Sampling Episode Report 

RRI Energy’s 

Keystone Generating Station 

Shelocta, PA 

Sampling Episode 6563 

Prepared for:

U.S. Environmental Protection Agency

Engineering and Analysis Division 

Office of Water 

1200 Pennsylvania Avenue, NW 

Washington, D.C. 20460 

Prepared by: 

Eastern Research Group, Inc.

14555 Avion Parkway 

Suite 200 

Chantilly, VA 20151 

 13 April 2012 

EPA Contract No. 68-C-02-095 

Work Assignment 9-29
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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 .........................................................................................2-1

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

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

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

3. 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 System.................................3-3

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

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

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

4. LABORATORY ANALYTICAL RESULTS AND DISCUSSION...................................................4-1

4.1 Measured and Calculated Results for Influent to FGD Wastewater Treatment 

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

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

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 .......................................................................................5-3

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
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LIST OF TABLES 

Page 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Table A-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD 

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

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

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

Table A-3. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD 

Wastewater Treatment System, Day 3 Analytical Results, Keystone ............................ A-5
LIST OF TABLES (Continued) 

Page 

iii

Table A-4. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Keystone ....................................................................................................................... A-63
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LIST OF FIGURES 

Page 

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

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

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 Collection Set-Up at the Effluent from the FGD Wastewater Treatment 

System..............................................................................................................................C-4
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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 September 12-17, 2010, at RRI Energy’s Keystone Generating Station (Keystone), located 

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

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

system and the effluent from the chemical precipitation system. 

1.1 Background of Detailed Study

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

identified metals and certain other constituents 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. 

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

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

its two generating units; 

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

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

includes the following steps: 

— Equalization, 

— Lime addition (pH adjustment/metal hydroxide precipitation) 

— Organosulfide addition, 

— Ferric chloride addition, 

— Polymer addition, 

— Clarification, 

— Hydrochloric acid addition (pH adjustment), 

— Antiscalant addition, 

— Heat extraction (cooling), and 

— Filtration (sand filters and polishing filters); and 
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 The plant operates selective catalytic reduction (SCR) systems on both generating 

units. 

1.3 Sampling Episode Overview

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

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

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

collection procedures used during the sampling episode. 

On Sunday, September 12, 2010, EPA arrived at Keystone 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 (September 13–17, 2010). The following personnel participated in 

EPA’s sample collection activities: 

 Ron Jordan, EPA/EAD; 

 Elizabeth Sabol, ERG; 

 Becky Schwantes, ERG; 

 Steve Strackbein, ERG; 

 Kim Wagoner, ERG; and 

 Jessica Wolford, ERG. 

In addition, during the sample collection, EPA collected split 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 Keystone’s representative and collected 

samples on behalf of the plant. 
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2. FACILITY OVERVIEW

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

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

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

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

Pennsylvania. 

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

sulfur dioxide (SO2) releases from the plant. The Unit 1 FGD system was installed in September 

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

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

control the discharges of the wastewater generated during the operation of the FGD scrubbers. 

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

treatment system is discussed further in Section 2.2. 

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

systems to control nitrogen oxide (NOx) releases from the plant. In January 2009, Keystone 

began operating the SCR systems year-round. Keystone also uses low NOx burners on Units 1 

and 2, which were installed in 1994 and 1995 respectively, to control NOx releases from the 

plant. 

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

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

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

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

pneumatically transferred to fly ash silos. 

Units 1 and 2 have the following configuration: 

 Boiler; 

 SCR system; 

 Air heater; 

 ESP; and 

 FGD scrubber system. 

2.1 FGD Scrubber System

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

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

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

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

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

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

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

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

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

is pumped to the various levels of the FGD scrubbers with the recycle pumps. Both absorbers 
2-2

have five spray levels, but the plant does not always operate all of them at the same time. The 

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

the slurry falls downward and the flue gas flows counter-current to the 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 settle on the 

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

tray has small holes in it that allow the flue gas to bubble 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 it reaches the reaction tank. 

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

(i.e., gypsum). 

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

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

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

solids level is between 18 and 22 percent. Keystone transfers the blowdown from the scrubber 

absorber to the gypsum dewatering operations. 

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

overflow from the primary hydrocyclones is monitored. If the chloride concentration in the 

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

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

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

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

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

never recycled back to the absorber. 

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

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

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

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

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

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

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

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

2.2 FGD Wastewater Treatment System

The FGD wastewater treatment system is designed to receive intermittent transfers of 

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

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

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

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

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

system is 450 gpm. 
2-3

Keystone operates the FGD wastewater treatment system 24 hours per day, 7 days per 

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

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

(TSS), total selenium, oil and grease, BOD5, beryllium, copper, lead, mercury, silver, 

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

treatment operations: 

 Equalization; 

 Lime addition (pH adjustment/metal hydroxide precipitation); 

 Organosulfide addition; 

 Ferric chloride addition; 

 Polymer addition; 

 Clarification; 

 Hydrochloric acid addition (pH adjustment); 

 Antiscalant addition; 

 Heat extraction (cooling); 

 Filtration (sand filters and polishing filters); and 

 Biocide addition. 

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

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

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

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

treatment operations. 

The secondary hydrocyclone overflow from the scrubbers is transferred to the purge tank 

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

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

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

also receives wastewater from the wastewater treatment sump and effluent from the FGD 

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

wastewater through the system. 

2.2.1 Physical/Chemical Separation 

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

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

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

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

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

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

where ferric chloride is added. 

After the flow splitter tank, polymer is injected into the wastewater as it flows to the 

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

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

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

approximately 65 percent of the sludge from the clarifier is recycled back to the desaturation 
2-4

tank, while the remainder is transferred to a sludge tank and then pumped to a filter press for 

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

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

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

equalization tank. 

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

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

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

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

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

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

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

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

the sand filters, the wastewater flows by gravity to the effluent tank. 

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

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

is sent to the filtrate sump. Wastewater in the filtrate sump flows back to the equalization tank. 

The FGD wastewater treatment system was originally designed such that the plant could bypass 

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

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

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

maximum). Therefore, Keystone plans to use the polishing filters full time in accordance with 

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

ranges from 16 to 18 hours. 

During the sampling episode, the polishing filters were replaced beginning on Monday, 

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

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

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

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

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

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

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

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

due to the availability of sand filters B and C. 

2.2.2 Sampling Points 

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

summarized below: 

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

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

sample was collected prior to any chemical addition or mixing with recycle 

streams); and 
2-5

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

polishing filters, prior to discharge. 
2-6 

Figure 2-1. Simplified Diagram of the FGD Wastewater Treatment System, Keystone
2-7 

Figure 2-2. Detailed Diagram of the FGD Wastewater Treatment System, Keystone 
3-1

3. SAMPLE COLLECTION

During the Keystone 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. Figures 2-1 

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

including sampling point locations. 

Table 3-1 lists the sampling points, 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 Keystone’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 Keystone’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 

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

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

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

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

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

the sample collection. 

On Day 1 only, prior to collecting the 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 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. 

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

of dissolved metals sample fractions. After all samples were collected at the sampling point for 
3-3

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

untouched to allow the solids in the wastewater to settle. 

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

temperature were measured immediately at the 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 Keystone’s representatives. Figure C-3, in Appendix C, is a 

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

The sampling team placed the end of the Teflon® tubing into the 10-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 80 to 100 minutes. Approximately 

1.0 - 1.5 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. 

3.1.2 Effluent from FGD Wastewater Treatment System 

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

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

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

 

1

 On all sampling days, the filter/tubing was purged with 1.0 to 1.5 liters and there was no need to change the filter. 
3-4

sample tap was located inside the FGD wastewater treatment building (see Figure 2-2 for the 

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

or rain concerns during the sample collection. 

ERG collected the effluent from the FGD wastewater treatment system composite 

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

volumes into two 20-liter containers. The 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 

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. 
3-5

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

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

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

with a ziptie. After purging the 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 Keystone’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 system. 

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

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

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

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

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

After the twenty-fourth aliquots were 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 

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 Keystone’s representatives. 

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

On Day 1 only, prior to 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 
3-6

metals. See Section 5.2.3 for a description of the dissolved metals field blank sample collection 

at the effluent from the FGD wastewater treatment system. 

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

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

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

sample, samplers collected the following 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-

6 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; however, the cyanide QC sample was 

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

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

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

3.2 List of Analytes and Sample Preservation

Samples collected at Keystone were 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, 
3-7

— 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 also placed the 

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

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

hexavalent chromium samples. All dissolved 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 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 four-color 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. During the preservation of the cyanide 

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

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

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

3.3 Plant Operational Data

During the EPA sampling episode, Keystone 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, 

 

2

 In this report, EPA uses the terms “total metals” and “total recoverable metals” interchangeably. 
3-8

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

presents information on the FGD scrubber 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: 

 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. 

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

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

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

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

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

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

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

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

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

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

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

them from raising the temperature in the cooler during shipment. 
3-9

Table 3-1. Sample Collection Information, Keystone

Sampling 

Point 

Number Sampling Point Description 

Type of 

Sample 

Sample Collection 

Date 

Sample Collection Time 

Influent to FGD Wastewater 

Treatment System – Day 1 

Grab 9/13/10 0935a and 1124b

Influent to FGD Wastewater 

Treatment System – Day 2 

Grab 9/14/10 0950a and 1123b

Influent to FGD Wastewater 

Treatment System – Day 3 

Grab 9/15/10 0910a and 1053b

SP-1 

Influent to FGD Wastewater 

Treatment System – Day 4 

Grab 9/16/10 0904a and 1053b

Composite 9/13/10 

 9/14/10

0700c 

0753d

Effluent from FGD Wastewater 

Treatment System – Day 1 

Grab 9/13/10 

 9/14/10 

0716e

, 1316f , and 1915 g 

0115 h 

Composite 9/14/10 

9/15/10 

0700c 

0748d 

Effluent from FGD Wastewater 

Treatment System – Day 2 

Grab 9/14/10 

 9/15/10 

0715e

, 1316f , and 1916 g 

0114 h 

Composite 9/15/10 

9/16/10 

0700c 

0743d 

Effluent from FGD Wastewater 

Treatment System – Day 3 

Grab 9/15/10 

9/16/10 

0718e

, 1315f , and 1914 g 

0115 h 

Composite 9/16/10 

9/17/10 

0707c 

0641d 

SP-2 

Effluent from FGD Wastewater 

Treatment System – Day 4 

Grab 9/16/10 

9/17/10 

0720e

, 1316f , and 1915 g 

0115 h 

Composite 9/14/10 

 9/15/10 

0700c 

0748d

SP-3 Duplicate of Effluent from FGD 

Wastewater Treatment System – 

Day 2 Grab 9/14/10 

 9/15/10 

0716e

, 1318f , and 1920 g 

0116 h 

SP-4 Influent to FGD Wastewater 

Treatment System Field Blank 

Grab 9/13/10 0916 i and 1116j

Composite 9/13/10 

9/14/10

0627k

0740l

Effluent from FGD Wastewater 

Treatment System Field Blank – 

Day 1 

Grab 9/13/10 0710m

Effluent from FGD Wastewater 

Treatment System Field Blank – 

Day 2 

Grab 9/14/10 0708m

Effluent from FGD Wastewater 

Treatment System Field Blank – 

Day 3 

Grab 9/15/10 0712m

SP-5 

Effluent from FGD Wastewater 

Treatment System Field Blank – 

Day 4 

Grab 9/16/10 0715m
3-10

a

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

and dissolved mercury) and classicals (BOD5, Group I, Group II, and total cyanide). 

b

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

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

c Started compositor. 

d

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

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

classicals (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 Keystone

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

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+

SP-3 Field 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+

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, Keystone 

Temperature (°C) 

pH 

Sampling (S.U.) 

Point 

Number Sampling Point Description Date Time 

Thermometer Probe Meter a Strips 

Waste 

Stream 

Flow Rate 

(gpm) 

Influent to FGD Wastewater Treatment System – Day 1

9/13/2010 0954 46 42 6.2 7 490

Influent to FGD Wastewater Treatment System – Day 2 

9/14/2010 1015 46 40.8 6.06 7 493 

Influent to FGD Wastewater Treatment System – Day 3 

9/15/2010 0924 39.5 41 6.19 6.5 490 

SP-1 

Influent to FGD Wastewater Treatment System – Day 4 

9/16/2010 0918 46 42 6.2 6.5 497 

9/13/10 0719 28 26.3 6.75 7 2479/13/10 1319 29 26.5 6.54 7 227 9/13/10 1923 29 27.7 6.56 7 230 

Effluent from FGD Wastewater Treatment System – Day 1

9/14/10 0120 26 25.7 6.50 7 200 9/14/10 0721 28 25 6.35 7 199 9/14/10 1320 28 27 6.40 7 173 9/14/10 1916 29 26.5 6.40 7 163 

Effluent from FGD Wastewater Treatment System – Day 2 

9/15/10 0115 28 25.8 6.47 7 170 

9/15/10 0720 28 25.6 6.54 7 2099/15/10 1315 28 26.1 6.67 6.5 1849/15/10 1914 29 27.8 6.50 7 222

Effluent from FGD Wastewater Treatment System – Day 3 

9/16/10 0115 28 26.7 6.57 7 208

9/16/10 0723 29 26 6.50 7 1689/16/10 1318 29 26.4 6.50 7 2059/16/10 1928 28 27.2 6.51 7 154

SP-2 

Effluent from FGD Wastewater Treatment System – Day 4 

9/17/10 0125 28 27.7 6.53 7.5 212

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. 
3-13 

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

Sample Number Sample Point Sample Description 

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

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

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

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

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

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

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

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

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

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

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

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

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

71904 SP-5, Day 4 Effluent to FGD Wastewater Treatment System Field Blank - Day 4 
3-14 

Table 3-5. Analytical Methods, Keystone

Parameter Method Number 

Maximum Holding 

Time a 

Classicals

Biochemical oxygen demand (BOD5) SM 5210 B 48 hours 

Chemical oxygen demand (COD) EPA 410.4 28 days 

Total suspended solids (TSS) SM 2540 D 7 days 

Total dissolved solids (TDS) SM 2540 C 7 days 

Sulfate EPA 300.0 28 days 

Chloride EPA 300.0 28 days 

Ammonia as nitrogen EPA 350.1 28 days 

Nitrate/nitrate as nitrogen EPA 353.2 28 days 

Total Kjeldahl nitrogen (TKN) EPA 351.2 28 days 

Total phosphorus EPA 365.1 28 days 

Total cyanide SM 4500 CN E 14 days 

Total and Dissolved Metals

Mercury EPA 1631E 90 days b 

Hexavalent chromium (dissolved only) EPA 218.6 28 days 

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

nickel, selenium, silver, thallium, and vanadium 

EPA 200.8 with 

collision cellc 

6 months 

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

iron, magnesium, manganese, molybdenum, sodium, 

tin, titanium, and zinc 

EPA 200.7 6 months 

a

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

b

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

Additionally, the samples must be preserved by the laboratory within 48 hours after sample collection. c

 EPA used an SOP developed specifically for analyzing FGD wastewater (see Appendix D). 
3-15 

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

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.
3-16 

Table 3-7. Sample Preservation Summary, Keystone

Sampling Point 

Number Analysis Date 

Chemical 

Added Initial pH Final pH 

Amount 

Added 

(drops) 

71891 Group II Volume 1 9/13/10 H2SO4 7 2 45 

71891 Group II Volume 2 9/13/10 H2SO4 7 2 45 

(NH4)2SO4

Buffer 

71891 Hexavalent Chromium 9/13/10 8 100 

NH4OH 

7 

9.3 23 

(NH4)2SO4

Buffer 

71900 Hexavalent Chromium Field 9 100 

Blank 

9/13/10

NH4OH 

5.5 

9.3 3 

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

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

71892 Group II Volume 1 9/14/10 H2SO4 6.5 2 55 

71892 Group II Volume 2 9/14/10 H2SO4 6.5 2 55 

71895 Group II Volume 1 9/14/10 H2SO4 7 2 45 

71895 Group II Volume 2 9/14/10 H2SO4 7 2 45 

(NH4)2SO4

Buffer 

71892 Hexavalent Chromium 9/14/10 7.7 50 

NH4OH 

6.5 

9.3 25 

(NH4)2SO4

Buffer 

71895 Hexavalent Chromium 9/14/10 8.0 100 

NH4OH 

7 

9.3 18 

(NH4)2SO4

Buffer 

71901 Hexavalent Chromium Field 8.7 100 

Blank 

9/14/10

NH4OH 

7 

9.3 4 

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

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

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

71893 Group II Volume 1 9/15/10 H2SO4 7 2 55 

71893 Group II Volume 2 9/15/10 H2SO4 7 2 55 

71896 Group II Volume 1 9/15/10 H2SO4 6.5 2 45 

71896 Group II Volume 2 9/15/10 H2SO4 6.5 2 45 

71899 Group II Volume 1 9/15/10 H2SO4 6.5 2 45 

71899 Group II Volume 2 9/15/10 H2SO4 6.5 2 45 

(NH4)2SO4

Buffer 

71896 Hexavalent Chromium 9/15/10 8.1 100 

NH4OH 

6.5 

9.3 18 

(NH4)2SO4

Buffer 

71899 Hexavalent Chromium - 8.1 100 

Duplicate 

9/15/10

NH4OH 

6.5 

9.3 18 

(NH4)2SO4

Buffer 

71893 Hexavalent Chromium 9/15/10 8.5 100 

NH4OH 

6.5 

9.3 25 
3-17 

Table 3-7. Sample Preservation Summary, Keystone

Sampling Point 

Number Analysis Date 

Chemical 

Added Initial pH Final pH 

Amount 

Added 

(drops) 

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

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

71897 Total Cyanide – QC b 9/15/10 NaOH 7 8 45 

71897 Total Cyanide – QC (2) b 9/15/10 NaOH 8 11 25 

71894 Group II Volume 1 9/16/10 H2SO4 6.5 2 55 

71894 Group II Volume 2 9/16/10 H2SO4 6.5 2 55 

71897 Group II Volume 1 9/16/10 H2SO4 7 2 45 

71897 Group II Volume 1 - QC 9/16/10 H2SO4 7 2 45 

71897 Group II Volume 2 9/16/10 H2SO4 7 2 45 

71897 Group II Volume 2 - QC 9/16/10 H2SO4 7 2 45 

(NH4)2SO4

Buffer 

71894 Hexavalent Chromium 9/16/10 7 20 

NH4OH 

7 

9.3 26 

(NH4)2SO4

Buffer 

71897 Hexavalent Chromium 9/16/10 8 100 

NH4OH 

7 

9.3 18 

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

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

71898 Total Cyanide-QC b 9/16/10 NaOH 6.5 11 75 

71898 Group II Volume 1 9/17/10 H2SO4 7 2 45 

71898 Group II Volume 2 9/17/10 H2SO4 7 2 45 

(NH4)2SO4

Buffer 

71898 Hexavalent Chromium 9/17/10 7.7 100 

NH4OH 

7 

9.3 18 

a

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

added to the sample bottle. 

