Sampling Episode Report 

Duke Energy Carolinas’ 

Allen Steam Station 

Belmont, NC 

Sampling Episode 6561 

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 Biological Reactors..................................................................................2-4

2.2.3 Sampling Points .......................................................................................2-5

3. SAMPLE COLLECTION .......................................................................................................3-8

3.1 Sampling Points, Sample Collection Methods, and Field Measurements ...........3-8

3.1.1 Influent to FGD Wastewater Treatment System......................................3-9

3.1.2 Influent to Bioreactor System ................................................................3-11

3.1.3 Effluent from Bioreactor System...........................................................3-13

3.2 List of Analytes and Sample Preservation.........................................................3-16

3.3 Plant Operational Data.......................................................................................3-17

3.4 Deviations from the Sampling and Analysis Plan .............................................3-17

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

5. DATA QUALITY.................................................................................................................5-1

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

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

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

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

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

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

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, Allen ..................................................................... 3-19

Table 3-2. Sample Collection at Allen Steam Station ............................................................... 3-21

Table 3-3. Field Measurements, Allen....................................................................................... 3-22

Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Allen........................... 3-24

Table 3-5. Analytical Methods, Allen........................................................................................ 3-25

Table 3-6. Summary of Sample Container and Planned Preservation, Allen............................ 3-26

Table 3-7. Sample Preservation Summary, Allen...................................................................... 3-27

Table 3-8. Generating Unit Operating Characteristics during Sample Collection, Allen ......... 3-30

Table 3-9. FGD Scrubber System Operating Characteristics, Allen ......................................... 3-31

Table 3-10. Coal Usage during Sample Collection, Allen......................................................... 3-32

Table 3-11. Scrubber Slurry Information during Sample Collection, Allen.............................. 3-33

Table 3-12. FGD Wastewater Treatment System Operation Information, Allen...................... 3-34

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

Table 4-2. Influent to the Bioreactor System, Allen................................................................... 4-7

Table 4-3. Effluent from the Bioreactor System, Allen............................................................ 4-11

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

Treatment System, Allen ............................................................................................... 4-15

Table 4-5. Metal Pollutants 4-Day Average Data Summary for FGD Wastewater 

Treatment System, Allen ............................................................................................... 4-16

Table 5-1. Field Duplicate Results – Influent to Bioreactor System, Allen ............................... 5-5

Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, Allen .......................... 5-9

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

Allen................................................................................................................................ A-1

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

Allen................................................................................................................................ A-4
LIST OF TABLES (Continued) 

Page 

iii

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

Allen................................................................................................................................ A-7

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

Allen.............................................................................................................................. A-10

Table A-5. Influent to Bioreactor System, Day 1 Analytical Results, Allen........................... A-13

Table A-6. Influent to Bioreactor System, Day 2 Analytical Results, Allen........................... A-16

Table A-7. Influent to Bioreactor System, Day 3 Analytical Results, Allen........................... A-19

Table A-8. Influent to Bioreactor System, Day 4 Analytical Results, Allen........................... A-22

Table A-9. Effluent from Bioreactor System, Day 1 Analytical Results, Allen...................... A-25

Table A-10. Effluent from Bioreactor System, Day 2 Analytical Results, Allen.................... A-28

Table A-11. Effluent from Bioreactor System, Day 3 Analytical Results, Allen.................... A-31

Table A-12. Effluent from Bioreactor System, Day 4 Analytical Results, Allen.................... A-34

Table A-13. Duplicate of Influent to Bioreactor System Analytical Results, Allen................ A-37

Table A-14. Duplicate of Effluent from Bioreactor System Analytical Results, Allen .......... A-40

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Allen................................. A-43

Table A-16. Influent to FGD Wastewater Treatment System Field Blank, Day 1 

Analytical Results, Allen .............................................................................................. A-48

Table A-17. Influent to Bioreactor System Field Blank, Day 1 Analytical Results, Allen..... A-50

Table A-18. Influent to Bioreactor System Field Blank, Day 2 Analytical Results, Allen..... A-52

Table A-19. Influent to Bioreactor System Field Blank, Day 3 Analytical Results, Allen..... A-53

Table A-20. Influent to Bioreactor System Field Blank, Day 4 Analytical Results, Allen..... A-54

Table A-21. Effluent from Bioreactor System Field Blank, Day 1 Analytical Results, 

Allen.............................................................................................................................. A-55

Table A-22. Effluent from Bioreactor System Field Blank, Day 2 Analytical Results, 

Allen.............................................................................................................................. A-57

Table A-23. Effluent from Bioreactor System Field Blank, Day 3 Analytical Results, 

Allen.............................................................................................................................. A-58
LIST OF TABLES (Continued) 

Page 

iv

Table A-24. Effluent from Bioreactor System Field Blank, Day 4 Analytical Results, 

Allen.............................................................................................................................. A-59
v

LIST OF FIGURES 

Page 

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

Figure 2-2. Physical/Chemical Separation and Biological Reactor Portion of FGD 

Wastewater Treatment System, Allen.............................................................................. 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 Influent to the Bioreactor System........................C-4

Figure C-5. Sample Tap and Tubing at the Effluent from the Bioreactor System ......................C-5
1-1

1. INTRODUCTION

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

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

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

and evaluate treatment technologies and best management practices used to reduce pollutant 

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

place August 1 - 6, 2010, at Duke Energy Carolinas’ Allen Steam Station (Allen), located in 

Belmont, North Carolina (Sampling Episode 6561). The focus of Episode 6561 was to 

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

system and the influent to and effluent from the FGD bioreactor treatment system. The influent 

to the bioreactor system also represents 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. 

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

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

generating units; 

 The plant operates two limestone forced oxidation wet FGD systems that service 

all five generating units; 

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

includes the following steps: 

— Equalization, 

— pH adjustment (lime addition), 

— Ferric chloride addition, 

— Polymer addition, 

— Clarification, 

— Filtration, and 

— Biological treatment (nitrogen and metals); 
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 The plant operates a selective non-catalytic reduction (SNCR) system on all five 

generating units; and 

 The plant produces a commercial-grade gypsum by-product. 

1.3 Sampling Episode Overview

EPA and its technical contractor, Eastern Research Group, Inc. (ERG) conducted a oneday pre-sampling site visit at Allen on October 22, 2009. The information collected during the 

pre-sampling site visit and subsequent follow-up telephone calls to Allen representatives was 

used to create Sampling Plan, Duke Energy Carolinas’ Allen Steam Station (Sampling Plan) [1], 

which describes the sample collection procedures used during the sampling episode. 

On Sunday, August 1, 2010, EPA arrived at Allen 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 (August 2 – 6, 2010). The following personnel participated in EPA’s sample 

collection activities: 

 Ron Jordan, EPA/EAD; 

 Bill Swietlik, EPA/EAD; 

 TJ Finseth, ERG; 

 Kavya Kasturi, ERG; 

 Lydia Lambert, ERG; 

 Jennifer Lewis, 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 Allen’s representative and collected 

samples on behalf of the plant. 
2-1

2. FACILITY OVERVIEW

Allen operates five steam electric units and each has a coal-fired boiler. Units 1 and 2 

came on line in 1957, and each has a capacity of 165 megawatts (MW). Units 3, 4, and 5 came 

on line in 1959, 1960, and 1961, respectively, and each has a capacity of 275 MW. All five 

generating units burn bituminous coal. The electric generating units at Allen are operated on a 

cycling basis and are not baseload units. The plant is located on 1,000 acres adjacent to the 

Catawba River. 

Allen recently retrofitted all five units with two FGD scrubber systems (Absorbers 1 and 

3) to control the sulfur dioxide (SO2) releases from the plant. Units 1, 2, and 5 exhaust to FGD 

Absorber 1 (which began operation in February 2009), and Units 3 and 4 exhaust to FGD 

Absorber 3 (which began operation in May 2009). The wet FGD scrubbers are designed to 

remove more than 95 percent of SO2 from the flue gas. With the recent addition of the FGD 

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

discharges of the wastewater generated during the operation of the FGD scrubbers. Sections 2.1 

and 2.2 further discuss the FGD scrubber systems and the FGD wastewater treatment system, 

respectively. 

Allen operates electrostatic precipitators (ESPs) to control fly ash and particulate 

emissions from the plant. Allen also operates SNCR systems year-round to control nitrogen 

oxide (NOx) emissions from the plant. Additionally, the boilers are operated with low-NOx

burners and a separated overfire air system. 

The ESPs at Allen are particulate control devices that are designed to remove 99.9 

percent of the fly ash and other particulates from the flue gas. Allen utilizes ESPs to remove the 

fly ash from all five generating units. The fly ash and other particulates are collected in hoppers 

and usually pneumatically transferred to fly ash silos. However, Allen also has the capability of 

handling the fly ash wet by sluicing the fly ash in the hoppers and transferring the fly ash 

transport water to the ash basin. Allen uses the wet fly ash handling system during start ups for 

the generating units until the units are burning 100 percent coal. Allen also uses the wet fly ash 

handling system if there are issues with the dry fly ash handling system. 

All five generating units have the following configuration: 

 Boiler (SNCR system contained in boiler); 

 Air preheater; 

 ESP; and 

 FGD scrubber system. 

2.1 FGD Scrubber System

Allen operates two wet FGD scrubber systems that treat the flue gas from all five electric 

generating units. 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 

transferred to the reject tank and then sent back to the ball mill for additional processing. The 
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overflow from the hydrocyclones, which is approximately 30 percent solids, is transferred to the 

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

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

pumps send the slurry to the various levels of the FGD scrubber. Both absorbers have four spray 

levels; however, the plant typically operates only three levels at one 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 countercurrent to the slurry, the spray droplets of the 

limestone slurry contact the flue gas and absorb the SO2, which reacts with the limestone 

particles and produces calcium sulfite. The spray droplets continue to flow downward in the 

scrubber until they reach the reaction tank. Allen bubbles air through the reaction tank to oxidize 

the calcium sulfite to calcium sulfate (i.e., gypsum). 

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

solids and/or chlorides concentration in the scrubbers. The chlorides concentration in the 

scrubbers is maintained between 3,000 and 10,000 ppm (parts per million), with a design 

maximum chlorides concentration of 12,000 ppm. The typical percentage of solids within the 

scrubber is 14 to 16 percent. 

The gypsum slurry 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 

gypsum from the primary hydrocyclones is transferred to the filter feed tank, which is then 

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

transferred to a holding tank and then pumped to the secondary hydrocyclones. The underflow 

from the secondary hydrocyclones is returned to the scrubber. The overflow from the secondary 

hydrocyclones is sent to the FGD wastewater treatment system. This FGD purge stream contains 

0.5 to 0.8 percent solids. 

Allen washes the gypsum sent to the vacuum filter belts with service water as it is applied 

to the belts to reduce the chlorides in the gypsum to typically less than 20 ppm. The vacuum 

filter belts dry the gypsum to a moisture content of approximately four percent. The gypsum 

produced at the plant must have a chloride content of less than 120 ppm and a moisture content 

of less than 10 percent to be sold to a wallboard manufacturer. Allen transfers the dry gypsum to 

a storage area and then trucks the gypsum to a wallboard manufacturer in Mount Holly, North 

Carolina. 

2.2 FGD Wastewater Treatment System

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

FGD wastewater from the FGD system, which consists of secondary hydrocyclone overflow, at a 

flow rate of approximately 400 gallons per minute (gpm). The FGD wastewater treatment system 

consists of chemical precipitation and biological treatment technologies. Allen installed the 

wastewater treatment system to treat the FGD scrubber purge wastewater to meet its permit 

limits, which include limits for total suspended solids (TSS) and selenium. The Allen FGD 

wastewater treatment system contains the following treatment operations: 
2-3

 Physical/Chemical Separation: 

— Equalization, 

— pH adjustment (lime addition), 

— Ferric chloride addition, 

— Polymer addition, 

— Clarification, and 

— Filtration; and 

 Biological Reactors: 

— Cooling (heat extraction), 

— Nutrient addition, 

— First-stage biological reaction, 

— Nutrient addition, and 

— Second-stage biological reaction. 

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 is a simplified diagram of the FGD wastewater treatment system, showing 

different portions of the system. Figure 2-2 is a diagram of the chemical precipitation and 

biological reactor portions of the treatment system. 

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. Allen also 

has a maintenance tank that is used as either a spare equalization tank or a spare sludge holding 

tank. During the sampling episode, the FGD influent wastewater was found to contain less than 

0.5 percent solids, had a pH between 6.5 and 7.0 S.U., and a temperature between 40 and 50°C. 

The equalization tank also receives water from the filtrate sump (which includes filter press 

filtrate), gravity filter backwash reject, backflush waste from the biological treatment system, 

and off-specification biological treatment effluent. 

2.2.1 Physical/Chemical Separation 

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

tank 1, in which lime is added to increase the pH to between 8.6 and 9.2 S.U.; reaction tank 2, 

designed for organosulfide addition, but which is only used to provide additional mixing; and 

reaction tank 3, in which ferric chloride is added. 

The overflow from reaction tank 3 flows through a flow splitter, which distributes the 

flow evenly to two clarifiers. Allen operates the two clarifiers in parallel, each capable of 

handling 100 percent of the waste stream flow. A polymer is added to the wastewater just before 

it enters the clarifiers. Hydrochloric acid is added to the wastewater at a point between the 

clarifiers and the sand filters to ensure that the pH is adjusted closer to neutral prior to the 

biological treatment system. After the hydrochloric acid addition, the overflow from the two 

clarifiers is split and sent through three sand filters in parallel, each of which can handle 75 

percent of the waste stream capacity. The sand filters are continuous backwash gravity filters and 

produce an effluent with a TSS concentration of approximately 1 to 2 ppm. The filter backwash 

is sent to a sump and then transferred to the equalization tank. 
2-4

The sludge collected in the clarifier is transferred to a sludge holding tank. A portion of 

the clarifier sludge is recycled from the sludge holding tank to reaction tank 1, while the majority 

is pumped to a filter press for dewatering. The solids are transferred to an off-site landfill and the 

filtrate is recycled to the equalization tank. 

2.2.2 Biological Reactors 

 Prior to entering the biological portion of the wastewater treatment system, the 

wastewater is cooled if necessary by heat exchangers to 95o F, the optimal temperature for the 

biological treatment system. The heat exchangers were constructed with a titanium alloy that can 

withstand the high levels of chlorides in the FGD wastewater entering the biological treatment 

system. When in use, the heat exchanger requires 300 to 350 gpm of cooling water. Allen adds 

nutrients (in the form of molasses) to the wastewater as it flows from the heat exchanger to the 

biological treatment system. The nutrients provide a source of carbon to feed the bacteria. 

In the bioreactor portion of the treatment, Allen treats the wastewater in two stages. Each 

stage contains eight bioreactor cells, which are operated in parallel. Each cell contains 20 feet of 

activated carbon media. Within the activated carbon bed, specialized microbes fill the voided 

areas and reduce selenium to its elemental form, while other metals are precipitated as sulfide 

complexes. The microbes also reduce the concentration of nitrogen present in the wastewater. 

The wastewater is divided evenly among the first stage of eight cells. The flow to each cell is 

sent to 16 distribution pipes to create an even distribution of flow into the top of the cell. The 

water level in the cell is designed to be approximately six inches above the activated carbon bed; 

however, at the time of the site visit, the water level was below the top of the carbon bed. 

Allen operates the bioreactors to achieve a negative oxidation reduction potential (ORP) 

within the system, which provides the optimum environment to reduce selenium to its elemental 

form. This ORP is controlled by the amount of nutrient that is fed to the system. The plant also 

controls the pH in the bioreactor cells to between 6.0 and 9.0 S.U. because extreme high or low 

pH levels could affect the performance of the microbes and potentially allow nondesirable 

microbes to propagate. 

The effluent from all eight of the first-stage bioreactor cells is combined in the first-stage 

effluent storage area. The wastewater is then transferred to the eight second-stage bioreactor 

cells, which are operated in parallel. Nutrients are added to the wastewater as feed for the 

microbes as the wastewater is transferred. As in the first stage, the wastewater is divided evenly 

among the eight second-stage cells and each cell has 16 distributor pipes to evenly distribute the 

flow into the cell. 

Occasionally the bioreactor cells must be backflushed to remove accumulated solids. The 

plant pumps the effluent from the first-stage bioreactor cells backwards through each cell and it 

overflows into a spillover chamber. The plant then returns the backwash overflow to the 

equalization tank at the start of the FGD wastewater treatment system. 

Because the first-stage bioreactor cells denitrify the waste stream, they produce nitrogen 

and carbon dioxide gas. To remove the gas from the cells, the plant occasionally performs a 

degassing operation where water is sent backwards through the cells, like a backflush, but the 

flush is only long enough for the gas to “burp” out of the system. The second-stage bioreactor 
2-5

cells are primarily anoxic and do not produce as much gas as the first-stage cells, requiring less 

frequent degassing than the first-stage cells. 

