# Sampling Episode Report

We Energies’

Pleasant Prairie Power Plant

Pleasant Prairie, WI

Sampling Episode 6559

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 .........................................................................................2-2

2.2 FGD Wastewater Treatment System ...................................................................2-3

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

2.2.2 Sampling Points .......................................................................................2-5

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 Wast ewater Treatment .............................................3-4

3.2 List of Analytes and Sample Preservation...........................................................3-7

3.3 Plant Operational Data.........................................................................................3-8

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

4. L ABORATORY 

# A NALYTICAL 

# R ESULTS AND 

# D ISCUSSION 

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

5. D ATA 

# Q UALITY 

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

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

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

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

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

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

5.2.4 Field Duplicates .......................................................................................5-4

6. R EFERENCES 

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

Appendix A: A NALYTICAL 

# R ESULTS



# Appendix B: 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 Info rmation, Pleasant Prairie ....................................................... 3-9

Table 3-2. Sample Collection at Pleasant Prairie....................................................................... 3-11

Table 3-3. Field Measurements, Pleasant Prairie....................................................................... 3-12

Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Pleasant Prairie .......... 3-14

Table 3-5. Analytical Met hods, Pleasant Prairie ....................................................................... 3-15

Table 3-6. Summary of Sample Container and Planned Preservation, Pl easant Prairie............ 3-16

Table 3-7. Sample Preservation Summary, Pleasant Prairie...................................................... 3-17

Table 3-8. Generating Unit Operating Character istics during Sample Collection, Pleasant

Prairie........................................................................................................................ ..... 3-19

Table 3-9. FGD Scrubber System Operating Characteristics, Pleasant Prairie ......................... 3-20

Table 3-10. Coal Usage during Sample Collection, Pleasant Prairie ........................................ 3-21

Table 3-11. Scrubber Slurry Information duri ng Sample Collection, Pleasant Prairie ............. 3-21

Table 3-12. FGD Wastewater Trea tment System Operation Information, Pleasant Prairie...... 3-22

Table 4-1. Influent to F GD Wastewater Treatment Syst em, Pleasant Prairie ............................ 4-4

Table 4-2. Effluent From FGD Wastewater Treatment Sy stem, Pleasant Prairie ...................... 4-8

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

Treatment System, Pleasant Prairie ............................................................................... 4-12

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

Treatment System, Pleasant Prairie ............................................................................... 4-13

Table 5-1. Field Blank Analytical Results, Pleasant Prairie....................................................... 5-5

Table 5-2. Field Duplicate Re sults – Effluent fr om FGD Wastewater Treatment System,

Pleasant Prairie............................................................................................................... .. 5-6

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

Pleasant Prairie............................................................................................................... . A-1

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

Pleasant Prairie............................................................................................................... . A-4

# LIST OF TABLES (Continued)

Page

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

Pleasant Prairie............................................................................................................... . A-7

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

Pleasant Prairie.............................................................................................................. A -10

Table A-5. Effluent from FG D Wastewater Treatment System, Day 1 Analytical Results,

Pleasant Prairie.............................................................................................................. A -13

Table A-6. Effluent from FG D Wastewater Treatment System, Day 2 Analytical Results,

Pleasant Prairie.............................................................................................................. A -16

Table A-7. Effluent from FG D Wastewater Treatment System, Day 3 Analytical Results,

Pleasant Prairie.............................................................................................................. A -19

Table A-8. Effluent from FG D Wastewater Treatment System , Day 4 Analytical Results,

Pleasant Prairie.............................................................................................................. A -22

Table A-9. Duplicate of Effl uent from FGD Wastewater Tr eatment System, Analytical

Results, Pleasant Prairie................................................................................................ A-25

Table A-10. Bottle Blank and Equipment Blank Analytical Data, Plea sant Prairie................. A-28

Table A-11. Influent to FGD Wastewater Treatment System Field Blank, Day 1

Analytical Results, Pleasant Prairie .............................................................................. A-33

Table A-12. Effluent from FGD Wastewater Treatment System Field Blank, Day 1

Analytical Results, Pleasant Prairie .............................................................................. A-35

Table A-13. Effluent from FGD Wastewater Treatment System Field Blank, Day 2

Analytical Results, Pleasant Prairie .............................................................................. A-37

Table A-14. Effluent from FGD Wastewater Treatment System Field Blank, Day 3

Analytical Results, Pleasant Prairie .............................................................................. A-38

Table A-15. Effluent from FGD Wastewater Treatment System Field Blank, Day 4

Analytical Results, Pleasant Prairie .............................................................................. A-39

# iv LIST OF FIGURES

Page

Figure 2.1. FGD Wastewater Treatment Syst em, Pleasant Prairie Power Plant.......................... 2-6

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 Tap and Tubing at the Effl uent from the FGD Wa stewater 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 June 20 - 25, 2010, at We Energies’ Pleasant Pr airie Power Plant (Pleasant Prairie), located

in Pleasant Prairie, Wisconsin (Sampling Ep isode 6559). The focus of Episode 6559 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.

Pleasant Prairie was selected by EPA for sampling based on the following site

characteristics:

 The plant is a coal-fired pow er plant that burns Powder River Basin (PRB) 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,

— 

# pH adjustment (lime addition),

— 

# Primary clarification,

— 

# Organosulfide addition,

— 

# Ferric chloride addition,

— 

# Polymer addition,

— 

# Secondary clarification;

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

units; and

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

1.3 Sampling Episode Overview

EPA and its technical contractor, Eastern Research Group, Inc. (ERG), conducted a oneday pre-sampling site visit at Pleasant Prairie on March 2, 2010 as part of the rulemaking. The

information collected during the pre-sa mpling site visit was used to create Sampling Plan, We

Energies’ Pleasant Prairie Power Station (Sampling Plan) [1], which describes the sample

collection procedures used during the sampling episode.

On Sunday, June 20, 2010, EPA arrived at Pleasant Prairie 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 (June 21 – 25, 2010). The following personnel participated in EPA’s

sample collection activities:

 Ron Jordan, EPA/EAD;

 TJ Finseth, ERG;

 Kavya Kasturi, ERG;

 Elizabeth Sabol, ERG;

 Becky Schwantes, ERG; and

 Kim Wagoner, 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 epis ode, UWAG acted as Pleasant Prairie’s representative and

collected samples on behalf of the plant.

# 2-1 2. F ACILITY 

# O VERVIEW



# Pleasant Prairie operates two steam electric generating units and each has a coal-fired

boiler. Units 1 and 2 each have a net capacity of 594 megawatts (MW), and came online in 1980

and 1985, respectively. The plant is located in Pleasant Prairie, Wisconsin, about 5 miles from

Lake Michigan.

Pleasant Prairie burns approximately 5.5 million tons of PRB coal each year. The plant

also burns bottom and fly ash from older power pl ants to reclaim some of the carbon in the ash.

The old ash is burned at approxi mately one to two percent wei ght of the total fuel burned.

Approximately three years prior to the sampling episode, Pleasant Prairie retrofitted both

units with FGD scrubber systems to control the sulfur dioxide (SO 2 

# ) releases from the plant. The

Unit 1 FGD system was installed in November 20 06, and the Unit 2 FGD system was installed in

March 2007. The wet FGD scrubbers remove approximately 97 to 98 percent of the SO 2 

# from

the flue gas. In addition to the FGD scrubbe r systems, Pleasant Prai rie installed an FGD

wastewater treatment system to control the disc harges of the wastewat er generated during the

operation of the FGD scrubbers. Sections 2.1 a nd 2.2 further discuss the FGD scrubber systems

and the FGD wastewater treatment system, respectively.

Pleasant Prairie retrofit ted Units 1 and 2 with SCR systems in 2006 and 2003,

respectively. The plant operates the SCR systems, which are used to control nitrogen oxide

(NO X 

# ) emissions, year round.

The electrostatic precipitators (ESPs) at Plea sant Prairie are particulate control devices

that are designed to remove 99.7 percent of the fly ash and other particulates from the flue gas.

Pleasant Prairie utilizes ESPs to remove the fly ash from both units. The fly ash and other

particulates are collected in hoppers and pneumatically conveyed to storage silos. Pleasant

Prairie markets the fly ash produced. There is no wa stewater discharge associated with the ESPs.

Pleasant Prairie installed a calcium bromid e injection system in November 2009 and

began continuous calcium bromide injection in January 2010. The system injects a solution of

calcium bromide on to the coal prior to it being pulverized. Adding the calcium bromide to the

coal enhances the oxidation of the mercury in the boiler and, therefore, results in better removals

of mercury in the downstream FGD system. Since the addition of the injection system, Pleasant

Prairie has noticed an increase in the mercury c oncentrations present in the gypsum, as well as

the sludge generated from the FGD wastewater treatment system.

Units 1 and 2 each have the following configuration:

 Boiler;

 SCR system;

 ESP; and

 FGD scrubber system.

# 2-2 2.1 FGD Scrubber System

Pleasant Prairie operates two identical wet F GD scrubber systems that treat the flue gas

from Units 1 and 2. The plant uses limestone slurry as the sorbent for SO 2 

# absorption. Limestone

and service water are fed to on-site ball mills, wh ich 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 to use in the FGD scrubber sy stem. The underflow from the hydrocyclones is

returned to the ball mill for additional processi ng. The overflow from the hydrocyclones, which

is approximately 40 to 50 percent solids (by weight), is transferre d to a limestone slurry storage

tank and used as fresh limestone slurry in the absorber.

The fresh limestone slurry is fed to the r eaction tank of the FGD scrubber system and the

recycle pumps send the slurry to the various le vels of the FGD scrubbe r (typically two of the

three spray levels are operating at one time). Th e slurry is pressurized and sprayed downward

into the scrubber vessel through the spray nozzles. As the slurry falls downward and the flue gas

flows countercurrent to the slurry, 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 reach th e dual flow tray, which forms a layer of slurry

that the flue gas must pass thr ough to exit the FGD scrubber system . The tray has small holes in

it that allow the flue gas to bubble through the limestone slurry layered on the tray, which

provides additional contact between the limestone slurry and the flue gas. The spray droplets

continue to flow downward in the scrubber until they reach the reaction tank. Pleasant Prairie

bubbles air through the reaction tank to oxidize th e calcium sulfite to calcium sulfate (i.e.,

gypsum).

The SO 2 

# removal in the FGD systems is optimized at a pH of 5.9; however the plant

operates the FGD systems at a pH of 5.6 to 5.7 to reduce the scaling poten tial in the system. The

limestone slurry feed rate is ad justed to maintain the pH in th e system at 5.6 to 5.7. In addition,

the plant operates the FGD systems to maintain a solids concentration in th e scrubber of 15 to 18

percent solids. When the solids concentration ex ceeds 18 percent, the plant blows down from the

FGD system. The blowdown from each FGD system lasts for about eight to ten hours each day

and is transferred to the gypsum dewatering ope rations. The plant staggers the blowdown from

the two units.

Pleasant Prairie also maintains the chloride concentration in the FGD scrubber systems

between 3,000 and 10,000 ppm. The maximum desi gn chlorides concentr ation is 15,000 ppm,

but the plant tries to keep the ch lorides concentration around 6,000 ppm.

The gypsum slurry for each scrubber is pum ped to its primary hydrocyclone, where the

solid gypsum is separated from the water by cen trifugal force. The solid gypsum is forced

outward to the walls of the hydrocyclones and fa lls downward, while the wa ter exits the top of

the hydrocyclones. The gypsum from the primar y hydrocyclones, which is approximately 50

percent solids, is transferred to the vacuum belt filters for fina l dewatering. The overflow from

both the Unit 1 and Unit 2 primary hydrocyc lones are commingled in the secondary

hydrocyclone feed tank and transferred to a common secondary hydrocyclone. The overflow

from the secondary hydrocyclone is transferre d to the FGD wastewater treatment system.

# 2-3 Pleasant Prairie washes the gypsum sent to the vacuum filter belts with service water, as

the gypsum slurry is poured onto the belts. The v acuum filter belts dry the gypsum to a moisture

content less than 10 percent. Pleasant Prairie sells the gypsum for use in wallboard

manufacturing or for agricultural purposes. Pleasant Prairie generates approximately 45,000

pounds of gypsum per hour, when th e plant is dewatering the gypsum.

The filtrate from the vacuum belt filters is collected and transferred back to the FGD

scrubber systems. Typically, the filtrate is tran sferred back to the Unit 1 FGD scrubber system;

however, the plant has the capability to send the filtrate to the Unit 2 FGD scrubber system.

2.2 FGD Wastewater Treatment System

The Pleasant Prairie FGD wastewater treatment system is designed to receive intermittent

transfers of wastewater from the FGD scr ubber system, which consists of secondary

hydrocyclone overflow, at a flow rate of a pproximately 40 gallons per minute (gpm). The

intermittent transfers typically o ccur twice per day. According to plant personnel, the secondary

hydrocyclone typically operates for ten hours and is then off for six hours and then operates for

ten hours again. The FGD wastewater treatment syst em is a chemical precipitation system and

contains the following treatment operations:

 Equalization tank;

 pH adjustment (lime addition);

 Primary clarification and polymer addition;

 Organosulfide and hydrochl oric acid addition;

 Ferric chloride addition;

 Mixing tank (with polymer addition);

 Flocculation tank;

 Secondary clarification; and

 pH adjustment (hydrochloric acid addition).

Figure 2-1, located at the end of this secti on, presents the process flow diagram of the

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

episode. Pleasant Prairie estimates that the tota l residence time of the FGD wastewater treatment

system is approximately 55 hours.

The secondary hydrocyclone overflow from the scrubbers is transferred directly to the

equalization tank at the start of the wastewater treatment system. During the sampling episode,

the FGD influent wastewater was found to cont ain 0.3 to 0.7 percent solids, had a pH between

5.8 and 6.8 S.U., and a temperature between 54 a nd 55 °C. The equalization tank also receives

water from the filtrate sump, which includes the f iltrate from the treatment system sludge filter

presses.

2.2.1 Physical/Chemical Separation

From the equalization tank, the wastewater en ters reaction tank 1, where hydrated lime is

added to raise the pH of the wastewater from 5.6 to 8.5 S.U. to precipitate the soluble metals as

insoluble hydroxides and oxyhydroxides. The reacti on tank also desaturates the gypsum in the

# 2-4 wastewater, which prevents gypsum scale forma tion in the downstream wastewater treatment

equipment. To desaturate the gypsum, some of the sludge from the downstream primary clarifier

is recycled back to reacti on tank 1 to provide seed crys tals for gypsum nucleation.

From reaction tank 1, the wastewater flows to the primary clarifier, where polymer is

added to aid in the settling of the solids. Pleasant Prairie stated that 96 per cent of the solids settle

out of the wastewater in the pr imary clarifier. The overflow from the primary clarifier flows to

reaction tank 2, where the plant adds organosulfi de and hydrochloric acid. When the plant first

began operating the treatment system , they used TMT 15® as the or ganosulfide. Since that time,

the plant has switched to using Nalmet 1689®, wh ich is an organosulfide that has a longer

polymer chain, and therefore, a higher molecula r weight, which helps aid in the settling of

precipitates. Pleasant Prairie also began adding hydrochloric acid to r eaction tank 2, which was

not in the initial design of the system, because the plant determined that they achieve better

removals of mercury when the syst em is operated at a lower pH.

From reaction tank 2, the wastewater flows to reaction tank 3, where ferric chloride is

added to the wastewater. The pH in reaction tank 3 is targeted at 7.0 to 7.2 S.U. The effluent

from reaction tank 3 flows to the flash mix ta nk, where polymer is added to the wastewater.

