: When the sample concentration is less than the detection limit, use SR = 0

for the purpose of calculating %R



## .

11.5 The relative percent difference (RPD) between sample duplicates is

calculated according to the following equation:



## Where:

DU1 = Sample result

DU2 = Sample duplicate result % 100

Value True LCS Value Found LRB

- Value Found LCS %       

 R

% 100

Value True ICV Value Found ICV %       

 R

% 100

Value True CCV Value Found CCV %       

 R

% 100

SA SR

- SSR %       

 R



#   100

2 1 2 1 / 2 1 /

  

 

 

 

 

 DU DU DU DU RPD

## D-16 11.6 The final concentration for an aqueous sample is calculated as follows:



## 2 1 g/L) ( Result

V D V C 



 



## Where:

C = Concentration from instrument readout, ppb

D = Instrument dilution factor

V1 = Final volume in liters after sample preparation

V2 = Initial volume of sample digested in liters

12.0 Method Performance

12.1 Method Detection Limit Study (MDL)

An initial method detection limit study must be performed on each instrument

before samples can be analyzed. MDL studies are conducted annually as

follows:

 

### Prepare seven samples at three to five times the estimated MDL

concentration. The MDL samples are prepared in the Synthetic FGD

wastewater matrix and in reagent water.

 

### Prepare and analyze the MDL standards as described in Section 10.

 

### Calculate the average concentration found in μg/L, and the standard

deviation of the concentration(s) in μg/L, for each analyte.

 

### The MDL is calculated as Students t for the 99 th 

### percentile times the standard

deviation of the MDL replicate results, following the procedure at 40CFR Part

136, Appendix B.

NOTE1: Perform the MDL study in the synthetic FGD

wastewater matrix. Spiking this matrix provides detection

limits that are better matched to the complex matrix

typical of FGD wastewater. These limits can be

significantly higher than those obtained in a reagent water

matrix. In some cases (zinc in particular), the level of

contamination in the synthetic FGD solution may be high

enough to result in somewhat elevated MDLs.

NOTE2: An FGD-MDL may be less than the MDL observed in

method blanks. If this occurs frequently, the FGD-MDL

should be elevated to the mean of the method blanks plus

the Student t factor times the standard deviation of the

method blanks.

12.2 Instrument Detection Limit Study

Instrument detection limit (IDL) studies are conducted quarterly for each

instrument and each mass used for analysis.

 

### Prepare ten blanks.

 

### Analyze the IDL blanks on three non-consecutive days.

 

### The IDL is equal to three times the standard deviation of the blank results.

## D-17 12.3 Demonstration of Capabilities

All personnel are required to perform an initial demonstration of proficiency

(IDOC) on the instrument they will be using for analysis prior to testing samples.

On-going proficiency must be demonstrated annually. IDOCs and on-going

proficiency demonstrations are conducted as follows.

Four aliquots of the ICV are analyzed using the same instrumental conditions

and procedures used to analyze samples. The analyst must employ ICV’s from

four distinct analytical sequences. Using these four ICV’s demonstrates the

analyst’s ability to optimize and calibrate the instrument and to prepare analytical

solutions. Calculate the average recovery and standard deviation of the recovery

for each analyte of interest.

 

### If any analyte does not meet the acceptance criteria, (85-115% recovery,

unless other criteria are established) the test must be repeated. Only those

analytes that did not meet criteria in the first test need to be evaluated.

Repeated failure for any analyte indicates the need for the laboratory to

evaluate the analytical procedure and take corrective action.

12.4 Training Requirements

12.4.1 Each analyst performing the method must complete a demonstration of

capability (DOC) by successfully preparing and/or analyzing four

consecutive LCSs, or a blind performance evaluation (PE) sample, or

other acceptable QC samples. Analysts who continue to perform the

method must successfully complete a demonstration of capability

annually.