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

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

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

sample at day 4; therefore, the Day 3 (71897) QC sample was not analyzed by the laboratory.
3-18 

Table 3-8. Generating Unit Operating Characteristics during Sample Collection, Keystone 

Unit ID Boiler Type 

Capacity 

(MW) 

Electricity Production 

(MW) 

(or Percent Capacity %)

SCR 

(No, On, Off) 

Particulate Control System 

(HS/CS ESP, or BH) 

1 Supercritical 850 net 96.6% ON CS ESP 

2 Supercritical 850 net 96.6% ON CS ESP 

CS ESP – Cold-side electrostatic precipitator. 
3-19 

Table 3-9. FGD Scrubber System Operating Characteristics, Keystone 

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 Wet FGD Yes Lime slurry None Plum Creek 98 2 Yes Wet FGD Yes Lime slurry None Plum Creek 98 
3-20

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

Day of 

Sampling 

Unit 

ID Coal Type 

Amount of Coal 

Used During Day 

of Sampling 

(tpd) 

Source of 

Coal (Coal 

Region and/or 

State) 

Percent 

Sulfur in 

Coal 

(%) 

Chlorine Content 

of Coal 

(ppm) 

1 Bituminous 7627 Western PA 2.56 995 

1 

2 Bituminous 7465 Western PA 2.56 995 

1 Bituminous 7589 Western PA 2.63 1279 

2 

2 Bituminous 7705 Western PA 2.63 1279 

1 Bituminous 7538 Western PA 2.37 949 

3 

2 Bituminous 7349 Western PA 2.37 949 

1 Bituminous 7142 Western PA 2.59 939 

4 

2 Bituminous 7430 Western PA 2.59 939 

Table 3-11. Scrubber Slurry Information during Sample Collection, Keystone Creek

Scrubber Slurry 

Blowdown Flow Rate 

Day of 

Sampling 

FGD 

System ID 

Associated 

Unit IDs 

Flow Rate 

(gpm) Duration 

Scrubber 

Slurry 

Percent 

Solids 

Time of 

Dewatering 

During 

Sampling Day a

Percent 

Filtrate 

Recycled 

Back to 

Scrubber 

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

1 

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

223 min 

100% 

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

2 

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

516 min 

100% 

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

3 

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

410 min 

100% 

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

4 

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

297 min 

100% 

a

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

specific periods of time are not presented in this table. 
3-21 

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

Scrubber Purge Chemical Usage 

Day of 

Sampling 

Flow Rate 

(gpm) 

Duration 

(hr) 

Lime 

(lbs/day) 

Ferric Chloride 

(lbs/day) 

Organosulfide: 

TMT-15 

(lbs/day) 

Polymer

Scaletrol P

9326 

(lbs/day

1 485 9hr 12min 6728a (3,500 mg/L) 815 a (55 ppm) 224 a (14 ppm) 19 (3 ppm) 2 486 12 hr 18 min 6728 a (3,500 mg/L) 815 a (55 ppm) 224 a (14 ppm) 19 (3 ppm) 3 488 7 hr 6728 a (3,500 mg/L) 815 a (55 ppm) 224 a (14 ppm) 19 (3 ppm) 4 485 1 hr 6725 a (3,500 mg/L) 815 a (55 ppm) 224 a (14 ppm) 19 (3 ppm) 

a – Estimated Values. 

Note: the values provided in parentheses are the setpoint for the chemical in the reaction tanks.
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. Section 4.1 discusses the methods used by the laboratories for the biphasic analysis of 

SP-1. Section 4.2 presents the laboratory analytical data for the influent to and 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 Keystone, 

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. 

4.1 Measured and Calculated Results for Influent to FGD Wastewater Treatment 

System Samples

The samples of the influent to the FGD wastewater treatment system were expected to 

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

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

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

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

laboratories to separate the aqueous and solid phases of the sample prior to conducting certain 

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

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

concentrations for the following phases of the sample: 

 Aqueous phase; 

 Solid phase; and 

 Total sample. 

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

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

This section describes the approaches used by each laboratory and presents the results of the 

analyses. 

Metals and Classicals Analyses

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

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

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

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

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

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

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

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

analyte. The solid portion of the samples associated with the 200.7 analysis were prepared and 

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

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

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

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

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

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

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

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

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

the leachate according the specified methods. 
4-3 

TestAmerica also dried the solids prior to analysis, so the solid concentration is on a dryweight basis. To calculate the total sample concentration from the solid and aqueous phase 

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

and filtrate volume. EPA developed the following equation to calculate the individual metal total 

concentrations for the sample. 

Sample

Filtrate Filtrate Solid Solid

V

(C V ) (C Wt ) TotalSampleConcentration     (4-1) 

where: 

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

VFiltrate = volume of the filtrate; 

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

WtSolid = weight of the solids in the sample; and 

VSample = volume of the original sample. 

TestAmerica used the same approach for the seven classical pollutants that were analyzed 

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

Kjeldahl nitrogen (TKN), and total phosphorus. 

Mercury Analyses

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

Method 1631E does not contain any language stating how wastewater samples with high solid 

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

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

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

solid and aqueous phases separately. 

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

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

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

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

EPA Method 1631B. Frontier digested the samples with aqua regia (HCl/HNO3) and then 

analyzed the samples using EPA Method 1631E. 

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

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

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

concentrations for the sample. 

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

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

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

rounded to three significant figures. 
4-4 

4.2 FGD Wastewater Treatment System

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

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

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

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

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

analytes for the four days of sampling at the 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 5-1 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. 
4-5 

Appendix Tables A-1 through A-13 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. 
4-6 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - 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. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. P – Sample was not preserved immediately following collection. 

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

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Classicals Ammonia mg/L 350.1 13.3 

F(P, Est) – 

S(P, Est) 14.1 

F(P, Est) – S(P, 

Est) 13.3 

F(P, Est) – 

S(P, Est) 11.8 

Nitrate Nitrite as N mg/L 353.2 11.4 

F(P, Est) – 

S(P) 13.4 

F(P, Est) – 

S(P) 13.4 

F(P, Est) – 

S(P) 11.0 

Nitrogen, Total Kjeldahl mg/L 351.2 57.2 

F(B,L, P, Est) – 

S(P, Est) 54.7 

F(B, L, P, Est) – 

S(P, Est) 51.5 

F(B, L, P, Est) 

– S(P, Est) 49.6 

Biochemical Oxygen Demand mg/L 5210B 10.0 S,Min 9.50 S,Min 13.0 S,Min 2.90 Chemical Oxygen Demand mg/L 410.4 1,400 420 360 450 Chloride mg/L 300.0, 9056 15,400 15,300 15,300 14,600 Sulfate mg/L 300.0, 9056 1,920 2,020 2,040 1,950 Cyanide, Total mg/L 4500 CN E 0.341 

F(H, P, Est) – 

S(H, P) 0.194 

F(H, P, Est) 

– S(H, P) 0.280 

F(H, P, Est) 

– S(H, P) 0.283 

Total Dissolved Solids mg/L 2540C 35,000 D,H,Est 35,000 H,Est 37,000 H,Est 35,000 Total Suspended Solids mg/L 2540D 26,000 29,000 20,000 55,000 Phosphorus, Total mg/L 365.1 1.12 

F(P) – S(P, 

Est) 11.0 

F(P) – 

S(P, Est) 1.06 

F(P) – 

S(P, Est) 0.198 
4-7 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - 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. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. P – Sample was not preserved immediately following collection. 

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

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Total Metals Aluminum ug/L 200.7, 6010B 1,000,000 F(^) 871,000 938,000 F (^) 922,00Antimony ug/L 200.8, 6020 44.9 29.6 38.7 39.6 Arsenic ug/L 200.8, 6020 3,080 2,470 2,720 2,560 Barium ug/L 200.7, 6010B 19,600 11,900 10,300 10,300 Beryllium ug/L 200.7, 6010B NQ (85.4) NQ (71.6) NQ (73.8) NQ (70Boron ug/L 200.7, 6010B 411,000 F(B) 391,000 F(B) 403,000 F(B) 394,00Cadmium ug/L 200.8, 6020 104 94.5 94.0 108 Calcium ug/L 200.7, 6010B 6,780,000 6,670,000 7,200,000 6,710,0Chromium ug/L 200.8, 6020 3,010 S(B) 2,410 S(B) 2,630 S(B) 2,590 Cobalt ug/L 200.7, 6010B 968 891 913 861 Copper ug/L 200.8, 6020 2,070 1,720 1,820 3,280 Iron ug/L 200.7, 6010B 2,670,000 2,320,000 2,470,000 2,350,0Lead ug/L 200.8, 6020 1,140 904 1,000 981 Magnesium ug/L 200.7, 6010B 2,880,000 2,780,000 2,790,000 2,750,0Manganese ug/L 200.7, 6010B 486,000 459,000 454,000 442,00Mercury ng/L 

1631E, FGS069 533,000 515,000 559,000 622,00

Molybdenum ug/L 200.7, 6010B 568 465 500 506 Nickel ug/L 200.8, 6020 5,640 S(B) 4,990 S(B) 5,020 S(B) 6,560 
4-8 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - 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. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. P – Sample was not preserved immediately following collection. 

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

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Selenium ug/L 200.8, 6020 4,200 3,740 4,380 4,000 Silver ug/L 200.8, 6020 NQ (8.55) NQ (7.12) NQ (7.83) 387 Sodium ug/L 200.7, 6010B 341,000 300,000 330,000 323,00Thallium ug/L 200.8, 6020 52.6 50.0 54.8 56.1 Tin ug/L 200.7, 6010B ND (1,860) ND (1,610) ND (1,600) ND (1,52Titanium ug/L 200.7, 6010B 7,350 5,520 5,940 6,240 Vanadium ug/L 200.8, 6020 4,010 3,190 3,440 3,270 Zinc ug/L 200.7, 6010B 6,100 5,310 5,390 5,460 Dissolved Metals Aluminum ug/L 200.7 ND (200) ND (200) ND (200) ND (20Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4Barium ug/L 200.7 400 380 370 360 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.0Boron ug/L 200.7 410,000 B 380,000 B 400,000 B 390,00Cadmium ug/L 200.8 93.0 84.0 77.0 86.0 Calcium ug/L 200.7 5,200,000 5,000,000 5,100,000 5,000,0
4-9 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - 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. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. P – Sample was not preserved immediately following collection. 

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

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.0Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10Cobalt ug/L 200.7 500 480 470 450 Copper ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.0Iron 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 (2.0Magnesium ug/L 200.7 2,900,000 2,800,000 2,800,000 2,800,0Manganese ug/L 200.7 470,000 440,000 450,000 440,00Mercury ng/L 1631E 1,410 899 251 1,100 Molybdenum ug/L 200.7 ND (40.0) ND (40.0) ND (40.0) ND (40Nickel ug/L 200.8 2,300 2,200 2,100 2,100 Selenium ug/L 200.8 1,100 B 1,200 B 1,200 B 1,400 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.0Sodium ug/L 200.7 330,000 300,000 310,000 320,00Thallium ug/L 200.8 29.0 26.0 26.0 29.0 
4-10 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - 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. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. P – Sample was not preserved immediately following collection. 

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

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (20Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20Vanadium ug/L 200.8 NQ (10.0) ND (10.0) NQ (10.0) ND (10Zinc ug/L 200.7 82.0 71.0 69.0 61.0 
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. 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. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. M – MS percent recovery outside the method-specified criteria, but within the laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. 

Table 4-2. Effluent from FGD Wastewater Treatment System, Keystone 

Effluent from FGD Wastewater Treatment Syst

Analyte Units Method Day 1 Day 2 Day 3 D

Classicals Ammonia mg/L 350.1 13.0 12.0 11.0 12.0 Nitrate Nitrite as N mg/L 353.2 9.70 M,Min 9.35 9.30 9.40 Nitrogen, Total Kjeldahl mg/L 351.2 22.0 B 20.0 20.0 B,4 85.0 Biochemical Oxygen Demand mg/L 5210B 8.50 S,Min 7.00 6.80 S,Min 3.50 Chemical Oxygen Demand mg/L 410.4 470 275 380 F,Min 320 Chloride mg/L 300.0 15,000 15,000 14,000 13,000 Sulfate mg/L 300.0 1,500 1,350 1,400 1,400 Cyanide, Total mg/L 4500 CN E 0.120 B < 0.115 ND (0.100) 0.100 Total Dissolved Solids mg/L 2540C 35,000 B 30,500 29,000 29,000 Total Suspended Solids mg/L 2540D 4.80 32.0 7.20 D,Est 9.60 Phosphorus, Total mg/L 365.1 1.20 1.10 1.20 1.10 Total Metals Aluminum ug/L 200.7 ND (200) NQ (200) ND (200) ND (200Antimony ug/L 200.8 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.0Arsenic ug/L 200.8 NQ (4.00) < 3.05 NQ (4.00) NQ (4.0Barium ug/L 200.7 320 300 290 280 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.0Boron ug/L 200.7 300,000 B 300,000 280,000 B,4 290,000 Cadmium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.0Calcium ug/L 200.7 6,300,000 6,100,000 5,600,000 4 5,600,00Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.0Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.
4-12 

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. 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. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. M – MS percent recovery outside the method-specified criteria, but within the laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. 

Table 4-2. Effluent from FGD Wastewater Treatment System, Keystone 

Effluent from FGD Wastewater Treatment Syst

Analyte Units Method Day 1 Day 2 Day 3 D

Copper ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.0Iron ug/L 200.7 NQ (200) B NQ (200) NQ (200) B NQ (200Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.0Magnesium ug/L 200.7 1,900,000 B 2,000,000 1,900,000 B,4 1,900,00Manganese ug/L 200.7 24,000 B 23,000 19,000 B,4 23,000 Mercury ng/L 1631E 119 108 78.6 31.2 Molybdenum ug/L 200.7 42.0 43.5 42.0 43.0 Nickel ug/L 200.8 6.80 7.50 8.60 7.00 Selenium ug/L 200.8 300 350 300 320 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) F ND (2.0Sodium ug/L 200.7 300,000 290,000 280,000 270,000 Thallium ug/L 200.8 11.0 10.5 9.70 11.0 Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.Vanadium ug/L 200.8 NQ (10.0) B NQ (10.0) NQ (10.0) B NQ (10.Zinc ug/L 200.7 ND (40.0) ND (40.0) NQ (40.0) ND (40.Dissolved Metals Aluminum ug/L 200.7 ND (200) ND (200) NQ (200) ND (200Antimony ug/L 200.8 ND (2.00) NQ (2.00) NQ (2.00) NQ (5.0Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (10.Barium ug/L 200.7 320 295 290 280 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.0Boron ug/L 200.7 300,000 B 295,000 280,000 B,4 290,000 
4-13 

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. 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. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. M – MS percent recovery outside the method-specified criteria, but within the laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. 