From the flash mix tank, the wastewater flows to the flocculation tank. Gentle mixing in the

flocculation tank allows de nser floc to form.

The wastewater from the flocculation tank flows to the secondary clarifier. The

secondary clarifier settle s the solids that were formed duri ng the chemical conditioning steps.

Pleasant Prairie operates an inclined-plate lamella separator type clarifier. Hydrochloric acid may

be added to the overflow from the secondary clarifie r to readjust the pH valu e, if needed, to meet

effluent limits. From the secondary clarifier, water flows to the effluent tank and is then

commingled with other waste st reams (e.g., cooling tower blowdow n) prior to discharging to

Lake Michigan. Pleasant Prairie commingles the effluent from the FGD wastewater treatment

plant with other plant wastewater to meet the fi nal outfall mercury and chloride limits. To meet

the effluent mercury limit, Pleasa nt Prairie must dilute the F GD wastewater at a 30:1 ratio.

Because Pleasant Prairie does not discharge cooling tower blowdown when the plant is

chlorinating the cooling system, the plant co ntinuously operated the effluent pumps and

transferred the flow to the filtrate sump so that ERG could collect the effluent sample for the

entire 24-hour period, even duri ng chlorination. Pleasant Prairie di rected the treated effluent

collected in the filtrate sump to the scrubber as make-up water so it would not impact the FGD

wastewater treatment system performance.

The sludge from the primary and secondary cl arifiers is transfe rred to sludge holding

tanks using sludge transfer pumps. A portion of the clarifier sludge is recycled from the sludge

holding tank to reaction tank 1, while the majority is pumped to a filter press for dewatering. The

solids are then stacked on-site prior to being transf erred to an off-site landfill. The filtrate is

transferred to the filtrate sump, the contents of which are recycled back to the equalization tank.

Pleasant Prairie typically operates the F GD wastewater treatment system Monday

through Saturday. The system is shut down Sunday to perform weekly cleaning and

maintenance. This weekly maintenance includes draining and flushing of the secondary clarifier

to avoid buildup from flocculati on. Pleasant Prairie pers onnel stated that the weekly maintenance

# 2-5 was performed on the Thursday prior to the EP A sampling episode (June 17, 2010) so the plant

could verify the system performance on Friday and have it available for the sampling episode on

Monday.

Pleasant Prairie has made the following modifi cations to the FGD wastewater treatment

system since the system first began operating in early 2007:

 Changed the type of organosulfide used in the system from TMT 15® to Nalmet®

1689 (described previously);

 Added a hydrochloric acid addition point to reaction tank 2 be cause the system

removes more mercury at a lower pH (described previously);

 Bypassed a set of sand filter s that were located after the secondary clarifiers

because of scaling issues (the sand filt ers are not shown in Figure 2-1); and

 Added the capability to use cartridge filtr ation to remove colloidal particles from

the wastewater after the sec ondary clarifier, which may build up in the system if

the plant recirculates the wastewater without discha rging for several weeks;

however the cartridge filtration is not used regularly (the cartridge filters are not

shown in Figure 2-1).

2.2.2 Sampling Points

Figure 2-1 shows the sampling points for the Pl easant Prairie 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

 A sample of the effluent from the FGD wastewater treatment system downstream

of the two effluent tanks prior to commi ngling with other stre ams for discharge.

# 2-6Figure 2.1. FGD Wastewater Treatment System, Pleasant Prairie Power Plant

# 3-1 3. S AMPLE 

# C OLLECTION



# During the Pleasant Prairie sampling episode, the 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. Figure 2-1 of

this report presents a flow diagram 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 split samples with Pleasant Prairie’s

representative by inserting a “Y” splitter into the sample tubi ng configuration at each sampling

point to allow for split sample collection. EPA co llected all samples (other than mercury and

cyanide) at all sampling points as “true” splits (i.e., samples 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 Pleasan t Prairie’s representative collected duplicate

samples, with one filling the bot tle immediately 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

# 3-2 the box and pull the bag over the open ing of the box, but is still able to see the sample bottles and

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 secondary hydrocyclone and ups tream of the equalization tank. Figure 2-1

identifies the sampling location for SP-1. This sa mple was collected as a grab sample because,

according to plant representatives, the wastewater characteristics of the pu rge to the wastewater

treatment system are fairly consistent during th e 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 sampling techniques . The sample tap was located inside the FGD

building (see Figure 2-1 for the sampling locat ion for SP-1). 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 tubing attached to the sample tap at the influent to the FGD wastewater treatment

system. The samplers attached the silicone tubi ng to the sample tap, opened the valve, and

allowed sample to flow through the tubing for two minutes before beginning to fill sample

containers. The samplers did not close the valv e 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.

# 3-3 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

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 Pleasant Prairie’s representati ves. 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 90 minutes. Approximately 0.5 - 1

liters 1 

# of sample were pumped through the tubing/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.

1 

# On day 1, the filter/tubing was purged for 1.5 liters for the field blank and 0.5 liters for the remaining samples. On

days 2, 3, and 4, the filter/tubing was purged for 1 liter. There was no need to change the filters on any of the

sampling days.

# 3-4 3.1.2 Effluent from FGD Wastewater Treatment

The effluent from FGD wastew ater treatment system (SP-2) was collected downstream of

the two effluent tanks prior to the effluent co mmingling with other wastewaters for discharge.

Pleasant Prairie installed a three-way splitter on th e sample tap that had three separate taps to

collect samples from the sampling point. The samp le tap was located inside the FGD wastewater

treatment building (see Figure 2-1 for the samp ling location for SP-2). Because the sampling

point was located inside, there were no wind or rain concerns during the sample collection.

However, the sampling team did observe that the close proximity of the co al pile resulted in a

significant amount of coal dust settling around a nd inside the building during coal loading

operations. The rate of coal dust accumulation was such that visible amounts of dust would

collect in less than 10 minutes. To minimize the amount of dust entering open tanks in the

treatment system building, the building doors were generally kept close d. Nevertheless, it is

possible that some amount of coal dust settled in the treatment system tanks and the pollutants

present in the coal dust may have affected the m easured concentrations in the treatment system

effluent.

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 automa tic 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

# 3-5 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 Appendi x C, is a picture of the composite sampling

set-up at the effluent from the FGD 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.

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 collect split samples with Pleasant Prairie’s

representatives; therefor e, duplicate samples were collected. ERG collected another set of total

and dissolved mercury samples every six hours th ereafter over the 24-h our period. The plastic

shroud was replaced for each set of mercury grab samples. After collect ing 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 the field measurement data for the

effluent from the FGD wastewater treatment.

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 Pleasant Prairie’ s representatives; therefore, duplicate samples were collected.

The total cyanide sample was immediately preserved. Lead acetate test strips and potassiumiodide starch test strips were used to measure for sulfides and oxidants, respectively. No sulfides

or oxidants were detected during this sampling episode at the effl uent from the FGD wastewater

treatment system. ERG samplers then preserved the total cyanide samples with sodium

hydroxide to a pH >10 S.U. and placed the samples on ice.

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 the two composite containers and the

composite containers were moved to the pump-off area where 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 vol ume 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

# 3-6 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 “t rue” split samples with Pleasant Prairie’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

metals. See Section 5.2.3 for a description of the dissolved and total 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-

5 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 samp ling episode. In addition, for all analytes, ERG

# 3-7 collected a duplicate sample of the FGD wastew ater treatment system (SP-3) on Day 2 of the

sampling episode.

3.2 List of Analytes and Sample Preservation

Samples collected at Pleasa nt Prairie were analyzed 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,

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 sa mples to <6°C. The sampling team did not place

the total and dissolved metals or the total and dissolved mercury samples on ice, which comports

with the requirements of Methods 200.7, 200.8 and 1631E. All dissolved metals samples, except

for mercury, were filtered in the field. The hexavalent chromium samples were preserved in the

field, but all other metals samples were acid-pre served prior to extraction at the laboratory. The

hexavalent chromium samples were preserve d with ammonium sulfate buffer solution and

2 

# In this report, EPA uses “total metals” and “total recoverable metals” interchangeably.

# 3-8 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 confirmed with fourcolor pH strips. Each total cyanide sample was te sted for sulfides and oxidants immediately after

sample collection. Because sulfides and oxidants we re not detected at any of the sampling points

during the sampling episode, the samplers did not need to dilute the samples or add sodium

arsenite to the samples. After testing for sulf ides and oxidants, the total cyanide samples were

preserved with sodium hydroxide to a pH >10 S.U. and placed on ice.

3.3 Plant Operational Data

During the EPA sampling episode, Pleasant Prai rie plant personnel provided the sampling

team with operational data for each of the gene rating units and the FGD scrubber system, as well

as operational and flow data for the FGD wastew ater treatment system. Table 3-8 presents the

unit operating characteristics, Table 3-9 presents the FGD scrubber system operating

characteristics, Table 3-10 presents informati on on the coal burned during the sampling episode,

Table 3-11 presents information on the FGD sc rubber slurry generation during the sampling

episode, and Table 3-12 presents th e FGD wastewater treatment syst em 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:

 Influent sample tap set up at SP-1 (Day 1): Before the sample line was purged

prior to sample collection, the second ary hydrocyclone became clogged. A plant

operator cleaned the blockage in the plugged hydrocyclone. Once the

hydrocyclone was operating, the line was purged for approximately 1 minute.

 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.

 pH field test measurements: The sampling team was una ble to locate the pH

measurement strips during the following samples: the effluent from the FGD

wastewater treatment system mercury grab samples 3 and 4 on day 1 and the

influent to the FGD wastewater treat ment system grab sample on day 2.

Therefore, the team only took a pH reading using the pH meter, not the pH strips

for these samples.

 Total mercury grab sample at SP-2 (Days 1 and 2): On days 1 and 2 of sample

collection at the effluent from the FGD wastewater treatment system (SP-2), the

inner bag for grab three of the four total mercury grab sample bottles was leaking.

The inner bag was removed from the outer bag, dried, and re-labeled. The

samplers placed the inner bag back in the outer bag.

# 3-9 Table 3-1. Sample Collection Information, Pleasant Prairie

Sampling

Point

Number Sampling Point Description Type of

Sample Sample

Collection Date Sample Collection

Time

Influent to FGD Wa stewater Treatment

System – Day 1 Grab 6/21/10 1013 a 

# and 1220 b



# Influent to FGD Wa stewater Treatment

System – Day 2 Grab 6/22/10 0939 a 

# and 1132 b



# Influent to FGD Wa stewater Treatment

System – Day 3 Grab 6/23/10 0917 a 

# and 1112 b 

# SP-1

Influent to FGD Wa stewater Treatment

System – Day 4 Grab 6/24/10 0924 a 

# and 1108 b



# Composite 6/21/10

6/22/10 0730 c



# 0827 d 

# Effluent from FGD Wastewater Treatment

System – Day 1

Grab 6/21/10

6/22/10 0748 e 

# , 1348 f 

# , and 1946 g



# 0147 h



# Composite 6/22/10

6/23/10 0728 c



# 0806 d 

# Effluent from FGD Wastewater Treatment

System – Day 2

Grab 6/22/10

6/23/10 0745 e 

# , 1348 f 

# , and 1947 g



# 0145 h



# Composite 6/23/10

6/24/10 0730 c



# 0810 d 

# Effluent from FGD Wastewater Treatment

System – Day 3

Grab 6/23/10

6/24/10 0743 e 

# , 1347 f 

# , and 1950 g



# 0147 h



# Composite 6/24/10

6/25/10 0729 c



# 0651 d 

# SP-2

Effluent from FGD Wastewater Treatment

System – Day 4

Grab 6/24/10

6/25/10 0749 e 

# , 1348 f 

# , and 1947 g



# 0147 h



# Composite 6/22/10

6/23/10 0728 c



# 0806 d 

# SP-3 Duplicate of Effluent from FGD

Wastewater Treatment System – Day 2

Grab 6/22/10

6/23/10 0747 e 

# , 1349 f 

# , and 1948 g



# 0146 h



# SP-4 Influent to FGD Wastewater Treatment

System Field Blank Grab 6/21/10 0958 i 

# and 1212 j



# Composite 6/21/10

6/22/10 0653 k



# 0813 l 

# Effluent from FGD Wastewater Treatment

System Field Blank – Day 1

Grab 6/21/10 0742 m



# Effluent from FGD Wastewater Treatment

System Field Blank – Day 2 Grab 6/22/10 0740 m



# Effluent from FGD Wastewater Treatment

System Field Blank – Day 3 Grab 6/23/10 0738 m 

# SP-5

Effluent from FGD Wastewater Treatment

System Field Blank – Day 4 Grab 6/24/10 0744 m

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).

# 3-10 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 Pleasant PrairieSamplingPointNumberSampling 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 FGDWastewater Treatment System4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-3 Duplicate of the Effluent fromFGD Wastewater TreatmentSystem1 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 FGDWastewater Treatment SystemField 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, Pleasant PrairiepH(S.U.)SamplingPointNumberSampling PointDescriptionDateTimeTemperature(°C)MeteraStripsWasteStream FlowRate(GPM)NotesInfluent to FGDWastewater TreatmentSystem – Day 16/21/2010 1029555.8 6 60Influent to FGDWastewater TreatmentSystem – Day 26/22/2010 0953556.4 NC 60Influent to FGDWastewater TreatmentSystem – Day 36/23/2010 0928556.34 7 60SP-1Influent to FGDWastewater TreatmentSystem – Day 46/24/2010 0935546.77 7 60Samplers noted that the sampleshad a dark brown color andappeared to be high in solids. Nodetected sulfides or oxidants intotal cyanide grab.6/21/10 0750436.6 6.540.36/21/10 1348436.9 6.5 386/21/10 194642.46.8 NC 38.1Effluent from FGDWastewater TreatmentSystem – Day 16/22/10 014742.46.9 NC 38.16/22/10 0750436.9 6.5 356/22/10 1352436.9 7 32.76/22/10 194741.56.9 7 35.0Effluent from FGDWastewater TreatmentSystem – Day 26/23/10 014543.36.9 6.5 34.96/23/10 0745446.87 7 356/23/10 1350446.85 7 356/23/10 195044.46.1 6.5 34.9SP-2Effluent from FGDWastewater TreatmentSystem – Day 36/24/10 015544.26.9 6.5 34.4Samples were clear and colorlessand did not have any observedparticulates. No detected sulfidesor oxidants in total cyanide grab.

# 3-13Table 3-3. Field Measurements, Pleasant PrairiepH(S.U.)SamplingPointNumberSampling PointDescriptionDateTimeTemperature(°C)MeteraStripsWasteStream FlowRate(GPM)Notes6/24/10 0752446.86 7 356/24/10 1350436.86 7 356/24/10 194743.86.9 6.5 35SP-2 Effluent from FGDWastewater TreatmentSystem – Day 46/25/10 014743.67.0 7 34.9Samples were clear and colorlessand did not have any observedparticulates. No detected sulfidesor oxidants in total cyanide grab.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.NC – Not collected. The sampling team was unable to locate the pH strips during the collection of these samples; therefore, thepH measurement was only takenwith the pH meter.