From the second stage of the bioreactor treatment system, the wastewater is commingled 

with the heat exchanger cooling water and transferred to the ash basin. The effluent from the ash 

basin is discharged to the Catawba River via Outfall 002. 

Because the steam electric generating units at Allen are operated on a cycling basis and 

are not baseload units, there are times when the units are shut down for a few days. During these 

shut-down periods, the wastewater treatment system does not receive any scrubber purge 

wastewater and, therefore, the plant has to find a way to feed the microbes to keep them alive. If 

Allen knows ahead of time that all units will be shut down for a couple of days, they can build up 

additional scrubber purge in the equalization and maintenance tanks and then operate the FGD 

wastewater treatment system at a reduced flow rate until they begin operating again. If the plant 

is down for several days without advanced knowledge, the plant can run service water through 

the system and feed nutrients to the bioreactors to sustain biological growth. 

2.2.3 Sampling Points 

Figure 2-2 presents the sampling points for the Allen 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); 

 An in-process sample of the influent to the bioreactor system, downstream of the 

sand filters and the holding tank and upstream of the heat exchanger; and 

 A sample of the effluent from the bioreactor system, downstream of the secondstage effluent storage area and upstream of where the FGD wastewater treatment 

effluent is commingled with the heat exchanger cooling water. 
2-6 

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

Figure 2-2. Physical/Chemical Separation and Biological Reactor Portion of FGD Wastewater Treatment 
3-8

3. SAMPLE COLLECTION

During the Allen 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 Influent to Bioreactor System; 

 SP-3 Effluent from Bioreactor System; 

 SP-4 Duplicate of Influent to Bioreactor System (SP-2); 

 SP-5 Duplicate of Effluent from Bioreactor System (SP-3); 

 SP-6 Influent to FGD Wastewater Treatment System (SP-1) Field Blank; 

 SP-7 Influent to Bioreactor System (SP-2) Field Blank; and 

 SP-8 Effluent from Bioreactor System (SP-3) Field Blank. 

For all the sampling points, EPA collected split samples with Allen’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 Allen’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 
3-9

“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 

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 sampling point was located outside, near the equalization tank. The sampling team 

set up a tent for the sample collection to protect the samplers from the heat. There was no rain 

during the sample collection. The sampling team did note, however, that on Day 1, there was a 

slight breeze during sample collection and on Day 4, there was some gypsum dust in the air near 

the sampling point due to truck traffic. 

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-6) for total mercury, total 

and dissolved metals, and dissolved hexavalent chromium. See Section 5.2.3 for a description of 

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

system. 

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

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

wastewater piping. The end of the silicone tubing was fitted with a “Y” splitter, with two 

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

picture of the tubing attached to the sample tap at the influent to the FGD wastewater treatment 

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

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

containers. The samplers did not close the valve until all samples were collected (except the 

dissolved metals samples). 

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

3.1: 
3-10

 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 

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 Allen’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 70 minutes. Approximately 0.5- 1 

liters 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. 
3-11

3.1.2 Influent to Bioreactor System 

The influent to the bioreactor system (SP-2) was collected downstream of the sand filters 

after the wastewater from the three filters is commingled. This sample tap is located downstream 

of the holding tank and upstream of the heat exchanger. Allen installed a three-way splitter on 

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

sample tap was located inside the FGD wastewater treatment building (see Figure 2-2 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 influent from the bioreactor 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-7) 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 influent to the bioreactor 

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 influent to the bioreactor system. 
3-12

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 influent to the bioreactor system. 

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

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

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

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

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

directly from the tap, ERG was not able to collect split samples with Allen’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 and a 

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

bioreactor 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 Allen’s representatives; therefore, duplicate samples were collected. 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 at the influent to the bioreactor system. ERG 

samplers then preserved the total cyanide samples with sodium hydroxide to a pH >10 S.U. and 

placed the samples on ice. 

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

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

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

composite containers were moved to the pump-off area where they remained on ice until 

individual sample bottles were filled. The samplers then began setting up the compositors for the 

next day of samples using new tubing sets and composite containers. The automatic compositor 

was programmed to collect the same volume on each day of sample collection. 

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

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

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 
3-13

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 Allen’s representative. 

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 influent to the bioreactor system, 

the samplers collected a field blank sample (SP-7) for dissolved and total metals. See Section 

5.2.3 for a description of the dissolved metals field blank sample collection at the influent to the 

bioreactor 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 influent to 

the bioreactor system. After the tubing and filter were purged with two 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 two 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. Once 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 influent to the bioreactor system (SP2) on Day 4 of the sampling episode. In addition, for all analytes, ERG collected a duplicate 

sample of the influent from bioreactor system (SP-4) on Day 3 of the sampling episode. 

3.1.3 Effluent from Bioreactor System 

The effluent from bioreactor system (SP-3) was collected downstream of the secondstage effluent storage tank from the second-stage bioreactor cells. Allen installed a three-way 

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

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

sampling location for SP-3). Because the sampling point was located inside, there were no wind 

or rain concerns during the sample collection. 

ERG collected the effluent from the bioreactor 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 
3-14

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-8) 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 bioreactor 

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-5, in Appendix C, is a picture of the composite sampling 

set-up at the effluent from the bioreactor 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 bioreactor system. 

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

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

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

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

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

directly from the tap, ERG was not able to collect split samples with Allen’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 
3-15

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 bioreactor 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 Allen’s representatives; therefore, duplicate samples were collected. 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 this sampling episode at the effluent from the bioreactor system. ERG 

samplers then preserved the total cyanide samples with sodium hydroxide to a pH >10 S.U. and 

placed the samples on ice. 

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

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

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

composite containers were moved to the pump-off area where they remained on ice until 

individual sample bottles were filled. The samplers then began setting up the compositors for the 

next day of samples using new tubing sets and composite containers. The automatic compositor 

was programmed to collect the same volume on each day of sample collection. 

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

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

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 Allen’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 bioreactor system, 

the samplers collected a field blank sample (SP-8) for dissolved and total metals. See Section 

5.2.3 for a description of the dissolved metals field blank sample collection at the effluent from 

the bioreactor 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 bioreactor 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: 
3-16

 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 bioreactor system 

(SP-3) on Day 3 of the sampling episode. In addition, for all analytes, ERG collected a duplicate 

sample of the effluent from bioreactor system (SP-5) on Day 2 of the sampling episode. 

3.2 List of Analytes and Sample Preservation

Samples collected at Allen were analyzed for the following pollutants: 

 Classicals: 

— Biochemical oxygen demand, 5-day (BOD5), 

— Chemical oxygen demand (COD), 

— Total suspended solids (TSS), 

— Total dissolved solids (TDS), 

— Sulfate, 

— Chloride, 

— Total Kjeldahl nitrogen (TKN), 

— Ammonia as nitrogen, 

— Nitrate/nitrite as nitrogen, 

— Total phosphorus, 

— Total cyanide; 

 Total Metals1

: 

— 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. 

 

1 In this report, EPA uses the term “total metals” and “total recoverable metals” interchangeably. 
3-17

 Dissolved Metals: 

— Same parameters as listed for total metals, plus hexavalent chromium. 

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

pollution control wastewaters, including contributions from coal, scrubber sorbents, treatment 

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

concentrations. 

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

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

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

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

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

and total cyanide samples on ice to cool the samples to <6°C. The sampling team did not place 

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

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

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

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

hexavalent chromium samples were preserved with ammonium sulfate buffer solution and 

ammonium hydroxide to a pH between 9.3 and 9.5 S.U. The Group II samples were preserved 

with sulfuric acid to a pH of <2 S.U. in the staging area, and the pH was confirmed with fourcolor pH strips. Each total cyanide sample was tested for sulfides and oxidants immediately after 

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

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

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

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

3.3 Plant Operational Data

During the EPA sampling episode, Allen plant personnel provided the sampling team 

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

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

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

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

presents information on the FGD scrubber slurry generation during the sampling episode, and 

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

3.4 Deviations from the Sampling and Analysis Plan

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

described below: 

 Preservation of hexavalent chromium: EPA 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. 
3-18

 Collection of composite metals and classicals samples at SP-2 (Day 4): On 

day 4 of sample collection at the influent to the bioreactor system (SP-2), the 

power failed resulting in missing sample aliquot number 14 for both the classicals 

and metals compositors. Both compositors collected sample aliquot 13 as 

scheduled at 20:59 for the metals and 21:01 for the classicals. The power failed at 

21:44 and was not restored until 23:28, at which time sample aliquot 15 was 

collected by the metals compositor followed immediately by the classicals 

compositor. Sample aliquot 16 was collected as scheduled at 23:59 for the metals 

and 0:01 for the classicals. 

 Collection of composite metals and classicals samples at SP-3 (Day 4): On day 

4 of sample collection at the effluent of the bioreactor system (SP-3), the power 

failed resulting in sample aliquot number 16 not being taken at the predetermined 

time. Both compositors collected sample aliquot 15 as scheduled, at 21:30 for 

metals and 21:32 for classicals. The power failed at 21:45 and was not restored 

until 23:26, at which time sample aliquot 16 was collected by the metals 

compositor followed immediately by the classicals compositor. Sample aliquot 

17 was collected as scheduled at 23:30 for the metals and 23:32 for the classicals. 

 Collection of total mercury sample at SP-1 (Day 4): On day 4 of sample 

collection at the influent to the FGD wastewater system (SP-1), Allen’s 

representatives collected the total metals volumes before collecting total and 

dissolved mercury samples. Allen’s representatives were collecting metals 

samples while ERG was collecting the total and dissolved mercury samples and 

vice versa. 
3-19

Table 3-1. Sample Collection Information, Allen 

Sampling 

Point 

Number Sampling Point Description 

Type of 

Sample 

Sample 

Collection Date Sample Collection Time

Influent to FGD Wastewater Treatment 

System – Day 1 

Grab 8/2/10 1022a and 1148b

Influent to FGD Wastewater Treatment 

System – Day 2 

Grab 8/3/10 1136a and 1312 b

Influent to FGD Wastewater Treatment 

System – Day 3 

Grab 8/4/10 1127a and 1311b

SP-1 

Influent to FGD Wastewater Treatment 

System – Day 4 

Grab 8/5/10 1139a and 1323b

Composite 8/2/10 

8/3/10

0900c 

1040d

Influent to Bioreactor System – Day 1 

Grab 8/2/10 

8/3/10 

0913e

, 1519f , and 2121 g 

0319 h 

Composite 8/3/10 

8/4/10 

0901c 

1031d 

Influent to Bioreactor System – Day 2 

Grab 8/3/10 

8/4/10 

0915e

, 1516f , and 2119 g 

0319 h 

Composite 8/4/10 

8/5/10 

0900c 

1017d 

Influent to Bioreactor System – Day 3 

Grab 8/4/10 

8/5/10 

0915e

, 1519f , and 2121 g 

0319 h 

Composite 8/5/10 

 8/6/10 

0900c 

0827d 

SP-2 

Influent to Bioreactor System – Day 4 

Grab 8/5/10 

 8/6/10 

0914e

, 1517f , and 2118 g 

0323 h 

Composite 8/2/10 

8/3/10 

0730c 

0952d 

Effluent from Bioreactor System – Day 1 

Grab 8/2/10 

8/3/10 

0742e

, 1349f , and 1948 g 

0149 h 

Composite 8/3/10 

8/4/10 

0729c 

0945d 

Effluent from Bioreactor System – Day 2 

Grab 8/3/10 

8/4/10 

0745e

, 1351f , and 1951 g 

0149h 

Composite 8/4/10 

8/5/10 

0731c 

0941d 

Effluent from Bioreactor System – Day 3 

Grab 8/4/10 

8/5/10 

0744e

, 1349f , and 1953 g 

0150h 

Composite 8/5/10 

 8/6/10 

0730c 

0655d 

SP-3 

Effluent from Bioreactor System – Day 4 

Grab 8/5/10 

 8/6/10 

0742e

, 1346f , and 1946 g 

0146h 

SP-4 Duplicate of Influent to Bioreactor System 

– Day 3 

Composite 8/4/10 

8/5/10 

0900c 

1018d 
3-20

Table 3-1. Sample Collection Information, Allen 

Sampling 

Point 

Number Sampling Point Description 

Type of 

Sample 

Sample 

Collection Date Sample Collection Time

Grab 8/4/10 

8/5/10 

0916e, 1520f , and 2123 g 

0321 h 

Composite 8/3/10 

8/4/10 

0729c 

0945d 

SP-5 Duplicate of Effluent from Bioreactor 

System – Day 2 

Grab 8/3/10 

8/4/10 

0745e

, 1351f , and 1951 g 

0149 h 

SP-6 Influent to FGD Wastewater Treatment 

System Field Blank 

Grab 8/2/10 1006i and 1141j

Composite 8/2/10 

8/3/10 

0810k

1028l

Influent to Bioreactor System Field Blank 

– Day 1 

Grab 8/2/10 0907m

Influent to Bioreactor System Field Blank 

– Day 2 

Grab 8/3/10 0909m

Influent to Bioreactor System Field Blank 

– Day 3 

Grab 8/4/10 0910m

SP-7 

Influent to Bioreactor System Field Blank 

– Day 4 

Grab 8/5/10 0908m

Composite 8/2/10 

8/3/10 

0649k

0940l

Effluent from Bioreactor System Field 

Blank – Day 1 

Grab 8/2/10 0737m

Effluent from Bioreactor System Field 

Blank – Day 2 

Grab 8/3/10 0738m

Effluent from Bioreactor System Field 

Blank – Day 3 

Grab 8/4/10 0740m

SP-8 

Effluent from Bioreactor System Field 

Blank – Day 4 

Grab 8/5/10 0737m

a

 Start time for the collection of the total metals samples (total metals by 200.7 and total metals by 200.8), total 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 metals compositor. The classical compositor was started approximately two minutes after the metals 

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 mercury, 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, dissolved metals by 200.8, and hexavalent chromium 

field blank samples. 

k

 Filled 20-liter field blank composite container with blank water. 

l Start time for the collection of total metals (total metals by 200.7 and total metals by 200.8) and dissolved metals 

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

m Start time for the collection of total mercury field blank samples.
3-21

Table 3-2. Sample Collection at Allen Steam Station

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 FGD Wastewater Treatment System 4 4 4 4 4 4 4 4 SP-2 Influent to Bioreactor System 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QSP-3 Effluent from Bioreactor System 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QSP-4 Duplicate of Influent to Bioreactor System 1 1 1 1 1 1 1 1 SP-5 Duplicate of Effluent from Bioreactor System 1 1 1 1 1 1 1 1 SP-6 Influent to FGD Wastewater Treatment System 

Field Blank 

1 1 1 1 1 1 

SP-7 Influent to Bioreactor System Field Blank 1 1 1 1 4 1 SP-8 Effluent from Bioreactor System Field Blank 1 1 1 1 4 1 Total Number of Samples 17+2QC 17+2QC 17+2QC 17+2QC 23+2QC 14+2QC 17+2QC 14+2Q

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 phosph
3-22

Table 3-3. Field Measurements, Allen

Temperature (°C) pH 

Sampling 

Point 

Number Sampling Point Description Date Time Thermometer Probe Metera Strips

Waste 

Stream Flow 

Rate (GPM) 

Influent to FGD Wastewater Treatment System – Day 1

8/2/10 1034 44 41.5 6.8 7 383b 

Influent to FGD Wastewater Treatment System – Day 2 

8/3/10 1150 44.5 48.5 6.72 7 375c

Influent to FGD Wastewater Treatment System – Day 3 

8/4/10 1144 44 47 6.77 7 374d

SP-1 

Influent to FGD Wastewater Treatment System – Day 4 

8/5/10 1159 44.5 47.0 6.72 7 377e

No detetotal cy

8/2/10 0917 38 36 6.88 7 2978/2/10 1522 39 37.4 6.90 7 3118/2/10 2125 38 36.6 6.95 7 304 

Influent to Bioreactor System – Day 1

8/3/10 0324 38 36.9 6.79 7 299 8/3/10 0925 36.9 38 6.99 7 287 8/3/10 1520 37.9 39 6.74 7 334 8/3/10 2122 37.9 39 6.69 7 281 

Influent to Bioreactor System – Day 2 

8/4/10 0325 37.6 39 6.66 7 285 

8/4/10 0920 38 39 6.60 7 292 8/4/10 1525 38.6 39.5 6.58 7 313 8/4/10 2129 38.7 39.5 6.90 NA 245 

Influent to Bioreactor System – Day 3 

8/5/10 0326 37.7 39.5 6.62 NA 233 

8/5/10 0917 39 NA 6.65 NA 200 8/5/10 1520 39 38.6 6.57 6 200 8/5/10 2122 38 36.7 6.88 6 221 

SP-2 

Influent to Bioreactor System – Day 4 

8/6/10 0326 38.5 37.2 6.96 6 221 

No detetotal cy
3-23

Table 3-3. Field Measurements, Allen

Temperature (°C) pH 

Sampling 

Point 

Number Sampling Point Description Date Time Thermometer Probe Metera Strips

Waste 

Stream Flow 

Rate (GPM) 

8/2/10 0745 33 31.8 6.88 7 3248/2/10 1352 33 32.6 6.80 7 3678/2/10 1954 33 32.6 6.79 7 283

Effluent from Bioreactor System – Day 1

8/3/10 0152 33 32.3 6.82 7 3458/3/10 0752 32.1 33.5 6.76 7 2678/3/10 1355 33.3 34 6.66 7 3448/3/10 1958 33.3 34 6.68 7 292

Effluent from Bioreactor System – Day 2 

8/4/10 0156 32.8 34 6.72 7 210

8/4/10 0749 32.8 34 6.82 8 2368/4/10 1355 33.7 34.5 6.73 7 3398/4/10 1957 33.8 34.5 6.71 NA 315

Effluent from Bioreactor System – Day 3 

8/5/10 0153 33.4 34 6.78 NA 226

8/5/10 0743 34 NA 6.8 NA 1908/5/10 1350 35 34.2 6.86 6 2278/5/10 1950 34 33.2 6.83 7 241

SP-3 

Effluent from Bioreactor System – Day 4 

8/6/10 0150 33.5 32.8 6.82 7 225

On day 

grab sa1950 coparticlebe fibroto 3 mm sulfidegrab.

a The pH meter was calibrated prior to the sampling episode and once every day during the sampling episode using prepackaged buffer b Based on average of flow meter measurements collected every minute from 1022 to 1036 on 8/2/10 (time of sample collection). c Based on average of flow meter measurements collected every minute from 1136 to 1149 on 8/3/10 (time of sample collection). d Based on average of flow meter measurements collected every minute from 1127 to 1143 on 8/4/10 (time of sample collection). e Based on average of flow meter measurements collected every minute from 1139 to 1159 on 8/5/10 (time of sample collection). 