Table 4-2. Effluent from FGD Wastewater Treatment System, Keystone 

Effluent from FGD Wastewater Treatment Syst

Analyte Units Method Day 1 Day 2 Day 3 D

Cadmium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.0Calcium ug/L 200.7 6,300,000 6,000,000 5,700,000 4 5,800,00Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.0Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10.Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.Copper ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.0Iron ug/L 200.7 ND (200) ND (200) NQ (200) ND (200Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.0Magnesium ug/L 200.7 1,900,000 1,950,000 1,900,000 4 1,900,00Manganese ug/L 200.7 24,000 22,500 18,000 4 22,000 Mercury ng/L 1631E 15.3 15.3 10.2 28.5 Molybdenum ug/L 200.7 42.0 43.0 42.0 44.0 Nickel ug/L 200.8 6.10 6.60 5.40 7.00 Selenium ug/L 200.8 320 B 360 320 B,4 300 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) F ND (2.0Sodium ug/L 200.7 300,000 290,000 280,000 280,000 Thallium ug/L 200.8 11.0 10.5 11.0 10.0 Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.Vanadium ug/L 200.8 NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.Zinc ug/L 200.7 ND (40.0) NQ (40.0) NQ (40.0) ND (40.
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

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

Analyte Units Method SP-1 

ClassicalsAmmonia mg/L 350.1 13.1 Nitrate Nitrite as N mg/L 353.2 12.3 Nitrogen, Total Kjeldahl mg/L 351.2 53.3 Biochemical Oxygen Demand mg/L 5210B 8.85 Chemical Oxygen Demand mg/L 410.4 658 Chloride mg/L 300.0, 9056 15,200 Sulfate mg/L 300.0, 9056 1,980 Cyanide, Total mg/L 4500 CN E 0.275 Total Dissolved Solids mg/L 2540C 35,500 Total Suspended Solids mg/L 2540D 32,500 Phosphorus, Total mg/L 365.1 3.34 
4-15 

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

NA – Not analyzed. 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. Metals Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment Syst

Influent to FGD

Wastewater Treatment

System (SP-1)

4-Day Average

Effluent from 

Wastewater T

System (S

4-Day Ave

Analyte Units Method Total Dissolved Total 

MetalsAluminum ug/L 200.7 933,000 ND (200) NQ (200) Antimony ug/L 200.8 38.2 ND (2.00) NQ (2.00) Arsenic ug/L 200.8 2,710 NQ (4.00) < 2.26 Barium ug/L 200.7 13,000 378 298 Beryllium ug/L 200.7 NQ (75.3) ND (2.00) ND (2.00) Boron ug/L 200.7 400,000 395,000 293,000 Cadmium ug/L 200.8 100 85.0 NQ (4.00) Calcium ug/L 200.7 6,840,000 5,080,000 5,900,000 Chromium ug/L 200.8 2,660 ND (8.00) ND (8.00) Chromium (VI) ug/L 218.6 NA ND (10.0) NA Cobalt ug/L 200.7 908 475 ND (20.0) Copper ug/L 200.8 2,220 NQ (4.00) ND (4.00) Iron ug/L 200.7 2,450,000 NQ (200) NQ (200) Lead ug/L 200.8 1,010 ND (2.00) ND (2.00) Magnesium ug/L 200.7 2,800,000 2,830,000 1,930,000 Manganese ug/L 200.7 460,000 450,000 22,300 Mercury ng/L 1631E 557,000 915 84.1 Molybdenum ug/L 200.7 510 ND (40.0) 42.6 Nickel ug/L 200.8 5,550 2,180 7.48 Selenium ug/L 200.8 4,080 1,230 318 Silver ug/L 200.8 < 99.7 ND (2.00) ND (2.00) Sodium ug/L 200.7 324,000 315,000 285,000 Thallium ug/L 200.8 53.4 27.5 10.6 
4-16 

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

NA – Not analyzed. 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. Metals Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment Syst

Influent to FGD

Wastewater Treatment

System (SP-1)

4-Day Average

Effluent from 

Wastewater T

System (S

4-Day Ave

Analyte Units Method Total Dissolved Total 

Tin ug/L 200.7 ND (1,650) ND (200) ND (200) Titanium ug/L 200.7 6,260 NQ (20.0) NQ (20.0) Vanadium ug/L 200.8 3,480 NQ (10.0) NQ (10.0) Zinc ug/L 200.7 5,570 70.8 NQ (40.0) 
5-1

5. DATA QUALITY

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

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

Rulemaking (QAPP) [2]. This section describes the QC 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 was 

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-14 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-14 presents all of the analytical 

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

collection of metals and mercury samples. 

5.2.3 Field Blanks 

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

contamination from sampling equipment, 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-6) 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 Keystone’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 detected at 

a concentration of 0.46 ng/L in the filtration blank performed for the fourth day of samples, which includes the 

influent to the FGD wastewater treatment system (day 2), the third and fourth grab sample for the effluent from the 

FGD wastewater treatment system (day 3), and the first and second grab samples for the effluent from the FGD 

wastewater treatment system (day 4). Mercury was not detected above the method detection limit (0.24 ng/L) in the 

filtration blanks performed for the first, second, third, or fifth day of samples.
5-3

The dissolved metals by 200.8, dissolved metals by 200.7, and dissolved hexavalent 

chromium field blank samples for the influent to the FGD 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 approximately 110 minutes, the sampling team began pumping off 

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

the tubing was purged with approximately one liter of blank water. The sample bottles were 

placed in a “cleanbox” and the ASTM Type 1 water was pumped through the tubing, capsule 

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

“true” split samples with Keystone’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 

Keystone’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. 

No metals were detected in the field blank samples above the quantitation limit, 

indicating that there was no contamination from the sample collection procedures. Appendix 

Tables A-15 through A-19 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). 

5.2.4 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 
5-4

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 5-1 presents analytical results and the RPD for SP3. Results are rounded to three significant digits. Appendix Tables A-10 and A-13 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). 
5-5 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quNC – 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 4-day average result indicates that all results were below the quantitation limit, but 

value. B – Analyte was found in the blank and sample. Min – Minimum value. S – Seed correction blank recovery low. 

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

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 12.0 12.0 Nitrate Nitrite as N 353.2 mg/L 9.40 9.30 Nitrogen, Total Kjeldahl 351.2 mg/L 19.0 B 21.0 B Biochemical Oxygen Demand 5210B mg/L 7.10 S,Min 6.90 S,Min Chemical Oxygen Demand 410.4 mg/L 310 240 Chloride 300.0 mg/L 15,000 15,000 Sulfate 300.0 mg/L 1,400 1,300 Cyanide, Total 4500 CN E mg/L NQ (0.100) 0.180 < Total Dissolved Solids 2540C mg/L 31,000 30,000 Total Suspended Solids 2540D mg/L 10.0 54.0 Phosphorus, Total 365.1 mg/L 1.10 1.10 Total MetalsAluminum 200.7 ug/L NQ (200) B ND (200) NAntimony 200.8 ug/L ND (2.00) NQ (2.00) NArsenic 200.8 ug/L 4.10 NQ (4.00) Barium 200.7 ug/L 300 300 Beryllium 200.7 ug/L ND (2.00) ND (2.00) NBoron 200.7 ug/L 290,000 B 310,000 B 3Cadmium 200.8 ug/L NQ (4.00) NQ (4.00) NCalcium 200.7 ug/L 6,000,000 6,200,000 6,
5-6 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quNC – 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 4-day average result indicates that all results were below the quantitation limit, but 

value. B – Analyte was found in the blank and sample. Min – Minimum value. S – Seed correction blank recovery low. 

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

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

Chromium 200.8 ug/L ND (8.00) ND (8.00) NCobalt 200.7 ug/L ND (20.0) ND (20.0) NCopper 200.8 ug/L ND (4.00) ND (4.00) NIron 200.7 ug/L NQ (200) B NQ (200) B NLead 200.8 ug/L ND (2.00) ND (2.00) NMagnesium 200.7 ug/L 2,000,000 B 2,000,000 B 2,Manganese 200.7 ug/L 23,000 B 23,000 B Mercury 1631E ng/L 110 105 Molybdenum 200.7 ug/L 44.0 43.0 Nickel 200.8 ug/L 7.50 7.50 Selenium 200.8 ug/L 350 350 Silver 200.8 ug/L ND (2.00) ND (2.00) NSodium 200.7 ug/L 290,000 290,000 2Thallium 200.8 ug/L 10.0 11.0 Tin 200.7 ug/L ND (200) ND (200) NTitanium 200.7 ug/L NQ (20.0) NQ (20.0) NVanadium 200.8 ug/L NQ (10.0) B NQ (10.0) B NZinc 200.7 ug/L ND (40.0) ND (40.0) NDissolved MetalsAluminum 200.7 ug/L ND (200) ND (200) NAntimony 200.8 ug/L NQ (2.00) ND (2.00) NArsenic 200.8 ug/L NQ (4.00) NQ (4.00) N
5-7 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quNC – 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 4-day average result indicates that all results were below the quantitation limit, but 

value. B – Analyte was found in the blank and sample. Min – Minimum value. S – Seed correction blank recovery low. 

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

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

Barium 200.7 ug/L 300 290 Beryllium 200.7 ug/L ND (2.00) ND (2.00) NBoron 200.7 ug/L 300,000 B 290,000 B 2Cadmium 200.8 ug/L NQ (4.00) NQ (4.00) NCalcium 200.7 ug/L 6,000,000 6,000,000 6,Chromium 200.8 ug/L ND (8.00) ND (8.00) NChromium (VI) 218.6 ug/L ND (10.0) ND (10.0) NCobalt 200.7 ug/L ND (20.0) ND (20.0) NCopper 200.8 ug/L ND (4.00) ND (4.00) NIron 200.7 ug/L ND (200) ND (200) NLead 200.8 ug/L ND (2.00) ND (2.00) NMagnesium 200.7 ug/L 2,000,000 1,900,000 1,Manganese 200.7 ug/L 23,000 22,000 Mercury 1631E ng/L 16.2 14.3 Molybdenum 200.7 ug/L 43.0 43.0 Nickel 200.8 ug/L 6.80 6.40 Selenium 200.8 ug/L 370 B 350 B Silver 200.8 ug/L ND (2.00) ND (2.00) NSodium 200.7 ug/L 290,000 290,000 2Thallium 200.8 ug/L 10.0 11.0 Tin 200.7 ug/L ND (200) ND (200) NTitanium 200.7 ug/L NQ (20.0) NQ (20.0) N
5-8 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quNC – 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 4-day average result indicates that all results were below the quantitation limit, but 

value. B – Analyte was found in the blank and sample. Min – Minimum value. S – Seed correction blank recovery low. 

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

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

Vanadium 200.8 ug/L NQ (10.0) NQ (10.0) NZinc 200.7 ug/L ND (40.0) NQ (40.0) N
6-1

6. REFERENCES

1. Eastern Research Group, Inc., 2010. Sampling Plan, RRI Energy’s Keystone Generating 

Station. September 3. DCN SE00504. 

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

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

3. U.S. EPA. 2001. Method 200.7: Determination of Metals and Trace Elements in Water 

and Wastes by Inductively Coupled Plasma – Atomic Emission Spectrometry. Revision 

4.4. 

4. U.S. EPA. 1994. Method 200.7: Determination of Trace Elements in Waters and Wastes 

by Inductively Coupled Plasma - Mass Spectrometry. Revision 5.4. 

 

 
Appendix A 

ANALYTICAL RESULTS 
A-1 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers associated with an associated with the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewate

System, Day 1 Analytical Results, Keystone 

Analyte

Aqueous Phase Result

(mg/L for Classicials;ug/L 

for Metals; and ng/L for 

Mercury)

Solid Phase Result

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury)

Calculated Total Sam

(mg/L for Classica

for Metals; and ng/L f

ClassicalsAmmonia 13 P,Est 34 P,Est 13.3 F(P, EstNitrate Nitrite as N 12 P,Est 6.6 J,P 11.4 F(P, ENitrogen, Total Kjeldahl 29 B,L,P,Est 900 P,Est 57.2 F(B,L, P, EChloride 16,000 13,000 15,400Sulfate 1,300 21,000 1,920Cyanide, Total 0.36 H,P,Est 0.15 J,H,P 0.341 F(H, P, EPhosphorus, Total 0.016 J,P 33 P,Est 1.12 F(J, P) Total MetalsAluminum ND (200) U,^ 30,000 1,000,000 FAntimony 1.6 J 1.3 44.9 Arsenic 3.5 J 92 3,080 Barium 270 580 19,600Beryllium ND (2) U 2.2 J 73.5 F(UBoron 410,000 B 830 411,000 Cadmium 86 0.7 104Calcium 5,000,000 63,000 6,780,000Chromium ND (8) U 90 B 3,010 F(UCobalt 500 15 968Copper 32 61 2,070
A-2 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers associated with an associated with the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewate

System, Day 1 Analytical Results, Keystone 

Analyte

Aqueous Phase Result

(mg/L for Classicials;ug/L 

for Metals; and ng/L for 

Mercury)

Solid Phase Result

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury)

Calculated Total Sam

(mg/L for Classica

for Metals; and ng/L f

Iron ND (200) U 80,000 2,670,000 Lead 7.5 34 1,140Magnesium 2,900,000 5,200 2,880,000Manganese 470,000 1,400 486,000Mercury 2,550 17,500 533,000Molybdenum ND (40) U 17 568 Nickel 2,100 110 B 5,640 Selenium 1,100 95 4,200Silver ND (2) U 0.23 7.68 Sodium 340,000 710 J 341,000 Thallium 17 1.1 52.6Tin ND (200) U ND (50) U ND (1,860) F(UTitanium ND (20) U 220 7,350 Vanadium ND (10) U 120 4,010 Zinc 93 180 6,100
A-3 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-2. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatm

Analytical Results, Keystone 

Analyte

Aqueous Phase Result 

(mg/L for Clasicals;

ug/L for Metals; and ng/L 

for Mercury)

Solid Phase Result

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury)

Calculated To

(mg/L for C

for Metals; and 

ClassicalsAmmonia 14 P,Est 29 P,Est 14.1 Nitrate Nitrite as N 14 P,Est 5 J,P 13.4 Nitrogen, Total Kjeldahl 32 B,L,P,Est 840 P,Est 54.7 F(BChloride 16,000 4,100 15,300Sulfate 1,300 27,000 2,020Cyanide, Total 0.2 H,P,Est 0.15 J,H,P 0.194 FPhosphorus, Total ND (0.05) U,P 380 P,Est 11 Total MetalsAluminum ND (200) U 30,000 871,000 Antimony 1.2 J 0.98 29.6 Arsenic 2.2 J 85 2,470 Barium 270 400 11,900Beryllium ND (2) U 2.1 J 61 Boron 390,000 B 730 391,000 Cadmium 77 0.74 94.5Calcium 4,800,000 73,000 6,670,000Chromium ND (8) U 83 B 2,410 Cobalt 480 15 891Copper 7.1 59 1,720Iron 47 J 80,000 2,320,000 
A-4 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-2. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatm

Analytical Results, Keystone 

Analyte

Aqueous Phase Result 

(mg/L for Clasicals;

ug/L for Metals; and ng/L 

for Mercury)

Solid Phase Result

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury)

Calculated To

(mg/L for C

for Metals; and 

Lead 3.5 31 904Magnesium 2,800,000 4,300 2,780,000Manganese 450,000 1,100 459,000Mercury 3,830 17,800 515,000Molybdenum ND (40) U 16 465 Nickel 2,200 100 B 4,990 Selenium 1,000 96 3,740Silver ND (2) U 0.2 5.81 Sodium 300,000 550 J 300,000 Thallium 16 1.2 50Tin ND (200) U ND (49) U ND (1,610) Titanium ND (20) U 190 5,520 Vanadium ND (10) U 110 3,190 Zinc 88 180 5,310
A-5 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-3. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewate

System, Day 3 Analytical Results, Keystone 

Analyte

Aqueous Phase Result

(mg/L for Classicals; ug/L 

for Metals; and ng/L for 

Mercury)

Solid Phase Result

(mg/kg for Classicals 

and Metals and ng/g for 

Mercury)

Calculated Total S

(mg/L for Class

for Metals; and ng/L 

ClassicalsAmmonia 13 P,Est 32 P,Est 13.3 F(P, ENitrate Nitrite as N 14 P,Est 4.3 J,P 13.4 F(P, Nitrogen, Total Kjeldahl 31 B,L,P,Est 710 P,Est 51.5 F(B, L, PChloride 16,000 4,500 15,300Sulfate 1,300 26,000 2,040Cyanide, Total 0.29 H,P,Est 0.19 J,H,P 0.28 F(H, P, Phosphorus, Total ND (0.05) U,P 34 P,Est 1.06 F(U, Total MetalsAluminum ND (200) U,^ 30,000 938,000 Antimony 1.3 J 1.2 38.7 Arsenic 1.8 J 87 2,720 Barium 280 320 10,300Beryllium ND (2) U 2.2 J 68.8 FBoron 400,000 B 780 403,000 Cadmium 73 0.8 94Calcium 5,000,000 79,000 7,200,000Chromium ND (8) U 84 B 2,630 FCobalt 470 15 913Copper 9.8 58 1,820
A-6 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-3. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewate

System, Day 3 Analytical Results, Keystone 

Analyte

Aqueous Phase Result

(mg/L for Classicals; ug/L 

for Metals; and ng/L for 

Mercury)

Solid Phase Result

(mg/kg for Classicals 

and Metals and ng/g for 

Mercury)

Calculated Total S

(mg/L for Class

for Metals; and ng/L 

Iron ND (200) U 79,000 2,470,000 Lead ND (2) U 32 1,000 Magnesium 2,800,000 4,600 2,790,000Manganese 440,000 1,200 454,000Mercury 3,510 17,500 559,000Molybdenum ND (40) U 16 500 Nickel 2,000 100 B 5,020 Selenium 1,000 110 4,380Silver ND (2) U 0.19 5.94 Sodium 330,000 570 J 330,000 Thallium 15 1.3 54.8Tin ND (200) U ND (45) U ND (1,600) FTitanium ND (20) U 190 5,940 Vanadium ND (10) U 110 3,440 Zinc 84 170 5,390
A-7 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-4. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Tr

Day 4 Analytical Results, Keystone 

Analyte

Aqueous Phase Result

(mg/L for Classicals; ug/L 

for Metals; and ng/L for 

Mercury)

Solid Phase Result

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury)

Calculated Total S

(mg/L for Class

for Metals; and ng/L 

ClassicalsAmmonia 12 P,Est 32 P,Est 11.8 F(P, Nitrate Nitrite as N 12 P,Est 5.1 J,P 11 F(PNitrogen, Total Kjeldahl 26 B,L,P,Est 880 P,Est 49.6 F(B, LChloride 16,000 4,900 14,600Sulfate 1,300 26,000 1,950Cyanide, Total 0.31 H,P,Est 0.12 J,H,P 0.283 F(H, PPhosphorus, Total 0.005 J,P 6.5 P,Est 0.198 F(JTotal MetalsAluminum 15 J,^ 31,000 922,000 Antimony 1 J 1.3 39.6 Arsenic 2.3 J 86 2,560 Barium 260 340 10,300Beryllium ND (2) U 2.2 J 65.4 Boron 410,000 B 800 394,000 Cadmium 83 1.1 108Calcium 5,000,000 74,000 6,710,000Chromium ND (8) U 87 B 2,590 Cobalt 460 15 861Copper 6.7 110 3,280
A-8 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-4. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Tr