# 3-14 Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Pleasant Prairie

Sample Number Sample Point Sample Description

71691 SP-1, Day 1 Influent to FGD Wastewater Treatment System - Day 1

71692 SP-1, Day 2 Influent to FGD Wastewater Treatment System - Day 2

71693 SP-1, Day 3 Influent to FGD Wastewater Treatment System - Day 3

71694 SP-1, Day 4 Influent to FGD Wastewater Treatment System - Day 4

71695 SP-2, Day 1 Effluent to FGD Wastewater Treatment System - Day 1

71696 SP-2, Day 2 Effluent to FGD Wastewater Treatment System - Day 2

71697 SP-2, Day 3 Effluent to FGD Wastewater Treatment System - Day 3

71698 SP-2, Day 4 Effluent to FGD Wastewater Treatment System - Day 4

71699 SP-3, Day 2 Duplicate of Effluent to FGD Wastewater Treatment System - Day 2

71700 SP-4, Day 1 Influent to FGD Wastewater Treatment System Field Blank - Day 1

71701 SP-5, Day 1 Effluent to FGD Wastewater Treatment System Field Blank - Day 1

71702 SP-5, Day 2 Effluent to FGD Wastewater Treatment System Field Blank - Day 2

71703 SP-5, Day 3 Effluent to FGD Wastewater Treatment System Field Blank - Day 3

71704 SP-5, Day 4 Effluent to FGD Wastewater Treatment System Field Blank - Day 4

# 3-15 Table 3-5. Analytical Met hods, Pleasant Prairie

Parameter Method Number

Classicals

Biochemical oxygen demand (BOD 5 

# ) SM 5210 B

Chemical oxygen demand (COD) EPA 410.4

Total suspended solids (TSS) SM 2540 D

Total dissolved solids (TDS) SM 2540 C

Sulfate EPA 300.0

Chloride EPA 300.0

Ammonia as nitrogen EPA 350.1

Nitrate/nitrate as nitrogen EPA 353.2

Total Kjeldahl nitrogen (TKN) EPA 351.2

Total phosphorus EPA 365.1

Total cyanide SM 4500 CN E

Total and Dissolved Metals

Mercury EPA 1631E

Hexavalent chromium (dissolved only) EPA 218.6

Antimony, arsenic, cadmium, chromium, copper, lead, manganese, nickel,

selenium, silver, thallium, vanadium, and zinc EPA 200.8 with collision cell 1



# Aluminum, barium, beryllium, boron, calcium, cobalt, iron, magnesium,

molybdenum, sodium, tin, and titanium EPA 200.7

1 

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

# 3-16 Table 3-6. Summary of Sample Container a nd Planned Preservation, Pleasant Prairie

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.

# 3-17 Table 3-7. Sample Preservation Summary, Pleasant Prairie

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

71691 Group II Volume 1 6/21/10 H 2 

# SO 4 

# 6.0 2 55

71691 Group II Volume 2 6/21/10 H 2 

# SO 4 

# 6.0 2 55

(NH 4 

# ) 2 

# SO 4



# Buffer 100 71691 Hexavalent Chromium 6/21/10

NH 4 

# OH 6.0 9.4

5

(NH 4 

# ) 2 

# SO 4



# Buffer 100 71700 Hexavalent Chromium Field

Blank 6/21/10

NH 4 

# OH 5.5 9.5

3

71691 Total Cyanide 6/21/10 NaOH 6.0 10 35

71692 Total Cyanide 6/22/10 NaOH 6.5 10 35

71695 Total Cyanide 6/21/10 NaOH 7.0 10 55

71692 Group II Volume 1 6/22/10 H 2 

# SO 4 

# 6.5 2 65

71692 Group II Volume 2 6/22/10 H 2 

# SO 4 

# 6.5 2 65

71695 Group II Volume 1 6/22/10 H 2 

# SO 4 

# 6.0 2 50

71695 Group II Volume 2 6/22/10 H 2 

# SO 4 

# 6.0 2 50

(NH 4 

# ) 2 

# SO 4



# Buffer 100 71692 Hexavalent Chromium 6/22/10

NH 4 

# OH 6.5 9.5

3

(NH 4 

# ) 2 

# SO 4



# Buffer 100 71695 Hexavalent Chromium 6/22/10

NH 4 

# OH 6.5 9.5

5

(NH 4 

# ) 2 

# SO 4



# Buffer 100 71701 Hexavalent Chromium Field

Blank 6/22/10

NH 4 

# OH 5.5 9.5

3

71696 Total Cyanide 6/22/10 NaOH 6.9 10 45

71699 Total Cyanide 6/22/10 NaOH 6.9 10 45

71693 Group II Volume 1 6/23/10 H 2 

# SO 4 

# 6.5 2 55

71693 Group II Volume 2 6/23/10 H 2 

# SO 4 

# 6.5 2 55

71696 Group II Volume 1 6/23/10 H 2 

# SO 4 

# 6.5 2 65

71696 Group II Volume 2 6/23/10 H 2 

# SO 4 

# 6.5 2 65

71699 Group II Volume 1-Duplicate 6/23/10 H 2 

# SO 4 

# 6.5 2 65

71697 Group II Volume 2-Duplicate 6/23/10 H 2 

# SO 4 

# 6.5 2 65

(NH 4 

# ) 2 

# SO 4



# Buffer 100 71693 Hexavalent Chromium 6/23/10

NH 4 

# OH 6.5 9.5

5

71696 Hexavalent Chromium 6/23/10 (NH 4 

# ) 2 

# SO 4



# Buffer 6.5 9.5 100

# 3-18 Table 3-7. Sample Preservation Summary, Pleasant Prairie

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

NH 4 

# OH 4

(NH 4 

# ) 2 

# SO 4



# Buffer 34 71699 Hexavalent Chromium -

Duplicate 6/23/10

NH 4 

# OH 6.5 9.5

5

71693 Total Cyanide 6/23/10 NaOH 6.5 10 40

71697 Total Cyanide 6/23/10 NaOH 6.1 10 50

71697 Total Cyanide - QC 6/23/10 NaOH 6.1 10 50

71694 Group II Volume 1 6/24/10 H 2 

# SO 4 

# 6.5 2 65

71694 Group II Volume 2 6/24/10 H 2 

# SO 4 

# 6.5 2 65

71697 Group II Volume 1 6/24/10 H 2 

# SO 4 

# 6.5 2 55

71697 Group II Volume 2 6/24/10 H 2 

# SO 4 

# 6.5 2 55

71697 Group II Volume 1 - QC 6/24/10 H 2 

# SO 4 

# 6.5 2 55

71697 Group II Volume 2 - QC 6/24/10 H 2 

# SO 4 

# 6.5 2 55

71698 Group II Volume 1 6/25/10 H 2 

# SO 4 

# 6.5 2 55

71698 Group II Volume 2 6/25/10 H 2 

# SO 4 

# 6.5 2 55

(NH 4 

# ) 2 

# SO 4



# Buffer 100 71694 Hexavalent Chromium 6/24/10

NH 4 

# OH 6.7 9.5

5

(NH 4 

# ) 2 

# SO 4



# Buffer 100 71697 Hexavalent Chromium - QC 6/24/10

NH 4 

# OH 6.5 9.5

4

(NH 4 

# ) 2 

# SO 4



# Buffer 100 71698 Hexavalent Chromium 6/25/10

NH 4 

# OH 6.5 9.5

5

71694 Total Cyanide 6/24/10 NaOH 6.5 10 40

71698 Total Cyanide 6/24/10 NaOH 6.5 10 40

# 3-19 Table 3-8. Generating Unit Operating Charact eristics during Sample Collection, Pleasant

Prairie

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 Riley Turbo Opposed

Wall - Fired 594 49,997 MWHr On CS ESP

2 Riley Turbo Opposed

Wall - Fired 594 50,540 MWhr On CS ESP



# CS ESP – Cold-side elect rostatic precipitator.

# 3-20Table 3-9. FGD Scrubber System OperatingCharacteristics, Pleasant PrairieUnit IDWet FGDSystem (Yes/No)Type ofScrubberForcedOxidation(Yes/No)SorbentAdditives (DBA,formic acid,etc.)FGD Make-upWater SourceSO2RemovalPercentageType of SolidsSeparation1 Yes Spray / Tray YesLimestoneSilicon antifoam17 gpd/unitLake Michigan 97% Primary / Sec HC2 Yes Spray / Tray YesLimestoneSilicon antifoam17 gpd/unitLake Michigan 96% Primary / Sec HC

# 3-21 Table 3-10. Coal Usage during Sample Collection, Pleasant Prairie

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 Sub Bit 8205.66 PRB/WY 0.5 % Est 42 ppm Est

1 2 Sub Bit 8059.82 PRB/WY 0.5 % Est 42 ppm Est

1 Sub Bit 8550.83 PRB/WY 0.5 % Est 42 ppm Est

2 2 Sub Bit 8365.23 PRB/WY 0.5 % Est 42 ppm Est

1 Sub Bit 8530.58 PRB/WY 0.5 % Est 42 ppm Est

3 2 Sub Bit 8276.14 PRB/WY 0.5 % Est 42 ppm Est

1 Sub Bit 8119.66 PRB/WY 0.5 % Est 42 ppm Est

4 2 Sub Bit 8371.29 PRB/WY 0.5 % Est 42 ppm Est



# Table 3-11. Scrubber Slurry Information durin g Sample Collection, Pleasant Prairie

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 Percent

Filtrate

Recycled

Back to

Scrubber

1 1 280 9.25 hr ~15% 0413 – 0900 EST,

1400 – 1830 EST 100%

1

2 2 280 9.0 hr ~15% 0830 – 1400 EST,

1600 – 1930 EST 100%

1 1 280 12.0 hr ~15% 0130 – 0800 EST

1300 – 1822 EST 100%

2

2 2 280 10.5 hr ~15% 0500 – 1100 EST,

1600 – 2030 EST 100%

1 1 280 8.5 hr ~15% 0125 – 0620 EST

1125 – 1500 EST 100%

3

2 2 280 10.0 hr ~15% 0620 – 1130 EST

1345 – 1500 EST

2230 – 2400 EST 100%

1 1 280 13.5 hr ~15% 0018 – 0710 EST

1725 – 2400 EST 100%

4

2 2 280 9.0 hr ~15% 0000 – 0312 EST

1400 – 1945 EST 100%

# 3-22Table 3-12. FGD Wastewater Treatment SystemOperation Information, Pleasant PrairieScrubber PurgeChemical UsageDay ofSamplingFlow Rate(GPM)aDurationACTLime(added to adjustpH 5.6 to 8.5)bFerric ChlorideACTOrganosulfideNalmet 168950 ppmACTPolymer:GE AE170320 ppm primary3.5 ppm sec ACTAcid:HCl 31%ACT1 60 18.0 hr 670 lb/day 40 mL/min 6 mL/min 4 mL/min ~5 mL/min2 60 16.25 hr 670 lb/day 40 mL/min 6 mL/min 4 mL/min ~5 mL/min3 60 17.5 hr 670 lb/day 40 mL/min 6 mL/min 4 mL/min ~5 mL/min4 60 20.25 hr 670 lb/day 40 mL/min 6 mL/min 4 mL/min ~5 mL/mina- Purge rate estimated from tank level changes. Similar to Secondary Hydrocyclone design data of 60 gpm to overflow/purgeb- Lime feeder operates 4 times per day for 10 minutes; feeder rate is 1000 lb/hr, 670 lbs/day. Checks against lime deliveries.ACT – Actual value during sampling episode.

# 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.

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 individual 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 Pleasant Prairie,

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, wher e three to five is the normal range.

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. Table 4-2 presents the

analytical results for all classical and metal analyt es for the four days of sampling at the effluent

from the FGD wastewater 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 5-2 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.

# 4-3 Appendix Tables A-1 through A-9 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.

# 4-4< - 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.+- The accuracy of the Day 1 dissolved mercury analytical result seems questionable based on the results from the other sampling days. If the Day 1 dissolved mercury result wasexcluded from the calculated average, the 4-day average would be 2,940 ng/L.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.Table 4-1. Influent to FGD Wastewater Treatment System, Pleasant PrairieInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageClassicalsAmmoniamg/L350.119.013.012.014.014.5Nitrate Nitrite as Nmg/L353.2150160160160158Nitrogen, Total Kjeldahlmg/L351.286.0472.0B16.0B76.0B62.5Biochemical Oxygen Demandmg/L5210BND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Chemical Oxygen Demandmg/L410.4420F460410400*423Chloridemg/L300.01,8001,8001,8001,8001,800Sulfatemg/L300.014,00016,00017,00017,00016,000Cyanide, Totalmg/L4500 CN E0.250B0.280B0.180B0.230B0.235Total Dissolved Solidsmg/L2540C23,00024,00024,00026,00024,300Total Suspended Solidsmg/L2540D3,8007,1003,3003,5004,430Phosphorus, Totalmg/L365.10.950B0.250BNQ (0.250)B0.0630B< 0.347Total MetalsAluminumug/L200.7110,000B,4130,000120,000140,000125,000Antimonyug/L200.865.063.063.060.062.8Arsenicug/L200.8150160140150150Bariumug/L200.7680F770750510678Berylliumug/L200.74.805.105.005.105.00Boronug/L200.711,000B,412,000B12,000B13,00012,000Cadmiumug/L200.89.2011.011.013.011.1Calciumug/L200.7670,000B,4690,000690,000700,000688,000Chromiumug/L200.81,4004,^1,000^9609801,090

# 4-5< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).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.+- The accuracy of the Day 1 dissolved mercury analytical result seems questionable based on the results from the other sampling days. If the Day 1 dissolved mercury result wasexcluded from the calculated average, the 4-day average would be 2,940 ng/L.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.Table 4-1. Influent to FGD Wastewater Treatment System, Pleasant PrairieInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageCobaltug/L200.7140140140140140Copperug/L200.81,30041,1001,0001,1001,130Ironug/L200.7400,000B,4420,000420,000410,000413,000Leadug/L200.82804280280280280Magnesiumug/L200.74,200,000B,44,200,000B4,000,0004,200,0004,150,000Manganeseug/L200.772,000B,476,000B73,00074,00073,800Mercuryng/L1631E2,020,0002,080,0002,060,0001,730,0001,970,000Molybdenumug/L200.7240240240240240Nickelug/L200.81,60041,4001,4001,4001,450Seleniumug/L200.820,000415,00015,000B15,000B16,300Silverug/L200.8NQ (2.00)FNQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)Sodiumug/L200.7470,0004510,000500,000520,000500,000Thalliumug/L200.811.012.011.010.011.0Tinug/L200.7NQ (200)NQ (200)NQ (200)NQ (200)NQ (200)Titaniumug/L200.74,50044,4004,3004,9004,530Vanadiumug/L200.81,40041,100B910970B1,100Zincug/L200.82,50041,300B1,4001,5001,680Dissolved MetalsAluminumug/L200.7NQ (200)NQ (200)B210NQ (200)^< 128Antimonyug/L200.83.803.403.704.103.75Arsenicug/L200.87.206.907.707.007.20

# 4-6< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).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.+- The accuracy of the Day 1 dissolved mercury analytical result seems questionable based on the results from the other sampling days. If the Day 1 dissolved mercury result wasexcluded from the calculated average, the 4-day average would be 2,940 ng/L.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.Table 4-1. Influent to FGD Wastewater Treatment System, Pleasant PrairieInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageBariumug/L200.790.0F96.097.085.092.0Berylliumug/L200.7NQ (2.00)NQ (2.00)NQ (2.00)ND (2.00)NQ (2.00)Boronug/L200.713,000413,000B13,000B13,000B13,000Cadmiumug/L200.84.504.406.90NQ (4.00)< 4.45Calciumug/L200.7550,0004550,000550,000560,000553,000Chromiumug/L200.8ND (8.00)^ND (8.00)^ND (8.00)^ND (8.00)^ND (8.00)Chromium (VI)ug/L218.6ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Cobaltug/L200.7110120120110115Copperug/L200.828.031.034.023.029.0Ironug/L200.7NQ (200)ND (200)NQ (200)NQ (200)NQ (200)Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.74,100,00044,000,000B3,800,000B3,800,000B3,930,000Manganeseug/L200.770,000472,000B70,00067,000B69,800Mercuryng/L1631E1.96+3,8602,3702,6002,210+Molybdenumug/L200.749.040.047.050.046.5Nickelug/L200.893049401,000870935Seleniumug/L200.83,60043,500B3,8003,900B3,700Silverug/L200.8ND (2.00)FND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.7510,0004470,000490,000490,000490,000Thalliumug/L200.89.309.809.709.509.58Tinug/L200.7NQ (200)NQ (200)NQ (200)NQ (200)NQ (200)Titaniumug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)