NA – Not analyzed. 
3-24

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

Sample Number Sample Point Sample Description 

71791 SP-1, Day 1 Influent to FGD Wastewater Treatment System - Day 1 

71792 SP-1, Day 2 Influent to FGD Wastewater Treatment System - Day 2 

71793 SP-1, Day 3 Influent to FGD Wastewater Treatment System - Day 3 

71794 SP-1, Day 4 Influent to FGD Wastewater Treatment System - Day 4 

71795 SP-2, Day 1 Influent to Bioreactor System - Day 1 

71796 SP-2, Day 2 Influent to Bioreactor System - Day 2 

71797 SP-2, Day 3 Influent to Bioreactor System - Day 3 

71798 SP-2, Day 4 Influent to Bioreactor System - Day 4 

71799 SP-3, Day 1 Effluent from Bioreactor System - Day 1 

71800 SP-3, Day 2 Effluent from Bioreactor System - Day 2 

71801 SP-3, Day 3 Effluent from Bioreactor System - Day 3 

71802 SP-3, Day 4 Effluent from Bioreactor System - Day 4 

71803 SP-4, Day 3 Duplicate of Influent to Bioreactor System - Day 3 

71804 SP-5, Day 2 Duplicate of Effluent from Bioreactor System - Day 2 

71805 SP-6, Day 1 Influent to FGD Wastewater Treatment System Field Blank - Day 1 

71806 SP-7, Day 1 Influent to Bioreactor System Field Blank - Day 1 

71807 SP-7, Day 2 Influent to Bioreactor System Field Blank - Day 2 

71808 SP-7, Day 3 Influent to Bioreactor System Field Blank - Day 3 

71809 SP-7, Day 4 Influent to Bioreactor System Field Blank - Day 4 

71810 SP-8, Day 1 Effluent from Bioreactor System Field Blank - Day 1 

71811 SP-8, Day 2 Effluent from Bioreactor System Field Blank - Day 2 

71812 SP-8, Day 3 Effluent from Bioreactor System Field Blank - Day 3 

71813 SP-8, Day 4 Effluent from Bioreactor System Field Blank - Day 4 
3-25

Table 3-5. Analytical Methods, Allen 

Parameter Method Number 

Classicals

Biochemical oxygen demand (BOD5) SM 5210 B 

Chemical oxygen demand (COD) EPA 410.4 

Total suspended solids (TSS) SM 2540 D 

Total dissolved solids (TDS) SM 2540 C 

Sulfate EPA 300.0 

Chloride EPA 300.0 

Ammonia as nitrogen EPA 350.1 

Nitrate/nitrate as nitrogen EPA 353.2 

Total Kjeldahl nitrogen (TKN) EPA 351.2 

Total phosphorus EPA 365.1 

Total cyanide SM 4500 CN E 

Total and Dissolved Metals

Mercury EPA 1631E 

Hexavalent chromium (dissolved only) EPA 218.6 

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

nickel, selenium, silver, thallium, vanadium, and zinc 

EPA 200.8 with collision cell1 

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

molybdenum, sodium, tin, and titanium 

EPA 200.7 

1

 EPA used an SOP developed specifically for analyzing FGD wastewater (see Appendix D).
3-26

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

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.
3-27 

Table 3-7. Sample Preservation Summary, Allen

Sampling Point 

Number Analysis Date 

Chemical 

Added Initial pH Final pH 

Amount 

Added 

(drops) 

71791 Group II Volume 1 8/2/10 H2SO4 7 2 28 

71791 Group II Volume 2 8/2/10 H2SO4 7 2 28 

(NH4)2SO4

Buffer 

71791 Hexavalent Chromium 8/2/10 6.0 8.3 100 

NH4OH 8.3 9.5 8 

(NH4)2SO4

Buffer 

71805 Hexavalent Chromium 8/2/10 8.7 8.7 100 

NH4OH 8.7 9.5 6 

71792 Total Cyanide 8/2/10 NaOH 7 10 9 

71795 Total Cyanide 8/2/10 NaOH 7 10 10 

71799 Total Cyanide 8/2/10 NaOH 7 10 10 

71792 Group II Volume 1 8/3/10 H2SO4 7 2 24 

71792 Group II Volume 2 8/3/10 H2SO4 7 2 24 

71795 Group II Volume 1 8/3/10 H2SO4 6 2 22 

71795 Group II Volume 2 8/3/10 H2SO4 6 2 22 

71799 Group II Volume 1 8/3/10 H2SO4 6 2 30 

71799 Group II Volume 2 8/3/10 H2SO4 6 2 30 

(NH4)2SO4

Buffer 

Not 

Measured 

71792 Hexavalent Chromium 8/3/10 8.5 100 

NH4OH 8.5 9.5 12 

(NH4)2SO4

Buffer 

71795 Hexavalent Chromium 8/3/10 6 8.5 100 

NH4OH 8.5 9.5 10 

(NH4)2SO4

Buffer 

71799 Hexavalent Chromium 8/3/10 6 8.7 100 

NH4OH 8.7 9.5 8 

(NH4)2SO4

Buffer 

71806 Hexavalent Chromium 8/3/10 6 8.5 100 

NH4OH 8.5 9.5 8 

(NH4)2SO4

Buffer 

71810 Hexavalent Chromium 8/3/10 6 8.7 100 

NH4OH 8.7 9.5 8 

71792 Total Cyanide 8/3/10 NaOH 7 10 10 

71796 Total Cyanide 8/3/10 NaOH 7 10 10 

71800 Total Cyanide 8/3/10 NaOH 7 10 15 

71804 Total Cyanide 8/3/10 NaOH 7 10 15 

71793 Group II Volume 1 8/4/10 H2SO4 7 2 28 

71793 Group II Volume 2 8/4/10 H2SO4 7 2 28 
3-28 

Table 3-7. Sample Preservation Summary, Allen

Sampling Point 

Number Analysis Date 

Chemical 

Added Initial pH Final pH 

Amount 

Added 

(drops) 

71796 Group II Volume 1 8/4/10 H2SO4 6 2 28 

71796 Group II Volume 2 8/4/10 H2SO4 6 2 28 

71800 Group II Volume 1 8/4/10 H2SO4 7 2 24 

71800 Group II Volume 2 8/4/10 H2SO4 7 2 24 

71804 Group II Volume 1 8/4/10 H2SO4 7 2 24 

71804 Group II Volume 2 8/4/10 H2SO4 7 2 24 

(NH4)2SO4

Buffer 

Not 

Measured 

71793 Hexavalent Chromium-QC 8/4/10 8.1 100 

NH4OH 8.1 9.5 12 

(NH4)2SO4

Buffer 

71796 Hexavalent Chromium 8/4/10 6 8.5 100 

NH4OH 8.5 9.5 10 

(NH4)2SO4

Buffer 

71800 Hexavalent Chromium 8/4/10 6 8.5 100 

NH4OH 8.5 9.5 10 

(NH4)2SO4

Buffer 

71804 Hexavalent Chromium 8/4/10 6 8.5 100 

NH4OH 8.5 9.5 10 

71793 Total Cyanide 8/4/10 NaOH 7 10 15 

71797 Total Cyanide 8/4/10 NaOH 7 10 10 

71801 Total Cyanide 8/4/10 NaOH 6.7 10 15 

71801 Total Cyanide-QC 8/4/10 NaOH 6.7 10 15 

71803 Total Cyanide 8/4/10 NaOH 7 10 10 

71794 Group II Volume 1 8/5/10 H2SO4 6 2 28 

71794 Group II Volume 2 8/5/10 H2SO4 6 2 28 

71797 Group II Volume 1 8/5/10 H2SO4 5 2 20 

71797 Group II Volume 2 8/5/10 H2SO4 5 2 20 

71801 Group II Volume 1 8/5/10 H2SO4 5 2 26 

71801 Group II Volume 2 8/5/10 H2SO4 5 2 26 

71801 Group II Volume 1-QC 8/5/10 H2SO4 5 2 26 

71801 Group II Volume 2-QC 8/5/10 H2SO4 5 2 26 

71803 Group II Volume 1-QC 8/5/10 H2SO4 5 2 20 

71803 Group II Volume 2-QC 8/5/10 H2SO4 5 2 20 

(NH4)2SO4

Buffer 

71794 Hexavalent Chromium 8/5/10 6 8.1 100 

NH4OH 8.1 9.5 14 
3-29 

Table 3-7. Sample Preservation Summary, Allen

Sampling Point 

Number Analysis Date 

Chemical 

Added Initial pH Final pH 

Amount 

Added 

(drops) 

(NH4)2SO4

Buffer 

71797 Hexavalent Chromium 8/5/10 5 8.7 100 

NH4OH 8.7 9.5 8 

(NH4)2SO4

Buffer 

71801 Hexavalent Chromium 8/5/10 5 8.7 100 

NH4OH 8.7 9.5 10 

(NH4)2SO4

Buffer 

71803 Hexavalent Chromium 8/5/10 5 8.7 100 

NH4OH 8.7 9.5 8 

71797 Total Cyanide 8/5/10 NaOH 7 10 10 

71798 Total Cyanide 8/5/10 NaOH 7 10 10 

71798 Total Cyanide-QC 8/5/10 NaOH 7 10 10 

71802 Total Cyanide 8/5/10 NaOH 7 10 15 

71798 Group II Volume 1 8/6/10 H2SO4 5 2 24 

71798 Group II Volume 2 8/6/10 H2SO4 5 2 24 

71798 Group II Volume 1-QC 8/6/10 H2SO4 5 2 24 

71798 Group II Volume 2-QC 8/6/10 H2SO4 5 2 24 

71802 Group II Volume 2 8/6/10 H2SO4 6 2 28 

71802 Group II Volume 1 8/6/10 H2SO4 6 2 28 

(NH4)2SO4

Buffer 

71798 Hexavalent Chromium 8/6/10 5 8.5 100 

NH4OH 8.5 9.5 8 

(NH4)2SO4

Buffer 

71802 Hexavalent Chromium 8/6/10 6 8.5 100 

NH4OH 8.5 9.5 8 
3-30 

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

Unit ID Boiler Type 

Capacity 

(MW) 

Electricity Production 

(MW) 

(or Percent Capacity %)

SNCR 

(No, On, Off) 

Particulate Control System 

(HS/CS ESP, or BH) 

1 Tangential Fired 185 65.9% On CS ESP 

2 Tangential Fired 185 64.3% On CS ESP 

3 Tangential Fired 300 62.3% On CS ESP 

4 Tangential Fired 300 75.3% On CS ESP 

5 Tangential Fired 300 60.3% On CS ESP 

CS ESP – Cold-side electrostatic precipitator. 
3-31 

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

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 Re

Percen

1 Yes Spray Yes Limestone None Catawba River 963 Yes Spray Yes Limestone None Catawba River 97
3-32

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

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 CAPP 1,335 WV/VA 0.96 1,200a 

2 CAPP 1,378 WV/VA 0.96 1,200a 

3 CAPP 736 WV/VA 0.96 1,200a 

4 CAPP 1,212 WV/VA 0.96 1,200a 

1 

5 CAPP 1,097 WV/VA 0.97 1,200a 

1 CAPP 662 KY 0.98 1,289 

2 CAPP 500 KY 0.98 1,289 

3 CAPP 1,799 KY 0.98 1,317 

4 CAPP 2,386 KY 0.98 1,317 

2 

5 CAPP 1,221 KY 0.96 1,266 

1 CAPP 1,645 KY 1.0 1,327 

2 CAPP 1,750 KY 1.0 1,327 

3 CAPP 3,081 KY 0.99 1,353 

4 CAPP 2,805 KY 0.99 1,353 

3 

5 CAPP 3,221 KY 0.99 1,297 

1 CAPP 1,228 KY 0.98 1,069 

2 CAPP 1,137 KY 0.98 1,069 

3 CAPP 2,260 KY 0.96 1,092 

4 CAPP 2,445 KY 0.96 1,092 

4 

5 CAPP 2,102 KY 1.01 1,061 

a

 – Estimated value. 

CAPP – Central Appalachian Coal. 

WV/VA – West Virginia/Virginia region. 
3-33

 

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

Scrubber Slurry 

Blowdown Flow Rate 

Day of 

Sampling 

FGD 

System ID 

Associated 

Unit IDs 

Flow Rate 

(gpm) Duration 

Scrubber 

Slurry 

Percent 

Solids 

Time of 

Dewatering 

During 

Sampling Day 

Percent 

Filtrate 

Recycled 

Back to 

Scrubber 

1 1/2/5 UREa 13 hrs 13% dewatered 5 times 100% 

1 

3 3/4 UREa 13 hrs 12% dewatered 5 times 100% 

1 1/2/5 UREa 12 hrs 14% dewatered 5 times 100% 

2 

3 3/4 UREa 9 hrs 14% dewatered 4 times 100% 

1 1/2/5 UREa 9 hrs 15% dewatered 4 times 100% 

3 

3 3/4 UREa

 8 hrs 15% dewatered 5 times 100% 

1 1/2/5 UREa 7 hrs 15% dewatered 3 times 100% 

4 

3 3/4 UREa

 6 hrs 15% dewatered 3 times 100% 

a

 – Unable to reasonably estimate. 
3-34 

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

Scrubber Purge Chemical Usage 

Day of 

Sampling 

Flow Rate 

(gpm) 

Duration 

(hr) Lime 

35% Ferric 

Chloride 

Organosulfide: 

NA 

Polymer

Nalco 713

1 375 17 pH – 8.5 S.U. 1,200 lbs 40 ppm 19.6 gpd NA 6.5 ppm 3.3 gpd 2 371 16 pH – 8.5 S.U. 1,200 lbs 40 ppm 19.2 gpd NA 6.5 ppm 3.1 gpd 3 371 14 pH – 8.5 S.U. 1,200 lbs 40 ppm 19.3 gpd NA 6.5 ppm 3.1 gpd 4 366 10 pH – 8.5 S.U. 1,200 lbs 40 ppm 14.7 gpd NA 6.5 ppm 2.3 gpd 
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 influent to and effluent from the bioreactor 

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 heated bromine monochloride digestion (i.e., sealed bottles 

in oven at 50 degrees C for six hours) prior to analysis using a method-compliant bubbler 

system. 