Day 4 Analytical Results, Keystone 

Analyte

Aqueous Phase Result

(mg/L for Classicals; ug/L 

for Metals; and ng/L for 

Mercury)

Solid Phase Result

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury)

Calculated Total S

(mg/L for Class

for Metals; and ng/L 

Iron ND (200) U 79,000 2,350,000 Lead ND (2) U 33 981 Magnesium 2,900,000 4,500 2,750,000Manganese 450,000 1,200 442,000Mercury 3,750 20,100 622,000Molybdenum ND (40) U 17 506 Nickel 2,000 160 B 6,560 Selenium 1,200 98 4,000Silver ND (2) U 13 387 Sodium 340,000 550 J 323,000 Thallium 16 1.4 56.1Tin ND (200) U ND (45) U ND (1,520) Titanium ND (20) U 210 6,240 Vanadium ND (10) U 110 3,270 Zinc 120 180 5,460
A-9 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Classical Pollutants - TotalAmmonia 350.1 mg/L NA 0.343 4.07 Nitrate Nitrite as N 353.2 mg/L NA 0.0596 0.855 Nitrogen, Total Kjeldahl 351.2 mg/L NA 2.43 13.4 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 40 160 800 1Chloride 300.0, 9056 mg/L NA 125 1,450 1Sulfate 300.0, 9056 mg/L NA 14.1 317 1Cyanide, Total 4500 CN E mg/L NA 0.022 0.11 0Total Dissolved Solids 2540C mg/L 1 160 330 3Total Suspended Solids 2540D mg/L 1 92 330 2Phosphorus, Total 365.1 mg/L NA 0.0317 0.21 Classicals Pollutants - Solid (dry weight)Ammonia 350.1 mg/Kg 1 4.1 10 Nitrate Nitrite as N 353.2 mg/Kg 1 0.72 20 Nitrogen, Total Kjeldahl 351.2 mg/Kg 5 62 260 Chloride 9056 mg/Kg 50 97 1,500 1Sulfate 9056 mg/Kg 50 85 2,500 2Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.5 Phosphorus, Total 365.1 mg/Kg 1 0.81 4.9 Classicals Pollutants -Filtered AqueousAmmonia 350.1 mg/L 1 0.22 4 
A-10 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chloride 300.0 mg/L 500 130 1,500 1Sulfate 300.0 mg/L 50 12 250 1Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 0Metals - Calculated TotalAluminum 200.7, 6010B ug/L NA 266 1,860 1,0Antimony 200.8, 6020 ug/L NA 1.61 15.2 Arsenic 200.8, 6020 ug/L NA 84.6 1,010 3Barium 200.7, 6010B ug/L NA 15 186 1Beryllium 200.7, 6010B ug/L NA 6.01 85.4 Boron 200.7, 6010B ug/L NA 323 6,340 41Cadmium 200.8, 6020 ug/L NA 6.15 25.4 Calcium 200.7, 6010B ug/L NA 3,930 17,700 6,7Chromium 200.8, 6020 ug/L NA 8.09 20.8 3Cobalt 200.7, 6010B ug/L NA 17.7 186 Copper 200.8, 6020 ug/L NA 24.3 87.2 2Iron 200.7, 6010B ug/L NA 664 2,660 2,6Lead 200.8, 6020 ug/L NA 1.88 11.9 1Magnesium 200.7, 6010B ug/L NA 1,110 12,700 2,8
A-11 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7, 6010B ug/L NA 28.8 634 48Mercury 1631E, FGS-069 ng/L NA 21,500 59,000 53Molybdenum 200.7, 6010B ug/L NA 44.9 368 Nickel 200.8, 6020 ug/L NA 5.88 28.7 5Selenium 200.8, 6020 ug/L NA 11.6 51.8 4Silver 200.8, 6020 ug/L NA 1.89 8.55 Sodium 200.7, 6010B ug/L NA 9,850 92,800 34Thallium 200.8, 6020 ug/L NA 0.673 8.55 Tin 200.7, 6010B ug/L NA 155 1,860 ND Titanium 200.7, 6010B ug/L NA 24.5 186 7Vanadium 200.8, 6020 ug/L NA 4.13 42.4 4Zinc 200.7, 6010B ug/L NA 75.3 538 6Metals - DissolvedAluminum 200.7 ug/L 2 9.4 200 ND Antimony 200.8 ug/L 2 0.72 2 NArsenic 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 NBoron 200.7 ug/L 50 170 5,000 41Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 5,2
A-12 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Chromium 200.8 ug/L 2 3.3 8 NChromium (VI) 218.6 ug/L 5 1.96 10 ND 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 NMagnesium 200.7 ug/L 50 540 10,000 2,9Manganese 200.7 ug/L 50 13 500 47Mercury 1631E ng/L 100 24.1 50.5 1Molybdenum 200.7 ug/L 2 1.6 40 ND Nickel 200.8 ug/L 2 0.89 4 2Selenium 200.8 ug/L 5 1.6 10 1Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 33Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 ND Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Metals - Filtered AqueousAluminum 200.7 ug/L 2 9.4 200 ND Antimony 200.8 ug/L 2 0.72 2 
A-13 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

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 NBoron 200.7 ug/L 50 170 5,000 41Cadmium 200.8 ug/L 10 5.9 20 Calcium 200.7 ug/L 50 1,700 10,000 5,0Chromium 200.8 ug/L 2 3.3 8 NCobalt 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 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 2,9Manganese 200.7 ug/L 50 13 500 47Mercury 1631E ng/L 500 122 255 2Molybdenum 200.7 ug/L 2 1.6 40 ND Nickel 200.8 ug/L 10 4.5 20 2Selenium 200.8 ug/L 10 3.1 20 1Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 34Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 ND 
A-14 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Titanium 200.7 ug/L 2 1.6 20 ND Vanadium 200.8 ug/L 2 1.7 10 ND Zinc 200.7 ug/L 2 9.1 40 Metals - Solid (dry weight)Aluminum 6010B mg/kg 5 7.7 50 3Antimony 6020 mg/kg 2 0.028 0.4 Arsenic 6020 mg/kg 50 2.5 30 Barium 6010B mg/kg 5 0.38 5 Beryllium 6010B mg/kg 5 0.16 2.5 Boron 6010B mg/kg 5 4.9 50 Cadmium 6020 mg/kg 2 0.019 0.2 Calcium 6010B mg/kg 5 70 250 6Chromium 6020 mg/kg 2 0.15 0.4 Cobalt 6010B mg/kg 5 0.5 5 Copper 6020 mg/kg 10 0.7 2.5 Iron 6010B mg/kg 5 19 74 8Lead 6020 mg/kg 2 0.036 0.3 Magnesium 6010B mg/kg 5 18 99 5Manganese 6010B mg/kg 5 0.5 5 1Mercury FGS-069 ng/g 40,000 704 1,940 1Molybdenum 6010B mg/kg 5 1.3 9.9 
A-15 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Nickel 6020 mg/kg 2 0.05 0.3 Selenium 6020 mg/kg 2 0.26 0.99 Silver 6020 mg/kg 2 0.04 0.2 Sodium 6010B mg/kg 5 290 2,500 Thallium 6020 mg/kg 2 0.007 0.2 Tin 6010B mg/kg 5 4.5 50 ND Titanium 6010B mg/kg 5 0.69 5 Vanadium 6020 mg/kg 2 0.076 0.99 Zinc 6010B mg/kg 5 2 15 
A-16 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Classical Pollutants - TotalAmmonia 350.1 mg/l NA 0.328 4.08 Nitrate Nitrite as N 353.2 mg/l NA 0.0567 0.771 Nitrogen, Total Kjeldahl 351.2 mg/l NA 2.1 12 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 10 41 200 Chloride 300.0, 9056 mg/l NA 124 1,440 1Sulfate 300.0, 9056 mg/l NA 16.3 379 Cyanide, Total 4500 CN E mg/l NA 0.0219 0.109 Total Dissolved Solids 2540C mg/L 1 160 330 3Total Suspended Solids 2540D mg/L 1 140 500 2Phosphorus, Total 365.1 mg/l NA 0.24 1.47 Classicals Pollutants - Solid (dry weight)Ammonia 350.1 mg/Kg 1 4.1 10 Nitrate Nitrite as N 353.2 mg/Kg 1 0.71 20 Nitrogen, Total Kjeldahl 351.2 mg/Kg 5 60 250 Chloride 9056 mg/Kg 20 38 580 Sulfate 9056 mg/Kg 100 170 4,900 2Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.5 Phosphorus, Total 365.1 mg/Kg 10 8.1 49 Classicals Pollutants -Filtered AqueousAmmonia 350.1 mg/L 1 0.22 4 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 
A-17 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chloride 300.0 mg/L 500 130 1,500 1Sulfate 300.0 mg/L 50 12 250 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 ND Metals - Calculated TotalAluminum 200.7, 6010B ug/L NA 227 1,610 8Antimony 200.8, 6020 ug/L NA 1.41 12.1 Arsenic 200.8, 6020 ug/L NA 14.2 158 Barium 200.7, 6010B ug/L NA 13.1 161 1Beryllium 200.7, 6010B ug/L NA 5.32 71.6 Boron 200.7, 6010B ug/L NA 301 6,170 3Cadmium 200.8, 6020 ug/L NA 6.09 24.2 Calcium 200.7, 6010B ug/L NA 3,590 16,500 6,Chromium 200.8, 6020 ug/L NA 6.91 17.8 Cobalt 200.7, 6010B ug/L NA 15.3 161 Copper 200.8, 6020 ug/L NA 19.2 67.7 Iron 200.7, 6010B ug/L NA 553 2,310 2,Lead 200.8, 6020 ug/L NA 1.62 9.74 Magnesium 200.7, 6010B ug/L NA 1,030 12,300 2,Manganese 200.7, 6010B ug/L NA 26.6 617 4Mercury 1631E, FGS-069 ng/L NA 20,000 54,900 5
A-18 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Molybdenum 200.7, 6010B ug/L NA 39.3 320 Nickel 200.8, 6020 ug/L NA 5.57 26.8 Selenium 200.8, 6020 ug/L NA 9.91 44.5 Silver 200.8, 6020 ug/L NA 1.61 7.12 Sodium 200.7, 6010B ug/L NA 9,290 117,000 3Thallium 200.8, 6020 ug/L NA 0.626 7.12 Tin 200.7, 6010B ug/L NA 132 1,610 ND Titanium 200.7, 6010B ug/L NA 21.3 161 Vanadium 200.8, 6020 ug/L NA 3.59 35 Zinc 200.7, 6010B ug/L NA 63.8 474 Metals - DissolvedAluminum 200.7 ug/L 2 9.4 200 NAntimony 200.8 ug/L 2 0.72 2 NArsenic 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 NBoron 200.7 ug/L 50 170 5,000 3Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 5,Chromium 200.8 ug/L 2 3.3 8 NChromium (VI) 218.6 ug/L 5 1.96 10 NCobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
A-19 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

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 NMagnesium 200.7 ug/L 50 540 10,000 2,Manganese 200.7 ug/L 50 13 500 4Mercury 1631E ng/L 100 24.1 50.5 Molybdenum 200.7 ug/L 2 1.6 40 NNickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 3Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 NZinc 200.7 ug/L 2 9.1 40 Metals - Filtered AqueousAluminum 200.7 ug/L 2 9.4 200 NAntimony 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 NBoron 200.7 ug/L 50 170 5,000 3Cadmium 200.8 ug/L 10 5.9 20 
A-20 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Calcium 200.7 ug/L 50 1,700 10,000 4,Chromium 200.8 ug/L 2 3.3 8 NCobalt 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 2,Manganese 200.7 ug/L 50 13 500 4Mercury 1631E ng/L 500 122 255 Molybdenum 200.7 ug/L 2 1.6 40 NNickel 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 NSodium 200.7 ug/L 10 920 50,000 3Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 NZinc 200.7 ug/L 2 9.1 40 Metals - Solid (dry weight)Aluminum 6010B mg/kg 5 7.5 49 3Antimony 6020 mg/kg 2 0.025 0.35 Arsenic 6020 mg/kg 10 0.45 5.3 
A-21 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Barium 6010B mg/kg 5 0.37 4.9 Beryllium 6010B mg/kg 5 0.16 2.4 Boron 6010B mg/kg 5 4.8 49 Cadmium 6020 mg/kg 2 0.017 0.18 Calcium 6010B mg/kg 5 68 240 7Chromium 6020 mg/kg 2 0.13 0.35 Cobalt 6010B mg/kg 5 0.49 4.9 Copper 6020 mg/kg 10 0.63 2.2 Iron 6010B mg/kg 5 18 73 8Lead 6020 mg/kg 2 0.032 0.27 Magnesium 6010B mg/kg 5 18 97 Manganese 6010B mg/kg 5 0.49 4.9 Mercury FGS-069 ng/g 40,000 691 1,900 1Molybdenum 6010B mg/kg 5 1.3 9.7 Nickel 6020 mg/kg 2 0.045 0.27 Selenium 6020 mg/kg 2 0.24 0.88 Silver 6020 mg/kg 2 0.036 0.18 Sodium 6010B mg/kg 5 290 2,400 Thallium 6020 mg/kg 2 0.0062 0.18 Tin 6010B mg/kg 5 4.4 49 NTitanium 6010B mg/kg 5 0.68 4.9 Vanadium 6020 mg/kg 2 0.068 0.88 Zinc 6010B mg/kg 5 1.9 15 
A-22 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Classical Pollutants - Total Ammonia 350.1 mg/l NA 0.336 4.1 Nitrate Nitrite as N 353.2 mg/l NA 0.0581 0.814 Nitrogen, Total Kjeldahl 351.2 mg/l NA 2.27 12.9 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0, 9056 mg/l NA 124 1,440 Sulfate 300.0, 9056 mg/l NA 16.7 390 Cyanide, Total 4500 CN E mg/l NA 0.022 0.11 Total Dissolved Solids 2540C mg/L 1 160 330 Total Suspended Solids 2540D mg/L 1 92 330 Phosphorus, Total 365.1 mg/l NA 0.0294 0.197 Classicals Pollutants - Solid (dry weight) Ammonia 350.1 mg/Kg 1 4.1 10 Nitrate Nitrite as N 353.2 mg/Kg 1 0.71 20 Nitrogen, Total Kjeldahl 351.2 mg/Kg 5 61 260 Chloride 9056 mg/Kg 20 38 580 Sulfate 9056 mg/Kg 100 170 4,900 Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.5 Phosphorus, Total 365.1 mg/Kg 1 0.79 4.8 Classicals Pollutants -Filtered Aqueous Ammonia 350.1 mg/L 1 0.22 4 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 50 12 250 
A-23 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Metals - Calculated Total Aluminum 200.7, 6010B ug/L NA 228 1,600 Antimony 200.8, 6020 ug/L NA 1.49 13.8 Arsenic 200.8, 6020 ug/L NA 16.1 182 Barium 200.7, 6010B ug/L NA 13.3 160 Beryllium 200.7, 6010B ug/L NA 5.36 73.8 Boron 200.7, 6010B ug/L NA 301 6,130 Cadmium 200.8, 6020 ug/L NA 6.14 24.9 Calcium 200.7, 6010B ug/L NA 3,610 16,600 Chromium 200.8, 6020 ug/L NA 7.5 19.4 Cobalt 200.7, 6010B ug/L NA 15.1 160 Copper 200.8, 6020 ug/L NA 21.9 78.8 Iron 200.7, 6010B ug/L NA 562 2,310 Lead 200.8, 6020 ug/L NA 1.75 10.6 Magnesium 200.7, 6010B ug/L NA 1,040 12,300 Manganese 200.7, 6010B ug/L NA 26.4 613 Mercury 1631E, FGS-069 ng/L NA 22,600 62,200 Molybdenum 200.7, 6010B ug/L NA 39 322 Nickel 200.8, 6020 ug/L NA 11.8 62.7 Selenium 200.8, 6020 ug/L NA 10.7 48.3 Silver 200.8, 6020 ug/L NA 1.75 7.83 Sodium 200.7, 6010B ug/L NA 8,610 81,400 Thallium 200.8, 6020 ug/L NA 0.651 7.83 Tin 200.7, 6010B ug/L NA 133 1,600 
A-24 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Titanium 200.7, 6010B ug/L NA 21.5 160 Vanadium 200.8, 6020 ug/L NA 3.89 38.8 Zinc 200.7, 6010B ug/L NA 64.9 475 Metals - Dissolved Aluminum 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 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 5 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 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 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 
A-25 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

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 200.7 ug/L 2 9.1 40 Metals - Filtered Aqueous Aluminum 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 10 5.9 20 Calcium 200.7 ug/L 50 1,700 10,000 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 Mercury 1631E ng/L 500 122 255 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 
A-26 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

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 200.7 ug/L 2 9.1 40 Metals - Solid (dry weight) Aluminum 6010B mg/kg 5 7 45 Antimony 6020 mg/kg 2 0.026 0.38 Arsenic 6020 mg/kg 10 0.48 5.7 Barium 6010B mg/kg 5 0.35 4.5 Beryllium 6010B mg/kg 5 0.15 2.3 Boron 6010B mg/kg 5 4.5 45 Cadmium 6020 mg/kg 2 0.018 0.19 Calcium 6010B mg/kg 5 64 230 Chromium 6020 mg/kg 2 0.14 0.38 Cobalt 6010B mg/kg 5 0.45 4.5 Copper 6020 mg/kg 10 0.67 2.4 Iron 6010B mg/kg 5 17 68 Lead 6020 mg/kg 2 0.034 0.28 Magnesium 6010B mg/kg 5 17 91 Manganese 6010B mg/kg 5 0.45 4.5 Mercury FGS-069 ng/g 40,000 707 1,950 Molybdenum 6010B mg/kg 5 1.2 9.1 Nickel 6020 mg/kg 10 0.24 1.4 Selenium 6020 mg/kg 2 0.25 0.94 
A-27 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