# 4-7< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).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.+- The accuracy of the Day 1 dissolved mercury analytical result seems questionable based on the results from the other sampling days. If the Day 1 dissolved mercury result wasexcluded from the calculated average, the 4-day average would be 2,940 ng/L.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.Table 4-1. Influent to FGD Wastewater Treatment System, Pleasant PrairieInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageVanadiumug/L200.8NQ (10.0)BNQ (10.0)BNQ (10.0)NQ (10.0)NQ (10.0)Zincug/L200.893.010011043.0B86.5

# 4-8Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.Table 4-2. Effluent From FGD Wastewater Treatment System, Pleasant PrairieEffluent from the FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmoniamg/L350.123.020.018.016.019.3Nitrate Nitrite as Nmg/L353.2160160160160160Nitrogen, Total Kjeldahlmg/L351.272.0B68.064.0B,452.064.0Biochemical Oxygen Demandmg/L5210BND (2.00)NQ (2.50)NQ (2.50)NQ (2.50)NQ (2.38)Chemical Oxygen Demandmg/L410.4390*455410F,*420419Chloridemg/L300.02,0002,0001,9001,9001,950Sulfatemg/L300.016,00016,00015,00015,00015,500Cyanide, Totalmg/L4500 CN E0.190B0.1850.240B,F0.180F0.199Total Dissolved Solidsmg/L2540C21,00023,50023,00022,000B22,400Total Suspended Solidsmg/L2540DNQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Phosphorus, Totalmg/L365.10.0700B< 0.0825NQ (0.0500)B,FNQ (0.0500)B< 0.0506Total MetalsAluminumug/L200.7680F< 410ND (200)NQ (200)< 323Antimonyug/L200.82.502.352.202.402.36Arsenicug/L200.86.404.805.005.305.38Bariumug/L200.768.069.074.073.071.0Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.710,000B,410,0009,300410,000B,49,830Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.7650,0004655,000660,0004660,0004656,000

# 4-9Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.Table 4-2. Effluent From FGD Wastewater Treatment System, Pleasant PrairieEffluent from the FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageChromiumug/L200.8ND (8.00)^ND (8.00)ND (8.00)ND (8.00)^ND (8.00)Cobaltug/L200.7ND (20.0)NQ (20.0)ND (20.0)NQ (20.0)NQ (20.0)Copperug/L200.8ND (4.00)NQ (4.00)ND (4.00)ND (4.00)NQ (4.00)Ironug/L200.7NQ (200)NQ (200)210390F< 200Leadug/L200.8ND (2.00)NQ (2.00)ND (2.00)ND (2.00)NQ (2.00)Magnesiumug/L200.73,700,000B,43,550,0003,700,00043,500,00043,610,000Manganeseug/L200.711,000B,411,00011,000411,000411,000Mercuryng/L1631E78.486.472.974.978.1Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)41.0< 25.3Nickelug/L200.8NQ (4.00)< 11.0NQ (4.00)7.30F< 5.58Seleniumug/L200.82,10042,1502,000B,42,00042,060Silverug/L200.8ND (2.00)FND (2.00)ND (2.00)FND (2.00)FND (2.00)Sodiumug/L200.7510,0004510,000530,0004500,0004513,000Thalliumug/L200.82.902.952.802.302.74Tinug/L200.7ND (200)NQ (200)ND (200)NQ (200)NQ (200)Titaniumug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Vanadiumug/L200.8ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Zincug/L200.8ND (10.0)< 9.50ND (10.0)NQ (10.0)< 6.13Dissolved MetalsAluminumug/L200.7ND (200)ND (200)NQ (200)^NQ (200)NQ (200)Antimonyug/L200.82.80< 1.752.602.70< 2.46

# 4-10Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.Table 4-2. Effluent From FGD Wastewater Treatment System, Pleasant PrairieEffluent from the FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageArsenicug/L200.84.905.404.204.904.85Bariumug/L200.767.069.072.069.069.3Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.710,000B,410,0009,900B,49,800B,49,930Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.7640,0004645,000660,0004610,0004639,000Chromiumug/L200.8ND (8.00)^ND (8.00)ND (8.00)^ND (8.00)^ND (8.00)Chromium (VI)ug/L218.6ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Cobaltug/L200.7ND (20.0)NQ (20.0)ND (20.0)NQ (20.0)NQ (20.0)Copperug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Ironug/L200.7NQ (200)NQ (200)NQ (200)NQ (200)NQ (200)Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.73,700,000B,43,550,0003,500,000B,43,500,000B,43,560,000Manganeseug/L200.711,000B,411,00010,000B,411,000410,800Mercuryng/L1631E22.827.020.519.022.3Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)Nickelug/L200.8NQ (4.00)NQ (4.00)6.10NQ (4.00)< 3.03Seleniumug/L200.82,100B,42,1002,000B,42,10042,080Silverug/L200.8ND (2.00)FND (2.00)ND (2.00)FND (2.00)FND (2.00)Sodiumug/L200.7530,0004530,000520,0004490,0004518,000Thalliumug/L200.82.502.652.302.902.59

# 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.Table 4-2. Effluent From FGD Wastewater Treatment System, Pleasant PrairieEffluent from the FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageTinug/L200.7ND (200)NQ (200)ND (200)NQ (200)NQ (200)Titaniumug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Vanadiumug/L200.8NQ (10.0)BND (10.0)ND (10.0)ND (10.0)NQ (10.0)Zincug/L200.819.0FND (10.0)ND (10.0)ND (10.0)< 8.50

# 4-12< - 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.Table 4-3. Classical Pollutants 4-Day Average Data Summaryfor FGD Wastewater Treatment System, Pleasant PrairieAnalyteUnitsMethodInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent fromFGD Wastewater TreatmentSystem (SP-2)4-Day AverageClassicalsAmmoniamg/L350.114.519.3Nitrate Nitrite as Nmg/L353.2158160Nitrogen, Total Kjeldahlmg/L351.262.564.0Biochemical Oxygen Demandmg/L5210BND (2.00)NQ (2.38)Chemical Oxygen Demandmg/L410.4423419Chloridemg/L300.01,8001,950Sulfatemg/L300.016,00015,500Cyanide, Totalmg/L4500 CN E0.2350.199Total Dissolved Solidsmg/L2540C24,30022,400Total Suspended Solidsmg/L2540D4,430NQ (4.00)Phosphorus, Totalmg/L365.1< 0.347< 0.0506

# 4-13< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).* - The 4-day average result includes an analytical result where the accuracy is questionable. If the questionable result wasexcluded from the calculated average, the 4-dayaverage would be 2,940 ng/L.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.Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, Pleasant PrairieInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent fromFGD Wastewater TreatmentSystem (SP-2)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedMetalsAluminumug/L200.7125,000< 128< 323NQ (200)Antimonyug/L200.862.83.752.36< 2.46Arsenicug/L200.81507.205.384.85Bariumug/L200.767892.071.069.3Berylliumug/L200.75.00NQ (2.00)ND (2.00)ND (2.00)Boronug/L200.712,00013,0009,8309,930Cadmiumug/L200.811.1< 4.45ND (4.00)ND (4.00)Calciumug/L200.7688,000553,000656,000639,000Chromiumug/L200.81,090ND (8.00)ND (8.00)ND (8.00)Chromium (VI)ug/L218.6NAND (10.0)NAND (10.0)Cobaltug/L200.7140115NQ (20.0)NQ (20.0)Copperug/L200.81,13029.0NQ (4.00)ND (4.00)Ironug/L200.7413,000NQ (200)< 200NQ (200)Leadug/L200.8280ND (2.00)NQ (2.00)ND (2.00)Magnesiumug/L200.74,150,0003,930,0003,610,0003,560,000Manganeseug/L200.773,80069,80011,00010,800Mercuryng/L1631E1,970,0002,210*78.122.3Molybdenumug/L200.724046.5< 25.3NQ (40.0)Nickelug/L200.81,450935< 5.58< 3.03Seleniumug/L200.816,3003,7002,0602,080Silverug/L200.8NQ (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.7500,000490,000513,000518,000Thalliumug/L200.811.09.582.742.59

# 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).* - The 4-day average result includes an analytical result where the accuracy is questionable. If the questionable result wasexcluded from the calculated average, the 4-dayaverage would be 2,940 ng/L.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.Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, Pleasant PrairieInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent fromFGD Wastewater TreatmentSystem (SP-2)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTinug/L200.7NQ (200)NQ (200)NQ (200)NQ (200)Titaniumug/L200.74,530ND (20.0)ND (20.0)ND (20.0)Vanadiumug/L200.81,100NQ (10.0)ND (10.0)NQ (10.0)Zincug/L200.81,68086.5< 6.13< 8.50

# 5-1 5. D ATA 

# Q UALITY



# Quality assurance/quality control (QA/QC) pro cedures applicable to the Pleasant Prairie

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 were

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-10 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 S ection 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-10 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-4) 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 Pleasant Prairie’s re presentative, using the sa me 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 bl ank for the dissolved mercury sample. Mercury was not

detected above the method detection limit (0.24 ng/L) in the filtration blanks performe d for any of the days of

samples.

# 5-3 The dissolved metals by 200.8, dissolved metals by 200.7, and dissolved hexavalant

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 around 120 minutes , the sampling team began pumping off the

ASTM Type 1 water from the 10-liter composite c ontainer. Prior to filling the sample bottles, the

tubing was purged for around 40 seconds. The sample bottles were placed in a “cleanbox” and

the ASTM Type 1 water was pumped through the t ubing, capsule filter, and “Y” splitter, and into

the sample bottles. EPA collected the field bla nk samples as “true” split samples with Pleasant

Prairie’s representative, using th e 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

Pleasant Prairie’s representative, using the same procedure discussed 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.

Table 5-1 presents the field blank analyt ical results for SP-4 and SP-5. Only those

analytes that were detected in the field blank samples at levels above the quantitation limit are

included in the table. Results are rounded to three significant digits . Appendix Tables A-11

through A-15 present all the analytical results for the field blanks from each of the sampling

points, including all qualified results and all results that were measured above the method

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

# 5-4 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

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 5-2 presents analytical results and the RPD for SP3. Results are rounded to three significant digits . Appendix Tables A-6 and A-9 present all the

analytical results for the efflue nt from the FGD wastewater trea tment 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).< - 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 average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.



# 5-5Table 5-1. Field Blank Analytical Results, Pleasant PrairieAnalyteSample DescriptionMethodUnitsConcentrationTotal MetalsNickelEffluent from FGD Wastewater Treatment System Field Blank - Day 1200.8ug/L6.20SeleniumInfluent to FGD Wastewater Treatment System Field Blank - Day 1200.8ug/L4.70< - 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 average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.



# 5-6Table 5-2. Field Duplicate Results– Effluent from FGD Wastewater Treatment System, Pleasant PrairieAnalyteMethodUnitsOriginalEffluent from FGDWastewater TreatmentSystem, Day 2Concentration(SP-2)DuplicateEffluent from FGDWastewater TreatmentSystem Concentration(SP-4)AverageResultRelativePercentDifferenceClassicalsAmmonia350.1mg/L20.020.020.00.00Nitrate Nitrite as N353.2mg/L1601601600.00Nitrogen, Total Kjeldahl351.2mg/L66.0B70.0B68.05.88Biochemical Oxygen Demand5210Bmg/LNQ (2.50)NQ (2.50)NQ (2.50)NCChemical Oxygen Demand410.4mg/L4404704556.59Chloride300.0mg/L2,0002,0002,0000.00Sulfate300.0mg/L16,00016,00016,0000.00Cyanide, Total4500 CN Emg/L0.210B0.160B0.18527.0Total Dissolved Solids2540Cmg/L24,00023,00023,5004.26Total Suspended Solids2540Dmg/LNQ (4.00)NQ (4.00)NQ (4.00)NCPhosphorus, Total365.1mg/L0.140BNQ (0.0500)B< 0.0825NCTotal MetalsAluminum200.7ug/L720FND (200)< 410NCAntimony200.8ug/L2.402.302.354.26Arsenic200.8ug/L4.704.904.804.17Barium200.7ug/L69.069.069.00.00Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L10,000B,410,000B10,0000.00Cadmium200.8ug/LND (4.00)ND (4.00)ND (4.00)NC< - 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 average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.



# 5-7Table 5-2. Field Duplicate Results– Effluent from FGD Wastewater Treatment System, Pleasant PrairieAnalyteMethodUnitsOriginalEffluent from FGDWastewater TreatmentSystem, Day 2Concentration(SP-2)DuplicateEffluent from FGDWastewater TreatmentSystem Concentration(SP-4)AverageResultRelativePercentDifferenceCalcium200.7ug/L650,0004660,000655,0001.53Chromium200.8ug/LND (8.00)ND (8.00)ND (8.00)NCCobalt200.7ug/LNQ (20.0)NQ (20.0)NQ (20.0)NCCopper200.8ug/LNQ (4.00)ND (4.00)NQ (4.00)NCIron200.7ug/LNQ (200)NQ (200)NQ (200)NCLead200.8ug/LNQ (2.00)ND (2.00)NQ (2.00)NCMagnesium200.7ug/L3,600,00043,500,0003,550,0002.82Manganese200.7ug/L11,000411,00011,0000.00Mercury1631Eng/L88.384.486.44.52Molybdenum200.7ug/LNQ (40.0)NQ (40.0)NQ (40.0)NCNickel200.8ug/L20.0FNQ (4.00)< 11.0NCSelenium200.8ug/L2,200B,42,100B2,1504.65Silver200.8ug/LND (2.00)FND (2.00)ND (2.00)NCSodium200.7ug/L510,0004510,000510,0000.00Thallium200.8ug/L3.102.802.9510.2Tin200.7ug/LND (200)NQ (200)NQ (200)NCTitanium200.7ug/LND (20.0)ND (20.0)ND (20.0)NCVanadium200.8ug/LND (10.0)ND (10.0)ND (10.0)NCZinc200.8ug/L14.0FND (10.0)< 9.50NCDissolved Metals< - 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 average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.



# 5-8Table 5-2. Field Duplicate Results– Effluent from FGD Wastewater Treatment System, Pleasant PrairieAnalyteMethodUnitsOriginalEffluent from FGDWastewater TreatmentSystem, Day 2Concentration(SP-2)DuplicateEffluent from FGDWastewater TreatmentSystem Concentration(SP-4)AverageResultRelativePercentDifferenceAluminum200.7ug/LND (200)ND (200)ND (200)NCAntimony200.8ug/LNQ (2.00)2.50< 1.75NCArsenic200.8ug/L5.505.305.403.70Barium200.7ug/L68.070.069.02.90Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L10,000B,410,000B10,0000.00Cadmium200.8ug/LND (4.00)ND (4.00)ND (4.00)NCCalcium200.7ug/L640,0004650,000645,0001.55Chromium200.8ug/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)NQ (20.0)NQ (20.0)NCCopper200.8ug/LND (4.00)ND (4.00)ND (4.00)NCIron200.7ug/LNQ (200)NQ (200)NQ (200)NCLead200.8ug/LND (2.00)ND (2.00)ND (2.00)NCMagnesium200.7ug/L3,500,000B,43,600,000B3,550,0002.82Manganese200.7ug/L11,000411,00011,0000.00Mercury1631Eng/L27.426.527.03.34Molybdenum200.7ug/LNQ (40.0)NQ (40.0)NQ (40.0)NCNickel200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCSelenium200.8ug/L2,00042,2002,1009.52< - 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 average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.



