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. INTRODUCTION .................................................................................................................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. FACILITY OVERVIEW ........................................................................................................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. SAMPLE COLLECTION .......................................................................................................3-1

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

3.1.1 Influent to FGD Wastewater Treatment System......................................3-2

3.1.2 Effluent from FGD Wastewater 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. LABORATORY ANALYTICAL RESULTS AND DISCUSSION...................................................4-1

5. DATA QUALITY.................................................................................................................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. REFERENCES .....................................................................................................................6-1

Appendix A: ANALYTICAL RESULTS

Appendix B: DATA REVIEW NARRATIVES

Appendix C: PICTURES FROM THE SAMPLING EPISODE

Appendix D: FGD ICP/MS SOP: INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY FOR 

TRACE ELEMENT ANALYSIS IN FLUE GAS DESULFURIZATION WASTEWATERS
ii

LIST OF TABLES 

Page 

Table 3-1. Sample Collection Information, 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 Methods, Pleasant Prairie ....................................................................... 3-15

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

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

Table 3-8. Generating Unit Operating Characteristics 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 during Sample Collection, Pleasant Prairie ............. 3-21

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

Table 4-1. Influent to FGD Wastewater Treatment System, Pleasant Prairie ............................ 4-4

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

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

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

Table 4-4. Metal Pollutants 4-Day Average Data Summary for FGD Wastewater 

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

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

Table 5-2. Field Duplicate Results – Effluent from 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 FGD Wastewater Treatment System, Day 1 Analytical Results, 

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

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

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

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

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

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

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

Table A-9. Duplicate of Effluent from FGD Wastewater Treatment System, Analytical 

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

Table A-10. Bottle Blank and Equipment Blank Analytical Data, Pleasant 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 System, 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 Influent 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 Effluent from the FGD Wastewater Treatment 

System..............................................................................................................................C-4
1-1 

1. INTRODUCTION

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 generated by coal-fired steam electric power plants 

and evaluate treatment technologies and best management practices 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 Prairie Power Plant (Pleasant Prairie), located 

in Pleasant Prairie, Wisconsin (Sampling Episode 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 present in the wastewater discharges from steam 

electric power plants that substantially contribute to the toxic loadings for the industry. 

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

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

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

the untreated FGD wastewaters and effluent quality from technologies designed to treat the 

wastewater. 

1.2 Power Plant Site Selection

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

configurations and characteristics of the plants. 

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

characteristics: 

 The plant is a coal-fired power 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 commercial-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-sampling 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 sampling 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 samples with the Utility 

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

industry. During the sampling episode, UWAG acted as Pleasant Prairie’s representative and 

collected samples on behalf of the plant. 
2-1 

2. FACILITY OVERVIEW

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 plants to reclaim some of the carbon in the ash. 

The old ash is burned at approximately one to two percent weight 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 (SO2) releases from the plant. The 

Unit 1 FGD system was installed in November 2006, and the Unit 2 FGD system was installed in 

March 2007. The wet FGD scrubbers remove approximately 97 to 98 percent of the SO2 from 

the flue gas. In addition to the FGD scrubber systems, Pleasant Prairie installed an FGD 

wastewater treatment system to control the discharges of the wastewater generated during the 

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

and the FGD wastewater treatment system, respectively. 

Pleasant Prairie retrofitted 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 

(NOX) emissions, year round. 

The electrostatic precipitators (ESPs) at Pleasant 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 wastewater discharge associated with the ESPs. 

Pleasant Prairie installed a calcium bromide 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 concentrations 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 FGD scrubber systems that treat the flue gas 

from Units 1 and 2. The plant uses limestone slurry as the sorbent for SO2 absorption. Limestone 

and service water are fed to on-site ball mills, which pulverize the limestone to create the slurry. 

From the ball mills, the slurry is transferred to hydrocyclones to collect limestone particles that 

are too large to use in the FGD scrubber system. The underflow from the hydrocyclones is 

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

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

tank and used as fresh limestone slurry in the absorber. 

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

recycle pumps send the slurry to the various levels of the FGD scrubber (typically two of the 

three spray levels are operating at one time). The 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 SO2, which reacts with the limestone particles and produces calcium sulfite. The 

spray droplets flow downward until they reach the dual flow tray, which forms a layer of slurry 

that the flue gas must pass through 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 the calcium sulfite to calcium sulfate (i.e., 

gypsum). 

The SO2 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 potential in the system. The 

limestone slurry feed rate is adjusted to maintain the pH in the system at 5.6 to 5.7. In addition, 

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

percent solids. When the solids concentration exceeds 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 operations. 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 design chlorides concentration is 15,000 ppm, 

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

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

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

outward to the walls of the hydrocyclones and falls downward, while the water exits the top of 

the hydrocyclones. The gypsum from the primary hydrocyclones, which is approximately 50 

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

both the Unit 1 and Unit 2 primary hydrocyclones are commingled in the secondary 

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

from the secondary hydrocyclone is transferred 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 vacuum 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 the 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 transferred 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 scrubber system, which consists of secondary 

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

intermittent transfers typically occur 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 system is a chemical precipitation system and 

contains the following treatment operations: 

 Equalization tank; 

 pH adjustment (lime addition); 

 Primary clarification and polymer addition; 

 Organosulfide and hydrochloric 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 section, presents the process flow diagram of the 

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

episode. Pleasant Prairie estimates that the total 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 contain 0.3 to 0.7 percent solids, had a pH between 

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

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

presses. 

2.2.1 Physical/Chemical Separation 

From the equalization tank, the wastewater enters 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 reaction tank also desaturates the gypsum in the 
2-4 

wastewater, which prevents gypsum scale formation in the downstream wastewater treatment 

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

is recycled back to reaction tank 1 to provide seed crystals 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 percent of the solids settle 

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

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

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

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

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

precipitates. Pleasant Prairie also began adding hydrochloric acid to reaction 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 system 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 tank, 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 denser floc to form. 

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

secondary clarifier settles the solids that were formed during 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 clarifier to readjust the pH value, if needed, to meet 

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

commingled with other waste streams (e.g., cooling tower blowdown) prior to discharging to 

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

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

the effluent mercury limit, Pleasant Prairie must dilute the FGD 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 continuously 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 during chlorination. Pleasant Prairie directed 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 clarifiers is transferred 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 transferred 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 FGD 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 flocculation. Pleasant Prairie personnel stated that the weekly maintenance 
2-5 

was performed on the Thursday prior to the EPA 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 modifications 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 because the system 

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

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

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

 Added the capability to use cartridge filtration to remove colloidal particles from 

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

the plant recirculates the wastewater without discharging 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 Pleasant 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 upstream of the equalization tank (i.e., the 

sample was collected prior to any chemical 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 commingling with other streams for discharge. 
2-6 

Figure 2.1. FGD Wastewater Treatment System, Pleasant Prairie Power Plant 
3-1 

3. SAMPLE COLLECTION

During the Pleasant Prairie sampling episode, the sampling team followed the collection 

protocols specified in the Sampling Plan. Section 3.1 describes the sampling points, sample 

collection methods, and field measurements. Section 3.2 describes the list of analytes and the 

sample preservation procedures. Section 3.3 discusses the plant operational data collected during 

the sampling episode. Finally, Section 3.4 discusses any deviations from the planned sampling 

activities. 