Min – Minimum value. P – Sample was not preserved immediately following collection. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Silver 6020 mg/kg 2 0.038 0.19 Sodium 6010B mg/kg 5 270 2,300 Thallium 6020 mg/kg 2 0.0066 0.19 Tin 6010B mg/kg 5 4.1 45 Titanium 6010B mg/kg 5 0.64 4.5 Vanadium 6020 mg/kg 2 0.073 0.94 Zinc 6010B mg/kg 5 1.8 14 
A-28 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

Sample-Specific 

MDL 

SampleSpecific QL 

Classical Pollutants - Total Ammonia 350.1 mg/l NA 0.32 3.91 Nitrate Nitrite as N 353.2 mg/l NA 0.0554 0.775 Nitrogen, Total Kjeldahl 351.2 mg/l NA 2.13 11.9 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0, 9056 mg/l NA 118 1,370 Sulfate 300.0, 9056 mg/l NA 15.9 371 Cyanide, Total 4500 CN E mg/l NA 0.021 0.105 Total Dissolved Solids 2540C mg/L 1 160 330 Total Suspended Solids 2540D mg/L 1 280 1,000 Phosphorus, Total 365.1 mg/l NA 0.0286 0.191 Classicals Pollutants - Solid (dry weight) Ammonia 350.1 mg/Kg 1 4.1 10 Nitrate Nitrite as N 353.2 mg/Kg 1 0.71 20 Nitrogen, Total Kjeldahl 351.2 mg/Kg 5 60 250 Chloride 9056 mg/Kg 20 38 580 Sulfate 9056 mg/Kg 100 170 4,900 Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.5 Phosphorus, Total 365.1 mg/Kg 1 0.81 4.9 
A-29 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

Sample-Specific 

MDL 

SampleSpecific QL 

Classicals Pollutants -Filtered Aqueous Ammonia 350.1 mg/L 1 0.22 4 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 50 12 250 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Metals - Calculated Total Aluminum 200.7, 6010B ug/L NA 217 1,520 Antimony 200.8, 6020 ug/L NA 1.42 12.8 Arsenic 200.8, 6020 ug/L NA 69.5 836 Barium 200.7, 6010B ug/L NA 12.4 152 Beryllium 200.7, 6010B ug/L NA 5.1 70.2 Boron 200.7, 6010B ug/L NA 284 5,850 Cadmium 200.8, 6020 ug/L NA 5.83 23.4 Calcium 200.7, 6010B ug/L NA 3,440 15,900 Chromium 200.8, 6020 ug/L NA 7.14 18.2 Cobalt 200.7, 6010B ug/L NA 14.4 152 Copper 200.8, 6020 ug/L NA 20.2 72 Iron 200.7, 6010B ug/L NA 534 2,200 Lead 200.8, 6020 ug/L NA 1.64 10.1 
A-30 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

Sample-Specific 

MDL 

SampleSpecific QL 

Magnesium 200.7, 6010B ug/L NA 993 11,700 Manganese 200.7, 6010B ug/L NA 25.1 585 Mercury 

1631E, FGS069 ng/L NA 22,000 60,600 

Molybdenum 200.7, 6010B ug/L NA 37.1 304 Nickel 200.8, 6020 ug/L NA 10.9 59.7 Selenium 200.8, 6020 ug/L NA 9.93 45.4 Silver 200.8, 6020 ug/L NA 6.18 29.2 Sodium 200.7, 6010B ug/L NA 8,190 77,400 Thallium 200.8, 6020 ug/L NA 0.614 7.16 Tin 200.7, 6010B ug/L NA 126 1,520 Titanium 200.7, 6010B ug/L NA 20.2 152 Vanadium 200.8, 6020 ug/L NA 3.64 36.4 Zinc 200.7, 6010B ug/L NA 61.7 452 Metals - Dissolved Aluminum 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 
A-31 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

Sample-Specific 

MDL 

SampleSpecific QL 

Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 5 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 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 5 1.6 10 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 200.7 ug/L 2 9.1 40 Metals - Filtered Aqueous 
A-32 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

Sample-Specific 

MDL 

SampleSpecific QL 

Aluminum 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 10 5.9 20 Calcium 200.7 ug/L 50 1,700 10,000 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 Mercury 1631E ng/L 500 122 255 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 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 
A-33 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

Sample-Specific 

MDL 

SampleSpecific QL 

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 200.7 ug/L 2 9.1 40 Metals - Solid (dry weight) Aluminum 6010B mg/kg 5 7 45 Antimony 6020 mg/kg 2 0.026 0.37 Arsenic 6020 mg/kg 50 2.3 28 Barium 6010B mg/kg 5 0.34 4.5 Beryllium 6010B mg/kg 5 0.15 2.3 Boron 6010B mg/kg 5 4.4 45 Cadmium 6020 mg/kg 2 0.017 0.18 Calcium 6010B mg/kg 5 64 230 Chromium 6020 mg/kg 2 0.14 0.37 Cobalt 6010B mg/kg 5 0.45 4.5 Copper 6020 mg/kg 10 0.65 2.3 Iron 6010B mg/kg 5 17 68 Lead 6020 mg/kg 2 0.033 0.28 Magnesium 6010B mg/kg 5 17 90 Manganese 6010B mg/kg 5 0.45 4.5 Mercury FGS-069 ng/g 40,000 712 1,960 Molybdenum 6010B mg/kg 5 1.2 9 
A-34 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. L – LFB or LCS percent recovery not within method-specified criteria, but is within laboratory-specified criteria. 

P – Sample was not preserved immediately following collection. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

Sample-Specific 

MDL 

SampleSpecific QL 

Nickel 6020 mg/kg 10 0.23 1.4 Selenium 6020 mg/kg 2 0.24 0.92 Silver 6020 mg/kg 10 0.19 0.92 Sodium 6010B mg/kg 5 270 2,300 Thallium 6020 mg/kg 2 0.0064 0.18 Tin 6010B mg/kg 5 4.1 45 Titanium 6010B mg/kg 5 0.63 4.5 Vanadium 6020 mg/kg 2 0.071 0.92 Zinc 6010B mg/kg 5 1.8 14 
A-35 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. M – MS percent recovery outside the method-specified criteria, but within the laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-9. Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Ke

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

Classicals Ammonia 350.1 mg/L 2 0.11 2 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 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 500 130 1,500 Sulfate 300.0 mg/L 50 12 250 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 5 0.025 0.25 Total Metals Aluminum 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 50 1,700 10,000 
A-36 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. M – MS percent recovery outside the method-specified criteria, but within the laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-9. Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Ke

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

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 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 10 3.1 20 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 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 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 
A-37 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. M – MS percent recovery outside the method-specified criteria, but within the laboratory-specified criteria. 

Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-9. Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Ke

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 5 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 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 5 1.6 10 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 200.7 ug/L 2 9.1 40 
A-38 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-10. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

Classicals Ammonia 350.1 mg/L 2 0.11 2 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 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 500 130 1,500 Sulfate 300.0 mg/L 50 12 250 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 5 0.025 0.25 Total Metals Aluminum 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 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 
A-39 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-10. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

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 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 5 1.6 10 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 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 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 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 5 1.96 10 
A-40 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-10. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

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 Mercury 1631E ng/L 5 1.21 2.52 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 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 200.7 ug/L 2 9.1 40 
A-41 

ND – Not detected (number in parentheses is the quantitation limit). 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. D – Laboratory duplicate RPD greater than method-specified criteria. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-11. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

Classicals Ammonia 350.1 mg/L 2 0.11 2 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 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 500 130 1,500 Sulfate 300.0 mg/L 50 12 250 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 5 0.025 0.25 Total Metals Aluminum 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 50 1,700 10,000 
A-42 

ND – Not detected (number in parentheses is the quantitation limit). 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. D – Laboratory duplicate RPD greater than method-specified criteria. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-11. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

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 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 5 1.6 10 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 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 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 
A-43 

ND – Not detected (number in parentheses is the quantitation limit). 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. D – Laboratory duplicate RPD greater than method-specified criteria. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-11. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 5 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 2 0.51 20 Mercury 1631E ng/L 5 1.21 2.52 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 5 1.2 5 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 200.7 ug/L 2 9.1 40 
A-44 

ND – Not detected (number in parentheses is the quantitation limit). 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. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-12. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

Classicals Ammonia 350.1 mg/L 2 0.11 2 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 5 1.9 25 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 500 130 1,500 Sulfate 300.0 mg/L 50 12 250 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 5 0.025 0.25 Total Metals Aluminum 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 50 1,700 10,000 
A-45 

ND – Not detected (number in parentheses is the quantitation limit). 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. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-12. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

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 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 100 31 200 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 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 5 1.8 5 Arsenic 200.8 ug/L 5 3.1 10 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 
A-46 

ND – Not detected (number in parentheses is the quantitation limit). 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. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-12. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 5 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 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 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 5 1.2 5 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 200.7 ug/L 2 9.1 40 
A-47 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-13. Duplicate of Effluent from Wastewater Treatment System, Day 2 Analytical Result

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

Classicals Ammonia 350.1 mg/L 2 0.11 2 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 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 500 130 1,500 Sulfate 300.0 mg/L 50 12 250 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 5 0.025 0.25 Total Metals Aluminum 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 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 
A-48 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-13. Duplicate of Effluent from Wastewater Treatment System, Day 2 Analytical Result

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

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 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 5 1.6 10 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 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 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 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 5 1.96 10 
A-49 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. Min – Minimum value. S – Seed correction blank recovery low. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-13. Duplicate of Effluent from Wastewater Treatment System, Day 2 Analytical Result

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL 

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 Mercury 1631E ng/L 5 1.21 2.52 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 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 200.7 ug/L 2 9.1 40 
a

 Aluminum was detected in two equipment blanks for the 10-liter composite container at 2.53 ug/L and 4.71 ug/L. 

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

A-50 

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

Analyte Method Process Units Concentration 

HDPE 250 ml Plastic Bottles – Bottle Blank (for metals and hexavalent chromium samples) 

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0) 

Antimony EPA 1638 Total Recoverable ug/L ND (0.020) 

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15) 

Barium EPA 1638 Total Recoverable ug/L ND (0.20) 

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

Boron EPA 1638 Total Recoverable ug/L ND (3.0) 

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020) 

Calcium EPA 1638 Total Recoverable ug/L ND (40) 

Chromium EPA 1638 Total Recoverable ug/L ND (0.10) 

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10) 

Copper EPA 1638 Total Recoverable ug/L ND (0.10) 

Iron EPA 1638 Total Recoverable ug/L ND (10) 

Lead EPA 1638 Total 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 quantitation limit). 

A-51 

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

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 quantitation limit). 

A-52 

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

Analyte Method Process Units Concentration 

Arsenic EPA 1638 Dissolved ug/L ND (0.50) 

Barium EPA 1638 Dissolved ug/L ND (0.10) 

Beryllium EPA 1638 Dissolved ug/L ND (0.10) 

Cadmium EPA 1638 Dissolved ug/L ND (0.10) 

Chromium EPA 1638 Dissolved ug/L ND (1.0) 

Cobalt EPA 1638 Dissolved ug/L ND (0.10) 

Copper EPA 1638 Dissolved ug/L ND (0.30) 

Lead EPA 1638 Dissolved ug/L ND (0.050) 

Manganese EPA 1638 Dissolved ug/L ND (0.50) 

Molybdenum EPA 1638 Dissolved ug/L ND (0.50) 

Nickel EPA 1638 Dissolved ug/L ND (0.50) 

Selenium EPA 1638 Dissolved ug/L ND (2.0) 

Silver EPA 1638 Dissolved ug/L ND (0.10) 

Thallium EPA 1638 Dissolved ug/L ND (0.050) 

Vanadium EPA 1638 Dissolved ug/L ND (1.0) 

Zinc EPA 1638 Dissolved ug/L ND (0.50) 

Sample Tap Tubing Set – Equipment Blank (seven feet of #73 silicone tubing, Y-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 quantitation limit). 

A-53 

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

Analyte Method Process Units Concentration 

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050) 

Tin EPA 1638 Total Recoverable ug/L ND (0.10) 

Titanium EPA 1638 Total Recoverable ug/L ND (0.50) 

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10) 

Zinc EPA 1638 Total Recoverable ug/L ND (0.20) 

Pump-Off Tubing Set – Equipment 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) 
a

 Aluminum was detected in two equipment blanks for the 10-liter composite container at 2.53 ug/L and 4.71 ug/L. 

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

A-54 

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

Analyte Method Process Units Concentration 

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

Boron EPA 1638 Total Recoverable ug/L ND (3.0) 

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020) 

Calcium EPA 1638 Total Recoverable ug/L ND (40) 

Chromium EPA 1638 Total Recoverable ug/L ND (0.10) 

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10) 

Copper EPA 1638 Total Recoverable ug/L ND (0.10) 

Iron EPA 1638 Total Recoverable ug/L ND (10) 

Lead EPA 1638 Total 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-55 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor 

Sample-Specific 

MDL 

Sample-Specific 

QL C

Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 NArsenic 200.8 ug/L 2 1.2 4 NBarium 200.7 ug/L 2 2.5 20 NBeryllium 200.7 ug/L 2 0.71 2 NBoron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 NCalcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 NCobalt 200.7 ug/L 2 1.1 20 NCopper 200.8 ug/L 2 0.96 4 NIron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 NMagnesium 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 NMolybdenum 200.7 ug/L 2 1.6 40 NNickel 200.8 ug/L 2 0.89 4 NSelenium 200.8 ug/L 2 0.62 4 NSilver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 

(

Thallium 200.8 ug/L 2 0.47 2 NTin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 N
A-56 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor 

Sample-Specific 

MDL 

Sample-Specific 

QL C

Vanadium 200.8 ug/L 2 1.7 10 NZinc 200.7 ug/L 2 9.1 40 NDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 NAntimony 200.8 ug/L 2 0.72 2 NArsenic 200.8 ug/L 2 1.2 4 NBarium 200.7 ug/L 2 2.5 20 NBeryllium 200.7 ug/L 2 0.71 2 NBoron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 NCalcium 200.7 ug/L 2 69 400 NChromium 200.8 ug/L 2 3.3 8 NChromium (VI) 218.6 ug/L 1 0.39 2 NCobalt 200.7 ug/L 2 1.1 20 NCopper 200.8 ug/L 2 0.96 4 NIron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 2 21 400 NManganese 200.7 ug/L 2 0.51 20 Molybdenum 200.7 ug/L 2 1.6 40 NNickel 200.8 ug/L 2 0.89 4 NSelenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 

(

Thallium 200.8 ug/L 2 0.47 2 NTin 200.7 ug/L 2 4.8 200 N
A-57 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit

Dilution 

Factor 

Sample-Specific 

MDL 

Sample-Specific 

QL C

Titanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 NZinc 200.7 ug/L 2 9.1 40 N
A-58 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific 

MDL 

SampleSpecific QL Concentrat

Total Metals Aluminum 200.7 ug/L 2 9.4 200 ND (200) Antimony 200.8 ug/L 2 0.72 2 ND (2) Arsenic 200.8 ug/L 2 1.2 4 ND (4) Barium 200.7 ug/L 2 2.5 20 ND (20) Beryllium 200.7 ug/L 2 0.71 2 ND (2) Boron 200.7 ug/L 2 6.7 200 67 Cadmium 200.8 ug/L 2 1.2 4 ND (4) Calcium 200.7 ug/L 2 69 400 83 Chromium 200.8 ug/L 2 3.3 8 ND (8) Cobalt 200.7 ug/L 2 1.1 20 ND (20) Copper 200.8 ug/L 2 0.96 4 ND (4) Iron 200.7 ug/L 2 32 200 ND (200) Lead 200.8 ug/L 2 0.73 2 ND (2) Magnesium 200.7 ug/L 2 21 400 30 Manganese 200.7 ug/L 2 0.51 20 3.6 Mercury 1631E ng/L 1 0.24 0.5 ND (0.5) Molybdenum 200.7 ug/L 2 1.6 40 ND (40) Nickel 200.8 ug/L 2 0.89 4 ND (4) Selenium 200.8 ug/L 2 0.62 4 ND (4) Silver 200.8 ug/L 2 0.59 2 ND (2) Sodium 200.7 ug/L 2 180 10,000 

ND 

(10,000) 

Thallium 200.8 ug/L 2 0.47 2 ND (2) 
A-59 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific 

