Sampling Episode Report 

Duke Energy Carolinas’ 

Belews Creek Steam Station 

Belews Creek, NC 

Sampling Episode 6558 

Prepared for:

U.S. Environmental Protection Agency

Engineering and Analysis Division 

Office of Water 

1200 Pennsylvania Avenue, NW 

Washington, D.C. 20460 

Prepared by: 

Eastern Research Group, Inc.

14555 Avion Parkway 

Suite 200 

Chantilly, VA 20151 

 13 April 2012 

EPA Contract No. 68-C-02-095 

Work Assignment 9-29 
i

CONTENTS 

Page 

1. INTRODUCTION .................................................................................................................1-1

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

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

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

2. FACILITY OVERVIEW ........................................................................................................2-1

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

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

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

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

3.1.2 Influent to Bioreactor System ..................................................................3-4

3.1.3 Effluent from Bioreactor System.............................................................3-7

3.2 List of Analytes and Sample Preservation...........................................................3-9

3.3 Plant Operational Data.......................................................................................3-11

3.4 Deviations from the Sampling and Analysis Plan .............................................3-11

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

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

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

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

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

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

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

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

6. REFERENCES .....................................................................................................................6-1

Appendix A: ANALYTICAL RESULTS

Appendix B: DATA REVIEW NARRATIVES

Appendix C: PICTURES FROM THE SAMPLING EPISODE

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

TRACE ELEMENT ANALYSIS IN FLUE GAS DESULFURIZATION WASTEWATERS
ii

LIST OF TABLES 

Page 

Table 3-1. Sample Collection Information, Belews Creek........................................................ 3-13

Table 3-2. Sample Collection at Belews Creek Steam Station.................................................. 3-16

Table 3-3. Field Measurements, Belews Creek ......................................................................... 3-17

Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Belews Creek ............. 3-19

Table 3-5. Analytical Methods, Belews Creek .......................................................................... 3-20

Table 3-6. Summary of Sample Container and Planned Preservation, Belews Creek .............. 3-21

Table 3-7. Sample Preservation Summary, Belews Creek ........................................................ 3-22

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

Creek.............................................................................................................................. 3-25

Table 3-9. FGD Scrubber System Operating Characteristics, Belews Creek............................ 3-26

Table 3-10. Coal Usage during Sample Collection, Belews Creek ........................................... 3-27

Table 3-11. Scrubber Slurry Information during Sample Collection, Belews Creek ................ 3-27

Table 3-12. FGD Wastewater Treatment System Operation Information, Belews Creek......... 3-28

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

Table 4-2. Influent to the Bioreactor System, Belews Creek ..................................................... 4-8

Table 4-3. Effluent from the Bioreactor System, Belews Creek .............................................. 4-12

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

Treatment System, Belews Creek.................................................................................. 4-16

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

Treatment System, Belews Creek.................................................................................. 4-17

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

Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, Belews Creek............. 5-8

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

Belews Creek .................................................................................................................. A-1
LIST OF TABLES (Continued) 

Page 

iii

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

Belews Creek .................................................................................................................. A-5

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

Belews Creek .................................................................................................................. A-8

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

Belews Creek ................................................................................................................ A-11

Table A-5. Influent to the Bioreactor System, Day 1 Analytical Results, Belews Creek ....... A-14

Table A-6. Influent to the Bioreactor System, Day 2 Analytical Results, Belews Creek ....... A-17

Table A-7. Influent to the Bioreactor System, Day 3 Analytical Results, Belews Creek ....... A-20

Table A-8. Influent to the Bioreactor System, Day 4 Analytical Results, Belews Creek ....... A-23

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

Creek............................................................................................................................. A-26

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

Creek............................................................................................................................. A-29

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

Creek............................................................................................................................. A-32

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

Creek............................................................................................................................. A-35

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

Creek............................................................................................................................. A-38

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

Belews Creek ................................................................................................................ A-41

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Belews Creek ................... A-44

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

Analytical Results, Belews Creek................................................................................. A-49