3.1 Sampling Points, Sample Collection Methods, and Field Measurements

This section describes the sampling points, 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, sampling point descriptions, type of sample 

collection, and sample collection dates and times. Table 3-2 lists 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 the field measurement data collected from each 

sampling point. Table 3-4 presents a crosswalk between 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 Wastewater Treatment System; 

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

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

 SP-5 Effluent from FGD Wastewater 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 tubing configuration at each sampling 

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

cyanide) at all sampling points as “true” splits (i.e., 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 Pleasant Prairie’s representative collected duplicate 

samples, with one filling the bottle 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 that secures itself open with clips. The “cleanbox” is double-bagged 

with a clear inner bag, enclosed in a translucent outer bag. The “cleanbox” is handled using 

“clean hands / dirty hands” techniques, whereby the inner bag is handled only by the “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 opening of the box, but is still able to see the sample bottles and 

tubing. The “cleanbox” minimizes potential atmospheric contamination during sample 

collection. Figure C-1, in Appendix C, is a picture 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 sealed 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 closed the sample bottle lid and sealed the inner 

bag as quickly as possible within 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 system (SP-1) was collected from a sample tap 

located on the secondary hydrocyclone and upstream of the equalization tank. Figure 2-1 

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

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

treatment system are fairly consistent during the purge. In addition, due to the relatively high 

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

split samples using composite sampling techniques. The sample tap was located inside the FGD 

building (see Figure 2-1 for the sampling location 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 samples 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 the silicone tubing was fitted with a “Y” splitter, with two 

additional lengths of silicone tubing 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 tubing 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 valve until all samples were collected (except the 

dissolved metals samples). 

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

3.1: 

 Total and dissolved mercury; 

 Total metals by 200.8; and 

 Total metals by 200.7. 
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 sampling 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 containers for biochemical oxygen demand (BOD5), Group I, 

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

Table 3-6 for a list of Group I and Group II analytes. BOD5, Group I, Group II, and total cyanide 

samples were immediately placed on ice after sample collection. 

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

potassium-iodide starch test strips were used to measure for sulfides and oxidants, respectively. 

No sulfides or oxidants were detected during the 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 were 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 the silicone tubing, which was a short distance downstream of the 

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

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

to collect “true” split samples with Pleasant Prairie’s representatives. Figure C-3, in Appendix C, 

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

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

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

solids in the wastewater had been settling for approximately 90 minutes. Approximately 0.5 - 1 

liters1

 of sample were pumped through the tubing/filter to purge the line before collecting 

samples. 

Samplers collected the following dissolved samples 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 immediately 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 wastewater treatment system (SP-2) was collected downstream of 

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

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

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

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

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

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

significant amount of coal dust settling around and 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 closed. 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 measured 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 compositors 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 compositor to collect sample volume for all classical 

analytes (i.e., BOD5, Group I, and Group II, excluding cyanide). In addition to collecting 

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

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

grab sample for cyanide during each compositing period. 

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

and dissolved metals by 200.7, and total and dissolved 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 two 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 configuration was set up such that one end was connected to the sample 

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

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

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

flow through both sets of tubing before calibrating 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 projected 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 and flowed directly to 
3-5 

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

the sampling program and was capable of purging the 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 plastic bag was placed on top of the trash cans 

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

set-up at the effluent from the 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 grab sample every day, ERG collected field blanks 

for total mercury samples. See Section 5.2.3 for a description 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 tap for two minutes, the samples were collected directly from the 

tap into the sample bottles. Because 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; therefore, duplicate samples were collected. ERG collected another set of total 

and dissolved mercury samples every six hours thereafter over the 24-hour period. The plastic 

shroud was replaced for each set of mercury grab samples. After collecting each set of mercury 

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

paper, a pH meter, and a thermometer. Table 3-3 presents the field measurement data for the 

effluent from the FGD wastewater treatment. 

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

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

Because total cyanide samples were collected directly from the tap, 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 effluent 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 collected in the two composite containers, ERG 

followed “clean hands / dirty hands” sampling techniques 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 volume on each day of sample collection. 

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

transferred the wastewater collected in the 20-liter containers into the individual sample 
3-6 

containers at the pump-off area. For this sampling 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 within 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 containers. 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 the silicone tubing, which was a short 

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

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

tubing. This set-up allowed EPA to collect “true” split samples with 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 collecting any samples of the effluent from the FGD wastewater 

treatment system, the samplers collected a field 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 samples 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 immediately 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 collected 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 previously filled 20-liter container. After the tubing was purged 

with 1-2 liters of sample, samplers filled containers for biochemical oxygen demand (BOD5), 

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. BOD5, Group I, and Group II samples were 

immediately placed on ice after 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 sampling episode. In addition, for all analytes, ERG 
3-7 

collected a duplicate sample of the FGD wastewater treatment system (SP-3) on Day 2 of the 

sampling episode. 

3.2 List of Analytes and Sample Preservation

Samples collected at Pleasant Prairie were analyzed for the following pollutants: 

 Classicals: 

Biochemical oxygen demand, 5-day (BOD5), 

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 Metals2: 

— 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 total metals, plus hexavalent chromium. 

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

pollution control wastewaters, including contributions from coal, scrubber sorbents, 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 sampling team preserved samples in accordance with 

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

collection, the samplers placed the BOD5, Group I, Group II, dissolved hexavalent chromium, 

and total cyanide samples on ice to cool the samples 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-preserved prior to extraction at the laboratory. The 

hexavalent chromium samples were preserved 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 tested for sulfides and oxidants immediately after 

sample collection. Because sulfides and oxidants were 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 sulfides 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 Prairie plant personnel provided the sampling 

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

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

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

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

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

episode, and Table 3-12 presents the FGD wastewater treatment system operating characteristics. 

3.4 Deviations from the Sampling and Analysis Plan

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

described below: 

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

prior to sample collection, the secondary 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 ammonium sulfate buffer solution was not 

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

sulfate buffer solution, followed by as much ammonium hydroxide as necessary 

to reach the desired pH. 

 pH field test measurements: The sampling team was unable 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 treatment 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 Wastewater Treatment 

System – Day 1 

Grab 6/21/10 1013a and 1220b

Influent to FGD Wastewater Treatment 

System – Day 2 

Grab 6/22/10 0939a and 1132b

Influent to FGD Wastewater Treatment 

System – Day 3 

Grab 6/23/10 0917a and 1112b

SP-1 

Influent to FGD Wastewater Treatment 

System – Day 4 

Grab 6/24/10 0924a and 1108b

Composite 6/21/10 

6/22/10

0730c 

0827d

Effluent from FGD Wastewater Treatment 

System – Day 1 

Grab 6/21/10 

6/22/10 

0748e

, 1348f , and 1946 g 

0147 h 

Composite 6/22/10 

 6/23/10 

0728c 

0806d 

Effluent from FGD Wastewater Treatment 

System – Day 2 

Grab 6/22/10 

6/23/10 

0745e

, 1348f , and 1947 g 

0145 h 

Composite 6/23/10 

6/24/10 

0730c 

0810d 

Effluent from FGD Wastewater Treatment 

System – Day 3 

Grab 6/23/10 

 6/24/10 

0743e

, 1347f , and 1950 g 

0147 h 

Composite 6/24/10 

6/25/10 

0729c 

0651d 

SP-2 

Effluent from FGD Wastewater Treatment 

System – Day 4 

Grab 6/24/10 

6/25/10 

0749e

, 1348f , and 1947 g 

0147 h 

Composite 6/22/10 

 6/23/10 

0728c 

0806d 

SP-3 Duplicate of Effluent from FGD 

Wastewater Treatment System – Day 2 

Grab 6/22/10 

6/23/10 

0747e

, 1349f , and 1948 g 

0146 h 

SP-4 Influent to FGD Wastewater Treatment 

System Field Blank 

Grab 6/21/10 0958 i and 1212j

Composite 6/21/10 

6/22/10

0653k

0813l

Effluent from FGD Wastewater Treatment 

System Field Blank – Day 1 

Grab 6/21/10 0742m

Effluent from FGD Wastewater Treatment 

System Field Blank – Day 2 

Grab 6/22/10 0740m

Effluent from FGD Wastewater Treatment 

System Field Blank – Day 3 

Grab 6/23/10 0738m

SP-5 

Effluent from FGD Wastewater Treatment 

System Field Blank – Day 4 

Grab 6/24/10 0744m

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 (BOD5, 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 (BOD5, 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 dissolved 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. 
3-11 