MDL 

SampleSpecific QL Concentrat

Tin 200.7 ug/L 2 4.8 200 ND (200) Titanium 200.7 ug/L 2 1.6 20 ND (20) Vanadium 200.8 ug/L 2 1.7 10 2.9 Zinc 200.7 ug/L 2 9.1 40 11 Dissolved Metals Aluminum 200.7 ug/L 2 9.4 200 ND (200) Antimony 200.8 ug/L 2 0.72 2 ND (2) Arsenic 200.8 ug/L 2 1.2 4 ND (4) Barium 200.7 ug/L 2 2.5 20 ND (20) Beryllium 200.7 ug/L 2 0.71 2 ND (2) Boron 200.7 ug/L 2 6.7 200 49 Cadmium 200.8 ug/L 2 1.2 4 ND (4) Calcium 200.7 ug/L 2 69 400 ND (400) Chromium 200.8 ug/L 2 3.3 8 ND (8) Chromium (VI) 218.6 ug/L 1 0.39 2 ND (2) Cobalt 200.7 ug/L 2 1.1 20 ND (20) Copper 200.8 ug/L 2 0.96 4 ND (4) Iron 200.7 ug/L 2 32 200 ND (200) Lead 200.8 ug/L 2 0.73 2 ND (2) Magnesium 200.7 ug/L 2 21 400 ND (400) Manganese 200.7 ug/L 2 0.51 20 0.6 Molybdenum 200.7 ug/L 2 1.6 40 ND (40) Nickel 200.8 ug/L 2 0.89 4 ND (4) Selenium 200.8 ug/L 2 0.62 4 0.72 
A-60 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific 

MDL 

SampleSpecific QL Concentrat

Silver 200.8 ug/L 2 0.59 2 ND (2) Sodium 200.7 ug/L 2 180 10,000 

ND 

(10,000) 

Thallium 200.8 ug/L 2 0.47 2 ND (2) Tin 200.7 ug/L 2 4.8 200 ND (200) Titanium 200.7 ug/L 2 1.6 20 ND (20) Vanadium 200.8 ug/L 2 1.7 10 2.1 Zinc 200.7 ug/L 2 9.1 40 ND (40) 
A-61 

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-17. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL Con

Total Metals Mercury 1631E ng/L 1 0.24 0.5 ND 
A-62 

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-18. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, K

Analyte Method Unit Dilution Factor Sample-Specific MDL Sample-Specific QL Con

Total Metals Mercury 1631E ng/L 1 0.24 0.5 ND (
A-63 

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-19. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, K

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific QL Con

Total Metals Mercury 1631E ng/L 1 0.24 0.5 ND 
Appendix B

DATA REVIEW NARRATIVES
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram, ERG

TJ Finseth, ERG

From: Donna Tedder, ERG

Laura Aviles-Alvarez, ERG

Date: 9/1/2011

Subject: FGS Data Review Narrative for Total and Dissolved Mercury – Episode 6563

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 6563 Total & Dissolved Mercury – Sample Identification

EPA 

Sample #

Lab Sample 

ID #

Sample 

Matrix Sample Description

Sampling 

Date

71891 1009100-03 Aqueous FGD Influent Day 1 9/13/2010

71891 1009100-04 Aqueous Dissolved FGD Influent, Day 1 9/13/2010

71892 1009111-08 Aqueous FGD Influent, Day 2 9/14/2010

71892 1009111-09 Aqueous Dissolved FGD Influent, Day 2 9/14/2010

71893 1009128-04 Aqueous FGD Influent, Day 3 9/15/2010

71893 1009128-05 Aqueous Dissolved FGD Influent, Day 3 9/15/2010

71894 1009134-03 Aqueous FGD Influent, Day 4 9/16/2010

71894 1009134-04 Aqueous Dissolved FGD Influent, Day 4 9/16/2010

71895 1009111-10 Aqueous FGD Effluent Day 1 9/14/2010

71895 1009111-11 Aqueous Dissolved FGD Effluent, Day 1 9/14/2010

71896 1009128-06 Aqueous FGD Effluent, Day 2 9/15/2010

71896 1009128-07 Aqueous Dissolved FGD Effluent, Day 2 9/15/2010

71897 1009134-05 Aqueous FGD Effluent, Day 3 9/16/2010

71897 1009134-06 Aqueous Dissolved FGD Effluent, Day 3 9/16/2010

71898 1009141-02 Aqueous FGD Effluent, Day 4 9/17/2010

71898 1009141-03 Aqueous Dissolved FGD Effluent, Day 4 9/17/2010

71899 1009128-08 Aqueous FGD Effluent Duplicate, Day 2 9/15/2010

71899 1009128-09 Aqueous Dissolved FGD Effluent Duplicate, Day 2 9/15/2010

71900 1009100-05 Aqueous FGD Influent Field Blank, Day 1 9/13/2010
2

Table 1. EPA Episode 6563 Total & Dissolved Mercury – Sample Identification

EPA 

Sample #

Lab Sample 

ID #

Sample 

Matrix Sample Description

Sampling 

Date

71901 1009100-08 Aqueous FGD Effluent Field Blank, Day 1 9/13/2010

71902 1009111-12 Aqueous FGD Effluent Field Blank, Day 2 9/14/2010

71903 1009128-12 Aqueous FGD Effluent Field Blank, Day 3 9/15/2010

71904 1009134-07 Aqueous FGD Effluent Field Blank, Day 4 9/16/2010

SUMMARY

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

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

dataset.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

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 

coefficient ≥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 criteria. Preparation Blanks F010073-

BLK5, F010073-BLK6, F010122-BLK6, F010122–BLK7, and F010123-BLK5 had 

mercury levels of 0.45, 0.29, 0.16, 0.13, and 0.09 ng/L, respectively. These blank results

were greater than the MDL (0.08 ng/L), but less than the RL (0.50 ng/L). Because all of 

the blank results were less than the RL, no samples were qualified based on these 

preparation blank results.

DUPLICATES

A field duplicate, Sample 71899, was collected on the Sample 71896. The total mercury 

relative percent difference (RPD) was 4.65% and the dissolved mercury RPD was 

12.46%. The method-suggested RPD criteria between field duplicates is 20%.
3

Laboratory duplicates were performed in this episode on samples 71891 and 71896. All 

RPDs were less than 20% (the method-suggested RPD criterion between field duplicates; 

the method does not require the analysis of laboratory duplicates).

LABORATORY CONTROL SAMPLES

All laboratory control samples were within Frontier’s control limits of 80-120% recovery

and 24% RPD, except F010073-BS3 (blank spike (BS)), which had a recovery of 121% 

recovery. Because this recovery does meet the ongoing precision and recovery (OPR)

criteria, and because the other BS samples and all initial and continuing calibration 

verification samples in this batch met method criteria, there was no need to qualify any 

data based on this BS failure.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

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

71891, 71896, and 71897 for the total mercury analyses. MS and MSDs were performed 

on sample 71897 for the dissolved mercury analyses. All aqueous MS/MSD recoveries 

were within method specifications of 71-125%. All RPDs met method-specified criteria.

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: 9/1/2011

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

Episode 6563

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

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

Sample Episode 6563. 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 6563 Total & Dissolved Metals – Sample Identification

EPA 

Sample 

#

EPA Sample Description Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71891 FGD Influent, Day 1 280-7312-1 Aqueous 9/13/2010 9/14/2010

71891 FGD Influent, Day 1 – Solid 280-7312-3 Solid 9/13/2010 9/14/2010

71891 FGD Influent, Day 1 - Filtrate 280-7312-4 Aqueous 9/13/2010 9/14/2010

71892 FGD Influent, Day 2 280-7362-1 Aqueous 9/14/2010 9/15/2010

71892 FGD Influent, Day 2 – Solid 280-7362-4 Solid 9/14/2010 9/15/2010

71892 FGD Influent, Day 2 – Filtrate 280-7362-5 Aqueous 9/14/2010 9/15/2010

71893 FGD Influent, Day 3 280-7401-1 Aqueous 9/15/2010 9/16/2010

71893 FGD Influent, Day 3 – Solid 280-7401-4 Solid 9/15/2010 9/16/2010

71893 FGD Influent, Day 3 – Filtrate 280-7401-5 Aqueous 9/15/2010 9/16/2010

71894 FGD Influent, Day 4 280-7482-1 Aqueous 9/16/2010 9/17/2010

71894 FGD Influent, Day 4 – Solid 280-7482-3 Solid 9/16/2010 9/17/2010

71894 FGD Influent, Day 4 - Filtrate 280-7482-4 Aqueous 9/16/2010 9/17/2010

71895 FGD Effluent, Day 1 280-7362-2 Aqueous 9/14/2010 9/15/2010

71896 FGD Effluent, Day 2 280-7401-2 Aqueous 9/15/2010 9/16/2010

71897 FGD Effluent, Day 3 280-7482-2 Aqueous 9/16/2010 9/17/2010

71898 FGD Effluent, Day 4 280-7536-1 Aqueous 9/17/2010 9/18/2010

71899 FGD Effluent, Day 2 -

Duplicate

280-7401-3 Aqueous 9/15/2010 9/16/2010
2

Table 1. EPA Episode 6563 Total & Dissolved Metals – Sample Identification

EPA 

Sample 

#

EPA Sample Description Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71900 FGD Influent Field Blank, 

Day 1

280-7312-2 Aqueous 9/13/2010 9/14/2010

71901 FGD Effluent Field Blank, 

Day 1

280-7362-3 Aqueous 9/14/2010 9/15/2010

SUMMARY

The samples were prepared for total and dissolved metals analysis according 

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

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

2010, based on EPA Method 200.8, by ICP/MS analysis. Any significant findings are 

summarized below. No additional data qualifiers were required.

• The serial dilution analysis for thallium in the solid phase of sample 71891 did not 

meet TestAmerica’s requirement of ±10% difference.

• The serial dilution analysis for total nickel in the filtrate phase of sample 71891 

did not meet TestAmerica’s requirement of ±10% difference.

• All matrix spike (MS)/matrix spike duplicates (MSD) for total and dissolved 

silver failed the 70–130% control limits, except for dissolved silver in the MS for 

sample 71897.

• All the MS/MSD RPDs for silver failed TestAmerica’s SOP control limits of 

±20%. 

• The MS/MSD RPD for total selenium for sample 71898 failed TestAmerica’s 

SOP control limits of ±20%.

• The post digestion spikes (PDS) for selenium in the solid phase for sample 71891 

failed the method criteria of 85–115%.

• The PDS for silver failed the method criteria of 85-115% for several samples.

INTERNAL STANDARDIZATION

All internal standards used by TestAmerica were within the method criteria. 
3

INITIAL CALIBRATION

Test America performed the initial calibrations on each analysis day or before each 

analysis if more than one analysis was performed in one day. The initial calibration for 

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

INITIAL AND CONTINUING CALIBRATION VERIFICATION (ICV/CCV)

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

performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANKS

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

above the MDL and flagged with a “J” qualifier. No additional qualifiers were required 

for method blanks.

All instrument blanks (ICB and CCB) were less than the reporting limit; however, some 

elements were above the MDL and flagged with a “J” qualifier. No additional qualifiers 

were required for instrument blanks.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed Test America’s SOP control limits of 50–150%.

LABORATORY CONTROL SAMPLES (LCS)

All LCS samples passed the method limits of 85–115%, with the exception of selenium 

in the solid sample LCS 280-34676/2-A at 84%; however, TestAmerica had a control 

limit set at 78–108%. No data was qualified based on this LCS.

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION

Based on TestAmerica’s SOP, all interference check sample A (ICSA) results had 

analytes of interest with concentrations less than the RL or less than five times the RL 

when known inherent contaminants are present in the stock solution used to make the 

ICS.

All interference check sample B (ICSAB) synthetic spikes recovered within 

TestAmerica’s SOP criteria of 70–130% of the true value.

SERIAL DILUTION (SRD)

The serial dilution performed for solid sample 71891 FGD Influent, Day 1 - Solid (280-

7312-3) failed Test America’s requirement of ±10% difference for thallium and was 

flagged “W”. The serial dilution performed for sample 71891 FGD Influent, Day 1 -
4

Filtrate (280-7312-4) failed Test America’s requirement of ±10% difference for nickel 

and was flagged “W”. All other elements passed Test America’s requirement of ±10% 

difference in the serial dilutions and required no further qualifiers.

FIELD DUPLICATES

The relative percent difference (RPD) of the field duplicates (71896/71899) were less

than ±20% for all values equal to or greater than the reporting limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

MS and MSD were performed on Samples 71897 and 71898. Many spike recoveries were 

outside the method control limits of 70–130% when sample concentrations exceeded the 

spike concentration by a factor of four or more, which have been flagged “4”. All 

MS/MSDs for total and dissolved silver failed the 70–130% method control limits with 

the exception of the dissolved silver in sample 71897 FGD Effluent, Day 3 MS. All the 

MS/MSD RPDs for silver failed TestAmerica’s SOP control limits of ±20%. The poor 

recoveries and RPD of silver are probably due to high sulfates in this episode’s samples 

that could form insoluble silver sulfide and/or silver sulfate. All other RPD results were 

less than the method required 20% with the exception of selenium for MSD sample 

71898 FGD Effluent, Day 4 (280-7536-1 MSD), which was 25%.

POST DIGESITON SPIKES

The PDS performed on solid sample 71891 FGD Influent, Day 1 - Solid (280-7312-3

PDS) failed Test America’s 75–125% control limits for selenium, which was flagged 

“W”. Silver failed Test America’s 85-115% control limits for the following samples: 

• Total silver for 71891 FGD Influent, Day 1 – Filtrate (280-7312-4 PDS);

• Total silver for 71897 FGD Effluent, Day 3 (280-7482-2 PDS);

• Dissolved silver for 71897 FGD Effluent, Day 3 (280-7482-2 PDS); and

• Dissolved silver for 71898 FGD Effluent, Day 4 (280-7536-1 PDS).

Each of these samples were flagged “W”. 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. Sample 71897 FGD Effluent, Day 3 (280-7482-2 PDS) also failed Test 

America’s 85-115% control limits for total selenium, and dissolved vanadium which 

were both flagged “W”. No additional qualifiers were required for PDS samples.

DETECTION LIMITS

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

of reagent water.
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram, ERG

TJ Finseth, ERG

From: Randy Mercurio, ERG

Date: 9/1/2011

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

Episode 6563

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

barium, beryllium, calcium, cobalt, iron, magnesium, manganese, molybdenum, sodium, 

tin, titanium, and zinc) for Sample Episode 6563. 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 6563 Total & Dissolved Metals – Sample Identification

EPA 

Sample # EPA Sample Description

Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71891 FGD Influent, Day 1 280-7312-1 Aqueous 9/13/2010 9/14/2010

71891 FGD Influent, Day 1 - Solids 280-7312-3 Solid 9/13/2010 9/14/2010

71891 FGD Influent, Day 1 - Filtrate 280-7312-4 Aqueous 9/13/2010 9/14/2010

71892 FGD Influent, Day 2 280-7362-1 Aqueous 9/14/2010 9/15/2010

71892 FGD Influent, Day 2 – Solids 280-7362-4 Solid 9/14/2010 9/15/2010

71892 FGD Influent, Day 2 – Filtrate 280-7362-5 Aqueous 9/14/2010 9/15/2010

71893 FGD Influent, Day 3 280-7401-1 Aqueous 9/15/2010 9/16/2010

71893 FGD Influent, Day 3 – Solids 280-7401-4 Solid 9/15/2010 9/16/2010

71893 FGD Influent, Day 3 – Filtrate 280-7401-5 Aqueous 9/15/2010 9/16/2010

71894 FGD Influent, Day 4 280-7482-1 Aqueous 9/16/2010 9/17/2010

71894 FGD Influent, Day 4 – Solids 280-7482-3 Solid 9/16/2010 9/17/2010

71894 FGD Influent, Day 4 - Filtrate 280-7482-4 Aqueous 9/16/2010 9/17/2010

71895 FGD Effluent, Day 1 280-7362-2 Aqueous 9/14/2010 9/15/2010

71896 FGD Effluent, Day 2 280-7401-2 Aqueous 9/15/2010 9/16/2010

71897 FGD Effluent, Day 3 280-7482-2 Aqueous 9/16/2010 9/17/2010

71898 FGD Effluent, Day 4 280-7536-1 Aqueous 9/17/2010 9/18/2010

71899 FGD Effluent, Day 2 - Duplicate 280-7401-3 Aqueous 9/15/2010 9/16/2010
2

Table 1. EPA Episode 6563 Total & Dissolved Metals – Sample Identification

EPA 

Sample # EPA Sample Description

Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71900 FGD Influent Field Blank, Day 1 280-7312-2 Aqueous 9/13/2010 9/14/2010

71901 FGD Effluent Field Blank, Day 1 280-7362-3 Aqueous 9/14/2010 9/15/2010

SUMMARY

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

TestAmerica’s SOP for ECP Analysis for Trace Metals by Method 200.7. Any significant 

findings are summarized below. No additional qualifiers were required.

The post digestion spikes (PDS) for total barium, total calcium, and total zinc in the 

filtrate phase for sample 71891 failed the method criteria of 85–115%.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INTERNAL STANDARDIZATION

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

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

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

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

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

performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit; however, some had levels above 

the MDL and were flagged with the “J” qualifier.

All instrument blanks (ICB and CCB) were less than the reporting limit; however, some 

elements were above the MDL and were flagged with the “J” qualifier.
3

LABORATORY CONTROL SAMPLES (LCS)

All LCSs passed the method control limits of 85–115%.

INTERFERENCE CHECK SOLUTIONS

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

data quality objectives met TestAmerica’s SOP criteria.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed Test America’s SOP control limits of 50–150%.

FIELD DUPLICATES

The total and dissolved relative percent differences (RPDs) of the field duplicate (71899) 

to parent sample (71896) were less than 20% for values greater than the reporting limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on the total and 

dissolved samples of 71897 and 71898. Some elements with high concentrations 

frequently failed the EPA 200.7 Method spike recovery control limits of 70–130% but 

were flagged with a “4” qualifier indicating that the concentration in the parent sample 

was greater than 4 times the spike and could not be reliably calculated. No MS/MSD 

spike recoveries failed the EPA 200.7 Method control limits of 70–130%, except those 

already qualified with a “4” as mentioned above, and therefore no additional data 

qualifiers were needed. In addition, all RPDs of the MS/MSDs were within

TestAmerica’s ± 20% requirements.