For the total and dissolved mercury samples from SP-2 and SP-3, 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 Allen, including all 

qualified results and all results that were measured above the method detection limit, but below 

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

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

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

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

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

TestAmerica’s long term blank studies. If the typical background blank levels for a given 

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

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

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

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

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

calculated 4-day average result for each analyte for the sampling point. Tables 4-2 and 4-3 

present the analytical results for all classical and metal analytes for the four days of sampling at 

the influent to the bioreactor system (SP-2) and the effluent from the bioreactor system (SP-3), 

respectively. 

Tables 4-1 through 4-3 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 sample-specific 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 (influent to the bioreactor system), a duplicate sample was collected on 

Day 3 of the sampling episode. The Day 3 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). For Table 4-3 

(effluent from the bioreactor system), a duplicate sample was collected on Day 2 of the sampling 

episode. The Day 2 results presented in Table 4-3 represent the average of the original and the 

duplicate sample results. Table 5-2 presents the analytical results for the original and duplicate 

results and the calculated 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 4-4 presents the 4-day average results for all classical analytes for the influent to 

the FGD wastewater treatment system (SP-1), the influent to the bioreactor system (SP-2), and 

the effluent from the bioreactor system (SP-3). Table 4-5 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), the influent to the bioreactor system (SP-2), and the effluent from the 

bioreactor system (SP-3). The results presented in this report are not paired results, meaning that 
4-3 

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. 

Appendix Tables A-1 through A-14 present all the analytical results from the influent to 

the FGD wastewater treatment system (SP-1), the influent to the bioreactor system (SP-2), the 

effluent from the bioreactor system (SP-3), the duplicate of the influent to the bioreactor system 

(SP-4), and the duplicate of the effluent from the bioreactor system (SP-5) sample analyses, 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

value. * - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 

4-4 

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

Influent to FGD Wastewater Treatment System 

Analyte Units Method Day 1 Day 2 Day 3 D

ClassicalsAmmonia mg/L 350.1 1.40 7.30 14.0 9.0Nitrate Nitrite as N mg/L 353.2 14.0 17.0 20.0 22.Nitrogen, Total Kjeldahl mg/L 351.2 16.0 21.0 26.0 45.Biochemical Oxygen Demand mg/L 5210B 40.0 B 9.70 B 9.40 6.6Chemical Oxygen Demand mg/L 410.4 110 * NQ (200) * 130 140 Chloride mg/L 300.0 2,800 3,400 4,200 5,20Sulfate mg/L 300.0 1,400 1,300 1,300 1,30Cyanide, Total mg/L 4500 CN E 0.250 0.340 0.190 0.24Total Dissolved Solids mg/L 2540C 7,000 8,900 11,000 11,0Total Suspended Solids mg/L 2540D 1,800 3,900 2,000 2,20Phosphorus, Total mg/L 365.1 0.350 NQ (0.0500) NQ (0.0500) NQ (0.0Total MetalsAluminum ug/L 200.7 70,000 76,000 72,000 71,0Antimony ug/L 200.8 9.30 11.0 11.0 12.Arsenic ug/L 200.8 120 140 140 140 Barium ug/L 200.7 750 880 930 990 Beryllium ug/L 200.7 10.0 12.0 12.0 12.Boron ug/L 200.7 54,000 B 62,000 B 80,000 B 100,0Cadmium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) 4.0Calcium ug/L 200.7 1,900,000 2,300,000 2,400,000 2,700,Chromium ug/L 200.8 120 ^ 140 ^ 130 ^ 140 Cobalt ug/L 200.7 52.0 59.0 64.0 67.Copper ug/L 200.8 140 160 160 180 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

value. * - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 

4-5 

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

Influent to FGD Wastewater Treatment System 

Analyte Units Method Day 1 Day 2 Day 3 D

Iron ug/L 200.7 64,000 69,000 68,000 70,0Lead ug/L 200.8 85.0 99.0 100 120 Magnesium ug/L 200.7 440,000 470,000 520,000 590,0Manganese ug/L 200.7 3,300 3,700 4,100 4,60Mercury ng/L 1631E 50,300 49,600 44,600 52,1Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) 41.Nickel ug/L 200.8 160 190 190 210 Selenium ug/L 200.8 1,500 1,700 1,800 1,80Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2Sodium ug/L 200.7 29,000 32,000 34,000 38,0Thallium ug/L 200.8 2.50 3.20 3.30 3.1Tin ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (2Titanium ug/L 200.7 1,400 1,500 1,600 1,60Vanadium ug/L 200.8 130 150 160 180 Zinc ug/L 200.8 220 280 280 330 Dissolved MetalsAluminum ug/L 200.7 NQ (200) NQ (200) ND (200) ND (2Antimony ug/L 200.8 2.00 2.80 3.50 4.0Arsenic ug/L 200.8 8.70 10.0 10.0 7.1Barium ug/L 200.7 250 310 410 500 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2Boron ug/L 200.7 50,000 B 59,000 B 80,000 B 100,0Cadmium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4Calcium ug/L 200.7 1,500,000 1,700,000 2,000,000 2,500,
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

value. * - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 

4-6 

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

Influent to FGD Wastewater Treatment System 

Analyte Units Method Day 1 Day 2 Day 3 D

Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (1Cobalt ug/L 200.7 NQ (20.0) 20.0 22.0 25.Copper ug/L 200.8 12.0 12.0 11.0 8.9Iron ug/L 200.7 ND (200) ND (200) ND (200) ND (2Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2Magnesium ug/L 200.7 400,000 440,000 500,000 550,0Manganese ug/L 200.7 2,800 3,100 3,600 4,00Mercury ng/L 1631E 15.2 21.0 16.4 75.Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) NQ (4Nickel ug/L 200.8 71.0 77.0 80.0 93.Selenium ug/L 200.8 230 290 340 400 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2Sodium ug/L 200.7 28,000 31,000 36,000 40,0Thallium ug/L 200.8 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (2Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (2Vanadium ug/L 200.8 ND (10.0) NQ (10.0) NQ (10.0) NQ (1Zinc ug/L 200.8 30.0 43.0 32.0 43.
Note: The Day 3 results represent the average of the original sample and the field duplicate (SP-4). See Section 5.2.4 for the analytical results for the 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

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

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

4-7 

Table 4-2. Influent to the Bioreactor System, Allen 

Influent to the Bioreactor System (SP-

Analyte Units Method Day 1 Day 2 Day 3 D

ClassicalsAmmonia mg/L 350.1 5.80 6.80 8.85 11.0 Nitrate Nitrite as N mg/L 353.2 14.0 13.0 13.0 13.0 Nitrogen, Total Kjeldahl mg/L 351.2 7.70 8.60 10.5 3.20 Biochemical Oxygen Demand mg/L 5210B 7.40 B 5.20 3.65 3.90 Chemical Oxygen Demand mg/L 410.4 NQ (200) * 79.0 < 72.0 84.0 Chloride mg/L 300.0 3,100 3,200 3,300 3,600 Sulfate mg/L 300.0 1,400 1,400 1,400 1,400 Cyanide, Total mg/L 4500 CN E NQ (0.100) NQ (0.100) 0.130 0.110 Total Dissolved Solids mg/L 2540C 7,500 7,800 7,150 7,800 Total Suspended Solids mg/L 2540D NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.Phosphorus, Total mg/L 365.1 0.0610 NQ (0.0500) NQ (0.0500) NQ (0.0Total MetalsAluminum ug/L 200.7 ND (200) ND (200) ND (200) NQ (20Antimony ug/L 200.8 2.20 2.20 2.30 2.90 Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.Barium ug/L 200.7 220 200 220 250 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.Boron ug/L 200.7 55,000 B 54,000 B 59,000 64,00Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.Calcium ug/L 200.7 1,600,000 1,600,000 1,700,000 1,800,0
Note: The Day 3 results represent the average of the original sample and the field duplicate (SP-4). See Section 5.2.4 for the analytical results for the 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

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

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

4-8 

Table 4-2. Influent to the Bioreactor System, Allen 

Influent to the Bioreactor System (SP-

Analyte Units Method Day 1 Day 2 Day 3 D

Chromium ug/L 200.8 ND (8.00) ^ ND (8.00) ^ ND (8.00) ND (8.Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20Copper ug/L 200.8 10.0 9.30 11.0 12.0 Iron ug/L 200.7 NQ (200) ND (200) NQ (200) NQ (20Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) NQ (2.Magnesium ug/L 200.7 420,000 400,000 420,000 420,00Manganese ug/L 200.7 400 340 440 520 Mercury ng/L 1631E 711 1,320 991 1,120 Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) NQ (40Nickel ug/L 200.8 8.20 7.90 8.10 7.90 Selenium ug/L 200.8 110 94.0 88.5 87.0 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.Sodium ug/L 200.7 31,000 29,000 30,500 31,00Thallium ug/L 200.8 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.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 ND (10.0) ND (10.0) ND (10.0) ND (10Zinc ug/L 200.8 NQ (10.0) NQ (10.0) NQ (10.0) NQ (10Dissolved MetalsAluminum ug/L 200.7 ND (200) ND (200) ND (200) ND (20Antimony ug/L 200.8 2.40 2.30 2.25 2.60 
Note: The Day 3 results represent the average of the original sample and the field duplicate (SP-4). See Section 5.2.4 for the analytical results for the 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

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

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

4-9 

Table 4-2. Influent to the Bioreactor System, Allen 

Influent to the Bioreactor System (SP-

Analyte Units Method Day 1 Day 2 Day 3 D

Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.Barium ug/L 200.7 220 210 220 250 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.Boron ug/L 200.7 57,000 B 56,000 B 58,500 63,00Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.Calcium ug/L 200.7 1,700,000 1,700,000 1,700,000 1,900,0Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10Cobalt ug/L 200.7 ND (20.0) NQ (20.0) NQ (20.0) NQ (20Copper ug/L 200.8 10.0 8.90 11.0 12.0 Iron ug/L 200.7 ND (200) ND (200) ND (200) ND (20Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.Magnesium ug/L 200.7 410,000 370,000 405,000 400,00Manganese ug/L 200.7 370 320 410 470 Mercury ng/L 1631E 219 483 304 361 Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) NQ (40Nickel ug/L 200.8 9.20 7.40 8.30 8.20 Selenium ug/L 200.8 98.0 93.0 86.5 87.0 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.Sodium ug/L 200.7 31,000 31,000 32,000 31,00
Note: The Day 3 results represent the average of the original sample and the field duplicate (SP-4). See Section 5.2.4 for the analytical results for the 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

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

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

4-10 

Table 4-2. Influent to the Bioreactor System, Allen 

Influent to the Bioreactor System (SP-

Analyte Units Method Day 1 Day 2 Day 3 D

Thallium ug/L 200.8 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.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 ND (10.0) ND (10.0) NQ (10.0) ND (10Zinc ug/L 200.8 12.0 NQ (10.0) NQ (10.0) NQ (10
Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-5). See Section 5.2.4 for the analytical results for the 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

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

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

4-11 

Table 4-3. Effluent from the Bioreactor System, Allen 

Effluent from the Bioreactor System (S

Analyte Units Method Day 1 Day 2 Day 3 D

ClassicalsAmmonia mg/L 350.1 13.0 F 11.0 11.0 12Nitrate Nitrite as N mg/L 353.2 NQ (0.100) 0.130 ND (0.100) NQ (0Nitrogen, Total Kjeldahl mg/L 351.2 14.0 4 12.5 12.0 13Biochemical Oxygen Demand mg/L 5210B NQ (2.50) B NQ (2.50) ND (2.00) NQ (Chemical Oxygen Demand mg/L 410.4 NQ (200) * 67.0 NQ (100) F 36Chloride mg/L 300.0 3,400 3,250 3,200 3,2Sulfate mg/L 300.0 1,500 1,500 1,400 1,4Cyanide, Total mg/L 4500 CN E 0.110 < 0.0800 0.120 B 0.1Total Dissolved Solids mg/L 2540C 8,000 8,400 7,100 7,5Total Suspended Solids mg/L 2540D NQ (4.00) NQ (4.00) NQ (4.00) NQ (Phosphorus, Total mg/L 365.1 0.110 0.160 0.190 F 0.1Total MetalsAluminum ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (Arsenic ug/L 200.8 ND (4.00) NQ (4.00) NQ (4.00) NQ (Barium ug/L 200.7 210 215 210 22Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (Boron ug/L 200.7 65,000 B,4 66,000 63,000 B,4 61,Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (Calcium ug/L 200.7 1,700,000 4 1,650,000 1,600,000 4 1,600
Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-5). See Section 5.2.4 for the analytical results for the 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

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

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

4-12 

Table 4-3. Effluent from the Bioreactor System, Allen 

Effluent from the Bioreactor System (S

Analyte Units Method Day 1 Day 2 Day 3 D

Chromium ug/L 200.8 ND (8.00) ^ ND (8.00) ND (8.00) ^ ND (Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (Copper ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (Iron ug/L 200.7 NQ (200) NQ (200) 210 NQ (Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (Magnesium ug/L 200.7 450,000 4 435,000 410,000 4 420Manganese ug/L 200.7 470 435 400 44Mercury ng/L 1631E 12.6 30.0 27.7 17Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) ND (Nickel ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (Selenium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (Sodium ug/L 200.7 33,000 32,500 31,000 31,Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (Vanadium ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) ND (Zinc ug/L 200.8 NQ (10.0) NQ (10.0) 15.0 NQ (Dissolved MetalsAluminum ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (
Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-5). See Section 5.2.4 for the analytical results for the 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

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

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

4-13 

Table 4-3. Effluent from the Bioreactor System, Allen 

Effluent from the Bioreactor System (S

Analyte Units Method Day 1 Day 2 Day 3 D

Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (Barium ug/L 200.7 220 220 210 1Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (Boron ug/L 200.7 71,000 B,4 66,500 63,000 B,4 57,Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (Calcium ug/L 200.7 1,900,000 4 1,700,000 1,600,000 4 1,700Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (Chromium (VI) ug/L 218.6 ND (2.00) ND (2.00) ND (2.00) ND (Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (Copper ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (Iron ug/L 200.7 NQ (200) B NQ (200) NQ (200) B NQ (Lead ug/L 200.8 ND (2.00) NQ (2.00) ND (2.00) ND (Magnesium ug/L 200.7 440,000 4 425,000 400,000 4 190Manganese ug/L 200.7 440 405 380 19Mercury ng/L 1631E 10.4 33.4 28.3 15Molybdenum ug/L 200.7 NQ (40.0) ND (40.0) ND (40.0) NQ (Nickel ug/L 200.8 NQ (4.00) NQ (4.00) ND (4.00) NQ (Selenium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (Sodium ug/L 200.7 34,000 33,500 32,000 16,Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (
Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-5). See Section 5.2.4 for the analytical results for the 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but 

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

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

4-14 

Table 4-3. Effluent from the Bioreactor System, Allen 

Effluent from the Bioreactor System (S

Analyte Units Method Day 1 Day 2 Day 3 D

Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (Vanadium ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) ND (Zinc ug/L 200.8 NQ (10.0) NQ (10.0) NQ (10.0) NQ (
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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. 

4-15 

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

Analyte Units Method

Influent to FGD 

Wastewater Treatment 

System (SP-1)

4-Day Average

Influent to 

Bioreactor 

System (SP-2)

4-Day Average

ClassicalsAmmonia mg/L 350.1 7.93 8.11 Nitrate Nitrite as N mg/L 353.2 18.3 13.3 Nitrogen, Total Kjeldahl mg/L 351.2 27.0 7.50 Biochemical Oxygen Demand mg/L 5210B 16.4 5.04 Chemical Oxygen Demand mg/L 410.4 < 120 < 83.8 Chloride mg/L 300.0 3,900 3,300 Sulfate mg/L 300.0 1,330 1,400 Cyanide, Total mg/L 4500 CN E 0.255 < 0.0850 Total Dissolved Solids mg/L 2540C 9,480 7,560 Total Suspended Solids mg/L 2540D 2,480 NQ (4.00) Phosphorus, Total mg/L 365.1 < 0.106 < 0.0340 
< - 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. 