# 5-9Table 5-2. Field Duplicate Results– Effluent from FGD Wastewater Treatment System, Pleasant PrairieAnalyteMethodUnitsOriginalEffluent from FGDWastewater TreatmentSystem, Day 2Concentration(SP-2)DuplicateEffluent from FGDWastewater TreatmentSystem Concentration(SP-4)AverageResultRelativePercentDifferenceSilver200.8ug/LND (2.00)FND (2.00)ND (2.00)NCSodium200.7ug/L520,0004540,000530,0003.77Thallium200.8ug/L2.702.602.653.77Tin200.7ug/LND (200)NQ (200)NQ (200)NCTitanium200.7ug/LND (20.0)ND (20.0)ND (20.0)NCVanadium200.8ug/LND (10.0)ND (10.0)ND (10.0)NCZinc200.8ug/LND (10.0)ND (10.0)ND (10.0)NC

# 6-1 6. R EFERENCES



# 1. Eastern Research Group, Inc., 2010. Sampling Plan, We Energies’ Pleasant Prairie

Power Station. June 3. DCN SE00506.

2. Eastern Research Group, Inc., 2010. Quality Assurance Project Plan for the Steam

Electric Effluent Guidelines Rulemaking . (October). DCN SE00058.

# Appendix A

ANALYTICAL RESULTSND – 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.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-1Table A-1. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L41.9419Nitrate Nitrite as N353.2mg/L200.382150Nitrogen, Total Kjeldahl351.2mg/L41.520864Biochemical Oxygen Demand5210Bmg/L10.242ND (2)UChemical Oxygen Demand410.4mg/L520100420FChloride300.0mg/L50131501,800Sulfate300.0mg/L5001202,50014,000Cyanide, Total4500 CN Emg/L10.020.10.25BTotal Dissolved Solids2540Cmg/L14710023,000Total Suspended Solids2540Dmg/L111403,800Phosphorus, Total365.1mg/L10.0050.050.95BTotal MetalsAluminum200.7ug/L29.4200110,000B,4Antimony200.8ug/L20.72265Arsenic200.8ug/L21.24150Barium200.7ug/L22.520680FBeryllium200.7ug/L20.7124.8Boron200.7ug/L26.720011,000B,4Cadmium200.8ug/L21.249.2Calcium200.7ug/L269400670,000B,4Chromium200.8ug/L50822001,4004,^Cobalt200.7ug/L21.120140Copper200.8ug/L50241001,3004Iron200.7ug/L232200400,000B,4Lead200.8ug/L5018502804ND – 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.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-2Table A-1. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0004,200,000B,4Manganese200.7ug/L501350072,000B,4Mercury1631Eng/L200,00049,700104,0002,020,000Molybdenum200.7ug/L21.640240Nickel200.8ug/L50221001,6004Selenium200.8ug/L501610020,0004Silver200.8ug/L20.5921.2J,FSodium200.7ug/L504,600250,000470,0004Thallium200.8ug/L20.47211Tin200.7ug/L24.820050JTitanium200.7ug/L21.6204,5004Vanadium200.8ug/L50422501,4004Zinc200.8ug/L501002502,5004Dissolved MetalsAluminum200.7ug/L29.4200120JAntimony200.8ug/L20.7223.8Arsenic200.8ug/L21.247.2Barium200.7ug/L22.52090FBeryllium200.7ug/L20.7120.84JBoron200.7ug/L26.720013,0004Cadmium200.8ug/L21.244.5Calcium200.7ug/L269400550,0004Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.120110Copper200.8ug/L20.96428ND – 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.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-3Table A-1. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationIron200.7ug/L23220037JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0004,100,0004Manganese200.7ug/L501350070,0004Mercury1631Eng/L10.240.51.96Molybdenum200.7ug/L21.64049Nickel200.8ug/L50221009304Selenium200.8ug/L20.6243,6004Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L504,600250,000510,0004Thallium200.8ug/L20.4729.3Tin200.7ug/L24.820020JTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7105.8J,BZinc200.8ug/L24.11093ND – 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.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).



# A-4Table A-2. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L20.94213Nitrate Nitrite as N353.2mg/L200.382160Nitrogen, Total Kjeldahl351.2mg/L41.52072BBiochemical Oxygen Demand5210Bmg/L10.242ND (2)UChemical Oxygen Demand410.4mg/L520100460Chloride300.0mg/L50131501,800Sulfate300.0mg/L5001202,50016,000Cyanide, Total4500 CN Emg/L10.020.10.28BTotal Dissolved Solids2540Cmg/L14710024,000Total Suspended Solids2540Dmg/L1281007,100Phosphorus, Total365.1mg/L50.0250.250.25BTotal MetalsAluminum200.7ug/L29.4200130,000Antimony200.8ug/L20.72263Arsenic200.8ug/L21.24160Barium200.7ug/L22.520770Beryllium200.7ug/L20.7125.1Boron200.7ug/L26.720012,000BCadmium200.8ug/L21.2411Calcium200.7ug/L269400690,000Chromium200.8ug/L50822001,000^Cobalt200.7ug/L21.120140Copper200.8ug/L50241001,100Iron200.7ug/L232200420,000Lead200.8ug/L501850280Magnesium200.7ug/L5054010,0004,200,000BND – 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.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).



# A-5Table A-2. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L501350076,000BMercury1631Eng/L200,00048,300101,0002,080,000Molybdenum200.7ug/L21.640240Nickel200.8ug/L50221001,400Selenium200.8ug/L501610015,000Silver200.8ug/L20.5921JSodium200.7ug/L504,600250,000510,000Thallium200.8ug/L20.47212Tin200.7ug/L24.820047JTitanium200.7ug/L21.6204,400Vanadium200.8ug/L50422501,100BZinc200.8ug/L501002501,300BDissolved MetalsAluminum200.7ug/L29.4200170J,BAntimony200.8ug/L20.7223.4Arsenic200.8ug/L21.246.9Barium200.7ug/L22.52096Beryllium200.7ug/L20.7121.2JBoron200.7ug/L26.720013,000BCadmium200.8ug/L21.244.4Calcium200.7ug/L269400550,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.120120Copper200.8ug/L20.96431Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UND – 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.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).



# A-6Table A-2. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0004,000,000BManganese200.7ug/L501350072,000BMercury1631Eng/L4,0009752,0403,860Molybdenum200.7ug/L21.64040Nickel200.8ug/L104.520940Selenium200.8ug/L20.6243,500BSilver200.8ug/L20.592ND (2)USodium200.7ug/L504,600250,000470,000Thallium200.8ug/L20.4729.8Tin200.7ug/L24.820014JTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7105.8J,BZinc200.8ug/L24.110100ND – 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.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).



# A-7Table A-3. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L20.94212Nitrate Nitrite as N353.2mg/L200.382160Nitrogen, Total Kjeldahl351.2mg/L10.38516BBiochemical Oxygen Demand5210Bmg/L10.242ND (2)UChemical Oxygen Demand410.4mg/L520100410Chloride300.0mg/L50131501,800Sulfate300.0mg/L5001202,50017,000Cyanide, Total4500 CN Emg/L10.020.10.18BTotal Dissolved Solids2540Cmg/L14710024,000Total Suspended Solids2540Dmg/L1281003,300Phosphorus, Total365.1mg/L50.0250.250.085J,BTotal MetalsAluminum200.7ug/L29.4200120,000Antimony200.8ug/L20.72263Arsenic200.8ug/L21.24140Barium200.7ug/L22.520750Beryllium200.7ug/L20.7125Boron200.7ug/L26.720012,000BCadmium200.8ug/L21.2411Calcium200.7ug/L269400690,000Chromium200.8ug/L101640960Cobalt200.7ug/L21.120140Copper200.8ug/L50241001,000Iron200.7ug/L232200420,000Lead200.8ug/L103.610280Magnesium200.7ug/L5054010,0004,000,000ND – 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.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).



# A-8Table A-3. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L501350073,000Mercury1631Eng/L200,00048,300101,0002,060,000Molybdenum200.7ug/L21.640240Nickel200.8ug/L50221001,400Selenium200.8ug/L103.12015,000BSilver200.8ug/L20.5920.82JSodium200.7ug/L504,600250,000500,000Thallium200.8ug/L20.47211Tin200.7ug/L24.820043JTitanium200.7ug/L21.6204,300Vanadium200.8ug/L108.450910Zinc200.8ug/L501002501,400Dissolved MetalsAluminum200.7ug/L29.4200210Antimony200.8ug/L20.7223.7Arsenic200.8ug/L21.247.7Barium200.7ug/L22.52097Beryllium200.7ug/L20.7121.1JBoron200.7ug/L26.720013,000BCadmium200.8ug/L21.246.9Calcium200.7ug/L269400550,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.120120Copper200.8ug/L20.96434Iron200.7ug/L232200190JLead200.8ug/L20.732ND (2)UND – 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.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).



# A-9Table A-3. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0003,800,000BManganese200.7ug/L501350070,000Mercury1631Eng/L10024.150.52,370Molybdenum200.7ug/L21.64047Nickel200.8ug/L50221001,000Selenium200.8ug/L20.6243,800Silver200.8ug/L20.592ND (2)USodium200.7ug/L504,600250,000490,000Thallium200.8ug/L20.4729.7Tin200.7ug/L24.820016JTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7103.7JZinc200.8ug/L24.110110ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - 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.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).



# A-10Table A-4. Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L20.94214Nitrate Nitrite as N353.2mg/L200.382160Nitrogen, Total Kjeldahl351.2mg/L41.52076BBiochemical Oxygen Demand5210Bmg/L10.242ND (2)UChemical Oxygen Demand410.4mg/L520100400*Chloride300.0mg/L50131501,800Sulfate300.0mg/L5001202,50017,000Cyanide, Total4500 CN Emg/L10.020.10.23BTotal Dissolved Solids2540Cmg/L14710026,000Total Suspended Solids2540Dmg/L1281003,500Phosphorus, Total365.1mg/L10.0050.050.063BTotal MetalsAluminum200.7ug/L502405,000140,000Antimony200.8ug/L20.72260Arsenic200.8ug/L21.24150Barium200.7ug/L22.520510Beryllium200.7ug/L20.7125.1Boron200.7ug/L501705,00013,000Cadmium200.8ug/L21.2413Calcium200.7ug/L269400700,000Chromium200.8ug/L101640980Cobalt200.7ug/L21.120140Copper200.8ug/L50241001,100Iron200.7ug/L232200410,000Lead200.8ug/L103.610280ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - 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.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).



# A-11Table A-4. Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0004,200,000Manganese200.7ug/L501350074,000Mercury1631Eng/L200,00048,300101,0001,730,000Molybdenum200.7ug/L21.640240Nickel200.8ug/L50221001,400Selenium200.8ug/L103.12015,000BSilver200.8ug/L20.5921JSodium200.7ug/L504,600250,000520,000Thallium200.8ug/L20.47210Tin200.7ug/L24.820041JTitanium200.7ug/L21.6204,900Vanadium200.8ug/L108.450970BZinc200.8ug/L501002501,500Dissolved MetalsAluminum200.7ug/L29.420046J,^Antimony200.8ug/L20.7224.1Arsenic200.8ug/L21.247Barium200.7ug/L22.52085Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00013,000BCadmium200.8ug/L21.243.6JCalcium200.7ug/L269400560,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI) 218.6 ug/L 1 1.96 10 ND (10) UCobalt 200.7 ug/L 2 1.1 20 110Copper 200.8 ug/L 2 0.96 4 23ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - 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.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).