SERIAL DILUTION (SRD)

Serial dilutions were performed for each batch of total and dissolved samples. All serial 

dilution percent differences were less than 10% as required by Test America’s SOP.

POST DIGESTION SPIKE

Both total and dissolved PDS samples performed passed the method criteria of 85–115%, 

with the exception of barium, calcium and zinc in the filtrate for sample 71891 FGD 

Influent, Day 1 (280-7312-4 PDS).

DETECTION LIMITS

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

of reagent water.
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram, ERG

TJ Finseth, ERG

From: Donna Tedder, ERG

Laura Aviles-Alvarez, ERG

Date: 9/1/2011

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

6563

Frontier Global Sciences (FGS) generated analytical data for dissolved hexavalent 

chromium for Sample Episode 6563. 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 and analyzed for dissolved hexavalent 

chromium.

Table 1. EPA Episode 6563 Dissolved Hexavalent Chromium–Sample Identification

EPA 

Sample 

#

Sample 

Matrix Sample Description

Sampling 

Date Analysis Date

71891 Aqueous FGD Influent Day 1 9/13/10 10/11/10

71892 Aqueous FGD Influent Day 2 9/14/10 10/11/10

71893 Aqueous FGD Influent Day 3 9/15/10 10/12/10

71894 Aqueous FGD Influent Day 4 9/16/10 10/12/10

71895 Aqueous FGD Effluent Day 1 9/14/10 10/12/10

71896 Aqueous FGD Effluent Day 2 9/15/10 10/12/10

71897 Aqueous FGD Effluent Day 3 9/16/10 10/12/10

71898 Aqueous FGD Effluent Day 4 9/17/10 10/12/10

71899 Aqueous FGD Effluent Dup Day 2 9/15/10 10/12/10

71900 Aqueous FGD Influent Field Blank Day 1 9/13/10 10/11/10

71901 Aqueous FGD Effluent Field Blank Day 1 9/14/10 10/11/10

SUMMARY

The samples were prepared for dissolved hexavalent chromium analysis according to 

FGS-129.01 Standard Operating Procedure (SOP), a modified EPA Method 218.6.
2

Several samples (71891, 71892, 71893, 71894, 71895, 71896, 71897, 71898, and 71899)

were diluted prior to analysis due to the presence of high levels of nontarget chloride 

interferences. 

There were no issues requiring additional data qualifiers for 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 within the ± 10% of true 

value required by the method.

CONTINUING CALIBRATION VERIFICATION

All CCVs met method-specified criteria, ± 10% of true value with recoveries ranging 

from 94.9 to 95.5%.

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) or laboratory fortified 

blank/duplicate (LFB/LFBD) passed method criteria of ± 10% of true value with 

recoveries of 101% and 102%. The method suggested that a second source quality 
3

control sample (QCS) must be analyzed by the laboratory at least once a quarter. The 

second source ICV meets this recommendation.

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). 

One field duplicate was collected and analyzed. Sample 71899 was a duplicate of 

effluent sample 71896. These samples were nondetects (NDs), indicating the analyte was 

not detected at or above the method detection limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The MS and matrix spike duplicate (MSD) were performed using a secondary source 

spike on samples 71891 and 71897. All MS/MSD recoveries with within 75%-125%, 

with RPDs of 2.63% and 1.88%, respectively.
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram, ERG

TJ Finseth, ERG

From: Donna Tedder, ERG

Date: 9/1/2011

Subject: TestAmerica Data Review Narrative for Classicals Analyses – Episode 6563

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry 

analyses for Sample Episode 6563. 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.

The TSS concentration of the influent samples was greater than one percent, so as 

requested, the laboratory separated the solid and liquid portions of the samples and 

analyzed both portions separately for the following analytes: 

• Ammonia, 

• Chloride,

• Cyanide, 

• Nitrate/Nitrite, 

• Phosphorus, 

• Sulfate, and

• TKN.

Table 1 summarizes the nine field samples analyzed by TestAmerica and particularly 

highlights how the laboratory split and analyzed the influent samples.
2

Table 1. EPA Episode 6563 Classical Analytes – Sample Identification

EPA

Sample #

Sample Description Sampling

Date

Sample

Matrix

Portion of 

Sample

Analytes 

71891 FGD Influent, Day 1 9/13/10

Water Entire 

Fraction

BOD5, COD, TDS, and 

TSS

Water Filtrate

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Sulfate, Phosphorus, and 

TKN

Solids Solids

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Sulfate, Phosphorus, and

TKN

71892 FGD Influent, Day 2 9/14/10

Water Entire 

Fraction

BOD5, COD, TDS, and 

TSS

Water Filtrate

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Sulfate, Phosphorus, and 

TKN

Solids Solids

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Sulfate, Phosphorus, and 

TKN

71893 FGD Influent, Day 3 9/15/10

Water Entire 

Fraction

BOD5, COD, TDS, and 

TSS

Water Filtrate

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Sulfate, Phosphorus, and 

TKN

Solids Solids

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Sulfate, Phosphorus, and 

TKN

71894 FGD Influent, Day 4 9/16/10

Water Entire 

Fraction

BOD5, COD, TDS, and 

TSS

Water Filtrate

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Sulfate, Phosphorus, and 

TKN

Solids Solids

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Sulfate, Phosphorus, and 

TKN

71895 FGD Effluent, Day 1 9/14/10 Water Entire 

Fraction All analytes
3

Table 1. EPA Episode 6563 Classical Analytes – Sample Identification

EPA

Sample #

Sample Description Sampling

Date

Sample

Matrix

Portion of 

Sample

Analytes 

71896 FGD Effluent, Day 2 9/15/10 Water Entire 

Fraction All analytes

71897 FGD Effluent, Day 3 9/16/10 Water Entire 

Fraction All analytes

71898 FGD Effluent, Day 4 9/17/10 Water Entire 

Fraction All analytes

71899 FGD Effluent -

Duplicate 9/15/10 Water Entire Fraction All analytes

SUMMARY

Unless otherwise noted below, all samples were analyzed within the holding time

specified in 40 CFR 136 Table II. 

TestAmerica could not use a preserved sample volume for phase separation. Therefore, 

they combined two of the unpreserved 250 mL metal sample volumes and phase 

separated this volume. After phase separation, TestAmerica preserved the samples 

accordingly. Because of this process, ammonia, nitrate/nitrite, TKN, phosphorus, and 

cyanide influent samples were not preserved immediately following sample collection as 

required by the method. 

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, 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 noted 

below.
4

If required by the method, a matrix spike (MS) sample was analyzed on sample 71897

(FGD effluent) for each analyte to check for matrix interferences. For some analytes, 

TestAmerica spiked more samples than required. All MS samples analyzed met the 

criteria specified in the method unless described below.

DATA NOTES/ISSUES

Ammonia

As stated above, filtrate and solid aliquots of samples 71891 - 71894 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

phase separation. Because these samples were not preserved immediately following 

sample collection, they were qualified as estimated values.

The data reviewer identified no other issues. All QC samples met the criteria specified in 

EPA Method 350.1.

BOD5

All glucose-glutamic acid standards and water blanks were analyzed appropriately and 

met the criteria specified in SM 5210B.

The RPD between sample 71897 and its laboratory duplicate was 23%, which is above 

both the method and laboratory criteria of 20%. Sample 71897 was qualified as an 

estimated value.

Three of the four batches had seed correction factors lower than 0.6 mg/L. The seed 

correction factors were 0.5373 mg/L, 0.552 mg/L, 0.6147 mg/L, and 0.576 mg/L for 

batches 31398, 31731, 31878, and 32012, respectively. TestAmerica did not flag these 

samples with an “s” to indicate the seed correction blank (SCB) recovery was low. A low 

seed correction factor indicates that samples may be biased low. Thus, samples 71891, 

71892, 71893, 71895, 71896, 71898, and 71899 were qualified as minimum values and 

for consistency were also flagged with an “s.” Due to the short holding time, the samples 

could not be reanalyzed.

Chloride and Sulfate

The analyzed results for the MS and matrix spike duplicate (MSD) samples associated 

with sample 71897 for both chloride and sulfate were above the calibration range. 

TestAmerica did not rerun the samples with a greater dilution factor because the MS and 

MSD percent recoveries were within the method control criteria. If reported, the MS and 

MSD results will be qualified as estimated values. 
5

COD

The percent recoveries for the MS and MSD analyses for sample 71897 (FGD effluent) 

were below the control limits of 90-110% required by EPA Method 410.4. The percent 

recoveries for the MS and MSD analyses were 89% and 82%, respectively. The low 

percent recovery could indicate that results for samples with the same matrix (FGD 

effluent) could be biased low. Sample 71897 was flagged as a minimum value. The LFBs 

associated with all samples met the method criteria.

The RPD between sample 71896 and its field duplicate 71899 was 25.5%. 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 EPA Method 410.4.

Cyanide

As stated above, filtrate and solid aliquots of samples 71891 - 71894 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

performing the phase separation. The solid aliquot results of samples 71891 - 71894 were 

already qualified by TestAmerica with a “J” meaning the results were estimated values 

because they were less than the RL, so no further qualification was necessary. Because 

the filtrate aliquots of samples 71891 - 71894 were not preserved immediately after 

sample collection, they were qualified as estimated values.

Both solid and filtrate volumes of samples 71891 - 71894 were analyzed 10, 9, 8, and 7 

days outside of the 14-day holding time. All of these samples were qualified by the lab 

with an “H,” meaning the samples were analyzed beyond the method-specified hold time. 

Because all of these samples were either qualified with a “J” meaning that the results 

were estimated values because they were less than the RL or they were qualified as 

estimated values because they were not preserved immediately after sample collection, no 

further qualification was necessary.

The analyzed results for sample 71896 and solid samples 71891 - 71894 were lower than 

the lowest calibration standard. Since all the samples were already qualified by 

TestAmerica with a “J” indicating that the results were estimated values because they 

were less than the RL, these samples did not need to be further qualified.

The RPD between sample 71896 and its field duplicate 71899 was 135%. The result for 

71896 was below the RL and flagged with a “J”, but the result for 71899 was above the 

RL. The low amount of cyanide present in these samples was likely the cause for the high 

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

there are no specific control limits for field duplicates specified in SM 4500 CN- E.

Cyanide was detected in the laboratory reagent blank associated with sample 71895 at 

0.00415 mg/L, which was greater than the MDL, but less than the RL. Since the blank 

result was less than the RL, no samples were qualified.
6

Nitrate/Nitrite

As stated above, filtrate and solid aliquots of samples 71891 - 71894 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

phase separation. The solid aliquot results of samples 71891 - 71894 were already 

qualified by TestAmerica with a “J” meaning the results were estimated values because 

they were less than the RL, so no further qualification was necessary. Because the filtrate 

aliquots of samples 71891 - 71894 were not preserved immediately after sample 

collection, they were qualified as estimated values.

The percent recoveries for the MS analysis for sample 71895 and the MS and MSD 

analyses for sample 71897 (FGD effluent) were below the control limits of 90-110% 

required by EPA Method 353.2 but within the laboratory control limits of 72-113%. The 

percent recoveries for the MS and MSD samples were 89% and 92% respectively for 

sample 71895 and were both 84% for sample 71897. The MS and MSD results for 

sample 71897 were above the calibration curve, but not reanalyzed using a higher 

dilution factor. Because the MS and MSD results for sample 71897 at 12.7 mg/L were 

more than ±10% greater than the highest calibration level (10.0 mg/L), the MS and MSD 

recoveries were considered unreliable. Because it was not possible to tell whether the low 

percent recovery was caused by matrix interferences or the MS and MSD results being 

above the calibration curve, sample 71897 was not qualified. Sample 71895 was qualified 

as a minimum value. The LFBs associated with all samples met the method criteria.

Phosphorus 

As stated above, filtrate and solid aliquots of samples 71891 - 71894 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

phase separation. The filtrate aliquot results of samples 71891 and 71894 were already 

qualified by TestAmerica with a “J” meaning the results were estimated values because 

they were less than the RL, so no further qualification was necessary. Phosphorus was not 

detected in the filtrate aliquots of samples 71892 and 71893, so these samples also did not 

need to be qualified. Because the solid aliquots of samples 71891 - 71894 were not 

preserved immediately after sample collection, they were qualified as estimated values.

Results for the filtrate volumes of samples 71891 and 71894 were below the lowest 

calibration standard. These samples were already qualified with a “J” meaning the results 

were estimated values because they were less than the RL, so no further qualification was 

necessary.
7

TDS

Samples 71891 - 71894 were analyzed 14, 13, 12, and 11 days, respectively, past the 7-

day hold time due to laboratory error. TestAmerica only qualified these samples with an 

“H”, so they were additionally qualified as estimated values.

All 14 samples analyzed for TDS did not achieve a constant weight after three drying 

cycles. The weight increased from the first weighing to the second weighing for samples 

71895, 71896, 71898, and 71899. SM 2540C warns that samples that contain high levels 

of calcium, magnesium, chloride, and sulfate may be hygroscopic, meaning they absorb 

moisture from the air. FGD wastewater contains high concentrations of all of these 

species, so this was likely the cause for the inconsistent weight calculations. The samples 

were not qualified, but results may be biased high. 

The RPD between sample 71897 and its laboratory duplicate was less than 10% as

required by SM 2540C. The RPD between sample 71891 and its laboratory duplicate was 

11%. Because the RPD was greater than the method control limits, sample 71891 was

qualified as an estimated value. 

TDS was detected at 8.0 mg/L, which is above the MDL (4.7 mg/L), but below the RL

(10 mg/L), in the LRB associated with sample 71895. Because the blank result was less 

than the RL, no samples needed to be qualified based on the LRB result. 

TKN

As stated above, filtrate and solid aliquots of samples 71891 - 71894 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

phase separation. Because these samples were not preserved immediately after sample 

collection, they were qualified as estimated values.

TKN was detected in the LRB associated with filtrate samples 71891 - 71894 at 0.133

mg/L and also detected in the LRB associated with samples 71895 - 71897 and 71899 at 

0.219 mg/L. The blank results were greater than the MDL (0.077 mg/L), but less than the 

RL (1.0 mg/L). Because the blank results were less than the RL, no samples were 

qualified based on the LRB results.

The LFB and LFBD percent recoveries associated with filtrate samples 71891 - 71894 

were not within the method criteria of 90-110%, but were within the laboratory criteria of 

77-115%. The percent recoveries of the LFB and LFBD were 84% and 86%, 

respectively. Filtrate samples 71891 - 71894 were already qualified as estimated values 

because the samples were not preserved immediately after sample collection, so there 

was no need to further qualify these samples as minimum values.

The percent recoveries for the MS and MSD analyses for sample 71897 (FGD effluent) 

did not meet the control limits (90-110%) specified in EPA Method 351.2 and did not 

meet the laboratory criteria of 54-131%. The MS and MSD percent recoveries were 
8

137% and 175%. TestAmerica flagged the MS/MSD samples with a “4” because the 

sample result was more than 4 times the spike amount indicating the control limits are not 

reliable. Thus, sample 71897 was not additionally qualified because of the high MS/MSD 

percent recoveries. The LFB associated with sample 71897 met the method criteria.

TSS 

The laboratory duplicate RPDs for samples 71891, 71893, and 71895 were less than 10% 

as required by SM 2540D. However, the RPD for sample 71897 and its laboratory 

duplicate was 12%. Because this RPD was above the method criteria, sample 71897 was

qualified as an estimated value.

The RPD between sample 71896 and its field duplicate 71899 was 138%. Even though 

the RPD was greater than 20%, the sample was not qualified because there are no specific 

control limits for field duplicates specified in SM 2540D.

Constant weight was not achieved after three drying cycles for sample 71899. SM 2540D 

warns that samples that contain high levels of calcium, magnesium, chloride, and sulfate 

may be hygroscopic, meaning they absorb moisture from the air. FGD wastewater 

contains high concentrations of all of these species, so this was likely the cause for the 

inconsistent weight calculations. The sample was not qualified, but results may be biased 

high.
9

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71891 

(filtrate)

Ammonia Estimate Value Sample not preserved 

immediately following 

collection.

13 mg/L

71892 

(filtrate)

Ammonia Estimate Value Sample not preserved 

immediately following 

collection.

14 mg/L

71893 

(filtrate)

Ammonia Estimate Value Sample not preserved 

immediately following 

collection.

13 mg/L

71894 

(filtrate)

Ammonia Estimate Value Sample not preserved 

immediately following 

collection.

12 mg/L

71891 

(solids)

Ammonia Estimate Value Sample not preserved 

immediately following 

collection.

34 mg/Kg

71892 

(solids)

Ammonia Estimate Value Sample not preserved 

immediately following 

collection.

29 mg/Kg

71893 

(solids)

Ammonia Estimate Value Sample not preserved 

immediately following 

collection.

32 mg/Kg

71894 

(solids)

Ammonia Estimate Value Sample not preserved 

immediately following 

collection.

32 mg/Kg

71891 BOD Minimum Value, 

s

SCB Recovery Low 10 mg/L

71892 BOD Minimum Value,

s

SCB Recovery Low 9.5 mg/L

71893 BOD Minimum Value,

s

SCB Recovery Low 13 mg/L

71895 BOD Minimum Value,

s

SCB Recovery Low 8.5 mg/L

71896 BOD Minimum Value,

s

SCB Recovery Low 7.1 mg/L

71897 BOD Estimated Value Lab duplicate RPD > 

method-specified 

criteria

6.8 mg/L

71898 BOD Minimum Value,

s

SCB Recovery Low 3.5 mg/L

71899 BOD Minimum Value,

s

SCB Recovery Low 6.9 mg/L
10

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71897 COD Minimum Value MS % recovery < 

method-specified 

criteria

380 mg/L

71891 

(filtrate)

Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 10 

days past hold time

0.36 mg/L

71892 

(filtrate)

Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 9 

days past hold time

0.20 mg/L

71893 

(filtrate)

Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 8 

days past hold time

0.29 mg/L

71894 

(filtrate)

Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 7 

days past hold time

0.31 mg/L

71891 

(filtrate)

Nitrate/Nitrite Estimated Value Sample not preserved 

immediately following 

collection.