4-16 

Table 4-5. Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment Sys

Influent to FGD 

Wastewater Treatment 

System (SP-1)

4-Day Average

Influent to 

Bioreactor 

System (SP-2)

4-Day Average

Analyte Units Method Total Dissolved Total Dissolved Tot

MetalsAluminum ug/L 200.7 72,300 NQ (200) NQ (200) ND (200) NQ (Antimony ug/L 200.8 10.8 3.08 2.40 2.39 ND (2Arsenic ug/L 200.8 135 8.95 NQ (4.00) NQ (4.00) NQ (4Barium ug/L 200.7 888 368 223 225 21Beryllium ug/L 200.7 11.5 ND (2.00) ND (2.00) ND (2.00) ND (2Boron ug/L 200.7 74,000 72,300 58,000 58,600 63,8Cadmium ug/L 200.8 < 2.50 NQ (4.00) ND (4.00) ND (4.00) ND (4Calcium ug/L 200.7 2,330,000 1,930,000 1,680,000 1,750,000 1,640Chromium ug/L 200.8 133 ND (8.00) ND (8.00) ND (8.00) ND (8Chromium (VI) ug/L 218.6 NA ND (10.0) NA ND (10.0) NA Cobalt ug/L 200.7 60.5 < 19.3 ND (20.0) NQ (20.0) ND (2Copper ug/L 200.8 160 11.0 10.6 10.5 ND (4Iron ug/L 200.7 67,800 ND (200) NQ (200) ND (200) < 1Lead ug/L 200.8 101 ND (2.00) NQ (2.00) ND (2.00) ND (2Magnesium ug/L 200.7 505,000 473,000 415,000 396,000 429,Manganese ug/L 200.7 3,930 3,380 425 393 43Mercury ng/L 1631E 49,200 31.9 1,040 342 21Molybdenum ug/L 200.7 < 25.3 NQ (40.0) NQ (40.0) NQ (40.0) NQ (4Nickel ug/L 200.8 188 80.3 8.03 8.28 NQ (4Selenium ug/L 200.8 1,700 315 94.9 91.1 NQ (4Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) ND (2Sodium ug/L 200.7 33,300 33,800 30,400 31,300 31,9Thallium ug/L 200.8 3.03 NQ (2.00) NQ (2.00) NQ (2.00) ND (2Tin ug/L 200.7 NQ (200) ND (200) ND (200) ND (200) ND (Titanium ug/L 200.7 1,530 NQ (20.0) NQ (20.0) NQ (20.0) NQ (2
< - 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. 

4-17 

Table 4-5. Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment Sys

Influent to FGD 

Wastewater Treatment 

System (SP-1)

4-Day Average

Influent to 

Bioreactor 

System (SP-2)

4-Day Average

Analyte Units Method Total Dissolved Total Dissolved Tot

Vanadium ug/L 200.8 155 NQ (10.0) ND (10.0) ND (10.0) ND (1Zinc ug/L 200.8 278 37.0 NQ (10.0) < 6.75 < 7
5-1 

5. DATA QUALITY

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

A-15 presents all of the analytical results from the bottle blank analyses for the bottles used to 

collect the metals and mercury samples. 
5-2 

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-15 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-6, SP-7, and SP-8) 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 samples2

. 

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 Allen’s representative, using the same procedure discussed in the 

sample collection description (Section 3.1). 

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-6) 

were collected by pouring ASTM Type 1 water through the funnel and tubing and into a 10-liter 

composite container. After approximately 90 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 0.75 liters of blank water. The sample bottles were placed 

 

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

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

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

detected above the method detection limit (0.24 ng/L) in the filtration blanks performed for the first, second, third, 

fourth, or fifth day of samples.
5-3 

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

description (Section 3.1). 

The total mercury field blank sample for the influent to the bioreactor system (SP-7) and 

for the effluent from the bioreactor system (SP-8) were 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 

influent to the bioreactor system (SP-7) and the effluent from the bioreactor system (SP-8) 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 at each point 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 

Allen’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-16 through A-24 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 

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. 
5-4 

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 influent to the 

bioreactor system (SP-4) and the effluent from the bioreactor system (SP-5) during day 3 and 

day 2 of the sampling episode, respectively. The duplicate samples were analyzed for all 

analytes. Tables 5-1 and 5-2 present the analytical results and the RPD for SP-4 and SP-5, 

respectively. Results are rounded to three significant digits. Appendix Tables A-7 and A-13 

present all the analytical results for the influent to the bioreactor system (SP-2) Day 3 and the 

duplicate of the influent to the bioreactor system (SP-4) 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). Appendix Tables A-10 and A-14 present all the analytical 

results for the effluent from the bioreactor system (SP-3) Day 2 and the duplicate of the effluent 

from the bioreactor system (SP-5) sample analyses, including all qualified results and all results 

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

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

presented in Appendix A with a J flag designation. A “NQ” for the 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. 

5-5 

5-5 

Table 5-1. Field Duplicate Results – Influent to Bioreactor System, Allen 

Analyte Method Units

Original Influent 

to Bioreactor 

System, Day 3 

Concentration (SP-2)

Duplicate Influent 

to Bioreactor 

System 

Concentration (SP-4)

Av

R

ClassicalsAmmonia 350.1 mg/L 8.90 8.80 Nitrate Nitrite as N 353.2 mg/L 13.0 13.0 Nitrogen, Total Kjeldahl 351.2 mg/L 10.0 11.0 Biochemical Oxygen Demand 5210B mg/L 3.60 3.70 3Chemical Oxygen Demand 410.4 mg/L NQ (100) 94.0 < Chloride 300.0 mg/L 3,200 3,400 3Sulfate 300.0 mg/L 1,400 1,400 1Cyanide, Total 4500 CN E mg/L 0.120 B 0.140 B 0Total Dissolved Solids 2540C mg/L 7,200 7,100 7Total Suspended Solids 2540D mg/L NQ (4.00) NQ (4.00) NQ Phosphorus, Total 365.1 mg/L NQ (0.0500) NQ (0.0500) NQ Total MetalsAluminum 200.7 ug/L ND (200) ND (200) ND Antimony 200.8 ug/L 2.30 2.30 2Arsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ Barium 200.7 ug/L 220 220 Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND Boron 200.7 ug/L 59,000 B 59,000 B 59Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND Calcium 200.7 ug/L 1,700,000 1,700,000 1,7Chromium 200.8 ug/L ND (8.00) ^ ND (8.00) ^ ND 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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

presented in Appendix A with a J flag designation. A “NQ” for the 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. 

5-6 

5-6 

Table 5-1. Field Duplicate Results – Influent to Bioreactor System, Allen 

Analyte Method Units

Original Influent 

to Bioreactor 

System, Day 3 

Concentration (SP-2)

Duplicate Influent 

to Bioreactor 

System 

Concentration (SP-4)

Av

R

Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND Copper 200.8 ug/L 11.0 11.0 Iron 200.7 ug/L ND (200) NQ (200) NQ Lead 200.8 ug/L ND (2.00) ND (2.00) ND Magnesium 200.7 ug/L 430,000 410,000 42Manganese 200.7 ug/L 440 440 Mercury 1631E ng/L 962 1,020 Molybdenum 200.7 ug/L NQ (40.0) NQ (40.0) NQ Nickel 200.8 ug/L 8.80 7.40 Selenium 200.8 ug/L 91.0 86.0 Silver 200.8 ug/L ND (2.00) ND (2.00) ND Sodium 200.7 ug/L 30,000 31,000 30Thallium 200.8 ug/L NQ (2.00) NQ (2.00) NQ Tin 200.7 ug/L ND (200) ND (200) ND Titanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ Vanadium 200.8 ug/L ND (10.0) ND (10.0) ND Zinc 200.8 ug/L NQ (10.0) NQ (10.0) NQ Dissolved MetalsAluminum 200.7 ug/L ND (200) ND (200) ND Antimony 200.8 ug/L 2.10 2.40 2Arsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ Barium 200.7 ug/L 220 220 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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

presented in Appendix A with a J flag designation. A “NQ” for the 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. 

5-7 

5-7 

Table 5-1. Field Duplicate Results – Influent to Bioreactor System, Allen 

Analyte Method Units

Original Influent 

to Bioreactor 

System, Day 3 

Concentration (SP-2)

Duplicate Influent 

to Bioreactor 

System 

Concentration (SP-4)

Av

R

Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND Boron 200.7 ug/L 59,000 B 58,000 B 5Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND Calcium 200.7 ug/L 1,700,000 1,700,000 1,7Chromium 200.8 ug/L ND (8.00) ND (8.00) ND Chromium (VI) 218.6 ug/L ND (10.0) ND (10.0) ND Cobalt 200.7 ug/L NQ (20.0) NQ (20.0) NQ Copper 200.8 ug/L 11.0 11.0 Iron 200.7 ug/L ND (200) ND (200) ND Lead 200.8 ug/L ND (2.00) ND (2.00) ND Magnesium 200.7 ug/L 420,000 390,000 40Manganese 200.7 ug/L 420 400 Mercury 1631E ng/L 306 301 Molybdenum 200.7 ug/L NQ (40.0) NQ (40.0) NQ Nickel 200.8 ug/L 8.60 8.00 Selenium 200.8 ug/L 86.0 87.0 Silver 200.8 ug/L ND (2.00) ND (2.00) ND Sodium 200.7 ug/L 32,000 32,000 32Thallium 200.8 ug/L NQ (2.00) NQ (2.00) NQ Tin 200.7 ug/L ND (200) ND (200) ND Titanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ Vanadium 200.8 ug/L ND (10.0) NQ (10.0) NQ 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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

presented in Appendix A with a J flag designation. A “NQ” for the 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. 

5-8 

5-8 

Table 5-1. Field Duplicate Results – Influent to Bioreactor System, Allen 

Analyte Method Units

Original Influent 

to Bioreactor 

System, Day 3 

Concentration (SP-2)

Duplicate Influent 

to Bioreactor 

System 

Concentration (SP-4)

Av

R

Zinc 200.8 ug/L NQ (10.0) NQ (10.0) NQ 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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

presented in Appendix A with a J flag designation. A “NQ” for the 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. 

5-9 

Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, Allen 

Analyte Method Units

Original Effluent 

from Bioreactor 

System, Day 2

Concentration (SP-3)

Duplicate 

Effluent from 

Bioreactor 

System 

Concentration (SP-5)

A

R

ClassicalsAmmonia 350.1 mg/L 11.0 11.0 Nitrate Nitrite as N 353.2 mg/L 0.130 0.130 Nitrogen, Total Kjeldahl 351.2 mg/L 12.0 13.0 Biochemical Oxygen Demand 5210B mg/L NQ (2.50) NQ (2.50) NQ Chemical Oxygen Demand 410.4 mg/L 79.0 55.0 Chloride 300.0 mg/L 3,200 3,300 Sulfate 300.0 mg/L 1,500 1,500 Cyanide, Total 4500 CN E mg/L 0.110 NQ (0.100) < Total Dissolved Solids 2540C mg/L 8,100 8,700 Total Suspended Solids 2540D mg/L NQ (4.00) NQ (4.00) NQ Phosphorus, Total 365.1 mg/L 0.160 0.160 Total MetalsAluminum 200.7 ug/L NQ (200) NQ (200) NAntimony 200.8 ug/L ND (2.00) ND (2.00) ND Arsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ Barium 200.7 ug/L 220 210 Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND Boron 200.7 ug/L 66,000 B 66,000 B 6Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND Calcium 200.7 ug/L 1,700,000 1,600,000 1,
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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

presented in Appendix A with a J flag designation. A “NQ” for the 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. 

5-10 

Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, Allen 

Analyte Method Units

Original Effluent 

from Bioreactor 

System, Day 2

Concentration (SP-3)

Duplicate 

Effluent from 

Bioreactor 

System 

Concentration (SP-5)

A

R

Chromium 200.8 ug/L ND (8.00) ^ ND (8.00) ^ ND Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND Copper 200.8 ug/L ND (4.00) ND (4.00) ND Iron 200.7 ug/L NQ (200) NQ (200) NLead 200.8 ug/L ND (2.00) ND (2.00) ND Magnesium 200.7 ug/L 440,000 430,000 4Manganese 200.7 ug/L 440 430 Mercury 1631E ng/L 28.4 31.5 Molybdenum 200.7 ug/L NQ (40.0) NQ (40.0) NQ Nickel 200.8 ug/L ND (4.00) NQ (4.00) NQ Selenium 200.8 ug/L NQ (4.00) NQ (4.00) NQ Silver 200.8 ug/L ND (2.00) ND (2.00) ND Sodium 200.7 ug/L 33,000 32,000 3Thallium 200.8 ug/L ND (2.00) ND (2.00) ND Tin 200.7 ug/L ND (200) ND (200) NTitanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ Vanadium 200.8 ug/L ND (10.0) ND (10.0) ND Zinc 200.8 ug/L NQ (10.0) NQ (10.0) NQ Dissolved MetalsAluminum 200.7 ug/L NQ (200) NQ (200) NAntimony 200.8 ug/L ND (2.00) ND (2.00) ND 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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

presented in Appendix A with a J flag designation. A “NQ” for the 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. 

5-11 

Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, Allen 

Analyte Method Units

Original Effluent 

from Bioreactor 

System, Day 2

Concentration (SP-3)

Duplicate 

Effluent from 

Bioreactor 

System 

Concentration (SP-5)

A

R

Arsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ Barium 200.7 ug/L 220 220 Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND Boron 200.7 ug/L 66,000 B 67,000 B 6Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND Calcium 200.7 ug/L 1,700,000 1,700,000 1,7Chromium 200.8 ug/L ND (8.00) ND (8.00) ND Chromium (VI) 218.6 ug/L ND (2.00) ND (2.00) ND Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND Copper 200.8 ug/L ND (4.00) ND (4.00) ND Iron 200.7 ug/L NQ (200) B NQ (200) B NLead 200.8 ug/L NQ (2.00) ND (2.00) NQ Magnesium 200.7 ug/L 430,000 420,000 4Manganese 200.7 ug/L 410 400 Mercury 1631E ng/L 33.1 33.7 Molybdenum 200.7 ug/L ND (40.0) ND (40.0) ND Nickel 200.8 ug/L NQ (4.00) ND (4.00) NQ Selenium 200.8 ug/L NQ (4.00) NQ (4.00) NQ Silver 200.8 ug/L ND (2.00) ND (2.00) ND Sodium 200.7 ug/L 34,000 33,000 3Thallium 200.8 ug/L ND (2.00) ND (2.00) ND 
< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

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

presented in Appendix A with a J flag designation. A “NQ” for the 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. 

5-12 

Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, Allen 

Analyte Method Units

Original Effluent 

from Bioreactor 

System, Day 2

Concentration (SP-3)

Duplicate 

Effluent from 

Bioreactor 

System 

Concentration (SP-5)

A

R

Tin 200.7 ug/L ND (200) ND (200) NTitanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ Vanadium 200.8 ug/L ND (10.0) ND (10.0) ND Zinc 200.8 ug/L NQ (10.0) NQ (10.0) NQ 
6-1

6. REFERENCES

1. Eastern Research Group, Inc., 2010. Sampling Plan, Duke Energy Carolinas’ Allen 

Steam Station. July 1. DCN SE00501. 

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

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

 
Appendix A 

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

* - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-1 

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

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.11 1 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.38 5 Biochemical Oxygen Demand 5210B mg/L 1 2.8 24 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 200 51 600 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 28 100 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 
ND – Not detected (number in parentheses is the quantitation limit). 

* - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-2 

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

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 4,000 965 2,020 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 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 
ND – Not detected (number in parentheses is the quantitation limit). 

* - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-3 

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

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 10 2.41 5.05 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

* - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-4 

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

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.11 1 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.38 5 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 10 41 200 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 28 100 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 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 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 
ND – Not detected (number in parentheses is the quantitation limit). 

* - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-5 

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

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 4,000 965 2,020 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 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 
ND – Not detected (number in parentheses is the quantitation limit). 

* - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-6 

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

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-7 

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

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 350.1 mg/L 2 0.11 2 Nitrate Nitrite as N 353.2 mg/L 5 0.095 0.5 Nitrogen, Total Kjeldahl 351.2 mg/L 4 1.5 20 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 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 28 100 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-8 

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

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 4,000 965 2,020 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 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 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-9 

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

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-10 

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

Analyte Methods Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.055 1 Nitrate Nitrite as N 353.2 mg/L 5 0.095 0.5 Nitrogen, Total Kjeldahl 351.2 mg/L 4 1.5 20 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 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 28 100 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-11 

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

Analyte Methods Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 4,000 965 2,020 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 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 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-12 

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

Analyte Methods Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

* - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-13 

Table A-5. Influent to Bioreactor System, Day 1 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.11 1 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 10 41 200 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 
ND – Not detected (number in parentheses is the quantitation limit). 

* - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-14 

Table A-5. Influent to Bioreactor System, Day 1 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 500 121 252 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 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 
ND – Not detected (number in parentheses is the quantitation limit). 

* - LCS or LCSD is outside the laboratory control limits. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-15 

Table A-5. Influent to Bioreactor System, Day 1 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-16 

Table A-6. Influent to Bioreactor System, Day 2 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.055 1 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-17 

Table A-6. Influent to Bioreactor System, Day 2 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 100 24.1 50.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 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 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-18 

Table A-6. Influent to Bioreactor System, Day 2 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 100 24.1 50.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-19 

Table A-7. Influent to Bioreactor System, Day 3 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.055 1 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 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 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-20 

Table A-7. Influent to Bioreactor System, Day 3 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 100 24.1 50.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 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 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-21 

Table A-7. Influent to Bioreactor System, Day 3 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 500 121 252 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

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

B – Analyte was found in the blank and sample. E – MS and/or MSD exceeded the calibration range. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-22 

Table A-8. Influent to Bioreactor System, Day 4 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 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 1 0.077 1 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 
ND – Not detected (number in parentheses is the quantitation limit). 