Table 3-2. Sample Collection at Pleasant Prairie

Sampling 

Point 

Number Sampling 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

GI 

a

SP-1 Influent to the FGD Wastewater 

Treatment System 

4 4 4 4 4 4 4 4 

SP-2 Effluent from the FGD 

Wastewater Treatment System 

4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1

SP-3 Duplicate of the Effluent from 

FGD Wastewater Treatment System 

1 1 1 1 1 1 1 1 

SP-4 Influent to the FGD Wastewater 

Treatment System Field Blank 

1 1 1 1 1 1 

SP-5 Effluent from the FGD 

Wastewater Treatment System Field Blank 

1 1 1 1 4 1 

Total Number of Samples 11+1QC 11+1QC 11+1QC 11+1QC 14+1QC 9+1QC 11+1QC 9+1QC 9+1

a – 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 phosp
3-12 

Table 3-3. Field Measurements, Pleasant Prairie

pH 

(S.U.) Sampling Point 

Number 

Sampling Point 

Description Date Time 

Temperature 

(°C) Meter a Strips 

Waste 

Stream Flow 

Rate 

(GPM) 

Influent to FGD Wastewater Treatment System – Day 1

6/21/2010 1029 55 5.8 6 60

Influent to FGD Wastewater Treatment System – Day 2 

6/22/2010 0953 55 6.4 NC 60 

Influent to FGD Wastewater Treatment System – Day 3 

6/23/2010 0928 55 6.34 7 60 

SP-1 

Influent to FGD Wastewater Treatment System – Day 4 

6/24/2010 0935 54 6.77 7 60 

Samplehad a dappearedetectetotal cy

6/21/10 0750 43 6.6 6.5 40.36/21/10 1348 43 6.9 6.5 386/21/10 1946 42.4 6.8 NC 38.1 

Effluent from FGD Wastewater Treatment System – Day 1

6/22/10 0147 42.4 6.9 NC 38.1 6/22/10 0750 43 6.9 6.5 35 6/22/10 1352 43 6.9 7 32.7 6/22/10 1947 41.5 6.9 7 35.0 

Effluent from FGD Wastewater Treatment System – Day 2 

6/23/10 0145 43.3 6.9 6.5 34.9 

6/23/10 0745 44 6.87 7 35 6/23/10 1350 44 6.85 7 35 6/23/10 1950 44.4 6.1 6.5 34.9 

SP-2 

Effluent from FGD Wastewater Treatment System – Day 3 

6/24/10 0155 44.2 6.9 6.5 34.4 

Sampleand did particulor oxid
3-13 

Table 3-3. Field Measurements, Pleasant Prairie

pH 

(S.U.) Sampling Point 

Number 

Sampling Point 

Description Date Time 

Temperature 

(°C) Meter a Strips 

Waste 

Stream Flow 

Rate 

(GPM) 

6/24/10 0752 44 6.86 7 35 6/24/10 1350 43 6.86 7 35 6/24/10 1947 43.8 6.9 6.5 35 

SP-2 Effluent from FGD 

Wastewater Treatment System – Day 4 

6/25/10 0147 43.6 7.0 7 34.9 

Sampleand did particulor oxid

a The pH meter was calibrated prior to the sampling episode and once every day during the sampling episode using prepackaged buffer 

and 10.0. NC – Not collected. The sampling team was unable to locate the pH strips during the collection of these samples; therefore, the pH mea

with 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 Methods, Pleasant Prairie 

Parameter Method Number 

Classicals

Biochemical oxygen demand (BOD5) 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 cell1

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 and Planned Preservation, Pleasant Prairie 

Parameter 

Sample 

Container and 

Volume 

QC Sample 

Container and 

Volume On-Site Preservation 

Classicals 

BOD5 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 

H2SO4 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, 

NaAsO2 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, TDS, sulfate, and chloride. 

(b) Group II includes ammonia as nitrogen, COD, nitrate/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 H2SO4 6.0 2 55 

71691 Group II Volume 2 6/21/10 H2SO4 6.0 2 55 

(NH4)2SO4

Buffer 

71691 Hexavalent Chromium 6/21/10 100 

NH4OH 

6.0 9.4 

5 

(NH4)2SO4

Buffer 

71700 Hexavalent Chromium Field 100 

Blank 

6/21/10

NH4OH 

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 H2SO4 6.5 2 65 

71692 Group II Volume 2 6/22/10 H2SO4 6.5 2 65 

71695 Group II Volume 1 6/22/10 H2SO4 6.0 2 50 

71695 Group II Volume 2 6/22/10 H2SO4 6.0 2 50 

(NH4)2SO4

Buffer 

71692 Hexavalent Chromium 6/22/10 100 

NH4OH 

6.5 9.5 

3 

(NH4)2SO4

Buffer 

71695 Hexavalent Chromium 6/22/10 100 

NH4OH 

6.5 9.5 

5 

(NH4)2SO4

Buffer 

71701 Hexavalent Chromium Field 100 

Blank 

6/22/10

NH4OH 

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 H2SO4 6.5 2 55 

71693 Group II Volume 2 6/23/10 H2SO4 6.5 2 55 

71696 Group II Volume 1 6/23/10 H2SO4 6.5 2 65 

71696 Group II Volume 2 6/23/10 H2SO4 6.5 2 65 

71699 Group II Volume 1-Duplicate 6/23/10 H2SO4 6.5 2 65 

71697 Group II Volume 2-Duplicate 6/23/10 H2SO4 6.5 2 65 

(NH4)2SO4

Buffer 

71693 Hexavalent Chromium 6/23/10 100 

NH4OH 

6.5 9.5 

5 

71696 Hexavalent Chromium 6/23/10 (NH4)2SO4

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) 

NH4OH 4 

(NH4)2SO4

Buffer 

71699 Hexavalent Chromium - 34 

Duplicate 

6/23/10

NH4OH 

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 H2SO4 6.5 2 65 

71694 Group II Volume 2 6/24/10 H2SO4 6.5 2 65 

71697 Group II Volume 1 6/24/10 H2SO4 6.5 2 55 

71697 Group II Volume 2 6/24/10 H2SO4 6.5 2 55 

71697 Group II Volume 1 - QC 6/24/10 H2SO4 6.5 2 55 

71697 Group II Volume 2 - QC 6/24/10 H2SO4 6.5 2 55 

71698 Group II Volume 1 6/25/10 H2SO4 6.5 2 55 

71698 Group II Volume 2 6/25/10 H2SO4 6.5 2 55 

(NH4)2SO4

Buffer 

71694 Hexavalent Chromium 6/24/10 100 

NH4OH 

6.7 9.5 

5 

(NH4)2SO4

Buffer 

71697 Hexavalent Chromium - QC 6/24/10 100 

NH4OH 

6.5 9.5 

4 

(NH4)2SO4

Buffer 

71698 Hexavalent Chromium 6/25/10 100 

NH4OH 

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 Characteristics 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 electrostatic precipitator. 
3-20 

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

Unit ID 

Wet FGD 

System (Yes/No) 

Type of 

Scrubber 

Forced 

Oxidation 

(Yes/No) Sorbent 

Additives (DBA, 

formic acid, 

etc.) 

FGD Make-up 

Water Source 

SO2 Rem

Percen

1 Yes Spray / Tray Yes Limestone Silicon antifoam 17 gpd/unit Lake Michigan 97% 2 Yes Spray / Tray Yes Limestone Silicon antifoam 17 gpd/unit Lake Michigan 96% 
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 during 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% 
3-22 

Table 3-12. FGD Wastewater Treatment System Operation Information, Pleasant Prair

Scrubber Purge Chemical Usage 

Day of 

Sampling 

Flow Rate 

(GPM)a 

Duration 

ACT 

Lime 

(added to adjust 

pH 5.6 to 8.5)b

Ferric Chloride 

ACT 

Organosulfide 

Nalmet 1689 

50 ppm 

 ACT 

Polymer

GE AE17

20 ppm prim

3.5 ppm sec 

1 60 18.0 hr 670 lb/day 40 mL/min 6 mL/min 4 mL/min 2 60 16.25 hr 670 lb/day 40 mL/min 6 mL/min 4 mL/min 3 60 17.5 hr 670 lb/day 40 mL/min 6 mL/min 4 mL/min 4 60 20.25 hr 670 lb/day 40 mL/min 6 mL/min 4 mL/min 

a - Purge rate estimated from tank level changes. Similar to Secondary Hydrocyclone design data of 60 gpm to overflow/purge b - 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. LABORATORY ANALYTICAL RESULTS AND DISCUSSION

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 were analyzed by Frontier Global Sciences 

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

nitrate membrane filters contained in disposable 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 temperature bromine monochloride 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 and analyzed as one sample. Frontier composited 

these samples by combining the entire sample bottle for each of four individual grab samples 

prior to digestion and analysis; however, if one or more of the 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 described 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 nitric 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 digestion according to SW846 Method 3010A. 