# A-12Table A-4. Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationIron 200.7 ug/L 2 32 200 39 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 3,800,000 BManganese 200.7 ug/L 50 13 500 67,000 BMercury 1631E ng/L 2,000 487 1,020 2,600Molybdenum 200.7 ug/L 2 1.6 40 50Nickel 200.8 ug/L 10 4.5 20 870Selenium 200.8 ug/L 10 3.1 20 3,900 BSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 50 4,600 250,000 490,000Thallium 200.8 ug/L 2 0.47 2 9.5Tin 200.7 ug/L 2 4.8 200 12 JTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 6 JZinc 200.8 ug/L 2 4.1 10 43 BND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-13Table A-5. Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLAnalyteClassicalsAmmonia350.1mg/L41.9423Nitrate Nitrite as N353.2mg/L200.382160Nitrogen, Total Kjeldahl351.2mg/L100.771072BBiochemical Oxygen Demand5210Bmg/L10.242ND (2)UChemical Oxygen Demand410.4mg/L520100390*Chloride300.0mg/L50131502,000Sulfate300.0mg/L5001202,50016,000Cyanide, Total4500 CN Emg/L10.020.10.19BTotal Dissolved Solids2540Cmg/L14710021,000Total Suspended Solids2540Dmg/L11.142JPhosphorus, Total365.1mg/L10.0050.050.07BTotal MetalsAluminum200.7ug/L29.4200680FAntimony200.8ug/L20.7222.5Arsenic200.8ug/L21.246.4Barium200.7ug/L22.52068Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720010,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400650,0004Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200120JLead200.8ug/L20.732ND (2)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-14Table A-5. Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLAnalyteMagnesium200.7ug/L5054010,0003,700,000B,4Manganese200.7ug/L501350011,000B,4Mercury1631Eng/L102.415.0578.4Molybdenum200.7ug/L21.64034JNickel200.8ug/L20.8942.5JSelenium200.8ug/L20.6242,1004Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L504,600250,000510,0004Thallium200.8ug/L20.4722.9Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.8Arsenic200.8ug/L21.244.9Barium200.7ug/L22.52067Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720010,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400640,0004Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-15Table A-5. Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLAnalyteIron200.7ug/L23220042JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0003,700,000B,4Manganese200.7ug/L501350011,000B,4Mercury1631Eng/L102.415.0522.8Molybdenum200.7ug/L21.64033JNickel200.8ug/L20.8943.1JSelenium200.8ug/L20.6242,100B,4Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L504,600250,000530,0004Thallium200.8ug/L20.4722.5Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7101.8J,BZinc200.8ug/L24.11019FND – 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.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-16Table A-6. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L41.9420Nitrate Nitrite as N353.2mg/L200.382160Nitrogen, Total Kjeldahl351.2mg/L100.771066BBiochemical Oxygen Demand5210Bmg/L10.32.51.7JChemical Oxygen Demand410.4mg/L520100440Chloride300.0mg/L50131502,000Sulfate300.0mg/L5001202,50016,000Cyanide, Total4500 CN Emg/L10.020.10.21BTotal Dissolved Solids2540Cmg/L14710024,000Total Suspended Solids2540Dmg/L11.142.4JPhosphorus, Total365.1mg/L10.0050.050.14BTotal MetalsAluminum200.7ug/L29.4200720FAntimony200.8ug/L20.7222.4Arsenic200.8ug/L21.244.7Barium200.7ug/L22.52069Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720010,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400650,0004Chromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.1201.2JCopper200.8ug/L20.9641.1JIron200.7ug/L232200150JLead200.8ug/L20.7321.4JND – 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.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-17Table A-6. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0003,600,0004Manganese200.7ug/L501350011,0004Mercury1631Eng/L204.8310.188.3Molybdenum200.7ug/L21.64035JNickel200.8ug/L20.89420FSelenium200.8ug/L20.6242,200B,4Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L504,600250,000510,0004Thallium200.8ug/L20.4723.1Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.11014FDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7221.9JArsenic200.8ug/L21.245.5Barium200.7ug/L22.52068Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720010,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400640,0004Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220037JND – 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.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-18Table A-6. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0003,500,000B,4Manganese200.7ug/L501350011,0004Mercury1631Eng/L5012.125.227.4Molybdenum200.7ug/L21.64032JNickel200.8ug/L20.8943.3JSelenium200.8ug/L20.6242,0004Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L504,600250,000520,0004Thallium200.8ug/L20.4722.7Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-19Table A-7. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L20.94218Nitrate Nitrite as N353.2mg/L500.955160Nitrogen, Total Kjeldahl351.2mg/L100.771064B,4Biochemical Oxygen Demand5210Bmg/L10.32.51.9JChemical Oxygen Demand410.4mg/L520100410F,*Chloride300.0mg/L50131501,900Sulfate300.0mg/L5001202,50015,000Cyanide, Total4500 CN Emg/L10.020.10.24B,FTotal Dissolved Solids2540Cmg/L1194023,000Total Suspended Solids2540Dmg/L11.142.4JPhosphorus, Total365.1mg/L10.0050.050.028J,B,FTotal MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.2Arsenic200.8ug/L21.245Barium200.7ug/L22.52074Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.72009,3004Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400660,0004Chromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200210Lead200.8ug/L20.732ND (2)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-20Table A-7. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0003,700,0004Manganese200.7ug/L501350011,0004Mercury1631Eng/L102.415.0572.9Molybdenum200.7ug/L21.64033JNickel200.8ug/L20.8942.4JSelenium200.8ug/L20.6242,000B,4Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L504,600250,000530,0004Thallium200.8ug/L20.4722.8Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.420017J,^Antimony200.8ug/L20.7222.6Arsenic200.8ug/L21.244.2Barium200.7ug/L22.52072Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,0009,900B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400660,0004Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-21Table A-7. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationIron200.7ug/L23220036JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0003,500,000B,4Manganese200.7ug/L501350010,000B,4Mercury1631Eng/L102.415.0520.5Molybdenum200.7ug/L21.64032JNickel200.8ug/L20.8946.1Selenium200.8ug/L20.6242,000B,4Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L504,600250,000520,0004Thallium200.8ug/L20.4722.3Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UND – 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.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-22Table A-8. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.94216Nitrate Nitrite as N353.2mg/L200.382160Nitrogen, Total Kjeldahl351.2mg/L100.771052Biochemical Oxygen Demand5210Bmg/L10.32.51.9JChemical Oxygen Demand410.4mg/L520100420Chloride300.0mg/L50131501,900Sulfate300.0mg/L5001202,50015,000Cyanide, Total4500 CN Emg/L10.020.10.18FTotal Dissolved Solids2540Cmg/L14710022,000BTotal Suspended Solids2540Dmg/L11.142JPhosphorus, Total365.1mg/L10.0050.050.018J,BTotal MetalsAluminum200.7ug/L29.420013JAntimony200.8ug/L20.7222.4Arsenic200.8ug/L21.245.3Barium200.7ug/L22.52073Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720010,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400660,0004Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.1203JCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200390FLead200.8ug/L20.732ND (2)UND – 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.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-23Table A-8. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0003,500,0004Manganese200.7ug/L501350011,0004Mercury1631Eng/L10024.150.574.9Molybdenum200.7ug/L21.64041Nickel200.8ug/L20.8947.3FSelenium200.8ug/L20.6242,0004Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L504,600250,000500,0004Thallium200.8ug/L20.4722.3Tin200.7ug/L24.820015JTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1104.2JDissolved MetalsAluminum200.7ug/L29.420011JAntimony200.8ug/L20.7222.7Arsenic200.8ug/L21.244.9Barium200.7ug/L22.52069Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.72009,800B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400610,0004Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.1203.1JCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220033JND – 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.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-24Table A-8. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0003,500,000B,4Manganese200.7ug/L501350011,0004Mercury1631Eng/L102.415.0519Molybdenum200.7ug/L21.64039JNickel200.8ug/L20.8943.5JSelenium200.8ug/L20.6242,1004Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L504,600250,000490,0004Thallium200.8ug/L20.4722.9Tin200.7ug/L24.820014JTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UND – 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.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).



# A-25Table A-9. Duplicate of Effluent from FGD Wastewater Treatment System, Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L41.9420Nitrate Nitrite as N353.2mg/L200.382160Nitrogen, Total Kjeldahl351.2mg/L100.771070BBiochemical Oxygen Demand5210Bmg/L10.32.51.9JChemical Oxygen Demand410.4mg/L520100470Chloride300.0mg/L50131502,000Sulfate300.0mg/L5001202,50016,000Cyanide, Total4500 CN Emg/L10.020.10.16BTotal Dissolved Solids2540Cmg/L14710023,000Total Suspended Solids2540Dmg/L11.141.2JPhosphorus, Total365.1mg/L10.0050.050.018J,BTotal MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.3Arsenic200.8ug/L21.244.9Barium200.7ug/L22.52069Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720010,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400660,000Chromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.1201.7JCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200100JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0003,500,000Manganese200.7ug/L501350011,000ND – 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.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).



# A-26Table A-9. Duplicate of Effluent from FGD Wastewater Treatment System, Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L5012.125.284.4Molybdenum200.7ug/L21.64038JNickel200.8ug/L20.8942.7JSelenium200.8ug/L20.6242,100BSilver200.8ug/L20.592ND (2)USodium200.7ug/L504,600250,000510,000Thallium200.8ug/L20.4722.8Tin200.7ug/L24.82008.2JTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.5Arsenic200.8ug/L21.245.3Barium200.7ug/L22.52070Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720010,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400650,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.1202.2JCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220051JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0003,600,000BManganese200.7ug/L501350011,000ND – 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.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).



# A-27Table A-9. Duplicate of Effluent from FGD Wastewater Treatment System, Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L5012.125.226.5Molybdenum200.7ug/L21.64039JNickel200.8ug/L20.8943.1JSelenium200.8ug/L20.6242,200Silver200.8ug/L20.592ND (2)USodium200.7ug/L504,600250,000540,000Thallium200.8ug/L20.4722.6Tin200.7ug/L24.82009.9JTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)U

# 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 report limit).



# A-28 Table A-10. Bottle Blank and Equipment Blan k Analytical Data, Pleasant Prairie

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 report limit).



# A-29 Table A-10. Bottle Blank and Equipment Blan k Analytical Data, Pleasant Prairie

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 report limit).



# A-30 Table A-10. Bottle Blank and Equipment Blan k Analytical Data, Pleasant Prairie

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 report limit).



# A-31 Table A-10. Bottle Blank and Equipment Blan k Analytical Data, Pleasant Prairie

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)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

# 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 report limit).



# A-32 Table A-10. Bottle Blank and Equipment Blan k Analytical Data, Pleasant Prairie

Analyte Method Process Units Concentration

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-33ND – 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.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-11. Influent to FGD Wastewater Treatment System Field Blank, Day 1 AnalyticalResults, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsAluminum200.7ug/L29.4200100J,BAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720050J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220046J,BLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400130J,BManganese200.7ug/L20.51202.4J,BMercury1631Eng/L10.240.5ND (0.5)UMolybdenum200.7ug/L21.6401.7JNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6244.7Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000230JThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6201.9JVanadium200.8ug/L21.7102.8JZinc200.8ug/L24.110ND (10)U

# A-34ND – 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.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-11. Influent to FGD Wastewater Treatment System Field Blank, Day 1 AnalyticalResults, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720044JCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L26940087JChromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400240JManganese200.7ug/L20.51204.4JMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6241.9JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000320JThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7104.1J,BZinc200.8ug/L24.110ND (10)U

# A-35ND – 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.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-12. Effluent from FGD Wastewater Treatment SystemField Blank, Day 1 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720043J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400100JChromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400250J,BManganese200.7ug/L20.51201J,BMercury1631Eng/L10.240.5ND (0.5)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.8946.2Selenium200.8ug/L20.6241.5JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7102.3J,BZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)U

# A-36ND – 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.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-12. Effluent from FGD Wastewater Treatment SystemField Blank, Day 1 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720045J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220087JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400110J,BManganese200.7ug/L20.51200.94J,BMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6241.1J,BSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000190JThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7102.3J,BZinc200.8ug/L24.110ND (10)U

# A-37ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-13. Effluent from FGD Wastewater Treatment SystemField Blank, Day 2 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-38J – Result measured above the MDL, but less than the quantitation limit.Table A-14. Effluent from FGD Wastewater Treatment SystemField Blank, Day 3 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.50.42J

# A-39ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-15. Effluent from FGD Wastewater Treatment SystemField Blank, Day 4 Analytical Results, Pleasant PrairieAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# Appendix B

DATA REVIEW NARRATIVES

# 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.

Donna Tedder, ERG

Date: 2/11/2011

Subject: FGS Data Review Narrative for Total and Dissolved Mercury – Episode 6559

Frontier Global Sciences (FGS) generated analytical data for total and dissolved mercury.

FGS analyzed the samples according to EPA Method 1631E for mercury by Cold Vapor

Atomic Fluorescence Spectrometry (CVAFS) analysis.

Table 1 summarizes the 23 samples (excluding laboratory filter blanks) FGS extracted

and analyzed for total and dissolved mercury.

Table 1. 

# EPA Episode 6559 Mercury– Sample Identification

EPA

Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

71691 1006188-01 Aqueous FGD Influent Day 1 6/21/2010

71691 1006188-02 Aqueous Dissolved FGD Influent Day 1 6/21/2010

71700 1006188-03 Aqueous FGD Influent Field Blank Day 1 6/21/2010

71701 1006188-06 Aqueous FGD Effluent Field Blank Day 1 6/21/2010

71692 1006199-01 Aqueous FGD Influent Day 2 6/22/2010

71692 1006199-02 Aqueous Dissolved FGD Influent Day 2 6/22/2010

71695 1006199-03 Aqueous FGD Effluent Day 1 6/22/2010

71695 1006199-04 Aqueous Dissolved FGD Effluent Day 1 6/22/2010

71702 1006199-05 Aqueous FGD Effluent Field Blank Day 2 6/22/2010

71703 1006205-06 Aqueous FGD Effluent Field Blank Day 3 6/23/2010

71693 1006205-07 Aqueous FGD Influent Day 3 6/23/2010

71693 1006205-08 Aqueous Dissolved FGD Influent Day 3 6/23/2010

71696 1006205-09 Aqueous FGD Effluent Day 2 6/23/2010

71696 1006205-10 Aqueous Dissolved FGD Effluent Day 2 6/23/2010

71699 1006205-11 Aqueous FGD Effluent – Duplicate Day 2 6/23/2010

71699 1006205-12 Aqueous Dissolved FGD Effl uent – Duplicate Day 2 6/23/2010

71694 1006217-01 Aqueous FGD Influent Day 4 6/24/2010

71694 1006217-02 Aqueous Dissolved FGD Influent Day 3 6/24/2010

71697 1006217-03 Aqueous FGD Effluent Day 3 6/24/2010



# 1

# Table 1. 

# EPA Episode 6559 Mercury– Sample Identification

EPA Lab Sample Sample Sampling

Sample # ID # Matrix Sample Description Date

71697 1006217-04 Aqueous Dissolved FGD Effluent Day 3 6/24/2010

71704 1006217-05 Aqueous FGD Effluent Field Blank Day 4 6/24/2010

71698 1006221-02 Aqueous FGD Effluent Day 4 6/25/2010

71698 1006221-03 Aqueous Dissolved FGD Effluent Day 4 6/25/2010



# SUMMARY

The samples were prepared according to EPA Method 1631E to be analyzed by CVAFS.

There were no findings from the data review th at required additional qualifiers in this

dataset.

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysis day. The initial calibration for

the CVAFS analysis consisted of a blank and five calibration standards with a correlation

factor ≥ 0.995. All method-specified criteria were met.

INITIAL AND CONTINUING CAL IBRATION VERIFICATIONS

All initial and continuing calibration verifi cations (ICVs, CCVs) met method-specified

criteria.

BLANKS

All the preparation blanks or laboratory reagent blanks (LRBs) and the continuing

calibration blanks (CCBs) met me thod-specified requirements.

DUPLICATES

Field duplicates, Sample 71699, were collected on the Sample 71696. The 71696/71699

total mercury RPD was 4.52% and the dissolv ed RPD was 3.34%. The method-suggest

RPD criteria between field duplicates is 20%.

Laboratory duplicates were pe rformed in this episode on samples 71692 and 71698, and

they all met the method-specified criteria.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

Matrix spikes (MS) and ma trix spike duplicates (MSD) were performed on samples

71692, 71695, 71696, 71694 and 71697. All recove ries were within method

2

# 3 specifications of 71-125%. The RPDs were 6.10, 0.248, 14.3, 0.935 and 0.299%

respectively.

DETECTION 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, EP A EAD

Deb Bartram, ERG

TJ Finseth, ERG

From: Randy Mercurio, ERG

Date: 3/29/2011

Subject: TestAmerica Data Review Narrative for Total and Disso lved Metals by 200.8 –

Episode 6559

TestAmerica generated analytical data for total and disso lved metals (antimony, arsenic,

cadmium, chromium, copper, lead, nickel, selenium, silver, thallium, vanadium, and zinc)

for Sample Episode 6559. The samples were analyzed according to EPA Method 200.8.

Table 1 summarizes the samples TestAmerica extracted a nd analyzed for total and

dissolved metals by EPA Method 200.8.

Table 1. 

# EPA Episode 6559 Total & Dissolved Metals– Sample Identification

EPA

Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71691 FGD Influent, Day1 280-4666-1 Aqueous 6/21/2010 6/22/2010

71700 FGD Influent Field Blank, Day 1 280-4666-2 Aqueous 6/21/2010 6/22/2010

71692 FGD Influent, Day 2 280-4707-1 Aqueous 6/22/2010 6/23/2010

71695 FGD Influent, Day 1 280-4707-2 Aqueous 6/22/2010 6/23/2010

71701 FGD Effluent Field Blank, Day 1 280-4707-3 Aqueous 6/22/2010 6/23/2010

71693 FGD Influent, Day 3 280-4753-1 Aqueous 6/23/2010 6/24/2010

71696 FGD Effluent, Day 2 280-4753-2 Aqueous 6/23/2010 6/24/2010

71699 FGD Effluent

- Duplicate, Day 2 280-4753-3 Aqueous 6/23/2010 6/24/2010

71694 FGD Influent, Day 4 280-4786-1 Aqueous 6/24/2010 6/25/2010

71697 FGD Effluent, Day 3 280-4786-2 Aqueous 6/24/2010 6/25/2010

71698 FGD Effluent, Day 4 280-4841-1 Aqueous 6/25/2010 6/26/2010



# SUMMARY

The samples were prepared for total and dissolved metals a nalysis according to

TestAmerica’s “FGD ICP/MS SOP: Inductively Coupled Plas ma Mass Spectrometry for

Trace Elements Analysis in Flue Gas Desulfurization Wa stewaters,” dated October 6,

2010, based on EPA Method 200.8, by ICP/MS analysis.

# 2

Any significant findings are summarized below. Specific r esults that required additional

qualifiers appear in Table 2.

• All MS/MSDs for total and dissolved silver failed the 70-130% control limits with

poor recoveries. The poor recoveries are probably due to hi gh sulfates in this

episode’s samples that could form insoluble silver sulfide and/or silver sulfate.