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

Belews Creek ................................................................................................................ A-51

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

Belews Creek ................................................................................................................ A-53
LIST OF TABLES (Continued) 

Page 

iv

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

Belews Creek ................................................................................................................ A-54

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

Belews Creek ................................................................................................................ A-55

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

Belews Creek ................................................................................................................ A-56

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

Belews Creek ................................................................................................................ A-58

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

Belews Creek ................................................................................................................ A-59

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

Belews Creek ................................................................................................................ A-60
v

LIST OF FIGURES 

Page 

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

Creek................................................................................................................................ 2-6

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

Wastewater Treatment System, Belews Creek ................................................................ 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 June 6 - 11, 2010, at Duke Energy Carolinas’ Belews Creek Steam Station (Belews Creek), 

located in Belews Creek, North Carolina (Sampling Episode 6558). The focus of Episode 6558 

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. 

Belews Creek was selected by EPA for sampling based on the following site 

characteristics: 

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

its two generating units; 

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

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

includes the following steps: 

— Equalization, 

— pH adjustment (lime addition), 

— Ferric chloride addition, 

— Polymer addition, 

— Clarification, 

— Filtration, 

— Biological treatment (nitrogen and metals), and 

 The plant operates selective catalytic reduction (SCR) systems on both units; and 

 The plant produces a commercial-grade gypsum by-product. 
1-2

1.3 Sampling Episode Overview

EPA and its technical contractor, Eastern Research Group, Inc. (ERG) conducted a oneday pre-sampling site visit at Belews Creek on March 12, 2008 as part of the detailed study. EPA 

also collected samples from the FGD wastewater treatment system at Belews Creek in October 

2008 as part of the detailed study. Data obtained from the October 2008 sampling episode can be 

found in the Final Sampling Episode Report Duke Energy Carolinas’ Belews Creek Steam 

Station (DCN 06197). The information collected during the pre-sampling site visit and during the 

October 2008 sampling episode was used to create Sampling Plan, Duke Energy Carolinas’ 

Belews Creek Steam Station (Sampling Plan) [1], which describes the sample collection 

procedures used during the sampling episode. 

On Sunday, June 6, 2010, EPA arrived at Belews Creek to meet with plant personnel, 

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

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

Monday through Friday (June 7 – 11, 2010). The following personnel participated in EPA’s 

sample collection activities: 

 Ron Jordan, EPA/EAD; 

 Jezebele Alicea, EPA/EAD; 

 TJ Finseth, ERG; 

 Elizabeth Sabol, ERG; 

 Becky Schwantes, ERG; 

 Kim Wagoner, ERG; and 

 Jessica Wolford, ERG. 

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

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

industry. During the sampling episode, UWAG acted as Belews Creek’s representative and 

collected samples on behalf of the plant. 
2-1

2. FACILITY OVERVIEW

Belews Creek operates two steam electric units and each has a coal-fired boiler. Belews 

Creek burns approximately 19,000 tons of eastern bituminous coal per day. Units 1 and 2, which 

came on line in 1974 and 1975, respectively, each have a capacity of 1,200 megawatts (MW). 

The Belews Creek plant and supporting facilities are located on approximately 700 acres in 

Belews Creek, NC, adjacent to Belews Lake. The plant owns approximately 7,000 acres adjacent 

to Belews Lake. 

In 2008, Belews Creek retrofitted both units with wet FGD scrubber systems to control 

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

February 2008, and the Unit 2 FGD system was installed in May 2008. The wet FGD scrubbers 

are designed to remove more than 95 percent of SO2 from the flue gas. With the addition of the 

FGD scrubber systems, Belews Creek 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. 

Belews Creek retrofitted Units 1 and 2 with SCR systems in August 2003 and February 

2004, respectively, to control nitrogen oxide (NOx) releases from the plant. Initially, Belews 

Creek was only operating the SCRs during ozone season, May through September; however, in 

January 2007, Belews Creek began operating the SCRs year-round. Belews Creek personnel 

stated that the plant plans to continue operating the SCRs year-round into the foreseeable future. 