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

TestAmerica. Similar to the metals analyzed 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 hours prior to being subjected to a closed vessel, 

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

The classical analytes were analyzed by TestAmerica and were digested, prepared, and 

analyzed according to the methods specified in Table 3-5. 

Appendix A provides all analytical results for all samples collected at Pleasant Prairie, 

including all qualified results and all results that were measured above the method detection 

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

For EPA Method 200.7, some of the quantitation 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 studies. If the typical background blank levels for a given 

element are variable or frequently elevated, then the quantitation limit may be raised to prevent 
4-2 

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

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

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 wastewater 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 analytes 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 analytes for which EPA conducted 

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

sample above the method detection limit, the result 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 wastewater 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 average of the original and the duplicate sample results. Table 5-2 presents the 

analytical results for the original and duplicate 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 quantitation limit, then all results were averaged 

together; 

 If at least one result was above the quantitation 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 reported 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 detection limit, then the sample-specific 

quantitation limits for all results were averaged 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 for all classical analytes for the influent to 

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

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

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

(SP-1) and the effluent from the 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), the effluent from the FGD wastewater treatment 

system (SP-2), and the duplicate of the effluent from the FGD wastewater treatment system (SP3) sample analyses, including J-values. 
4-4 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. 

+ - 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 d

excluded 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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 Prairie 

Influent to FGD Wastewater Treatment Syste

Analyte Units Method Day 1 Day 2 Day 3 Day 4 

ClassicalsAmmonia mg/L 350.1 19.0 13.0 12.0 14.0 Nitrate Nitrite as N mg/L 353.2 150 160 160 160 Nitrogen, Total Kjeldahl mg/L 351.2 86.0 4 72.0 B 16.0 B 76.0 Biochemical Oxygen Demand mg/L 5210B ND (2.00) ND (2.00) ND (2.00) ND (2.00) Chemical Oxygen Demand mg/L 410.4 420 F 460 410 400 Chloride mg/L 300.0 1,800 1,800 1,800 1,800 Sulfate mg/L 300.0 14,000 16,000 17,000 17,000 Cyanide, Total mg/L 4500 CN E 0.250 B 0.280 B 0.180 B 0.230 Total Dissolved Solids mg/L 2540C 23,000 24,000 24,000 26,000 Total Suspended Solids mg/L 2540D 3,800 7,100 3,300 3,500 Phosphorus, Total mg/L 365.1 0.950 B 0.250 B NQ (0.250) B 0.0630 Total MetalsAluminum ug/L 200.7 110,000 B,4 130,000 120,000 140,000 Antimony ug/L 200.8 65.0 63.0 63.0 60.0 Arsenic ug/L 200.8 150 160 140 150 Barium ug/L 200.7 680 F 770 750 510 Beryllium ug/L 200.7 4.80 5.10 5.00 5.10 Boron ug/L 200.7 11,000 B,4 12,000 B 12,000 B 13,000 Cadmium ug/L 200.8 9.20 11.0 11.0 13.0 Calcium ug/L 200.7 670,000 B,4 690,000 690,000 700,000 Chromium ug/L 200.8 1,400 4,^ 1,000 ^ 960 980 
4-5 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. 

+ - 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 d

excluded 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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 Prairie 

Influent to FGD Wastewater Treatment Syste

Analyte Units Method Day 1 Day 2 Day 3 Day 4 

Cobalt ug/L 200.7 140 140 140 140 Copper ug/L 200.8 1,300 4 1,100 1,000 1,100 Iron ug/L 200.7 400,000 B,4 420,000 420,000 410,000 Lead ug/L 200.8 280 4 280 280 280 Magnesium ug/L 200.7 4,200,000 B,4 4,200,000 B 4,000,000 4,200,000 Manganese ug/L 200.7 72,000 B,4 76,000 B 73,000 74,000 Mercury ng/L 1631E 2,020,000 2,080,000 2,060,000 1,730,000 Molybdenum ug/L 200.7 240 240 240 240 Nickel ug/L 200.8 1,600 4 1,400 1,400 1,400 Selenium ug/L 200.8 20,000 4 15,000 15,000 B 15,000 Silver ug/L 200.8 NQ (2.00) F NQ (2.00) NQ (2.00) NQ (2.00) Sodium ug/L 200.7 470,000 4 510,000 500,000 520,000 Thallium ug/L 200.8 11.0 12.0 11.0 10.0 Tin ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200) Titanium ug/L 200.7 4,500 4 4,400 4,300 4,900 Vanadium ug/L 200.8 1,400 4 1,100 B 910 970 Zinc ug/L 200.8 2,500 4 1,300 B 1,400 1,500 Dissolved MetalsAluminum ug/L 200.7 NQ (200) NQ (200) B 210 NQ (200) Antimony ug/L 200.8 3.80 3.40 3.70 4.10 Arsenic ug/L 200.8 7.20 6.90 7.70 7.00 
4-6 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. 

+ - 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 d

excluded 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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 Prairie 

Influent to FGD Wastewater Treatment Syste

Analyte Units Method Day 1 Day 2 Day 3 Day 4 

Barium ug/L 200.7 90.0 F 96.0 97.0 85.0 Beryllium ug/L 200.7 NQ (2.00) NQ (2.00) NQ (2.00) ND (2.00) Boron ug/L 200.7 13,000 4 13,000 B 13,000 B 13,000 Cadmium ug/L 200.8 4.50 4.40 6.90 NQ (4.00) Calcium ug/L 200.7 550,000 4 550,000 550,000 560,000 Chromium ug/L 200.8 ND (8.00) ^ ND (8.00) ^ ND (8.00) ^ ND (8.00) Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10.0) Cobalt ug/L 200.7 110 120 120 110 Copper ug/L 200.8 28.0 31.0 34.0 23.0 Iron ug/L 200.7 NQ (200) ND (200) NQ (200) NQ (200) Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Magnesium ug/L 200.7 4,100,000 4 4,000,000 B 3,800,000 B 3,800,000 Manganese ug/L 200.7 70,000 4 72,000 B 70,000 67,000 Mercury ng/L 1631E 1.96+ 3,860 2,370 2,600 Molybdenum ug/L 200.7 49.0 40.0 47.0 50.0 Nickel ug/L 200.8 930 4 940 1,000 870 Selenium ug/L 200.8 3,600 4 3,500 B 3,800 3,900 Silver ug/L 200.8 ND (2.00) F ND (2.00) ND (2.00) ND (2.00) Sodium ug/L 200.7 510,000 4 470,000 490,000 490,000 Thallium ug/L 200.8 9.30 9.80 9.70 9.50 Tin ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200) Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) 
4-7 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. 