• The relative percent difference (RPD) for total nickel for the field duplicate

samples 71696 and 71699 was 152.4%; however, the duplicate sample wa s less

than the reporting limit; therefore, the RPD could not be calculated accurately.

The RPD for dissolved antimony was 27.3%.

INSTRUMENT TUNE CONDITIONS

The tune condition, background counts per second (Cps), were not monitored for mass 75

for calibration blanks. Based on the calibration blank, th e background counts for mass 75

were always greater than 10 Cps, which is the required cr iteria according to Section

10.3.3 of TestAmerica’s SOP.

INTERNAL STANDARDIZATION

All internal standards used by TestAmerica were within th e method criteria.

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial

calibration for the ICP-MS analysis consisted of a bla nk and four calibration standards.

INITIAL AND CONTINUING CALIBRATION VERIFICATION

The initial calibration verifications (ICV) and continu ing calibration verifications (CCV)

performed by TestAmerica all had recoveries within the m ethod criteria.

BLANKS

All the method blanks were less than the reporting limit ; however, some elements were

found above the method detection limit (MDL) and were fl agged with the “J” qualifier

indicating the concentrations were an estimated value.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank

(CCB)) were less than the reporting limit; however, so me elements were above the MDL

and were flagged with the “J” qualifier.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s 50 – 150% recovery lim its.

# 3

LABORATORY CONTROL SAMPLES (LCS)

All LCS samples passed the QC limits of 85-115%.

SYNTHETIC FGD INTERFERENCE CHECK SOLUTIONS

The ICSA solution for the method 200.8 analysis exceeded t he acceptance limits for

Chromium in analytical batches 280-21281, 280-21283, 280-21287, 280-21288, 280-

21290, 280-21291 and 280-21294. The lab has confirmed with the vendor that Chromium

is a trace impurity in the ICSA solution. Therefore, c orrective action was deemed

unnecessary; the associated data have been flagged “^”.

SERIAL DILUTION

Serial dilutions were performed for each batch of total and dissolved samples. No QC

criteria are required by EPA Method 200.8 or TestAmerica’s SOP for these samples.

Most samples had concentrations less than the RL so a percent difference was not

calculated; however, those samples with significant c oncentrations did have percent

differences calculated and met the typical <10% criteri on, with the exception of total

arsenic and dissolved selenium for Sample 71691.

FIELD/LABORATORY DUPLICATES

The RPD of the field duplicates 71696/71699 were less than 20% fo r all values equal to

or greater than the reporting limit.

The RPD of the laboratory duplicate samples for Sampl e 71697 were less than 20% for

all values above the reporting limit, with the exception of dissolved arsenic, which had an

RPD of 26%. Even though the RPD was greater than 20%, the dissolved arsenic result

was not qualified because there are no specific control limits for laboratory duplicates

specified in EPA Method 200.8.

MATRIX SPIKE (MS) AND MATIX SPIKE DUPLICATES (MSD)

Matrix spikes and matrix spike duplicates were performed o n Samples 71691, 71695,

71696, 71697 and 71698. Many spike recoveries were outside the method control limits

of 70-130% when sample concentrations exceeded the spike conc entration by a factor of

four or more, which have been flagged with a “4” qualifier. Otherwise, the MS/MSD

spike recoveries were always within the control limit s of 70-130% with the exception of

all MS/MSDs for total and dissolved silver. The poor recov eries for silver are probably

due to high sulfates in this episode’s samples that could f orm insoluble silver sulfide

and/or silver sulfate. The RPD for all MS/MSD passed th e method-specified criteria of 20

percent.

# 4

POST DIGESITON SPIKES (PDS)

All post digestion spikes passed TestAmerica’s 85-115% recover y criteria with the

exception of the following:

• Total and dissolved silver for sample 71691 FGD Influent, Day 1 (280-4666-1);

• Dissolved zinc for sample 71695 FGD Effluent, Day 1 (280-4707-2);

• Total nickel and silver for sample 71696 FGD Effluent, Day 2 (280 -4753-2);

• Total and dissolved silver for sample 71697 FGD Effluent, Day 3 (280-4786-2);

and

• Total silver for sample 71698 FGD Effluent, Day 4 (280-4841-1).

The poor recoveries of silver are probably due to high sulf ates in this episode’s samples

that could form insoluble silver sulfide and/or silver sulfa te.

DETECTION LIMITS

The laboratory performed an MDL study in the synthetic F GD wastewater matrix, instead

of reagent water.

Table 2. Data Review Summary

Sample Analyte Qualifier/Action Reason Level Detected

71691 Ag Matrix

Interference Failed MS/MSD 1.2 μ g/L (total)

71691 Ag Matrix

Interference Failed MS/MSD &

RPD ND (dissolved)

71695 Ag Matrix

Interference Failed MS/MSD ND (total)

71695 Ag Matrix

Interference Failed MS/MSD ND (dissolved)

71696 Ag Matrix

Interference Failed MS/MSD &

RPD ND (total)

71696 Ag Matrix

Interference Failed MS/MSD &

RPD ND (dissolved)

71696 Ni Matrix

Interference Failed MS/MSD 20 μ g/L (total)

71696 Zn Matrix

Interference Failed MS/MSD 14 μ g/L (total)

71697 Ag Matrix

Interference Failed MS/MSD &

RPD ND (total)

71697 Ag Matrix

Interference Failed MS/MSD &

RPD ND (dissolved)

71698 Ag Matrix

Interference Failed MS/MSD &

RPD ND (total)

# 5 Table 2. Data Review Summary

Sample Analyte Qualifier/Action Reason Level Detected

71698 Ag Matrix

Interference Failed MS/MSD &

RPD ND (dissolved)

# 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: 3/29/2011

Subject: TestAmerica Data Review Narrative fo r Total and Dissolved Metals by 200.7 –

Episode 6559

TestAmerica generated analytical data for to tal and dissolved metals (aluminum, boron,

barium, beryllium, calcium, cobalt, iron, magnesium, molybdenum, sodium, tin, titanium,

manganese) for Sample Episode 6559. The sa mples were analyzed according to EPA

Method 200.7.

Table 1 summarizes the samples TestAmerica extracted and analyzed for total and

dissolved metals by EPA Method 200.7.

Table 1. 

# EPA Episode 6559 Total & Dissolved Metals – Sample Identification

EPA

Sample

# EPA Sample Description Lab

Sample ID

# Sample

Matrix Sampling

Date Receipt

Date

71691 FGD Influent, Day1 280-4666-1 Aqueous 6/21/2010 6/22/2010

71700 FGD Influent Field Blank, Day 1 280-4666-2 Aqueous 6/21/2010 6/22/2010

71692 FGD Influent, Day 2 280-4707-1 Aqueous 6/22/2010 6/23/2010

71695 FGD Effluent, Day 1 280-4707-2 Aqueous 6/22/2010 6/23/2010

71701 FGD Effluent Field Blank, Day 1 280-4707-3 Aqueous 6/22/2010 6/23/2010

71693 FGD Influent, Day 3 280-4753-1 Aqueous 6/23/2010 6/24/2010

71696 FGD Effluent, Day 2 280-4753-2 Aqueous 6/23/2010 6/24/2010

71699 FGD Effluent - Duplicate, Day 2 280-4753-3 Aqueous 6/23/2010 6/24/2010

71694 FGD Influent, Day 4 280-4786-1 Aqueous 6/24/2010 6/25/2010

71697 FGD Effluent, Day 3 280-4786-2 Aqueous 6/24/2010 6/25/2010

71698 FGD Effluent, Day 4 280-4841-1 Aqueous 6/25/2010 6/26/2010



# SUMMARY

The samples were prepared for total and dissolved metals analysis according to

TestAmerica’s SOP for ICP Analysis for Tr ace Metals by Method 200.7. Any significant

findings are summarized below. Specific results that required additional qualifiers appear

in Table 2.

1

#  In Method Blank 280-21582, the concentrat ion of iron (115 ug/L) was greater

than the reporting lim it (100 ug/ L) and it was not flagged.

 The continuing calibration verificati on 280-22121/107 failed the method criteria

for aluminum. All associated samples were either flagged or reanalyzed for

aluminum; therefore, no additional qualifications were required.

 The laboratory duplicate analysis of sample 71697 FGD Effluent, Day 3 (280-

4786-2) for dissolved iron had an RPD of 143% and was not flagged but was

mentioned in the narrative.

 The MS/MSD spike recoveries that fa iled the EPA Method 200.7 control limits of

70–130% are as follows: total and dissolv ed barium (71691 MS); total barium

(71691 MSD); total aluminum (71695 MS/MSD); and total iron (71698

MS/MSD).

SAMPLE RECEIPT, HANDLIN G, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INTERNAL STANDARDIZATION

While the internal standard (ISTD) Yttrium wa s used for these analyses, no checks on the

ISTD recoveries in the ±30% criterion of the calibration bl ank as per Section 9.11 of the

SOP were seen. All ISTD were within the control limits.

INITIAL CALIBRATION

TestAmerica performed the initial calibra tions on each analysis day. The initial

calibration for the ICP analysis consisted of a blank and one calibration standard.

INITIAL AND CONTINUING CAL IBRATION VERIFICATIONS

All initial calibration verifications (ICV) ha d recoveries within the method criteria.

All continuing calibration verifications (CCV ) performed by TestAmerica passed with

the exception of CCV 280-22121/10 7, which failed the method criteria for aluminum. All

associated samples were either flagged or reanalyzed for aluminum; therefore, no

additional qualificati ons were required.

BLANKS

All the method blanks were less than the re porting limit with the exception of iron in

Method Blank 280-21582 where the concentration of iron (115 ug/L) was greater than the

reporting limit (100 ug/L). The two iron results associated with this method blank were

both flagged “B,” meaning that the element was found in the blank and the sample. The

iron result for Sample 71691 was m easured at over 1,000 times th e blank level; therefore,

2

# the sam ple required no further qualifica tion. The iron result for Sample 71700 was

flagged with a “J” qualifier; therefore, the sample re quired no further qualification.

All instrument blanks (initial calibration blank (ICB) and conti nuing calibration blank

(CCB)) were less than the reporting limit; howev er, some elements were above the MDL

and were flagged with the “J” qualifier.

LABORATORY CONTROL SAMPLES (LCS)

All LCSs passed the control limits of 85-115%.

INTERFERENCE CHECK SOLUTIONS

Interference checks were perfor med using the synthetic matrix as the check solution. All

recoveries met TestAm erica’s SOP criteria.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed the control limits of 50 – 150%.

SERIAL DILUTION

Serial dilutions were performed for each batc h of total and dissolved samples. Sample

71691 failed the method required ±10% differen ce for total boron (12%), barium (13%),

calcium (15%), cobalt (12%), and iron (15%). Samples 71695 and 71696 failed for total

aluminum (104% and 105%), respectively. Th ese elements were all flagged “V” as

failing the QC criteria. These dilution tests i ndicate there may be a chemical or physical

interference according to Section 9.5.2 of the 200.7 Method.

FIELD/LABORATORY DUPLICATES

The RPD of the field duplicate passed the QC criteria.

The laboratory duplicate anal ysis of sample 71697 FGD Effluent, Day 3 (280-4786-2) for

dissolved iron had an RPD of 143% and wa s not flagged but was mentioned in the

narrative. The parent sample value (36 ug/L) was less than the reporting limit, but the

duplicate value (219 ug/L) was above the reporting limit; therefore, the RPD could not be

accurately calculated.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

Matrix spikes (MS) and ma trix spike duplicates (MSD) were performed on samples

71691, 71695, 71696, 71697 and 71698. Many elements with high concentrations

frequently failed the method spike recovery limits of 70-130% but were flagged with a

“4” qualifier indicating that the concentration in the parent sample was greater than four

times the spike and could not be reliably cal culated. In addition, so me elements were

flagged with the “4” qualifier when the pare nt sample was greater than four times the

3

# 4 spike concentration, even if the MS/MSD r ecoveries did not fail the 70-130% recovery

criteria. In these instances, the “4” qualifi ers were removed from the sample result.

Otherwise, the MS/MSD spike recoveries we re always within the method control limits

of 70-130% with exception of the following:

 Total and dissolved barium (71691 MS);

 Total barium (71691 MSD);

 Total aluminum (71695 MS/MSD);

 Total aluminum (71696 MS/MSD); and

 Total iron (71698 MS/MSD).

The total barium MS/MSD, dissolved barium MS, total barium serial dilution and total

barium post digestion spike failed for sample 71691 (280-4666-1). Because of the

combined failure of these quality control checks, the barium results for Sample 71691

were flagged as estimated values due to matrix interferences.

All RPDs between the MS and MSD were within ± 20%, with the exception of total iron

(49%) for MS/MSD sample 71698 FGD Effluent, Day 4 (280-4841-1).

DETECTION LIMITS

The laboratory performed an MDL study in the synthetic FGD wastewater matrix, instead

of reagent water.

Table 2. Data Review Summary

Sample Analyte Qualifier/Action Reason Level Detected

71691 Barium Matrix

Interference Failed MS/MSD,

Serial Dilution &

Post Spike 680 μ g/L (total)

71691 Barium Matrix

Interference Failed MS 90 μ g/L (dissolved)

71695 Aluminum Matrix

Interference Failed MS/MSD,

Serial Dilution 680 μ g/L (total)

71696 Aluminum Matrix

Interference Failed MS/MSD,

Serial Dilution 720 μ g/L (total)

71698 Iron Matrix

Interference Failed MS/MSD 390 μ g/L (total)

# 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

Donna Tedder, ERG

Date: 2/11/2011

Subject: FGS Data Review Narrative for Dissolved Hexavalent Chromium – Episode

6559

Frontier Global Sciences (FGS) generated an alytical data for dissolved hexavalent

chromium for Sample Episode 6559. FGS anal yzed the samples according to a modified

EPA Method 218.6 for dissolved hexavalent chromium by Liquid Chromatography –

Inductively Coupled Plasma Ma ss Spectrometry (LC-ICP-MS).

Table 1 summarizes the samples FGS extrac ted analyzed for di ssolved hexavalent

chromium.

Table 1. 

# EPA Episode 6559 Dissolved Hexavalent Chromium – Sample Identification

EPA

Sample

# Sample

Matrix Sample Description Sampling

Date Analysis Date

71691 Aqueous FGD Influent Day 1 6/21/10 6/30/10

71692 Aqueous FGD Influent Day 2 6/22/10 6/30/10

71693 Aqueous FGD Influent Day 3 6/23/10 6/30/10

71694 Aqueous FGD Influent Day 4 6/24/10 6/30/10

71695 Aqueous FGD Effluent Day 1 6/22/10 6/30/10

71696 Aqueous FGD Effluent Day 2 6/23/10 6/30/10

71697 Aqueous FGD Effluent Day 3 6/24/10 6/30/10

71698 Aqueous FGD Effluent Day 4 6/25/10 6/30/10

71699 Aqueous FGD Effluent Day 2 Duplicate 6/23/10 6/30/10

71700 Aqueous FGD Influent Field Blank Day 1 6/21/10 6/30/10

71701 Aqueous FGD Effluent Field Blank Day 1 6/22/10 6/30/10



# SUMMARY

The samples were prepared for dissolved hexavalent chromium analysis according to

FGS-129.01 Standard Operating Procedure (S OP), a modified EPA Method 218.6. All

1

# sam ples were diluted prior to analysis due to the presence of high levels of nontarget

chloride interferences.

There were no issues requiring qualifiers with the hexavalent chromium data in this

episode.

SAMPLE RECEIPT, HANDLIN G, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INITIAL PRECISION AND ACCURACY/RECOVERY

The initial precision and reco very (IPR) performed by FGS had recoveries within the

method criteria.