12 mg/L

71892 

(filtrate)

Nitrate/Nitrite Estimated Value Sample not preserved 

immediately following 

collection.

14 mg/L

71893 

(filtrate)

Nitrate/Nitrite Estimated Value Sample not preserved 

immediately following 

collection.

14 mg/L

71894 

(filtrate)

Nitrate/Nitrite Estimated Value Sample not preserved 

immediately following 

collection.

12 mg/L

71895 Nitrate/Nitrite Minimum Value MS % recovery < 

method-specified 

criteria

9.7 mg/L

71891 

(solids)

Phosphorus Estimated Value Sample not preserved 

immediately following 

collection.

33 mg/Kg

71892 

(solids)

Phosphorus Estimated Value Sample not preserved 

immediately following 

collection.

380 mg/Kg
11

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71893 

(solids)

Phosphorus Estimated Value Sample not preserved 

immediately following 

collection.

34 mg/Kg

71894 

(solids)

Phosphorus Estimated Value Sample not preserved 

immediately following 

collection.

6.5 mg/Kg

71891 TDS H, Estimated 

Value

Analyzed 14 days past 

hold time, Lab duplicate 

RPD > methodspecified criteria

35,000 

mg/L

71892 TDS H, Estimated 

Value

Analyzed 13 days past 

hold time

35,000 

mg/L

71893 TDS H, Estimated 

Value

Analyzed 12 days past 

hold time

37,000 

mg/L

71894 TDS H, Estimated 

Value

Analyzed 11 days past 

hold time

35,000 

mg/L

71897 TSS Estimated Value Lab duplicate RPD > 

method-specified 

criteria

7.2 mg/L

71891 

(filtrate)

TKN Estimated Value Sample not preserved 

immediately following 

collection. LFB % 

recovery < methodspecified criteria

29 mg/L

71892 

(filtrate)

TKN Estimated Value Sample not preserved 

immediately following 

collection. LFB % 

recovery < methodspecified criteria

32 mg/L

71893 

(filtrate)

TKN Estimated Value Sample not preserved 

immediately following 

collection. LFB % 

recovery < methodspecified criteria

31 mg/L

71894 

(filtrate)

TKN Estimated Value Sample not preserved 

immediately following 

collection. LFB % 

recovery < methodspecified criteria

26 mg/L

71891 

(solids)

TKN Estimated Value Sample not preserved 

immediately following 

collection.

900 mg/Kg
12

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71892

(solids)

TKN Estimated Value Sample not preserved 

immediately following 

collection.

840 mg/Kg

71893

(solids)

TKN Estimated Value Sample not preserved 

immediately following 

collection.

710 mg/Kg

71894

(solids)

TKN Estimated Value Sample not preserved 

immediately following 

collection.

880 mg/Kg
Appendix C 

PICTURES FROM THE SAMPLING EPISODE 
C-1 

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

 
C-2 

Figure C-2. Sample Tap at the Influent to the FGD 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. 

4.0 Interferences

4.1 Isobaric Interferences 

Isobaric interferences in the ICP/MS are caused by isotopes of different elements 

forming ions with the same nominal mass-to-charge ratio (m/z). The 
D-3 

recommended ions used for the elements in this procedure do not have 

elemental isobaric interferences, except for a very small interference from 

krypton on 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 

analyte. Consideration should also be given to matching internal 

standards to analytes with similar ionization potentials. 

 Matrix effects are monitored by comparing the internal standard intensity 

in the sample to the internal standard intensity of the calibration blank. 

The internal standards must be between 60% and 125% of the calibration 
D-4 

blank. If they are outside this window the sample is diluted by a factor of 

2 (1:1) and is reanalyzed. 

 Memory effects are dependent on the relative concentration differences 

between samples and/or standards which are analyzed sequentially. The 

rinse period between samples must be long enough to eliminate 

significant memory interference (see section 10.3.6). 

5.0 Safety 

This procedure may involve hazardous material, operations and equipment. This 

procedure does not purport to address all of the safety problems associated with its use. 

It is the responsibility of the user of the method to follow appropriate safety, waste 

disposal and health practices under the assumption that all samples and reagents are 

potentially hazardous. Safety glasses, gloves, lab coats and closed-toe, nonabsorbent 

shoes are required. 

5.1 Specific Safety Concerns or Requirements 

5.1.1 Eye protection that satisfies ANSI Z87.1, laboratory coat, and 

nonpowdered nitrile or latex gloves must be worn while handling 

samples, standards, solvents, and reagents. Disposable gloves that 

have been contaminated must be removed and discarded; nondisposable gloves must be cleaned immediately. 

5.1.2 The ICP plasma emits strong UV light and is harmful to vision. All 

analysts must avoid looking directly at the plasma. The RF Generator 

produces strong radio frequency waves, most of which are unshielded. 

People with pacemakers should not go near the instrument while in 

operation. 

5.2 Primary Materials Used 

The following is a list of the materials used in this method, which have a serious 

or significant hazard rating. Note: This list does not include all materials 

used in the method. The table contains a summary of the primary hazards 

listed in the MSDS for each of the materials listed in the table. 
D-5 

Material (1) Hazards Exposure 

Limit (2) Signs and Symptoms of Exposure 

Nitric Acid Corrosive 

Oxidizer 

Poison 

2 ppmTWA 

4 ppmSTEL 

Nitric acid is extremely 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. 
D-6 

6.2 Supplies 

 Argon gas: High purity grade (99.99%). 

 Helium gas: High purity grade (99.99%). 

 Hydrogen gas: High purity grade (99.99%). 

 Calibrated automatic pipettes or Class A glass volumetric pipettes. 

7.0 Reagents and Standards

7.1 Storage and Shelf-Life 

7.1.1 All standards must be stored in glass, FEP fluorocarbon or previously 

unused polyethylene or polypropylene bottles. Standards stored at 

concentrations as received from the vendor and mid-level dilutions must 

be replaced prior to the expiration date assigned by the vendor. If no 

expiration date is provided, the stocks and mid-level standards may be 

stored for up to one year. They must be replaced sooner if verification 

from an independent source indicates a problem (See section 10.3.5 for 

initial calibration verification acceptance criteria). 

7.1.2 Working standards, i.e., all standards at concentrations ready to 

analyze on the ICP/MS (all except tuning mixes, ICSA and ICSAB 

mixes, which are received at ready-to-use concentrations), are prepared 

fresh daily. 

7.2 Standards

7.2.1 Tuning Solution, 10 ppb 

The tuning solution stock is purchased as a custom multi-element mix. 

The concentrations of the constituents are shown in Attachment 5. 

Prepare the Tuning Solution as detailed below. 

 Obtain a clean 100 mL volumetric flask. 

 Place 50 mL of reagent water and 2 mL of conc. 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% 
D-7 

HCl acid matrix. Suggested concentrations are given in Attachment 8, 

but the laboratory may adjust calibration standard concentrations as 

appropriate for the instrument and samples. At a minimum, a 3 point 

curve must be used. 

7.2.4 Individual FGD Interference check solutions. 

7.2.4.1 All individual FGD interference check solutions should be 

made up in the same acid matrix as the calibration standards. 

7.2.4.2 Chloride, 10,000 mg/L 

7.2.4.3 Calcium, 5,000 mg/L 

7.2.4.4 Sulfate, 4,000 mg/L 

7.2.4.5 Magnesium, 3,000 mg/L 

7.2.4.6 Sodium, 2,000 mg/L 

7.2.4.7 Boron, 500 mg/L 

7.2.4.8 Iron, 500 mg/L

7.2.4.9 Nitrate, 250 mg/L 

7.2.4.10 Manganese, 200 mg/L 

7.2.4.11 Bromide, 100 mg/L 

7.2.4.12 Fluoride, 100 mg/L 

7.2.4.13 Selenium, 20 mg/L

7.2.4.14 Vanadium, 10 mg/L

7.2.4.15 Zinc, 2 mg/L

7.2.4.16 Chromium, 1 mg/L

7.2.4.17 Copper, 1 mg/L

7.2.5 Mixed Interference Check Solution (Synthetic FGD Wastewater) 

7.2.5.1 Chloride, 5,000 mg/L 

7.2.5.2 Calcium, 2,000 mg/L 

7.2.5.3 Magnesium, 1,000 mg/L 

7.2.5.4 Sulfate, 2,000 mg/L 

7.2.5.5 Sodium, 1,000 mg/L 

7.2.5.6 Butanol, 2000ppm 

7.2.6 Initial Calibration Verification (ICV) Standard 

The ICV stock is from a source different than the source for the 

calibration standards. Each day of analysis, the ICV standard is 

prepared in 2% 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 

Containe

r 

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 
D-9 

wastewaters are being analyzed, and after any major changes to instrument 

operating conditions. Concentrations of target elements observed should be less 

than their reporting limits. In some cases it may not be possible to obtain 

interference check solutions that are completely free of contamination. In this 

case, results up to 5X the reporting limit are acceptable if it is possible to 

demonstrate that the isotopic ratios correspond to natural abundances. For 

example, the natural abundances of zinc isotopes are 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) 

MS is prepared by taking a second aliquot of a selected sample and spiking it 

with the analytes of interest as summarized in Attachment 8. An MSD is 
D-11 

prepared by taking a third aliquot of a selected sample and spiking it with the 

analytes of interest as summarized in Attachment 8. The MS and MSD are 

processed in the same manner as the samples. One MS/MSD pair must be 

processed every 10 samples. 

Acceptance Criteria: Control limits are based on three standard deviations of 

past laboratory results. These limits are not to exceed 

70-130% recovery, and 20% relative percent difference 

(RPD). The control limits are maintained in the LIMS 

system. If the sample concentration for a specific analyte 

in the sample selected for spiking is greater than the 

concentration added by the spike, then recovery 

accuracy will be reduced. In this case a dilution test may 

be performed. A 1:5 dilution should agree within 20% of 

the original determination. If not, a physical or chemical 

interference is suspected, and must be discussed in the 

sample narrative. 

Corrective Action: If MS/MSD results and any applicable dilution tests do 

not meet the acceptance criteria and all other quality 

control criteria have been met, then a matrix interference 

is suspected. Failed matrix spikes are flagged, and are 

discussed in the final report case narrative. 

9.9 Internal Standards Evaluation for Samples 

The internal standards in samples must be between 60 and 125% of the intensity 

in the calibration blank. If the sample intensities fall outside this range, the 

calibration blank is reanalyzed to confirm the instrument has not drifted out of 

control. If the criteria is met, the sample is diluted by a factor of 2 (1:1) and 

reanalyzed. IS limits and corrective actions for standards and blanks are 

described in Section 10. 

10.0 Procedure

10.1 One-time procedural variations are allowed only if deemed necessary in the 

professional judgment of the supervisor to accommodate variation in sample 

matrix, radioactivity, chemistry, sample size, or other parameters. Any variation 

in procedure shall be completely documented. Any unauthorized deviations from 

this procedure must also be documented as a nonconformance, with a cause 

and corrective action described. 

10.2 Sample Preparation 

10.2.1 EPA Method 1638 was used as the reference for the digestion of the 

samples in which Section 12.2.8 describes Closed Vessel digestion. 

10.2.2 Transfer a 50mL (+/- 0.5mL) aliquot from a well mixed acid preserved 

sample to a 50mL digestion tube. 

10.2.3 Add 0.5mL of concentrated nitric acid and 0.25 mL hydrochloric acid. 

10.2.4 Spike the LCS and MS/MSD samples per spiking protocols. 
D-12 

10.2.5 The total volume of the solution in the tube is now greater than 50 mLs. 

The final volume will be 50 ml following the procedure to eliminate the 

discrepancy in the initial and final volumes. 

10.2.6 Tightly cap each digestion vessel. 

10.2.7 Place the digestion tube into a block digester adjusted to achieve a 

temperature of approximately 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). 

Acceptance Criteria: The ICV recovery must be within 90-110%. 

Additionally, the internal standard recoveries for 
D-13 

200.8 must fall between 60 and 125% of true 

values. The ICV can be reanalyzed, but must 

be successful twice in succession or corrective 

action must be taken. 

Corrective Action: If the ICV results are outside of the acceptance 

limits, investigate the accuracy of the 

standards, correct as necessary, and 

recalibrate. 

10.3.6 Calibration Blank 

Checks for the memory effects described at Section 4.4 may be 

accomplished by analysis of an initial calibration blank (ICB) after the 

ICV. Continuing calibration blanks (CCBs) are analyzed after each 

continuing calibration verification. 

Acceptance Criteria: Results for the calibration blanks must be less 

than the RL. 

Corrective Action: If the calibration blank exceeds acceptance 

limits, then the possibility of instrument 

contamination should be examined, particularly 

the possibility of carry-over from high level 

samples. The blank can be reanalyzed, and if 

successful, analysis can continue. However, 

samples tested after high-level samples should 

be retested. If the reanalysis is not successful, 

then the analysis should be terminated. After 

the problem is corrected, recalibrate and 

reanalyze all samples tested since the last 

acceptable CCB. 

10.3.7 Reporting Limit (RL) Verification Standard 

An independent standard is analyzed after the ICV to monitor the lab’s 

ability to produce reliable results at RL-level concentrations. The RL 

verification standard is analyzed after the daily ICB. 

Acceptance Criteria: For project reporting limits at or above two 

times the MDL, the results should be within 

50% of the expected value. Some programs 

may require tighter control, in which case the 

RLs will need to be three or more times the 

MDL concentration. 

Corrective Action: If the RL verification fails to meet acceptance 

limits, data for the associated samples must be 

assessed. For example, if the results are high, 

consider blank contamination, and if the results 

are low, consider MDL verifications. At a 

minimum, sample results must be qualified in 

the final report. 

10.3.8 Continuing Calibration Verification (CCV) Standard 

A 50 g/L CCV standard is analyzed after every set of ten samples and 

at the end of the analytical sequence. 
D-14 

Acceptance Criteria: The CCV recovery must be within 85-115%. In 

addition, the IS recovery must be within 60-

125%. If CCV results are not within these 

limits, the CCV can be reanalyzed, but it must 

be successful twice in succession or further 

corrective action must be taken. 

Corrective Action: If the CCV fails acceptance criteria, then the 

analysis should be terminated. Recalibrate and 

reanalyze all samples tested since the last 

acceptable CCB. 

10.4 Sample Analysis 

10.4.1 Report the average of at least three integrations for all field and QC 

samples analyzed. 

10.4.2 Flush the system with the rinse blank for at least 30 seconds between 

samples and standards during the analytical run. Evaluate the 

effectiveness of this time and increase the flush time, if needed. 

10.4.3 It may be valuable to monitor additional isotopes for elements that are 

potentially susceptible to interferences. In particular, monitoring 

additional isotopes for selenium may help data analysis. 

10.4.4 Dilute and reanalyze samples that are more concentrated than the 

highest calibration standard for an analyte or specific isotope of interest. 

No analyte may be reported from an analysis of a diluted sample in 

which the analyte concentration is less than 5 times the RL. 

The analytical run sequence should be performed as follows to meet all 

quality control criteria: 

Instrument initialization 

Warm-up 

Tune instrument 

Perform mass calibration 

Perform resolution check 

Validate tuning criteria 

Calibration blank 

Calibration standard 1 

Calibration standard 2 

Calibration standard 3 

ICV 

ICB 

RL verification standard 

Synthetic FGD matrix 

Spiked synthetic FGD matrix 

Carryover check 

CCV 

CCB 

10 Samples (which can include all sample types) 

CCV 

CCB 
D-15 

11.0 Calculations / Data Reduction

11.1 LCS percent recoveries are calculated according to the equation:

11.2 ICV percent recoveries are calculated according to the equation:

11.3 CCV percent recoveries are calculated according to the equation:

11.4 Matrix Spike Recoveries are calculated according to the following equation:

Where: 

SSR = Spike Sample Result 

SR = Sample Result 

SA = Spike Added 

NOTE: When the sample concentration is less than the detection limit, use SR = 0 

for the purpose of calculating %R. 

11.5 The relative percent difference (RPD) between sample duplicates is 

calculated according to the following equation:

Where: 

DU1 = Sample result 

DU2 = Sample duplicate result 

100%

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 
D-26 

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-27 

Attachment 8: Calibration, Calibration Verification, and Spike Concentrations 

Element 

Initial Calibration 

(g/L) 

ICV 

(g/L)

CCV 

(g/L)

LCS

(g/L)

MS/MSD 

(g/L)

Aluminum 100, 1,000, 10,000 4000 5000 4000 4000 

Arsenic 1, 10, 100 40 50 40 40 

Cadmium 1, 10, 100 40 50 40 40 

Chromium 1, 10, 100 40 50 40 40 

Copper 1, 10, 100 40 50 40 40 

Lead 1, 10, 100 40 50 40 40 

Manganese 1, 10, 100 40 50 40 40 

Nickel 1, 10, 100 40 50 40 40 

Selenium 1, 10, 100 40 50 40 40 

Silver 1, 10, 100 40 50 40 40 

Thallium 1, 10, 100 40 50 40 40 

Vanadium 1, 10, 100 40 50 40 40 

Zinc 1, 10, 100 40 50 40 40 

Additional elements may be included in the calibration solution at the above levels. Levels 

may be adjusted to meet specific requirements. 

####