+ - 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 d

excluded 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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 Prairie 

Influent to FGD Wastewater Treatment Syste

Analyte Units Method Day 1 Day 2 Day 3 Day 4 

Vanadium ug/L 200.8 NQ (10.0) B NQ (10.0) B NQ (10.0) NQ (10.0) Zinc ug/L 200.8 93.0 100 110 43.0 
4-8 

Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for the analytical results for the < - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. * - 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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 Prairie

Effluent from the FGD Wastewater Treatment S

Analyte Units Method Day 1 Day 2 Day 3 D

ClassicalsAmmonia mg/L 350.1 23.0 20.0 18.0 16.0 Nitrate Nitrite as N mg/L 353.2 160 160 160 160 Nitrogen, Total Kjeldahl mg/L 351.2 72.0 B 68.0 64.0 B,4 52.0 Biochemical Oxygen Demand mg/L 5210B ND (2.00) NQ (2.50) NQ (2.50) NQ (2.Chemical Oxygen Demand mg/L 410.4 390 * 455 410 F,* 420 Chloride mg/L 300.0 2,000 2,000 1,900 1,90Sulfate mg/L 300.0 16,000 16,000 15,000 15,00Cyanide, Total mg/L 4500 CN E 0.190 B 0.185 0.240 B,F 0.18Total Dissolved Solids mg/L 2540C 21,000 23,500 23,000 22,00Total Suspended Solids mg/L 2540D NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.Phosphorus, Total mg/L 365.1 0.0700 B < 0.0825 NQ (0.0500) B,F NQ (0.0Total MetalsAluminum ug/L 200.7 680 F < 410 ND (200) NQ (20Antimony ug/L 200.8 2.50 2.35 2.20 2.40 Arsenic ug/L 200.8 6.40 4.80 5.00 5.30 Barium ug/L 200.7 68.0 69.0 74.0 73.0 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.Boron ug/L 200.7 10,000 B,4 10,000 9,300 4 10,00Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.Calcium ug/L 200.7 650,000 4 655,000 660,000 4 660,0
4-9 

Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for the analytical results for the < - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. * - 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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 Prairie

Effluent from the FGD Wastewater Treatment S

Analyte Units Method Day 1 Day 2 Day 3 D

Chromium ug/L 200.8 ND (8.00) ^ ND (8.00) ND (8.00) ND (8.Cobalt ug/L 200.7 ND (20.0) NQ (20.0) ND (20.0) NQ (20Copper ug/L 200.8 ND (4.00) NQ (4.00) ND (4.00) ND (4.Iron ug/L 200.7 NQ (200) NQ (200) 210 390 Lead ug/L 200.8 ND (2.00) NQ (2.00) ND (2.00) ND (2.Magnesium ug/L 200.7 3,700,000 B,4 3,550,000 3,700,000 4 3,500,0Manganese ug/L 200.7 11,000 B,4 11,000 11,000 4 11,00Mercury ng/L 1631E 78.4 86.4 72.9 74.9 Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) 41.0 Nickel ug/L 200.8 NQ (4.00) < 11.0 NQ (4.00) 7.30 Selenium ug/L 200.8 2,100 4 2,150 2,000 B,4 2,00Silver ug/L 200.8 ND (2.00) F ND (2.00) ND (2.00) F ND (2.Sodium ug/L 200.7 510,000 4 510,000 530,000 4 500,0Thallium ug/L 200.8 2.90 2.95 2.80 2.30 Tin ug/L 200.7 ND (200) NQ (200) ND (200) NQ (20Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20Vanadium ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) ND (10Zinc ug/L 200.8 ND (10.0) < 9.50 ND (10.0) NQ (10Dissolved MetalsAluminum ug/L 200.7 ND (200) ND (200) NQ (200) ^ NQ (20Antimony ug/L 200.8 2.80 < 1.75 2.60 2.70 
4-10 

Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for the analytical results for the < - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. * - 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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 Prairie

Effluent from the FGD Wastewater Treatment S

Analyte Units Method Day 1 Day 2 Day 3 D

Arsenic ug/L 200.8 4.90 5.40 4.20 4.90 Barium ug/L 200.7 67.0 69.0 72.0 69.0 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.Boron ug/L 200.7 10,000 B,4 10,000 9,900 B,4 9,80Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.Calcium ug/L 200.7 640,000 4 645,000 660,000 4 610,0Chromium ug/L 200.8 ND (8.00) ^ ND (8.00) ND (8.00) ^ ND (8.Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10Cobalt ug/L 200.7 ND (20.0) NQ (20.0) ND (20.0) NQ (20Copper ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.Iron ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (20Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.Magnesium ug/L 200.7 3,700,000 B,4 3,550,000 3,500,000 B,4 3,500,0Manganese ug/L 200.7 11,000 B,4 11,000 10,000 B,4 11,00Mercury ng/L 1631E 22.8 27.0 20.5 19.0 Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) NQ (40Nickel ug/L 200.8 NQ (4.00) NQ (4.00) 6.10 NQ (4.Selenium ug/L 200.8 2,100 B,4 2,100 2,000 B,4 2,10Silver ug/L 200.8 ND (2.00) F ND (2.00) ND (2.00) F ND (2.Sodium ug/L 200.7 530,000 4 530,000 520,000 4 490,0Thallium ug/L 200.8 2.50 2.65 2.30 2.90 
4-11 

Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for the analytical results for the < - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. * - 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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 Prairie

Effluent from the FGD Wastewater Treatment S

Analyte Units Method Day 1 Day 2 Day 3 D

Tin ug/L 200.7 ND (200) NQ (200) ND (200) NQ (20Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20Vanadium ug/L 200.8 NQ (10.0) B ND (10.0) ND (10.0) ND (10Zinc ug/L 200.8 19.0 F ND (10.0) ND (10.0) ND (10
4-12 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. 

Table 4-3. Classical Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System

Analyte Units Method

Influent to FGD 

Wastewater Treatment

System (SP-1)

4-Day Average

Efflue

FGD Wastew

System 

4-Day 

ClassicalsAmmonia mg/L 350.1 14.5 1Nitrate Nitrite as N mg/L 353.2 158 1Nitrogen, Total Kjeldahl mg/L 351.2 62.5 6Biochemical Oxygen Demand mg/L 5210B ND (2.00) NQ Chemical Oxygen Demand mg/L 410.4 423 4Chloride mg/L 300.0 1,800 1Sulfate mg/L 300.0 16,000 15Cyanide, Total mg/L 4500 CN E 0.235 0Total Dissolved Solids mg/L 2540C 24,300 22Total Suspended Solids mg/L 2540D 4,430 NQ Phosphorus, Total mg/L 365.1 < 0.347 < 0
4-13 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu* - The 4-day average result includes an analytical result where the accuracy is questionable. If the questionable result was excluded from the calculataverage 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, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. 

Table 4-4. Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, Ple

Influent to FGD 

Wastewater Treatment

System (SP-1)

4-Day Average 

Effluent 

FGD Wastewat

System 

4-Day A

Analyte Units Method Total Dissolved Total 

MetalsAluminum ug/L 200.7 125,000 < 128 < 323 Antimony ug/L 200.8 62.8 3.75 2.36 Arsenic ug/L 200.8 150 7.20 5.38 Barium ug/L 200.7 678 92.0 71.0 Beryllium ug/L 200.7 5.00 NQ (2.00) ND (2.00) Boron ug/L 200.7 12,000 13,000 9,830 Cadmium ug/L 200.8 11.1 < 4.45 ND (4.00) Calcium ug/L 200.7 688,000 553,000 656,000 Chromium ug/L 200.8 1,090 ND (8.00) ND (8.00) Chromium (VI) ug/L 218.6 NA ND (10.0) NA Cobalt ug/L 200.7 140 115 NQ (20.0) Copper ug/L 200.8 1,130 29.0 NQ (4.00) Iron ug/L 200.7 413,000 NQ (200) < 200 Lead ug/L 200.8 280 ND (2.00) NQ (2.00) Magnesium ug/L 200.7 4,150,000 3,930,000 3,610,000 Manganese ug/L 200.7 73,800 69,800 11,000 Mercury ng/L 1631E 1,970,000 2,210* 78.1 Molybdenum ug/L 200.7 240 46.5 < 25.3 Nickel ug/L 200.8 1,450 935 < 5.58 Selenium ug/L 200.8 16,300 3,700 2,060 Silver ug/L 200.8 NQ (2.00) ND (2.00) ND (2.00) Sodium ug/L 200.7 500,000 490,000 513,000 Thallium ug/L 200.8 11.0 9.58 2.74 
4-14 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu* - The 4-day average result includes an analytical result where the accuracy is questionable. If the questionable result was excluded from the calculataverage 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, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 

value. 