13.0 Pollution Control

13.1.1 For information about pollution prevention that may be applicable to

laboratory operations, consult “Less is Better: Laboratory Chemical

Management for Waste Reduction” available from the American

Chemical Society’s Department of Government Relations and Science

Policy, 1155 16th Street N.W., Washington, D.C., 20036, or online at

http://www.ups.edu/x7432.xml.

14.0 Waste Management

All waste must be disposed of in accordance with Federal, State, and local

regulations.

15.0 References / Cross-References

15.1 EPA Method 200.8, “Determination of Trace Elements in Waters and Wastes

by Inductively Coupled Plasma - Mass Spectrometry”, Revision 5.4, EMMC

Version.

15.2 EPA Method 1638, “Determination of Trace Elements in Ambient Waters by

Inductively Coupled Plasma – Mass Spectrometry, January 1996

## D-18 16.0 Attachments

Attachment 1: Recommended Elemental Equations

Attachment 2: Internal Standards and Corresponding Metals

Attachment 3: Sample Preservation and Holding Times

Attachment 4: Suggested Mass Choices

Attachment 5: Tuning Solution

Attachment 6: Suggested Tuning and Response Factor Criteria

Attachment 7: Summary of Quality Control Requirements

Attachment 8: Calibration, Calibrati on Verification, and Spike Concentrations

## D-19 Attachment 1

Recommended Elemental Equations



## Element Isobaric

Correction Mathematical Equation

Pb None (1.0000)(208M) + (1.0000)(207M) +

(1.0000)(206M)

6Li Li (natural) (1.0000)(6M) - (0.0813)(7M)

In Sn (1.0000)(115M) - (0.0149)(118M)

The 6 

### Li correction equation is only needed if 6Li is us ed as an internal standard for low mass elements.

Attachment 2: Internal Standards and Corresponding Metals



## Internal Std. Associated elements 1,2



## Sc Na, Mg, Al, K, Ca, V, Cr, Mn

Ge Fe, Ni, Cu, Zn, As, Se

In Ag, Cd

Ho Tl, Pb

Footnote: (1) Na, Mg, K, Ca and Fe are included in the synthetic FGD wastewater but their

analytical determination is optional – the in terferences caused by these elements are more

important than the determination of their exact concentration.

(2) Other internal standards may be used. For example, 6 

### Li, Ga, Rh, Bi, Ho and Tb may be

considered for use as internal standards.

## D-20 Attachment 3: Sample Preservation and Holding Times



## Measurement

Parameter Container (1) Preservative (2) Maximum Holding

Time (3)

Waters:

Metals (4) P,G HNO 3 

## to pH < 2 6 months

Soils/Sediments/Wastes:

The preservation required for soil/sediment/waste samples is maintenance at 4°C ( ± 2°C)

until digestion.

Footnotes : (1) Polyethylene (P) or glass (G).

(2) Sample preservation is performed by the sampler immediately upon sample

collection or shipped to the laboratory unpreserved for preservation at the

laboratory.

(3) Samples must be analyzed as soon as possible after collection. The times listed

are the maximum times that sample may be held before analysis and still

considered valid. Holding times are calcu lated from the date when the sample

was collected.

(4) Samples are filtered immediately on-site by the sampler before adding

preservative for dissolved elements.

## D-21 Attachment 4: Suggested Mass Choices

Masses listed indicate the masses which have the most impact on data quality and the elemental

equations used to collect the data.



## Mass Element of Interest Analysis mode

27 Aluminum No gas

75 Arsenic He

111 Cadmium He

52 Chromium He

63 Copper He

208, 207, 206 Lead No gas or He

24 Magnesium No gas

55 Manganese He

60 Nickel He

39 Potassium No gas or He

78 Selenium He (H 2 

## )

107 Silver He

23 Sodium No gas or He

205 Thallium No gas or He

51 Vanadium He

66 Zinc He

NOTE : It is strongly recommended that elements other than those of interest be

monitored to indicate other potential molecular interferences which could

affect the data quality.

## D-22 Attachment 5: Tuning Solution

A tuning solution containing elements representing all of the mass regions of interest must be analyzed.