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

B – Analyte was found in the blank and sample. E – MS and/or MSD exceeded the calibration range. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-23 

Table A-8. Influent to Bioreactor System, Day 4 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 500 121 252 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 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 
ND – Not detected (number in parentheses is the quantitation limit). 

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

B – Analyte was found in the blank and sample. E – MS and/or MSD exceeded the calibration range. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-24 

Table A-8. Influent to Bioreactor System, Day 4 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 500 121 252 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

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

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-25 

Table A-9. Effluent from Bioreactor System, Day 1 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 350.1 mg/L 2 0.22 2 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 4 0.31 4 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 10 41 200 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 
ND – Not detected (number in parentheses is the quantitation limit). 

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

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-26 

Table A-9. Effluent from Bioreactor System, Day 1 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
ND – Not detected (number in parentheses is the quantitation limit). 

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

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-27 

Table A-9. Effluent from Bioreactor System, Day 1 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-28 

Table A-10. Effluent from Bioreactor System, Day 2 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 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 4 0.31 4 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-29 

Table A-10. Effluent from Bioreactor System, Day 2 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-30 

Table A-10. Effluent from Bioreactor System, Day 2 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

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

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-31 

Table A-11. Effluent from Bioreactor System, Day 3 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 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 4 0.31 4 Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 
ND – Not detected (number in parentheses is the quantitation limit). 

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

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-32 

Table A-11. Effluent from Bioreactor System, Day 3 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
ND – Not detected (number in parentheses is the quantitation limit). 

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

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-33 

Table A-11. Effluent from Bioreactor System, Day 3 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 10 2.41 5.05 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-34 

Table A-12. Effluent from Bioreactor System, Day 4 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 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 2 0.15 2 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-35 

Table A-12. Effluent from Bioreactor System, Day 4 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 1 4.7 100 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 1 1.2 10 Beryllium 200.7 ug/L 1 0.36 1 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 1 0.39 2 Cobalt 200.7 ug/L 1 0.57 10 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 1 16 100 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 1 11 200 Manganese 200.7 ug/L 1 0.25 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-36 

Table A-12. Effluent from Bioreactor System, Day 4 Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 1 0.81 20 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 1 92 5,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 1 2.4 100 Titanium 200.7 ug/L 1 0.82 10 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-37 

Table A-13. Duplicate of Influent to Bioreactor System Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Classicals Ammonia 350.1 mg/L 1 0.055 1 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-38 

Table A-13. Duplicate of Influent to Bioreactor System Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 100 24.1 50.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 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 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-39 

Table A-13. Duplicate of Influent to Bioreactor System Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 500 121 252 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-40 

Table A-14. Duplicate of Effluent from Bioreactor System Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

ClassicalsAmmonia 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 4 0.31 4 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 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 19 40 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 10 33 1,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 10 340 2,000 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 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-41 

Table A-14. Duplicate of Effluent from Bioreactor System Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 
ND – Not detected (number in parentheses is the quantitation limit). 

^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

A-42 

Table A-14. Duplicate of Effluent from Bioreactor System Analytical Results, Allen 

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
a

 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-43 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Allen

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-44 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Allen

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-45 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Allen

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-46 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Allen

Analyte Method Process Units Concentration 

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

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

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

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

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

Pump-Off Tubing Set – Equipment Blank (Three feet of Teflon® tubing, 10 feet of #73 silicone tubing, Ysplitter, and two pieces of 5 feet of #24 silicone tubing for total and dissolved sample collection for metals)

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

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

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

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

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

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

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

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

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

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

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

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

Lead EPA 1638 Total Recoverable ug/L ND (0.040) 

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5) 

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

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050) 

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

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

Selenium EPA 1638 Total Recoverable ug/L ND (0.60) 

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

Sodium EPA 1638 Total Recoverable ug/L ND (20) 

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

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

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

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

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

T-Splitter Tubing Set – Equipment Blank (Ten feet of #73 silicone tubing, T-splitter, six feet of #73 silicone 

tubing, and 15 feet of #73 silicone tubing for total and dissolved sample collection for metal composites)

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

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

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

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

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

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

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

A-47 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Allen

Analyte Method Process Units Concentration 

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

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

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

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

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

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

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

Lead EPA 1638 Total Recoverable ug/L ND (0.040) 

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5) 

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

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050) 

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

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

Selenium EPA 1638 Total Recoverable ug/L ND (0.60) 

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

Sodium EPA 1638 Total Recoverable ug/L ND (20) 

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

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

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

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

Zinc EPA 1638 Total Recoverable ug/L ND (0.20) 
A-48 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-16. Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical Res

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 NManganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 NThallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
A-49 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-16. Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical Res

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Dissolved MetalsAluminum 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 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 NChromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 Magnesium 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 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 NThallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
A-50 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 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-17. Influent to Bioreactor System Field Blank, Day 1 Analytical Results, Alle

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Total MetalsAluminum 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 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 NChromium 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 NLead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 NManganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 NThallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 N
A-51 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-17. Influent to Bioreactor System Field Blank, Day 1 Analytical Results, Alle

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 NCadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 NChromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 Magnesium 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 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 NThallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
A-52 

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. Influent to Bioreactor System Field Blank, Day 2 Analytical Results, Alle

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
A-53 

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. Influent to Bioreactor System Field Blank, Day 3 Analytical Results, Alle

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
A-54 

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-20. Influent to Bioreactor System Field Blank, Day 4 Analytical Results, Alle

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
A-55 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-21. Effluent from Bioreactor System Field Blank, Day 1 Analytical Results, All

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Total MetalsAluminum 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 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 NChromium 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 NLead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 NManganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 NThallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 N
A-56 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-21. Effluent from Bioreactor System Field Blank, Day 1 Analytical Results, All

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 NCadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 NChromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 Magnesium 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 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 NThallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 
A-57 

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-22. Effluent from Bioreactor System Field Blank, Day 2 Analytical Results, All

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL Concentra

Total MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5
A-58 

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-23. Effluent from Bioreactor System Field Blank, Day 3 Analytical Results, All

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
A-59 

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-24. Effluent from Bioreactor System Field Blank, Day 4 Analytical Results, All

Analyte Method Units

Dilution

Factor

SampleSpecific MDL Sample Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
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: Randy Mercurio, ERG

Donna Tedder, ERG

Date: 9/1/2011

Subject: FGS Data Review Narrative for Total and Dissolved Mercury – Episode 6561

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 37 samples (excluding laboratory filter blanks) FGS extracted 

and analyzed for total and dissolved mercury. 

Table 1. EPA Episode 6561 Total & Dissolved Mercury – Sample Identification

EPA 

Sample #

Lab Sample 

ID #

Sample 

Matrix Sample Description

Sampling 

Date

71791 1008018-01 Aqueous FGD Influent Day 1 8/2/2010

71791 1008018-02 Aqueous Dissolved FGD Influent, Day 1 8/2/2010

71792 1008031-13 Aqueous FGD Influent, Day 2 8/3/2010

71792 1008031-14 Aqueous Dissolved FGD Influent, Day 2 8/3/2010

71793 1008045-01 Aqueous FGD Influent, Day 3 8/4/2010

71793 1008045-02 Aqueous Dissolved FGD Influent, Day 3 8/4/2010

71794 1008062-01 Aqueous FGD Influent, Day 4 8/5/2010

71794 1008062-02 Aqueous Dissolved FGD Influent, Day 4 8/5/2010

71795 1008031-15 Aqueous FGD Bioreactor Influent, Day 1 8/3/2010

71795 1008031-16 Aqueous Dissolved FGD Bioreactor Influent, Day 2 8/3/2010

71796 1008045-03 Aqueous FGD Bioreactor Influent, Day 2 8/4/2010

71796 1008045-04 Aqueous Dissolved FGD Bioreactor Influent, Day 2 8/4/2010

71797 1008062-03 Aqueous FGD Bioreactor Influent, Day 3 8/5/2010

71797 1008062-04 Aqueous Dissolved FGD Bioreactor Influent, Day 3 8/5/2010

71798 1008072-03 Aqueous FGD Bioreactor Influent , Day 4 8/6/2010

71798 1008072-04 Aqueous Dissolved FGD Bioreactor Influent , Day 4 8/6/2010

71799 1008031-17 Aqueous FGD Bioreactor Effluent, Day 1 8/3/2010

71799 1008031-18 Aqueous Dissolved FGD Bioreactor Effluent, Day 1 8/3/2010

71800 1008045-05 Aqueous FGD Bioreactor Effluent, Day 2 8/4/2010
2

Table 1. EPA Episode 6561 Total & Dissolved Mercury – Sample Identification

EPA 

Sample #

Lab Sample 

ID #

Sample 

Matrix Sample Description

Sampling 

Date

71800 1008045-06 Aqueous Dissolved FGD Bioreactor Effluent, Day 2 8/4/2010

71801 1008062-05 Aqueous FGD Bioreactor Effluent, Day 3 8/5/2010

71801 1008062-06 Aqueous Dissolved FGD Bioreactor Effluent, Day 3 8/5/2010

71802 1008072-05 Aqueous FGD Bioreactor Effluent , Day 4 8/6/2010

71802 1008072-06 Aqueous Dissolved FGD Bioreactor Effluent , Day 4 8/6/2010

71803 1008062-07 Aqueous FGD Bioreactor Influent Duplicate 8/5/2010

71803 1008062-08 Aqueous Dissolved FGD Bioreactor Influent Duplicate 8/5/2010

71804 1008045-07 Aqueous FGD Bioreactor Effluent Duplicate, Day 2 8/4/2010

71804 1008045-08 Aqueous Dissolved FGD Bioreactor Effluent Duplicate, 

Day 2

8/4/2010

71805 1008018-03 Aqueous FGD Influent Field Blank, Day 1 8/2/2010

71806 1008018-06 Aqueous FGD Bioreactor Influent Field Blank, Day 1 8/2/2010

71807 1008031-19 Aqueous FGD Bioreactor Influent Field Blank, Day 2 8/3/2010

71808 1008045-15 Aqueous FGD Bioreactor Influent Field Blank, Day 3 8/4/2010

71809 1008062-13 Aqueous FGD Bioreactor Influent Field Blank, Day 4 8/5/2010

71810 1008018-09 Aqueous FGD Bioreactor Effluent Field Blank, Day 1 8/2/2010

71811 1008031-12 Aqueous FGD Bioreactor Effluent Field Blank, Day 2 8/3/2010

71812 1008045-16 Aqueous FGD Bioreactor Effluent Field Blank, Day 3 8/4/2010

71813 1008062-14 Aqueous FGD Bioreactor Effluent Field Blank, Day 4 8/5/2010

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.
3

BLANKS

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

calibration blanks (CCBs) met method-suggested criteria. Preparation Blanks F009001-

BLK2 and F009002-BLK4 had mercury levels of 0.10 and 0.27 ng/L, respectively, which 

are greater than the MDL, but less than the reporting limit. These blank results were 

appropriately fagged with a “J” qualifier.

DUPLICATES

Field duplicates, Sample 71804, were collected on Sample 71800. The 71800/71804

total mercury relative percent difference (RPD) was 10.4% and the dissolved mercury 

RPD was 1.8%. The method-suggested RPD criterion between field duplicates is 20%.

Laboratory duplicates were performed in this episode on samples 71795, 71796 and

71801. All RPDs were less than 20% (the method-suggested RPD criterion between field 

duplicates; the method does not require the analysis of laboratory duplicates).

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

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

71796 and 71801 for the total mercury analyses. MS and MSDs were performed on 

samples 71791, 71795, 71801 & 71798 for the dissolved mercury analyses. All 

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 

 Donna Tedder, ERG 

Date: 9/1/2011

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

Episode 6561

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

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

for Sample Episode 6561. 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 6561 Total & Dissolved Metals – Sample Identification 

EPA 

Sample # EPA Sample Description 

Lab Sample 

ID # 

Sample 

Matrix 

Sampling 

Date 

Receipt 

Date 

71791 FGD Influent, Day 1 280-5932-1 Aqueous 8/2/2010 8/3/2010

71792 FGD Influent, Day 2 280-5964-1 Aqueous 8/3/2010 8/4/2010

71793 FGD Influent, Day 3 280-6008-1 Aqueous 8/4/2010 8/5/2010

71794 FGD Influent, Day 4 280-6067-4 Aqueous 8/5/2010 8/6/2010

71795 FGD Bioreactor Influent, Day 1 280-5964-2 Aqueous 8/3/2010 8/4/2010

71796 FGD Bioreactor Influent, Day 2 280-6008-2 Aqueous 8/4/2010 8/5/2010

71797 FGD Bioreactor Influent, Day 3 280-6067-1 Aqueous 8/5/2010 8/6/2010

71798 FGD Bioreactor Influent, Day 4 280-6117-1 Aqueous 8/6/2010 8/7/2010

71799 FGD Bioreactor Effluent, Day 1 280-5964-3 Aqueous 8/3/2010 8/4/2010

71800 FGD Bioreactor Effluent, Day 2 280-6008-3 Aqueous 8/4/2010 8/5/2010

71801 FGD Bioreactor Effluent, Day 3 280-6067-2 Aqueous 8/5/2010 8/6/2010

71802 FGD Bioreactor Effluent, Day 4 280-6117-2 Aqueous 8/6/2010 8/7/2010

71803 FGD Bioreactor Influent -

Duplicate, Day 3 

280-6067-3 Aqueous 8/5/2010 8/6/2010

71804 FGD Bioreactor Effluent -

Duplicate, Day 2 

280-6008-4 Aqueous 8/4/2010 8/5/2010

71805 FGD Influent Field Blank, Day 

1 

280-5932-2 Aqueous 8/2/2010 8/3/2010

71806 FGD Bioreactor Influent Field 

Blank, Day 1 

280-5964-4 Aqueous 8/3/2010 8/4/2010
2

Table 1. EPA Episode 6561 Total & Dissolved Metals – Sample Identification 

EPA 

Sample # EPA Sample Description 

Lab Sample 

ID # 

Sample 

Matrix 

Sampling 

Date 

Receipt 

Date 

71810 FGD Bioreactor Effluent Field 

Blank, Day 1 

280-5964-5 Aqueous 8/3/2010 8/4/2010

SUMMARY 

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

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

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

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

There were no findings from the data review that required additional qualifiers (excluding 

those identified by the laboratory) in this dataset. 

INTERNAL STANDARDIZATION 

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

INITIAL CALIBRATION 

TestAmerica 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. 

BLANKS 

All the method blanks were less than the reporting limit (RL). No additional qualifiers 

were required for method blanks. 

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

(CCB)) were less than the RL; however, antimony was above the instrument detection 

limit (IDL) in one ICB and was flagged with the “J” qualifier. 

REPORTING LIMIT VERIFICATION STANDARD (CRI) 

All CRI samples passed TestAmerica’s 50–150% recovery limits. 
3

LABORATORY CONTROL SAMPLES (LCS) 

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

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. 

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

Chromium in analytical batch 280-27123. The lab has confirmed with the vendor that 

Chromium is a trace impurity in the ICSA solution. Therefore, corrective action was 

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

SERIAL DILUTION 

The serial dilution performed for the total and dissolved sample 71799 FGD Bioreactor 

Effluent, Day 1 (280-5964-3) met TestAmerica’s criteria of ±10% difference. 

FIELD DUPLICATES 

The relative percent difference (RPD) of the field duplicates 71800/71804 and 

71797/71803 were less than 20% for all values greater than the reporting limit. None of 

the total or dissolved analytes in parent sample 71800 and field duplicate sample 71804 

were above the RL so the RPD could not be accurately determined. The RPD for all total 

and dissolved analytes above the reporting limit in parent sample 71797 and field 

duplicate sample 71803 were less than TestAmerica’s ±20% requirement. 

MATRIX SPIKE AND MATIX SPIKE DUPLICATES 

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

71799, 71801 and 71798. Many spike recoveries were outside the method control limits 

of 70–130% when sample concentrations exceeded the spike concentration by a factor of 

four or more, which have been flagged with a “4” qualifier indicating concentrations in 

the parent samples were greater than four times the spike amounts. Otherwise, all 

MS/MSD spike recoveries were within the method control limits of 70-130%. In 

addition, the RPD for all MS/MSD passed the method-specified criteria of 20 percent. 
4

POST DIGESITON SPIKES 

The post digestion spike performed on sample 71799 FGD Bioreactor Effluent, Day 1 

(280-5964-3) for total and dissolved analytes passed TestAmerica’s 85–115% control 

limits. 