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

are designed to remove 99.8 percent of the fly ash and other particulates from the flue gas. 

Belews Creek utilizes ESPs to remove the fly ash from both units. The fly ash and other 

particulates are collected in hoppers and typically are pneumatically transferred to fly ash silos. 

However, Belews Creek also has the capability of handling the fly ash wet by sluicing the fly ash 

in the hoppers and transferring the fly ash sluice water to the ash basin. 

Units 1 and 2 have the following configuration: 

 Boiler; 

 Air preheater; 

 SCR system; 

 ESP; and 

 FGD scrubber system. 

2.1 FGD Scrubber System

Belews Creek operates a wet FGD scrubber system on both Units 1 and 2, downstream of 

the ESP, to control the emission of sulfur dioxide from the unit. The plant uses limestone slurry 

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

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

transferred to hydrocyclones to collect limestone particles that are too large for use in the FGD 

system. The underflow from the hydrocyclones is transferred to the reject tank and then sent 

back to the ball mill for additional processing. The overflow from the hydrocyclones, which is 
2-2

approximately 27 to 30 percent solids (by weight), 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 (typically three of four spray 

levels are operating 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. Belews 

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

gypsum). 

Belews Creek intermittently blows down the gypsum slurry from the reaction tank to 

maintain the solids concentration in the scrubbers around 15 percent solids. The chlorides 

concentration in the scrubbers is maintained between 8,000 and 10,000 parts per million (ppm), 

with a design maximum chlorides concentration of 12,000 ppm. Belews Creek transfers the 

blowdown from the scrubber to the gypsum dewatering operations. 

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 or sent to the filter feed tank. The 

overflow from the secondary hydrocyclones is sent to the purge tank and then pumped to the 

FGD wastewater treatment system. 

Belews Creek washes the gypsum sent to the vacuum filter belts with service water, as it 

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

approximately 10 percent. Belews Creek transfers the dry gypsum to an uncovered gypsum 

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

Carolina, approximately 105 miles from the plant. Belews Creek generates approximately 

500,000 tons of gypsum per year; however, plant personnel stated that the gypsum production is 

dependent on the coal being burned and sulfur content of the coal. 

2.2 FGD Wastewater Treatment System

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

FGD wastewater from the purge tank, which contains secondary hydrocyclone overflow, at a 

flow rate varying from 350 to 600 gallons per minute (gpm) for approximately 18 hours per day, 

with a total daily flow rate of approximately 489,000 gallons per day (gpd). According to Belews 

Creek personnel, the flow rate to the equalization tank varies depending on whether one or both 

of the scrubbers are purging. 

The plant operates the FGD wastewater treatment system 24 hours per day. Belews Creek 

installed the wastewater treatment system to treat the FGD scrubber purge wastewater to meet its 
2-3

permit limits, which include limits for total suspended solids (TSS) and selenium. The Belews 

Creek FGD wastewater treatment system contains the following treatment operations: 

 Physical/Chemical Separation; 

— Equalization, 

— pH adjustment (lime addition), 

— Ferric chloride addition, 

— Polymer addition, 

— Clarification, 

— 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 from 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. During the 

sampling episode, the FGD influent wastewater was found to contain less than 0.5 percent solids, 

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

also receives 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 8.5 and 9.2 S.U. (target 8.8 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. From reaction tank 3, the 

wastewater flows to a mix chamber where polymer (Nalco 71307) is added. 

From the mix chamber, the wastewater flow splits and enters two clarifiers in parallel. 