ON-GOING PRECISION AND ACCURACY/RECOVERY

The analytical method did not require the an alysis of an on-going precision and recovery

(OPR).

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysis day. The initial calibration for

the LC-ICP-MS analysis consisted of a bl ank and eight calibration standards with a

correlation factor ≥ 0.995 as required by the method.

A secondary source initial calib ration verification (ICV) wa s analyzed and passed ± 10%

of true value required by the method.

CONTINUING CALIBRATION VERIFICATION

All CCVs met method-specified criteria, ±10% of true va lue, except the CCV3 with a

low recovery of 87.6%. All samples affect ed by these failing CCVs were successfully

reanalyzed with acceptable CCVs.

BLANK

All of the preparation blanks/laboratory reagent blanks (LRBs) and the continuing

calibration blanks (CCBs) met me thod-specified requirements.

OTHER CHECKS

The laboratory control sample/duplicate (LCS /LCSD) passed method criteria (± 10% of

true value).

2

# 3 DETECTION 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 duplicat es performed in this episod e other than a duplicate of

the LCSD and a duplicate of the matrix spike (MS).

Two field duplicates were collected and analyzed. Sample 71699 was a duplicate of

sample 71696. 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 MSs and matrix spike duplicates (MSDs) were performed using a secondary source

spike on samples 71697 and 71698. All MS/MSD recoveries were within 75%-125%,

with an RPD of 1.20 and 4.41%, respectively.

# 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: Becky Schwantes, ERG

Date: 2/11/2011

Subject: TestAmerica Data Review Narrative fo r Classicals Analyses – Episode 6559

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry

analyses for Sample Episode 6559. All sample s were tested for the following analytes:

 Ammonia by EPA method 350.1,

 Biochemical Oxygen Demand – 5 day (BOD 5 

# ) by SM 5210B,

 Chloride and Sulfate 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 Dissolved Solids (TDS) by SM 2540C,

 Total Kjeldahl Nitrogen (TKN) by EPA Method 351.2, and

 Total Suspended Solids (TSS) by SM 2540D.

Table 1 summarizes the nine samples that Te stAmerica analyzed for the above analytes.

Table 1. EPA Episode 6559 Classical An alytes – Sample Identification

EPA

Sample # Sample

Matrix Sample Description Sampling

Date

71691 Water FGD Influent, Day 1 06/21/10

71692 Water FGD Influent, Day 2 06/22/10

71693 Water FGD Influent, Day 3 06/23/10

71694 Water FGD Influent, Day 4 06/24/10

71695 Water FGD Effluent, Day 1 06/22/10

71696 Water FGD Effluent, Day 2 06/23/10

71697 Water FGD Effluent, Day 3 06/24/10

71698 Water FGD Effluent, Day 4 06/25/10

71699 Water FGD Effluent-Duplicate 06/23/10

1

# SUMMARY

All sam ples were preserved appropriately and analyzed within the holding time specified

in 40 CFR 136 Table II.

One field duplicate sample was collected and analyzed for each analyte. The relative

percent difference (RPD) between the sample and its duplicate was less than 20% unless

otherwise noted below.

If applicable, the appropriate number of standards was used to create a calibration curve.

If sample results were above the highest standa rd used to create the curve, the sample was

diluted and reanalyzed. All sample results we re between the lowest and highest standards

unless noted below. Additionally, unless otherwise noted, all calibration blanks and

calibration verification samples met th e criteria specified in the method.

If required by the method, the quality control sample (QCS), a sec ondary source standard

used to verify calibration, was always within the control limits speci fied 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 detected above the reporting limit (RL) in the LRBs. If required by the method, all

laboratory fortified blanks (LFB) met the crit eria specified in the method unless specified

below.

If required by the method, a matrix spike (M S) sample was analyzed for each analyte on

sample 71697 (FGD effluent) to check for matr ix interferences. For some analytes,

TestAmerica spiked more than one sample. All MS samples analyzed met the criteria

specified in the method unl ess described below.

DATA NOTES/ISSUES

Ammonia

The laboratory diluted the MS/MSD samples for 71697 by two fold af ter distillation, but

the diluted result was still above the highest calibration standard. The laboratory did not

reanalyze these samples with a higher dilution factor because the MS/MSD percent

recoveries were within the control limits specified by EP A Method 350.1. Therefore, if

the MS/MSD results for sample 71697 are report ed, they will be qualified as estimated

values. The diluted result for sample 71697 wa s within the calibrati on range; therefore,

this sample does not need to be qualified.

2

# BOD 5



# TestAmerica analyzed at least 5 dilutions, but no dilutions had a dissolved oxygen (DO)

depletion greater than 2.0 mg/L for samples 71691-71695. Therefore, BOD 5 

# was reported

as non-detect for these samples. All glucos e-glutamic acid standards and water blanks

were analyzed appropriately and me t the criteria specified in SM 5210B.

TestAmerica analyzed four laborato ry duplicates on samples 71694, 71696, 71697, and

71698. Three of these laboratory duplicate samp les passed the criteria specified in SM

5210B (i.e., RPD <20%). The result for sample 71697 was 1.9 mg/L and the result for its

duplicate was not detected; therefore, a RPD c ould not be determined for this sample and

its duplicate.

Chloride and Sulfate

The laboratory diluted the MS/MSD samples for 71697 by 500 fold to calculate sulfate

and by 50 fold to calculate chloride, but the diluted results were still above the highest

calibration standard. The laboratory did not reanalyze these samples with a higher

dilution factor because the MS/MSD percent r ecoveries were within the control limits

specified by EPA Method 300.0. Therefore, if the MS/MSD results for sample 71697 are

reported, they will be qualified as estimated values. The diluted result for sample 71697

was within the calibration range; therefore, th is sample does not need to be qualified.

COD

Test America analyzed both a LFB and LFBD for COD. The percent recoveries for the

LFB and LFBD associated with samples 71694, 71695, and 71697 were 89% and 95%

respectively. The LFB percent recovery did not meet the method control limits of 90-

110%, but did meet the historical laboratory criteria (80-115%). B ecause the laboratory

originally had analyzed the percent recovery against the historical criteria, this LFB

failure was not noted until after the hold time had expired, so the samples were not

reanalyzed. The laboratory qua lified these samples with a “*” indicating that the LFB or

LFBD was not within the method cont rol limits. Samples 71694, 71695, and 71697 were

additionally qualified as minimum values.

The percent recoveries for the MS and MS D samples associated with 71697 were 74%

and 75% respectively. These per cent recoveries did not meet the method control limits of

90-110%. Because the percent recoveries for both the MS and MSD samples were so

much lower than the method control limits, likely the MS/MSD failure was not solely

caused by the poor laboratory spiking procedures sugg ested by the LFB failure.

Therefore, these results indica te that samples with the same matrix (FGD effluent) could

be biased low. Sample 71697 was flagged as a minimum value.

The percent recoveries for the MS and MS D samples associated with 71691 were 75%

and 80%, respectively. These percent recoveri es also did not meet the method control

limits. However, the LFB/LFBD associated with sample 71691 met the method criteria.

3

# These low percen t recoveries indicate that samples with the same matrix (FGD influent)

could be biased low. Sample 71691 was qualified as a minimum value.

Cyanide

Cyanide was detected at 0.00242 mg/L in the LRB associated with the following

samples: 71691-71697, and 71699. Although this conc entration is grea ter than the MDL

(0.0020 mg/L), it is lower than the RL (0.010 mg/L). Because the blank result was less

than the RL, no samples were qualified based on the LRB result.

All samples were diluted prior to distillation by a factor of 10 due to matrix interferences.

The laboratory stated that the samples foamed during preparation and in order to protect

the instruments, the samples needed to be diluted. All sample results were within the

calibration range used by the lab (0.01 mg/L – 0.4 mg/L).

The RPD between sample 71696 and its fi eld duplicate 71699 for cyanide was 27%.

Even though the RPD was greater than 20%, the sample was not qualified because there

are no specific control limits for fi eld duplicates speci fied in SM 4500 CN - 

# E.

SM 4500 CN

- 

# E does not require the laboratory to an alyze MS/MSD samples, so there are

no control limits specified in the method. Th e laboratory performed MS/MSD analysis on

samples 71697 and 71698. As shown by Table 2, the MS/MSD percent recoveries for

both these samples were below the laborator y control limits of 90-110%. These results

indicate that cyanide samples with a similar matrix (FGD effluent) are likely to be biased

low because of matrix inte rferences. Because SM 4500 CN

- 

# E does not require MS/MSD

analysis, the samples were not qualified.

Table 2. MS/MSD Results for Total Cyanide Analysis

Sample

Number Type Result Spike

Amount Spike Result Percent

Recovery

71697 MS 0.24 mg/L 1.00 mg/L 0.998 mg/L 76%

71697 MSD 0.24 mg/L 1.00 mg/L 0.896 mg/L 66%

71698 MS 0.18 mg/L 1.00 mg/L 0.768 mg/L 59%

71698 MSD 0.18 mg/L 1.00 mg/L 0.632 mg/L 45%

4

# Nitrate/Nitrite

TestAm erica performed an MS/MSD analysis on samples 71695 and 71697. All percent

recoveries were within the control limits specified in the method (90-110%) except for

the MSD sample for 71695, which had a percent recovery of 86%. Because EPA Method

353.2 does not require MSD samples to meet the above criteria, sample 71695 was not

qualified. Furthermore, the laboratory diluted the MS/MSD samples for 71695 by 20

fold, but the diluted result was still above the highest calibration standard. The percent

recovery for the MS sample was within the control limits specified in the method, so the

laboratory did not dilute and rerun the MS/MSD samples. T hus, if reported, the MS/MSD

results for sample 71695 will be qualified as estimated values.

Phosphorus

Phosphorus was detected at 0.0107 mg/L in the LRB associated with all samples.

Although this concentration is more than th e MDL (0.005 mg/L), it is less than the RL

(0.050 mg/L). Because the blank result was less than the RL, no samples were qualified

based on the LRB result.

The RPD between sample 71696 and its field duplicate 71699 for phosphorus was 154%.

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 the EPA Method 365.1.

The percent recoveries for the MS and MSD analyses for sample 71697 were not within

the method control limits of 90-110% or within the laboratory cont rol limits of 71-128%.

The percent recoveries for the MS and MS D samples were 62% and 65%. Results for

samples with a similar matrix (i.e., FGD effl uent) may be biased low because of matrix

interferences. Sample 71697 was already qua lified by TestAmerica with a “J” meaning

the result was an estimated value because it was less than the RL. Therefore, there was no

need to further qualify the sample as a mi nimum value. The LFB associated with all

samples met the method criteria.

The analyzed results for the following samp les were less than the lowest calibration

standard (0.025 mg/L): 71693, 71698, and 71699. However, these samples were already

qualified by the laboratory with a “J” meaning the sample result was an estimated value

because it was below the RL, so no further action was taken.

TDS

The RPDs for laboratory duplicates from samples 71696 and 71697 were less than 10%

as required by SM 2540C.

TDS was detected at 9.0 mg/L in the LRB a ssociated with sample 71698. This result was

above the MDL, but below the RL, so there was no need to qualify the sample further.

5

# Three sam ples (71692, 71693, and 71698) analyzed for TDS did not achieve a constant

weight after three drying cycles. In two of these samples, the weight increased from the

first weighing to the second weighing. Met hod 2540C warns that samples which contain

high levels of calcium, magnesium, chloride , and sulfate may be hygroscopic meaning

they absorb moisture from the air. FGD wastew ater contains high concentrations of all of

these species, so this was likely the cause for the inconsistent weight calculations. These

samples were not qualified, but results may be biased high.

TKN

TKN was detected at 0.153 mg/L in the L RB associated with the following samples

71692-71697, and 71699. The blank result was above the MDL, but below the RL, so no

samples were qualified based on the LRB result.

TestAmerica performed MS/MSD anal ysis on samples 71691, 71697, and 71698. As

shown by Table 3, the percent recoveries for the MS/MSD analysis for all three samples

did not meet the control limits of 90-110% specified in EPA Me thod 351.2. All MS/MSD

samples analyzed, except for the MSD analysis for sample 71691, also did not meet the

laboratory control limits of 54-131%.

Table 3. MS/MSD Results for TKN Analysis

Sample

Number Type Result Spike

Amount Spike Result Percent

Recovery

71691 MS 86 mg/L 15.0 mg/L 93.6 mg/L 49%

71691 MSD 86 mg/L 15.0 mg/L 99.2 mg/L 86%

71697 MS 64 mg/L 3.00 mg/L 68.2 mg/L 147%

71697 MSD 64 mg/L 3.00 mg/L 69.3 mg/L 183%

71698 MS Not analyzed by TestAmerica.

71698 MSD 52 mg/L 3.00 mg/L 60.3 mg/L 277%

TestAmerica flagged the MS/MSD samples of 71691 and 71697 with a “4” because the

sample result was more than 4 times the spik e amount indicating the control limits are not

reliable. TestAmerica did not flag the MS D sample associated with 71698 even though

the sample result was more than 4 times the spike amount, so this sample was flagged

with a “4”. These samples were not qualif ied further because it is not possible to

determine if MS/MSD failures were a result of matrix interferences or caused by the low

spike level. The LFBs associated with all samples met the method criteria.

TSS

The RPDs for laboratory duplicates for samples 71691, 71692, 71693, and 71698 were

less than 10%, as re quired by SM 2540D. However, the RPD for sample 71697 and its

duplicate was 15%. Sample 71697 was already qualified by TestAmerica with a “J”

meaning the result was an estimated value becau se it was less than the RL, so no further

action was taken.

6

# 7 The RPD between sample 71696 and its field duplicate 71699 for TSS was 66.7%. The

sample concentrations for 71696 and 71699 were greater than the MDL, but less than the

RL. These low concentrations might be th e reason 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 duplicat es specified in the method.

Table 4. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level Detected

71694 COD Minimum value LFB % recovery

below methodspecified criteria 400 mg/L

71695 COD Minimum value LFB % recovery

below methodspecified criteria 390 mg/L

71697 COD Minimum value LFB % recovery

below methodspecified criteria,

MS % recovery

below methodspecified criteria 410 mg/L

71691 COD Minimum value MS % recovery

below methodspecified criteria 420 mg/L

71698 (MSD

Sample) TKN “4” Sample result > 4

times spike

amount 60.3 mg/L

# Appendix C

PICTURES FROM THE SAMPLING EPISODE

# C

- 1 Figure C

- 1. Sampler Working Inside a “Cleanbox”

# C

- 2 Figure C

- 2

. Sample Tap and Tubing at the Influent to the FGD Wastewater Treatment

System

# C

- 3 Figure C

- 3

. Sample Collection Set Up at the Pump

- Off Station

# C

- 4 Figure C

- 4

. Composite Sample Collection Set Up at the Effluent 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.

# D-3 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

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

# D-4 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

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.

6.2 Supplies

 

# Argon gas: High purity grade (99.99%).

# D-6  

# 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%

HCl acid matrix. Suggested concentrations are given in Attachment 8,

but the laboratory may adjust calibration standard concentrations as

# D-7 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

Container 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

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

# D-9 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)

# D-11 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

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).

# D-13 Acceptance Criteria: The ICV recovery must be within 90-110%.

Additionally, the internal standard recoveries for

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

# D-14 A 50  g/L CCV standard is analyzed after every set of ten samples and

at the end of the analytical sequence.

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 sa mples 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 Acceptance 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 Attachment 7: Summary of Quality Control Requirements (continued)

QC Parameter Frequency Acceptance 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-26 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.

####