Below are two groups of suggested solutions which cover a typical mass calibration range.

Method 200.8



## Element Concentration (  g/L)

Mg 10

Rh 10

Ba 10

Be 10

U 10

Ce 10

Y 10

Pb 10

Li 10

Co 10

In 10

Tl 10

## D-23 Attachment 6: Suggested Tuning and Response Factor Criteria

No Gas Mode

Li7 >2000cps

Tl205 >3000cps

CeO/Ce 156/140 1%

Ce++/Ce+ 70/140 <3%

He Mode:

ArAr 78 2-3 counts/sec

ArCl 75 2-3 counts/sec

## D-24 Attachment 7: Summary of Quality Control Requirements



## QC Parameter Frequency Acceptanc e Criteria Corrective Action

ICV/QCS Beginning of every

analytical run. 90 - 110% recovery.

200.8 IS, 60-125% rec. Terminate analysis;

correct the problem;

recalibrate.

ICB/CCB Immediately after each

ICV. The result is < RL

200.8 IS, 60-125% rec. Terminate analysis;

correct the problem;

recalibrate.

Synthetic FGD

interference check Prior to initiating

analysis and at least

quarterly. Result for target

elements is < RL,

unless actual presence

of target element can

be demonstrated, in

which case result is <

5X RL. Correct the problem

prior to sample

analysis.

Individual element

interference checks Prior to initiating

analysis and at least

quarterly. Result for target

elements is < RL,

unless actual presence

of target element can

be demonstrated, in

which case result is <

5X RL. Correct the problem

prior to sample

analysis.

CCV Beginning and end of

run and every 10

samples OR every 2

hours, whichever is

more frequent.

Beginning and end of

each lot. 90 - 110% recovery.

IS, 60-125% rec. If unacceptable,

terminate analysis;

correct the problem;

recalibrate the

instrument, reverify

calibration and rerun

all samples since the

last acceptable CCV.

CCB Immediately following

each CCV. The result must be <

RL

200.8 IS, 60-125%

rec. If unacceptable,

terminate analysis;

correct the problem,

recalibrate the

instrument, reverify

calibration and rerun

all samples since the

last acceptable CCB.

## D-25

## D-26 Attachment 7: Summary of Quality Control Requirements (continued)



## QC Parameter Frequency Acceptanc e Criteria Corrective Action

Method

Blank/Laboratory

Reagent Blank One per lot of 20 field

samples or fewer. The result must be less

than the RL.

Sample results greater

than 10x the blank

concentration or

samples for which the

contaminant is < RL,

do not require

redigestion or

reanalysis. Re-run once. If > than

the RL, Redigest and

reanalyze samples.

Note exceptions under

criteria section.

See Section 9.4 for

additional

requirements.

Matrix

Spike/Laboratory

Fortified Matrix One every ten samples

or fewer. Must be within

laboratory control

limits. See section 9.6 for

additional

requirements.

## D-27 Attachment 8: Calibration, Calibration Verification, and Spike Concentrations



## Element Initial Calibration

(  g/L) ICV

(  g/L) CCV

(  g/L) LCS

(  g/L) MS/MSD

(  g/L)

Aluminum 100, 1,000, 10,000 4000 5000 4000 4000

Arsenic 1, 10, 100 40 50 40 40

Cadmium 1, 10, 100 40 50 40 40

Chromium 1, 10, 100 40 50 40 40

Copper 1, 10, 100 40 50 40 40

Lead 1, 10, 100 40 50 40 40

Manganese 1, 10, 100 40 50 40 40

Nickel 1, 10, 100 40 50 40 40

Selenium 1, 10, 100 40 50 40 40

Silver 1, 10, 100 40 50 40 40

Thallium 1, 10, 100 40 50 40 40

Vanadium 1, 10, 100 40 50 40 40

Zinc 1, 10, 100 40 50 40 40

Additional elements may be included in the calib ration solution at the above levels. Levels

may be adjusted to meet specific requirements.

####