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

Donna Tedder, ERG

Date: 9/1/2011

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

Episode 6561

TestAmerica 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 6561. 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 6561 Total & Dissolved Metals – Sample Identification

EPA 

Sample # EPA Sample Description

Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71791 FGD Influent, Day 1 280-5932-1 Aqueous 8/2/2010 8/3/2010

71792 FGD Influent, Day 2 280-5964-1 Aqueous 8/3/2010 8/4/2010

71793 FGD Influent, Day 3 280-6008-1 Aqueous 8/4/2010 8/5/2010

71794 FGD Influent, Day 4 280-6067-4 Aqueous 8/5/2010 8/6/2010

71795 FGD Bioreactor Influent, Day 1 280-5964-2 Aqueous 8/3/2010 8/4/2010

71796 FGD Bioreactor Influent, Day 2 280-6008-2 Aqueous 8/4/2010 8/5/2010

71797 FGD Bioreactor Influent, Day 3 280-6067-1 Aqueous 8/5/2010 8/6/2010

71798 FGD Bioreactor Influent, Day 4 280-6117-1 Aqueous 8/6/2010 8/7/2010

71799 FGD Bioreactor Effluent, Day 1 280-5964-3 Aqueous 8/3/2010 8/4/2010

71800 FGD Bioreactor Effluent, Day 2 280-6008-3 Aqueous 8/4/2010 8/5/2010

71801 FGD Bioreactor Effluent, Day 3 280-6067-2 Aqueous 8/5/2010 8/6/2010

71802 FGD Bioreactor Effluent, Day 4 280-6117-2 Aqueous 8/6/2010 8/7/2010

71803 FGD Bioreactor Influent -

Duplicate, Day 3

280-6067-3 Aqueous 8/5/2010 8/6/2010

71804 FGD Bioreactor Effluent -

Duplicate, Day 2

280-6008-4 Aqueous 8/4/2010 8/5/2010

71805 FGD Influent Field Blank, Day 1 280-5932-2 Aqueous 8/2/2010 8/3/2010
2

Table 1. EPA Episode 6561 Total & Dissolved Metals – Sample Identification

EPA 

Sample # EPA Sample Description

Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71806 FGD Bioreactor Influent Field 

Blank, Day 1

280-5964-4 Aqueous 8/3/2010 8/4/2010

71810 FGD Bioreactor Effluent Field 

Blank, Day 1

280-5964-5 Aqueous 8/3/2010 8/4/2010

SUMMARY

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

TestAmerica’s SOP for ICP Analysis for Trace Metals by Method 200.7.

There were no findings from the data review that required additional qualifiers (excluding 

those identified by the laboratory) in this dataset. 

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 (RL); however, some elements

had levels greater than the method detection limit (MDL) and were flagged with the “J” 

qualifier.

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

(CCB)) were less than the RL; however, some elements had levels greater than 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 

recoveries met the method-specified criteria.

SERIAL DILUTION

Serial dilutions were performed for each batch of total and dissolved samples. All serial 

dilution percent differences were less than 10% as required by TestAmerica’s SOP.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s control limits of 50–150%.

FIELD DUPLICATES

The relative percent difference (RPD) of the field duplicates 71800/71804 and 

71797/71803 were less than 20% for all total and dissolved values greater than the RL.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on the total and 

dissolved samples of 71798, 71799 and 71801. Many spike recoveries were outside the 

method control limits of 70-130% when sample concentrations exceeded the spike 

concentrations by a factor of four or more, which have been flagged with a “4” qualifier 

indicating concentrations in the parent samples were greater than four times the spike 

amounts. Otherwise, all MS/MSD spike recoveries were within the 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% requirement.

POST DIGESTION SPIKE

The post digestion spike performed on sample 71799 FGD Bioreactor Effluent, Day1 

passed TestAmerica’s control limits of 85-115% recovery for all total and dissolved 

analytes except total sodium and dissolved manganese. The post digestion spike 

performed on sample 71798 FGD Bioreactor Influent, Day 4 passed TestAmerica’s 

control limits of 85-115% recovery for all total and dissolved analytes except total 

sodium. 
4

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

Date: 9/1/2011

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

6561

Frontier Global Sciences (FGS) generated analytical data for dissolved hexavalent 

chromium for Sample Episode 6561. 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 6561 Dissolved Hexavalent Chromium – Sample Identification

EPA 

Sample 

#

Sample 

Matrix Sample Description

Sampling 

Date Analysis Date

71791 Aqueous FGD Influent Day 1 8/2/10 8/9/10

71792 Aqueous FGD Influent Day 2 8/3/10 8/9/10

71793 Aqueous FGD Influent Day 3 8/4/10 8/9/10

71794 Aqueous FGD Influent Day 4 8/5/10 8/30/10

71795 Aqueous FGD Bioreactor Influent Day 1 8/3/10 8/9/10

71796 Aqueous FGD Bioreactor Influent Day 2 8/4/10 8/9/10

71797 Aqueous FGD Bioreactor Influent Day 3 8/5/10 8/30/10

71798 Aqueous FGD Bioreactor Influent Day 4 8/6/10 8/30/10

71799 Aqueous FGD Bioreactor Effluent Day 1 8/3/10 8/9/10

71800 Aqueous FGD Bioreactor Effluent Day 2 8/4/10 8/30/10

71801 Aqueous FGD Bioreactor Effluent Day 3 8/5/10 8/30/10

71802 Aqueous FGD Bioreactor Effluent Day 4 8/6/10 8/30/10

71803 Aqueous FGD Bioreactor Influent Dup Day 3 8/5/10 8/30/10

71804 Aqueous FGD Bioreactor Effluent Dup Day 2 8/4/10 8/30/10

71805 Aqueous FGD Influent Field Blank Day 1 8/2/10 8/9/10

71806 Aqueous FGD Bioreactor Influent Field Blank Day 1 8/3/10 8/9/10

71810 Aqueous FGD Bioreactor Effluent Field Blank Day 1 8/3/10 8/9/10
2

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.

Several samples (71791, 71792, 71793, 71794, 71795, 71796, 71797, 71798, and 71803)

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 analyzed and passed ± 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 95 to 109%.

BLANK

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

calibration blanks (CCBs) met method-specified requirements. 
3

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 102% and 102%. A second set of LFB/LFBD, for the later analysis date,

had recoveries of 100% and 99.3%. The method suggested that a second source quality 

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). 

Two field duplicates were collected and analyzed. Sample 71803 was a duplicate of 

sample 71797. These samples were nondetects (NDs), indicating the analyte was not 

detected at or above the method detection limit. Sample 71804 was a duplicate of sample 

71800. These samples were also NDs.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The MS and matrix spike duplicate (MSD) were performed using a secondary source 

spike on samples 71791 and 71801. All MS/MSD recoveries were within 75%-125%, 

with RPDs of 1.47% and 4.44%, 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 6561

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry 

analyses for Sample Episode 6561. All samples were tested for the following analytes: 

• Ammonia by EPA method 350.1, 

• Biochemical Oxygen Demand – 5 day (BOD5) by SM 5210B, 

• Chloride and Sulfate by EPA method 300.0, 

• Chemical Oxygen Demand (COD) by EPA method 410.4, 

• Cyanide by SM 4500 CN- E, 

• Nitrate/Nitrite by EPA method 353.2,

• Phosphorus by EPA method 365.1, 

• Total Dissolved Solids (TDS) by SM 2540C, 

• Total Kjeldahl Nitrogen (TKN) by EPA method 351.2, and 

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

Table 1 summarizes the 14 samples that TestAmerica analyzed for the above analytes.

Table 1. EPA Episode 6561 Classical Analytes – Sample Identification

EPA

Sample #

Sample

Matrix Sample Description

Sampling

Date

71791 Water FGD Influent, Day 1 8/2/10

71792 Water FGD Influent, Day 2 8/3/10

71793 Water FGD Influent, Day 3 8/4/10

71794 Water FGD Influent, Day 4 8/5/10

71795 Water FGD Bioreactor Influent, Day 1 8/3/10

71796 Water FGD Bioreactor Influent, Day 2 8/4/10

71797 Water FGD Bioreactor Influent, Day 3 8/5/10

71798 Water FGD Bioreactor Influent, Day 4 8/6/10

71799 Water FGD Bioreactor Effluent, Day 1 8/3/10

71800 Water FGD Bioreactor Effluent, Day 2 8/4/10

71801 Water FGD Bioreactor Effluent, Day 3 8/5/10
2

Table 1. EPA Episode 6561 Classical Analytes – Sample Identification

EPA

Sample #

Sample

Matrix Sample Description

Sampling

Date

71802 Water FGD Bioreactor Effluent, Day 4 8/6/10

71803 Water FGD Bioreactor Influent - Duplicate 8/5/10

71804 Water FGD Bioreactor Effluent - Duplicate 8/4/10

SUMMARY

All samples were analyzed within the holding time specified in 40 CFR 136 Table II. All 

samples were preserved appropriately.

Two field duplicate samples were collected and analyzed for each analyte. The relative 

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

otherwise noted below. 

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

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

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

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

calibration verification samples met the criteria specified in the method.

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

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

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

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

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

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

below.

If required by the method, a matrix spike (MS) sample was analyzed. Two MS samples 

were run on samples 71798 (FGD bioreactor influent) and 71801 (FGD bioreactor 

effluent) for each analyte to check for matrix interferences in these matrices. 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

The percent recoveries for the MS and MSD analysis for sample 71799 (FGD bioreactor 

effluent) were 112% and 116%, respectively, which are above the laboratory and method 

control limits of 90-110%. Sample 71799 was qualified as a maximum value. The LFB 

associated with this sample met the method criteria.
3

BOD5

Even though TestAmerica ran five dilutions on sample 71801, no dilutions had a 

dissolved oxygen (DO) depletion greater than 2.0 mg/L. Therefore, BOD5 was reported 

as not detected for this sample.

All glucose-glutamic acid standards and laboratory duplicates were analyzed 

appropriately and met the criteria specified in SM 5210B. BOD was not detected above 

the RL in any method blank; however, for batch 25403, the results for the three 

water/unseeded blanks were 0.24 mg/L, 0.21 mg/L, and 0.21 mg/L. All of these results 

were greater than the method control criteria of 0.20 mg/L. Because of these detections in 

the water/unseeded blanks, samples 71791, 71792, 71795, and 71799 were qualified with 

a “B” meaning the analyte was found in the sample and the blank. 

Chloride and Sulfate

The MS/MSD results of samples 71798 and 71801 for sulfate were above the calibration 

curve. TestAmerica did not reanalyze the samples with a higher dilution factor because 

the percent recoveries were within EPA Method 300.0 control limits. If reported, these 

MS/MSD results will be qualified as estimated values.

COD

The percent recovery of the LFB associated with batch 25742 was 88.9%, which was less 

than the method control criteria of 90-110%, but did meet the historical laboratory criteria 

of 80-115%. The LFBD percent recovery (96.7%) did meet the method criteria. Because 

the laboratory originally had analyzed the percent recovery against the historical criteria, 

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

not reanalyzed. The laboratory qualified these samples with a “*” indicating that the 

LFB or LFBD was not within the control limits. Samples 71792, 71795, and 71799 were 

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

value because it was less than the RL, so no further action was taken.

Samples 71795 and 71801 were diluted by 10 fold because of matrix interferences 

determined by the chloride prescreening. The diluted results were below the lowest

calibration standard; however, these samples were already qualified by the laboratory 

with a “J” meaning the sample result was an estimated value because it was less than the 

RL, so no further action was taken.

The RPD between sample 71797 and its field duplicate 71803 was 26.5% and the RPD 

between sample 71800 and its field duplicate 71804 was 35.8%. Even though these RPDs 

were greater than 20%, the samples were not qualified because there are no specific 

control limits for field duplicates specified in EPA method 410.4.
4

The percent recoveries for the MS/MSD analysis for sample 71798 (FGD bioreactor 

influent) and for the MS analysis for sample 71801 (FGD bioreactor effluent) were below 

the control limits of 90-110% required by EPA Method 410.4. The percent recoveries for 

the MS and MSD analyses for sample 71798 were 75% and 77%, respectively, and the 

percent recoveries for the MS and MSD analyses for sample 71801 were 89% and 96%,

respectively. The LFB associated with these samples met the method criteria. Sample 

71798 was qualified as a minimum value. Results for samples with a similar matrix (i.e., 

FGD bioreactor influent) could also be biased low. Sample 71801 was already qualified 

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

was less than the RL; therefore, this sample was not additionally qualified as a minimum 

value.

Cyanide 

Cyanide was detected at 0.00240 mg/L in the method blank associated with samples 

71794, 71797, 71798, 71801, 71802, and 71803. Although this concentration is greater 

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

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

The RPD between sample 71800 and its field duplicate 71804 was 21.1%. Even though 

this RPD was greater than 20%, the samples were not qualified because there are no 

specific control limits for field duplicates specified in SM 4500 CN- E.

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

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

the instruments, the samples needed to be diluted. The results of the diluted sample for 

71795, 71796, and 71804 were below the lowest calibration standard used by the 

laboratory (0.01 mg/L). However, these samples were already qualified by the laboratory 

with a “J” meaning the sample result was an estimated value because it was less than the 

RL, so no further action was taken.

Nitrate/Nitrite

The result for sample 71799 was below the lowest calibration standard. However, this 

sample was already qualified by the laboratory with a “J” meaning the sample result was 

an estimated value because it was less than the RL, so no further action was taken.

The percent recovery for the MS analysis for sample 71798 (FGD bioreactor influent) 

was below the control limits of 90-110% required by the method and below the 

laboratory control limits of 72-113%. The percent recoveries of the MS and MSD 

samples were 70% and 102%, respectively. TestAmerica qualified both the MS and MSD 

results for sample 71798 with an “E” meaning that the results exceeded the calibration 

range. The MSD sample result was above the highest calibration standard and even 

though the MS sample result was within the calibration range, it was expected to be 

above the highest calibration standard. If the MSD result is reported, it will be qualified 

as an estimated value because the result was above the highest calibration standard.
5

The MS percent recovery for sample 71799 (FGD bioreactor effluent) was not within the 

method control limits, but was within the laboratory control limits. The percent 

recoveries of the MS and MSD samples were 112% and 107%, respectively. Sample 

71799 was already qualified by the laboratory with a “J” meaning the sample result was 

an estimated value because it was less than the RL, so there was no need to further 

qualify the result as a maximum value. 

Phosphorus 

The results for Samples 71792, 71793, and 71798 were less than the lowest calibration 

standard (0.025 mg/L). However, these samples were already qualified by the laboratory

with a “J” meaning the sample result was an estimated value because it was less than the 

RL, so no further action was taken.

The percent recoveries for the MS and MSD analyses for samples 71798 and 71801 were 

not within the control limits of 90-110% specified in EPA Method 365.1, but were within 

the laboratory control limits of 71-128%. The percent recoveries for MS and MSD 

analyses on sample 71798 were both 73% and the percent recoveries for MS and MSD 

analyses on sample 71801 were both 74%. The results may be biased low for samples 

with similar matrixes (i.e., FGD bioreactor influent and FGD bioreactor effluent) because 

of matrix interferences. Sample 71801 was qualified as a minimum value because the MS 

percent recovery was below the method specified criteria. Sample 71798 was already 

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

because it was less than the RL, so there was no need to further qualify the result as a 

minimum value. 

The RPD between sample 71797 and its field duplicate 71803 for phosphorus was 25.8%. 

The results for these samples were greater than the MDL, but less than the RL. These low 

concentrations might be the reason for the high RPD. Even though the RPD was greater 

than 20%, the sample was not qualified because there are no specific control limits for 

field duplicates specified in EPA Method 365.1.

TDS

Constant weight was not achieved after 3 drying cycles for samples 71791, 71795, 71796, 

71797, 71798, 71799, 71800, 71801, 71802, 71803, and 71804. For samples 71791, 

71795, 71796, 71797, 71798, 71799, 71800, 71801, and 71803 the weight increased from 

the first weighing to the second weighing. Method 2540C warns that samples which 

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

meaning they absorb moisture from the air. FGD wastewater contains high concentrations 

of all of these species. This was likely the cause for the inconsistent weight calculations.

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

At least one laboratory duplicate was analyzed per batch. The RPDs for all laboratory 

duplicates analyzed were less than 10% as required by SM 2540C. 
6

TKN

The percent recoveries for the MS and MSD analyses for sample 71798 (Bioreactor

influent) did not meet the method control limits of 90%-110% or the laboratory criteria of 

54%-131%. The MS and MSD percent recoveries were 202% and 206%, respectively. 