Table 4-4. Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, Ple

Influent to FGD 

Wastewater Treatment

System (SP-1)

4-Day Average 

Effluent 

FGD Wastewat

System 

4-Day A

Analyte Units Method Total Dissolved Total 

Tin ug/L 200.7 NQ (200) NQ (200) NQ (200) Titanium ug/L 200.7 4,530 ND (20.0) ND (20.0) Vanadium ug/L 200.8 1,100 NQ (10.0) ND (10.0) Zinc ug/L 200.8 1,680 86.5 < 6.13 
5-1 

5. DATA QUALITY

Quality assurance/quality control (QA/QC) procedures 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 procedures 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 laboratories for the analysis of samples collected 

during this episode. ERG verified that the performance of the laboratories selected were 

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

prepared written data review narratives describing any qualifications of the analytical data from 

this episode. The data review narratives 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 Sampling Plan discusses field QC specifications. 

5.2.1 Bottle Blanks 

ERG collects bottle blanks to evaluate possible 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 bottles, Frontier Global Sciences (Frontier). 

Frontier collected the bottle blanks for the metals sample bottles by filling the precleaned 

bottle with reagent water, preserving the sample with 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 blanks for the 10- and 20-liter composite 

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

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

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

ASTM Type 1 water. Albion Environmental then 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 blanks, 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 used for the sample analyses (i.e., 200 ug/L); 

therefore, this contamination did not affect the results of the sampling episode. Appendix Table 
5-2 

A-10 presents all of the analytical results from the bottle blank analyses 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 (as described in Section 

5.2.3) include the sampling equipment and therefore would identify whether the sampling 

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

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

equipment supplied for the episode. 

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

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

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

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

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

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

contamination from the sampling equipment. Appendix 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, sampling 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 samples3

. 

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

for the influent to the FGD wastewater treatment system (SP-4) were collected by pouring 

ASTM Type 1 water through a precleaned funnel attached to the silicone 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 filling 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 representative, using the same procedure discussed 

in the sample collection description (Section 3.1). 

 

3 EPA did not collect a dissolved mercury field blank sample because the sample filtration was performed at the 

laboratory to minimize potential mercury contamination. The laboratory performed a filtration blank prior to 

filtering the sample, which is assessed as the field blank for the dissolved mercury sample. Mercury was not 

detected above the method detection limit (0.24 ng/L) in the filtration blanks performed 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 wastewater treatment system (SP-4) 

were collected by pouring ASTM Type 1 water through the funnel and tubing 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 container. 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 tubing, capsule filter, and “Y” splitter, and into 

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

Prairie’s representative, using the same procedure discussed in the sample collection description 

(Section 3.1). 

The total mercury field blank sample for the effluent from the FGD wastewater treatment 

system (SP-5) was collected by shrouding one of the three taps on the sample tap splitter with a 

clear plastic bag. Before purging 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 system (SP-5) were collected by filling a 20-liter 

composite container with ASTM Type 1 water. The same T-splitter tubing used to fill the metals 

composite container was used with a pump to fill 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 other 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. The vented cap used for the field 

blank collection was the same cap that was later used for the metals composite container. 

After 24 hours, the ASTM Type 1 water in the 20-liter field blank 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 pumped through the tubing and “Y” splitter, and 

into the sample bottles. EPA collected the field 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 bottles, 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 analytical 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 duplicate samples are separate samples collected from the same 

location as the original sample. The duplicate is filled immediately after the original sample and 

is stored and analyzed independently. The RPD between the two sample results is examined to 

determine the precision of the data. EPA used the following equation to calculate the RPD for 

the duplicate sample results. 

100

2

S D

S D

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 duplicate samples for the effluent from the 

FGD wastewater treatment system (SP-3) during 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 effluent from the FGD wastewater treatment system (SP-2) Day 2 and 

the duplicate of the effluent from the FGD wastewater treatment system (SP-3) sample analyses, 

including all qualified results and all results that were measured above the method detection 

limit, but below the quantitation limit (i.e., J-values). 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 leas^ - 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 

5-5 

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

Analyte Sample Description Method Units 

Total MetalsNickel Effluent from FGD Wastewater Treatment System Field Blank - Day 1 200.8 ug/L Selenium Influent to FGD Wastewater Treatment System Field Blank - Day 1 200.8 ug/L 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 leas^ - 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 

5-6 

Table 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Pleasa

Analyte Method Units

Original 

Effluent from FGD 

Wastewater Treatment 

System, Day 2 

Concentration 

(SP-2)

Duplicate

Effluent from FGD 

Wastewater Treatment 

System Concentration 

(SP-4)

A

R

ClassicalsAmmonia 350.1 mg/L 20.0 20.0 Nitrate Nitrite as N 353.2 mg/L 160 160 Nitrogen, Total Kjeldahl 351.2 mg/L 66.0 B 70.0 B Biochemical Oxygen Demand 5210B mg/L NQ (2.50) NQ (2.50) NChemical Oxygen Demand 410.4 mg/L 440 470 Chloride 300.0 mg/L 2,000 2,000 Sulfate 300.0 mg/L 16,000 16,000 Cyanide, Total 4500 CN E mg/L 0.210 B 0.160 B Total Dissolved Solids 2540C mg/L 24,000 23,000 2Total Suspended Solids 2540D mg/L NQ (4.00) NQ (4.00) NPhosphorus, Total 365.1 mg/L 0.140 B NQ (0.0500) B < Total MetalsAluminum 200.7 ug/L 720 F ND (200) Antimony 200.8 ug/L 2.40 2.30 Arsenic 200.8 ug/L 4.70 4.90 Barium 200.7 ug/L 69.0 69.0 Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND Boron 200.7 ug/L 10,000 B,4 10,000 B Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 leas^ - 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 

5-7 

Table 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Pleasa

Analyte Method Units

Original 

Effluent from FGD 

Wastewater Treatment 

System, Day 2 

Concentration 

(SP-2)

Duplicate

Effluent from FGD 

Wastewater Treatment 

System Concentration 

(SP-4)

A

R

Calcium 200.7 ug/L 650,000 4 660,000 6Chromium 200.8 ug/L ND (8.00) ND (8.00) ND Cobalt 200.7 ug/L NQ (20.0) NQ (20.0) NCopper 200.8 ug/L NQ (4.00) ND (4.00) NIron 200.7 ug/L NQ (200) NQ (200) NLead 200.8 ug/L NQ (2.00) ND (2.00) NMagnesium 200.7 ug/L 3,600,000 4 3,500,000 3,Manganese 200.7 ug/L 11,000 4 11,000 Mercury 1631E ng/L 88.3 84.4 Molybdenum 200.7 ug/L NQ (40.0) NQ (40.0) NNickel 200.8 ug/L 20.0 F NQ (4.00) Selenium 200.8 ug/L 2,200 B,4 2,100 B Silver 200.8 ug/L ND (2.00) F ND (2.00) ND Sodium 200.7 ug/L 510,000 4 510,000 5Thallium 200.8 ug/L 3.10 2.80 Tin 200.7 ug/L ND (200) NQ (200) NTitanium 200.7 ug/L ND (20.0) ND (20.0) ND Vanadium 200.8 ug/L ND (10.0) ND (10.0) ND Zinc 200.8 ug/L 14.0 F ND (10.0) Dissolved Metals
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 leas^ - 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 

5-8 

Table 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Pleasa

Analyte Method Units

Original 

Effluent from FGD 

Wastewater Treatment 

System, Day 2 

Concentration 

(SP-2)

Duplicate

Effluent from FGD 

Wastewater Treatment 

System Concentration 

(SP-4)

A

R

Aluminum 200.7 ug/L ND (200) ND (200) NAntimony 200.8 ug/L NQ (2.00) 2.50 Arsenic 200.8 ug/L 5.50 5.30 Barium 200.7 ug/L 68.0 70.0 Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND Boron 200.7 ug/L 10,000 B,4 10,000 B Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND Calcium 200.7 ug/L 640,000 4 650,000 6Chromium 200.8 ug/L ND (8.00) ^ ND (8.00) ^ ND Chromium (VI) 218.6 ug/L ND (10.0) ND (10.0) ND Cobalt 200.7 ug/L ND (20.0) NQ (20.0) NCopper 200.8 ug/L ND (4.00) ND (4.00) ND Iron 200.7 ug/L NQ (200) NQ (200) NLead 200.8 ug/L ND (2.00) ND (2.00) ND Magnesium 200.7 ug/L 3,500,000 B,4 3,600,000 B 3,Manganese 200.7 ug/L 11,000 4 11,000 Mercury 1631E ng/L 27.4 26.5 Molybdenum 200.7 ug/L NQ (40.0) NQ (40.0) NNickel 200.8 ug/L NQ (4.00) NQ (4.00) NSelenium 200.8 ug/L 2,000 4 2,200 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented 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 leas^ - 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 

5-9 

Table 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Pleasa

Analyte Method Units

Original 

Effluent from FGD 

Wastewater Treatment 

System, Day 2 

Concentration 

(SP-2)

Duplicate

Effluent from FGD 

Wastewater Treatment 

System Concentration 

(SP-4)

A

R

Silver 200.8 ug/L ND (2.00) F ND (2.00) ND Sodium 200.7 ug/L 520,000 4 540,000 5Thallium 200.8 ug/L 2.70 2.60 Tin 200.7 ug/L ND (200) NQ (200) NTitanium 200.7 ug/L ND (20.0) ND (20.0) ND Vanadium 200.8 ug/L ND (10.0) ND (10.0) ND Zinc 200.8 ug/L ND (10.0) ND (10.0) ND 
6-1

6. REFERENCES

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 RESULTS 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-1 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 4 1.9 4 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 4 1.5 20 Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 50 13 150 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 11 40 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 50 82 200 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 50 24 100 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 50 18 50 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-2 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 200,000 49,700 104,000 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 50 22 100 Selenium 200.8 ug/L 50 16 100 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 50 42 250 Zinc 200.8 ug/L 50 100 250 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-3 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 50 22 100 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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-4 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 2 0.94 2 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 4 1.5 20 Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 50 13 150 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 28 100 Phosphorus, Total 365.1 mg/L 5 0.025 0.25 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 50 82 200 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 50 24 100 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 50 18 50 Magnesium 200.7 ug/L 50 540 10,000 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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-5 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 200,000 48,300 101,000 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 50 22 100 Selenium 200.8 ug/L 50 16 100 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 50 42 250 Zinc 200.8 ug/L 50 100 250 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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-6 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 4,000 975 2,040 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 10 4.5 20 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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-7 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 2 0.94 2 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.38 5 Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 50 13 150 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 28 100 Phosphorus, Total 365.1 mg/L 5 0.025 0.25 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 10 16 40 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 50 24 100 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 10 3.6 10 Magnesium 200.7 ug/L 50 540 10,000 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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-8 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 200,000 48,300 101,000 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 50 22 100 Selenium 200.8 ug/L 10 3.1 20 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 10 8.4 50 Zinc 200.8 ug/L 50 100 250 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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-9 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 100 24.1 50.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 50 22 100 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – 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-10 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 2 0.94 2 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 4 1.5 20 Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 50 13 150 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 28 100 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 50 240 5,000 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 10 16 40 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 50 24 100 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 10 3.6 10 
ND – 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-11 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 200,000 48,300 101,000 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 50 22 100 Selenium 200.8 ug/L 10 3.1 20 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 10 8.4 50 Zinc 200.8 ug/L 50 100 250 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
ND – 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-12 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 2,000 487 1,020 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 10 4.5 20 Selenium 200.8 ug/L 10 3.1 20 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-13 

Table A-5. Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 4 1.9 4 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 10 0.77 10 Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 50 13 150 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
ND – 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-14 

Table A-5. Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 10 2.41 5.05 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
ND – 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-15 

Table A-5. Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 10 2.41 5.05 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-16 

Table A-6. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 4 1.9 4 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 10 0.77 10 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 50 13 150 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-17 

Table A-6. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-18 

Table A-6. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 50 12.1 25.2 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-19 

Table A-7. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 2 0.94 2 Nitrate Nitrite as N 353.2 mg/L 50 0.95 5 Nitrogen, Total Kjeldahl 351.2 mg/L 10 0.77 10 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 50 13 150 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
ND – 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-20 

Table A-7. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 10 2.41 5.05 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
ND – 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 laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-21 

Table A-7. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 10 2.41 5.05 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-22 

Table A-8. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.94 2 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 10 0.77 10 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 50 13 150 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-23 

Table A-8. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 100 24.1 50.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

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-24 

Table A-8. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Pleasa

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 10 2.41 5.05 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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-25 

Table A-9. Duplicate of Effluent from FGD Wastewater Treatment System, Analytical Results, Ple

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 4 1.9 4 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 10 0.77 10 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 50 13 150 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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-26 

Table A-9. Duplicate of Effluent from FGD Wastewater Treatment System, Analytical Results, Ple

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Mercury 1631E ng/L 50 12.1 25.2 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 50 13 500 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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-27 

Table A-9. Duplicate of Effluent from FGD Wastewater Treatment System, Analytical Results, Ple

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Mercury 1631E ng/L 50 12.1 25.2 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 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-28 

Table A-10. Bottle Blank and Equipment Blank 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 Recoverable 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 Recoverable 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 Blank Analytical Data, Pleasant Prairie

Analyte Method Process Units Concentration 

Lead EPA 1638 Total Recoverable 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 Recoverable 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 Blank (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)

Aluminuma 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 Blank 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-splitter, and two pieces of 5 

feet of #24 silicone tubing for sample collection 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 Recoverable 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 Recoverable 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 Blank 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 Blank (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 dissolved 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 Recoverable 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 Recoverable 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 #73 silicone tubing, T-splitter, six feet of #73 silicone 

tubing, and 15 feet of #73 silicone tubing for total and dissolved sample collection 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 Blank 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 Recoverable 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 Recoverable 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-33 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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 Analytical Results, P

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
A-34 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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 Analytical Results, P

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
A-35 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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 System Field Blank, Day 1 Analytical Results

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 NThallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 
A-36 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 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 System Field Blank, Day 1 Analytical Results

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
A-37 

ND – 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 System Field Blank, Day 2 Analytical Results

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
A-38 

J – Result measured above the MDL, but less than the quantitation limit. 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
A-39 

ND – 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 System Field Blank, Day 4 Analytical Results

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
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 Effluent – 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 that 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 CALIBRATION VERIFICATIONS 

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

criteria. 

BLANKS 

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

calibration blanks (CCBs) met method-specified requirements. 

DUPLICATES 

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

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

RPD criteria between field duplicates is 20%. 

Laboratory duplicates were performed 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 matrix spike duplicates (MSD) were performed on samples 

71692, 71695, 71696, 71694 and 71697. All recoveries 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, EPA EAD 

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Randy Mercurio, ERG 

Date: 3/29/2011

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

Episode 6559

TestAmerica generated analytical data for total and dissolved 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 and 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 analysis according to 

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

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

2010, based on EPA Method 200.8, by ICP/MS analysis. 
2

Any significant findings are summarized below. Specific results 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 high 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 was 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, the background counts for mass 75 

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

10.3.3 of TestAmerica’s SOP. 

INTERNAL STANDARDIZATION 

All internal standards used by TestAmerica were within the method criteria. 

INITIAL CALIBRATION 

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

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

INITIAL AND CONTINUING CALIBRATION VERIFICATION 

The initial calibration verifications (ICV) and continuing calibration verifications (CCV) 

performed by TestAmerica all had recoveries within the method 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 flagged 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, some 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 limits. 
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 the 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, corrective 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 concentrations did have percent 

differences calculated and met the typical <10% criterion, 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% for all values equal to 

or greater than the reporting limit. 

The RPD of the laboratory duplicate samples for Sample 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 on 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 concentration 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 limits of 70-130% with the exception of 

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

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

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

percent. 
4

POST DIGESITON SPIKES (PDS) 

All post digestion spikes passed TestAmerica’s 85-115% recovery 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 sulfates in this episode’s samples 

that could form insoluble silver sulfide and/or silver sulfate. 