The LFB associated with this sample met the method criteria. These percent recoveries 

suggest that results could be biased high for samples with a similar matrix (i.e., bioreactor 

influent). Sample 71798 was qualified as a maximum value.

TSS 

At least one laboratory duplicate was analyzed per batch. The RPDs for laboratory 

duplicates for samples 71791, 71792, 71794, and 71798 were less than 10% as required 

by Method SM2540D. However, the RPD for sample 71801 was 15%. The results for 

sample 71801 and its laboratory duplicate were both qualified by the laboratory with a 

“J” meaning the sample result was an estimated value because it was less than the RL, so 

sample 71801 was not additionally qualified. 

The RPD between sample 71797 and its field duplicate 71803 was 28.6%. The RPD 

between sample 71800 and its field duplicate 71804 was also 28.6%. The results for these 

four samples were less than the reporting limit. These low concentrations could have 

caused the high RPDs. Even though these RPDs were greater than 20%, the samples were 

not qualified because there are no specific control limits for field duplicates specified in 

SM 2540D.

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level Detected

71799 Ammonia Maximum Value MS % recovery 

above methodspecified criteria

13 mg/L

71791 BOD B Unseeded water 

blank > methodspecified criteria

40 mg/L

71792 BOD B Unseeded water 

blank > methodspecified criteria

9.7 mg/L

71795 BOD B Unseeded water 

blank > methodspecified criteria

7.4 mg/L

71799 BOD B Unseeded water 

blank > methodspecified criteria

1.7 mg/L
7

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level Detected

71798 COD Minimum Value MS % recovery 

below methodspecified criteria

84 mg/L

71798 Nitrate/Nitrite Minimum Value MS % recovery 

below methodspecified criteria

13 mg/L

71801 Total 

Phosphorus

Minimum Value MS % recovery 

below methodspecified criteria

0.19 mg/L

71798 TKN Maximum Value MS % recovery 

above methodspecified criteria

3.2 mg/L
Appendix C

PICTURES FROM THE SAMPLING EPISODE
C-1

Figure C-1. Sampler Working Inside a “Cleanbox”
C-2

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

System
C-3

Figure C-3. Sample Collection Set Up at the Pump-Off Station
C-4

Figure C-4. Composite Sample Collection Set Up at the Influent to the Bioreactor System
C-5

Figure C-5. Composite Sample Collection Set Up at the Effluent from the Bioreactor 

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 
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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 
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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 
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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. 
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Material (1) Hazards Exposure 

Limit (2) Signs and Symptoms of Exposure 

Nitric Acid Corrosive 

Oxidizer 

Poison 

2 ppmTWA 

4 ppmSTEL 

Nitric acid is extremely hazardous; it is corrosive, reactive, 

an oxidizer, and a poison. Inhalation of vapors can cause 

breathing difficulties and lead to pneumonia and pulmonary 

edema, which may be fatal. Other symptoms may include 

coughing, choking, and irritation of the nose, throat, and 

respiratory tract. Can cause redness, pain, and severe skin 

burns. Concentrated solutions cause deep ulcers and stain 

skin a yellow or yellow-brown color. Vapors are irritating and 

may cause damage to the eyes. Contact may cause severe 

burns and permanent eye damage. 

Material (1) Hazards Exposure 

Limit (2) Signs and Symptoms of Exposure 

Hydrochloric 

Acid

Corrosive 

Poison 

5 ppmCeiling Inhalation of vapors can cause coughing, choking, 

inflammation of the nose, throat, and upper respiratory tract, 

and in severe cases, pulmonary edema, circulatory failure, 

and death. Can cause redness, pain, and severe skin burns. 

Vapors are irritating and may cause damage to the eyes. 

Contact may cause severe burns and permanent eye 

damage. 

1 – Always add acid to water to prevent violent reactions. 

2 – Exposure limit refers to the OSHA regulatory exposure limit. 

6.0 Equipment and Supplies

6.1 Instrumentation 

 Inductively Coupled Plasma Mass Spectrometer (ICP/MS) capable of providing 

resolution, less than or equal to 0.9 amu at 10% peak height from 6-253 amu 

and 1.0 amu at 5% peak height from 6-253 amu with a data system that allows 

corrections for isobaric interferences and the application of the internal standard 

technique. The ICP/MS must be equipped with a collision cell for the removal of 

molecular interferences. This procedure was developed using an Agilent 7500 

or 7700 instrument equipped with a high matrix interface. The interface extends 

the amounts of total dissolved solids that may be measured into the percent 

concentration range. Any collision cell instrumentation that meets the 

specifications in this procedure may be used. 

 A discrete sample introduction system enables the use of only the exact amount 

of sample volume required for data acquisition. 

 Accessories and configuration that are designed to accommodate samples with 

high levels of dissolved solids should be used. 

 This sampling system results in less matrix being deposited in the system 

during analysis and minimizes the rinse times normally needed for difficult 

matrices. 

 Autosampler with autosampler tubes. 

 Appropriate water cooling device. 

 Block digester with tubes. 

6.2 Supplies 

 Argon gas: High purity grade (99.99%). 
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 Helium gas: High purity grade (99.99%). 

 Hydrogen gas: High purity grade (99.99%). 

 Calibrated automatic pipettes or Class A glass volumetric pipettes. 

7.0 Reagents and Standards

7.1 Storage and Shelf-Life 

7.1.1 All standards must be stored in glass, FEP fluorocarbon or previously 

unused polyethylene or polypropylene bottles. Standards stored at 

concentrations as received from the vendor and mid-level dilutions must 

be replaced prior to the expiration date assigned by the vendor. If no 

expiration date is provided, the stocks and mid-level standards may be 

stored for up to one year. They must be replaced sooner if verification 

from an independent source indicates a problem (See section 10.3.5 for 

initial calibration verification acceptance criteria). 

7.1.2 Working standards, i.e., all standards at concentrations ready to 

analyze on the ICP/MS (all except tuning mixes, ICSA and ICSAB 

mixes, which are received at ready-to-use concentrations), are prepared 

fresh daily. 

7.2 Standards

7.2.1 Tuning Solution, 10 ppb 

The tuning solution stock is purchased as a custom multi-element mix. 

The concentrations of the constituents are shown in Attachment 5. 

Prepare the Tuning Solution as detailed below. 

 Obtain a clean 100 mL volumetric flask. 

 Place 50 mL of reagent water and 2 mL of conc. HNO3 and 0.5 

mL of conc. HCl in the flask. 

 Swirl to mix. 

 Pipet 0.1mL of the Tuning Solution Stock into the flask. 

 Dilute to volume with reagent water. Stopper and mix. 

7.2.2 PA Tuning Solution 

The dual detector solution may be commercially purchased as a custom 

multi-element mix. 

Prepare the PA Tuning Solution as detailed below. 

 Add approximately 50 mL of the 2% HNO3 / 0.5% HCl to a 100 

mL volumetric flask. 

 Prepare at a concentration recommended by the instrument 

manufacturer. 

7.2.3 Calibration Standards 

Stock calibration standards are purchased as custom multi-element 

mixes or as single element solutions. Each day of analysis, the 

standards are diluted to working levels using 2% nitric acid and 0.5% 

HCl acid matrix. Suggested concentrations are given in Attachment 8, 

but the laboratory may adjust calibration standard concentrations as 
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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. 

7.2.7 Continuing Calibration Verification (CCV) Standard 
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The CCV is prepared from the same source as the calibration 

standards. The CCV standards are prepared fresh each day of analysis 

in 2% HNO3/0.5% HCl. The concentrations are shown in Attachment 8. 

Prepare the Working CCV as detailed below. 

 Dilute by 2X a known volume of the Working Calibration 

Standard in the 2% HNO3 / 0.5% HCl acid matrix. 

7.2.8 Spiking Stock Solution 

The spike stock solution is prepared from the same stocks as the 

calibration standards using the 2% HNO3 / 0.5% HCl acid matrix. Spike 

concentrations are listed in Attachment 8. 

7.3 Reagents

7.3.1 Reagent Water - ASTM Type I or equivalent for the elements of 

interest, generated using an ion-exchange water polishing system 

capable of achieving 18.0 megohm-cm.

7.3.2 Blank Matrix 2% HNO3 and 0.5% HCl. 

8.0 Sample Collection, Preservation, Shipment and Storage

Sample container, preservation techniques and holding times may vary and are 

dependent on sample matrix, method of choice, regulatory compliance, and/or specific 

contract or client requests. Listed below are the holding times and the references that 

include preservation requirements. 

Matrix Sample 

Container 

Min. Sample 

Size Preservation Holding Time Reference 

Waters HDPE 50 mLs HNO3, pH < 2 180 Days 40 CFR Part 136.3

Soils Glass or 

HDPE 

4 oz Cool 4 + 2oC 180 Days N/A 

9.0 Quality Control 

9.1 Quality control requirements are also summarized in Attachment 7. 

9.2 Ongoing data quality checks are compared with established performance criteria 

to determine if the results of analyses meet the performance characteristics of 

the method. Any QC result that fails to meet control criteria must be 

documented. 

9.3 Individual interference check solutions 

The individual interference check solutions listed in section 7.2.6 are analyzed 

prior to initiating sample analysis, and at least once per quarter while FGD 

wastewaters are being analyzed, and after any major changes to instrument 

operating conditions. Concentrations of target elements observed should be less 

than their reporting limits. In some cases it may not be possible to obtain 

interference check solutions that are completely free of contamination. In this 

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 
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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. 
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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 
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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. 
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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 
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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 

11.0 Calculations / Data Reduction
D-15 

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 

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

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 

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.

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. 
D-17 

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 

16.0 Attachments

Attachment 1: Recommended Elemental Equations 

Attachment 2: Internal Standards and Corresponding Metals 

Attachment 3: Sample Preservation and Holding Times 
D-18 

Attachment 4: Suggested Mass Choices 

Attachment 5: Tuning Solution 

Attachment 6: Suggested Tuning and Response Factor Criteria 

Attachment 7: Summary of Quality Control Requirements 

Attachment 8: Calibration, Calibration Verification, and Spike Concentrations
D-19 

Attachment 1 

Recommended Elemental Equations 

Element 

Isobaric 

Correction Mathematical Equation 

Pb None (1.0000)(208M) + (1.0000)(207M) + (1.0000)(206M) 

6Li Li (natural) (1.0000)(6M) - (0.0813)(7M) 

In Sn (1.0000)(115M) - (0.0149)(118M) 

The 6

Li correction equation is only needed if 6Li is used as an internal standard for low mass elements. 

Attachment 2: Internal Standards and Corresponding Metals 

Internal Std. Associated elements1,2

Sc Na, Mg, Al, K, Ca, V, Cr, Mn 

Ge Fe, Ni, Cu, Zn, As, Se 

In Ag, Cd 

Ho Tl, Pb 

Footnote: (1) Na, Mg, K, Ca and Fe are included in the synthetic FGD wastewater but their 

analytical determination is optional – the interferences caused by these elements are more 

important than the determination of their exact concentration. 

(2) Other internal standards may be used. For example, 6

Li, Ga, Rh, Bi, Ho and Tb may be 

considered for use as internal standards. 
D-20 

Attachment 3: Sample Preservation and Holding Times 

Measurement 

Parameter

Container (1) Preservative (2) Maximum Holding 

Time (3)

Waters: 

Metals (4) P,G HNO3 to pH < 2 6 months 

Soils/Sediments/Wastes: 

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

digestion. 

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

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

collection or shipped to the laboratory unpreserved for preservation at the 

laboratory. 

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

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

considered valid. Holding times are calculated from the date when the sample 

was collected. 

 (4) Samples are filtered immediately on-site by the sampler before adding 

preservative for dissolved elements. 
D-21 

Attachment 4: Suggested Mass Choices 

Masses listed indicate the masses which have the most impact on data quality and the elemental 

equations used to collect the data. 

Mass Element of Interest Analysis mode 

27 Aluminum No gas 

75 Arsenic He 

111 Cadmium He 

52 Chromium He 

63 Copper He 

208, 207, 206 Lead No gas or He 

24 Magnesium No gas 

55 Manganese He 

60 Nickel He 

39 Potassium No gas or He 

78 Selenium He (H2) 

107 Silver He 

23 Sodium No gas or He 

205 Thallium No gas or He 

51 Vanadium He 

66 Zinc He 

NOTE: It is strongly recommended that elements other than those of interest be 

monitored to indicate other potential molecular interferences which could 

affect the data quality. 
D-22 

Attachment 5: Tuning Solution 

A tuning solution containing elements representing all of the mass regions of interest must be analyzed. 

Below are two groups of suggested solutions which cover a typical mass calibration range. 

Method 200.8 

Element Concentration (g/L) 

Mg 10 

Rh 10 

Ba 10 

Be 10 

U 10 

Ce 10 

Y 10 

Pb 10 

Li 10 

Co 10 

In 10 

Tl 10 
D-23 

Attachment 6: Suggested Tuning and Response Factor Criteria 

No Gas Mode

Li7 >2000cps 

Tl205 >3000cps 

CeO/Ce 156/140 1% 

Ce++/Ce+ 70/140 <3% 

He Mode:

ArAr 78 2-3 counts/sec 

ArCl 75 2-3 counts/sec 
D-24 

Attachment 7: Summary of Quality Control Requirements 

QC Parameter Frequency Acceptance Criteria Corrective Action 

ICV/QCS Beginning of every 

analytical run. 

90 - 110% recovery. 

200.8 IS, 60-125% rec. 

Terminate analysis; 

correct the problem; 

recalibrate. 

ICB/CCB Immediately after each 

ICV. 

The result is < RL 

200.8 IS, 60-125% rec. 

Terminate analysis; 

correct the problem; 

recalibrate. 

Synthetic FGD 

interference check 

Prior to initiating 

analysis and at least 

quarterly. 

Result for target elements 

is < RL, unless actual 

presence of target 

element can be 

demonstrated, in which 

case result is < 5X RL. 

Correct the problem prior 

to sample analysis. 

Individual element 

interference checks 

Prior to initiating 

analysis and at least 

quarterly. 

Result for target elements 

is < RL, unless actual 

presence of target 

element can be 

demonstrated, in which 

case result is < 5X RL. 

Correct the problem prior 

to sample analysis. 

CCV Beginning and end of run 

and every 10 samples OR

every 2 hours, whichever 

is more frequent. 

Beginning and end of 

each lot. 

90 - 110% recovery. 

IS, 60-125% rec. 

If unacceptable, 

terminate analysis; 

correct the problem; 

recalibrate the 

instrument, reverify 

calibration and rerun all 

samples since the last 

acceptable CCV. 

CCB Immediately following 

each CCV. 

The result must be < RL 

200.8 IS, 60-125% rec. 

If unacceptable, 

terminate analysis; 

correct the problem, 

recalibrate the 

instrument, reverify 

calibration and rerun 

all samples since the 

last acceptable CCB. 
D-25 

Attachment 7: Summary of Quality Control Requirements (continued) 

QC Parameter Frequency Acceptance Criteria Corrective Action 

Method 

Blank/Laboratory 

Reagent Blank 

One per lot of 20 field 

samples or fewer. 

The result must be less 

than the RL. 

Sample results greater 

than 10x the blank 

concentration or samples 

for which the 

contaminant is < RL, do 

not require redigestion or 

reanalysis. 

Re-run once. If > than 

the RL, Redigest and 

reanalyze samples. 

Note exceptions under 

criteria section. 

See Section 9.4 for 

additional requirements. 

Matrix Spike/Laboratory 

Fortified Matrix 

One every ten samples or 

fewer. 

Must be within 

laboratory control limits. 

See section 9.6 for 

additional requirements. 
D-26 

Attachment 8: Calibration, Calibration Verification, and Spike Concentrations 

Element 

Initial Calibration 

(g/L) 

ICV 

(g/L)

CCV 

(g/L)

LCS

(g/L)

MS/MSD 

(g/L)

Aluminum 100, 1,000, 10,000 4000 5000 4000 4000 

Arsenic 1, 10, 100 40 50 40 40 

Cadmium 1, 10, 100 40 50 40 40 

Chromium 1, 10, 100 40 50 40 40 

Copper 1, 10, 100 40 50 40 40 

Lead 1, 10, 100 40 50 40 40 

Manganese 1, 10, 100 40 50 40 40 

Nickel 1, 10, 100 40 50 40 40 

Selenium 1, 10, 100 40 50 40 40 

Silver 1, 10, 100 40 50 40 40 

Thallium 1, 10, 100 40 50 40 40 

Vanadium 1, 10, 100 40 50 40 40 

Zinc 1, 10, 100 40 50 40 40 

Additional elements may be included in the calibration solution at the above levels. Levels 

may be adjusted to meet specific requirements. 

####