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 Ag Matrix 

Interference 

Failed MS/MSD 1.2 μg/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 μg/L (total) 

71696 Zn Matrix 

Interference 

Failed MS/MSD 14 μg/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 for Total and Dissolved Metals by 200.7 – 

Episode 6559

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

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

manganese) for Sample Episode 6559. The samples 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 Trace 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 concentration of iron (115 ug/L) was greater 

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

 The continuing calibration verification 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 failed the EPA Method 200.7 control limits of 

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

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

MS/MSD). 

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES 

There were no sample receipt issues in this data package. 

INTERNAL STANDARDIZATION 

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

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

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

INITIAL CALIBRATION 

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

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

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS 

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

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

the exception of CCV 280-22121/107, which failed the method criteria for aluminum. All 

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

additional qualifications were required. 

BLANKS 

All the method blanks were less than the reporting 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 measured at over 1,000 times the blank level; therefore, 

2
the sample required no further qualification. The iron result for Sample 71700 was 

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

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

(CCB)) were less than the reporting limit; however, 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 performed using the synthetic matrix as the check solution. All 

recoveries met TestAmerica’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 batch of total and dissolved samples. Sample 

71691 failed the method required ±10% difference 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. These elements were all flagged “V” as 

failing the QC criteria. These dilution tests indicate 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 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 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 matrix 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 calculated. In addition, some elements were 

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

3
4

spike concentration, even if the MS/MSD recoveries did not fail the 70-130% recovery 

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

Otherwise, the MS/MSD spike recoveries were 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 μg/L (total) 

71691 Barium Matrix 

Interference 

Failed MS 90 μg/L (dissolved) 

71695 Aluminum Matrix 

Interference 

Failed MS/MSD, 

Serial Dilution 

680 μg/L (total) 

71696 Aluminum Matrix 

Interference 

Failed MS/MSD, 

Serial Dilution 

720 μg/L (total) 

71698 Iron Matrix 

Interference 

Failed MS/MSD 390 μg/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 analytical data for dissolved hexavalent 

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

EPA Method 218.6 for dissolved hexavalent chromium by Liquid Chromatography – 

Inductively Coupled Plasma Mass Spectrometry (LC-ICP-MS). 

Table 1 summarizes the samples FGS extracted analyzed for dissolved 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 (SOP), a modified EPA Method 218.6. All 

1
samples 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, HANDLING, AND STORAGE ISSUES 

There were no sample receipt issues in this data package. 

INITIAL PRECISION AND ACCURACY/RECOVERY 

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

method criteria. 

ON-GOING PRECISION AND ACCURACY/RECOVERY 

The analytical method did not require the analysis 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 blank and eight calibration standards with a 

correlation factor ≥0.995 as required by the method. 

A secondary source initial calibration verification (ICV) was analyzed and passed ± 10% 

of true value required by the method. 

CONTINUING CALIBRATION VERIFICATION 

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

low recovery of 87.6%. All samples affected 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 method-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 duplicates performed in this episode 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 for Classicals Analyses – Episode 6559 

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry 

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

 Ammonia by EPA method 350.1, 

 Biochemical Oxygen Demand – 5 day (BOD5) 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 TestAmerica analyzed for the above analytes. 

Table 1. EPA Episode 6559 Classical Analytes – 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 samples 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 standard used to create the curve, the sample was 

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

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

calibration verification samples met the criteria specified in the method. 

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

used to verify calibration, was always within the control limits specified by the method. 

As described below, the analyte of interest was detected above the method detection limit 

(MDL) in some laboratory reagent blanks (LRB). However, the analyte of interest was 

never detected above the reporting limit (RL) in the LRBs. If required by the method, all 

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

below. 

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

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

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

specified in the method unless described below. 

DATA NOTES/ISSUES 

Ammonia 

The laboratory diluted the MS/MSD samples for 71697 by two fold after 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 EPA Method 350.1. 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, 

this sample does not need to be qualified. 

2 
BOD5 

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, BOD5 was reported 

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

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

TestAmerica analyzed four laboratory duplicates on samples 71694, 71696, 71697, and 

71698. Three of these laboratory duplicate samples 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 could 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 recoveries 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, this 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%). Because 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 qualified these samples with a “*” indicating that the LFB or 

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

additionally qualified as minimum values. 

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

and 75% respectively. These percent 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 suggested by the LFB failure. 

Therefore, these results indicate 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 MSD samples associated with 71691 were 75% 

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

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

3 
These low percent 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 concentration is greater 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 field 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 field duplicates specified in SM 4500 CN- E. 

SM 4500 CN-

 E does not require the laboratory to analyze MS/MSD samples, so there are 

no control limits specified in the method. The 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 laboratory 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 interferences. 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 

TestAmerica 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. Thus, 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 the 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 control limits of 71-128%. 

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

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

interferences. Sample 71697 was already qualified 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 minimum value. The LFB associated with all 

samples met the method criteria. 

The analyzed results for the following samples 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 associated 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 samples (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. Method 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 wastewater 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 LRB 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 analysis 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 Method 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 spike amount indicating the control limits are not 

reliable. TestAmerica did not flag the MSD 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 qualified 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 required 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 because 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 the 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 duplicates 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: INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY FOR TRACE 

ELEMENT ANALYSIS IN FLUE GAS DESULFURIZATION WASTEWATERS
D-1 

FGD ICP/MS SOP: Inductively Coupled 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) H2 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 78Se, 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 H2 gases. Common examples are potential interferences from 

40Ar35Cl or 40Ca35Cl on 75As, or 35Cl16O on 51V, or 40Ar12C on 52Cr. 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 150Nd and 150Dy 

(potential interference on 75As and from 156Gd (potential interference on 78Se). 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 78Se would be: 

78Se = 78Se – (156Gd/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 hazardous; it is corrosive, reactive, 

an oxidizer, and a poison. Inhalation 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, throat, 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 collision 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. HNO3 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% HNO3 / 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% HNO3 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% HNO3/0.5% 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% HNO3 / 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% HNO3 / 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% HNO3 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 HNO3, pH < 2 180 Days 40 CFR Part 136.3

Soils Glass or 

HDPE 

4 oz Cool 4 + 2oC 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 Zn64 48.6%; Zn66 27.9%; 

Zn67 4.1%; Zn68 18.8%; Zn70 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 Zn70 in the above example will be 

masked by Ge70) 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 Zn64

48.6%; Zn66 27.9%; Zn67 4.1%; Zn68 18.8%; Zn70 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 Zn70 in the above example will be masked by Ge70) 

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 85o

C. 

10.2.8 Heat for 2 hours after 85o

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%

LCSTrue Value

LCS Found Value - LRB Found Value % 



 



 R 

100%

ICV True Value

ICV Found Value % 



 



 R 

100%

CCV True Value

CCV Found Value % 



 



 R 

100%

SA

SSR - SR % 



 



 R 

  100

1 2 2

1

/ 1 2/





















  DU DUDU DU RPD
D-16 

11.6 The final concentration for an aqueous sample is calculated as follows:

2

1 Result ( g/L) V

C V  D

 

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 99th 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, Calibration 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 used as an internal standard for low mass elements. 

Attachment 2: Internal Standards and Corresponding Metals 

Internal Std. Associated elements1,2

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 interferences 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 HNO3 to pH < 2 6 months 

Soils/Sediments/Wastes: 

The preservation required for soil/sediment/waste samples is maintenance at 4°C ( ± 2°C) until 

digestion. 

Footnotes: (1) Polyethylene (P) or glass (G). 

 (2) Sample preservation is performed by the sampler immediately upon sample 

collection or shipped to the laboratory unpreserved for preservation at the 

laboratory. 

 (3) Samples must be analyzed as soon as possible after collection. The times listed 

are the maximum times that sample may be held before analysis and still 

considered valid. Holding times are calculated 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 (H2) 

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 calibration solution at the above levels. Levels 

may be adjusted to meet specific requirements. 

####