Each of the clarifiers is capable of handling 100 percent of the waste stream capacity. Typically 

both clarifiers are in operation. However, during the scheduled sampling event one clarifier was 

out of service for preventative maintenance. The clarifiers are solids contact clarifiers that 

contain a sludge bed that facilitates removal of the solids in the wastewater. Hydrochloric acid is 

added to the wastewater at a point between the clarifiers and the sand filters to adjust the pH 

prior to the biological treatment system. The target pH after hydrochloric acid addition is 6.8 

S.U. After the hydrochloric acid addition, the overflow from the two clarifiers is split and sent 

through three sand filters in parallel. Each of the sand filters can handle 75 percent of the waste 
2-4

stream capacity. The target maximum TSS level for the sand filter effluent is 50 ppm; however, 

the plant tries to achieve an effluent TSS concentration below 20 ppm. The sand filters are 

continuous backwash gravity filters. The filter backwash is sent to a sump, and then transferred 

to the equalization tank. 

The sludge from the clarifiers is transferred to a sludge storage tank. A portion of the 

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

pumped to a filter press for dewatering. Belews Creek achieves a solids concentration of 15 

percent in the sludge tank. The filter press cake is transferred to the fly ash landfill and the 

filtrate is sent to the filtrate sump. Each filter press operation produces an average of 28,000 lbs 

of filter cake. Belews Creek performs approximately 10 filter press operations per week. 

2.2.2 Biological Reactors 

In the bioreactor portion of the treatment system, Belews Creek treats the wastewater in 

two stages. Each stage contains eight bioreactor cells, which are operated in parallel. Each cell 

contains an activated carbon bed. Within the activated carbon bed, specialized microbes fill the 

voided areas and reduce the nitrogen and metals, specifically selenium, in the wastewater. The 

microbes selected for the bioreactor system have the ability to reduce selenium to its elemental 

form, while other metals are precipitated as sulfide complexes. The wastewater from the sand 

filters is transferred to a holding tank prior to entering a heat exchanger to reduce the temperature 

from approximately 110o

F to 95oF. As the wastewater flows from the heat exchanger to the first 

stage of bioreactor cells, Belews Creek adds nutrients (molasses-based), which provide a source 

of carbon to feed the bacteria. The wastewater is divided evenly among the eight first-stage 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 cells is approximately three feet above the activated 

carbon bed. 

Belews Creek 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 for 

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 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 need to 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. 
2-5

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 

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 biological treatment system, wastewater is transferred to 

two wetland supply tanks, which is then transferred directly to the ash basin. According to plant 

personnel, the treated FGD wastewater, excluding cooling water, represents approximately seven 

percent of the total flow discharge from the ash basin to the Dan River, via NPDES Outfall 003. 

2.2.3 Sampling Points 

Figure 2-2 shows the sampling points for the Belews Creek 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 downstream of the second-stage 

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, Belews Cre
2-7 

FGD Scrubber Purge 

(from Purge Tank)

Lime

Polymer

Equalization 

Tank Reaction Tank 1 Reaction 

Tank 2

Reaction 

Tank 3

SP-1

SP-2

Indicates a Sampling Point

Ferric 

Chloride

Filter

2

Holding 

Tank

Clarifier 1

Sludge 

Storage 

Tank

Filter Press

Sump

Filter 

Backwash

Filter

1

Solids to Fly 

Wastewater Flow Ash Landfill

Sludge Flow

Intermittent Wastewater Flow

Clarifier 

Sludge

Mix 

Chamber

Clarifier 2

Filter

3

Cooling Water

Nutrient

First-Stage 

Bioreactors 

(8)

First-Stage 

Effluent 

Storage

Second-Stage 

Bioreactors 

(8)

Second-Stage 

Effluent 

Storage

To Ash Basin

Bio Reactor Backflush

Hydrochloric 

Acid

SP-3

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

Creek
3-1

3. SAMPLE COLLECTION

During the Belews Creek 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 Belews Creek’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 Belews Creek’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 
3-2

“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. There was no rain 

during the sample collection. 

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

treatment system (SP-1), the sampling team collected field blanks (SP-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). 
3-3

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

3.1: 

 Total and dissolved mercury; 

 Total metals by 200.8; and 

 Total metals by 200.7. 

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

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

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 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 Belews Creek’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 - 2 

liters1

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

samples. 

 

1 During day 1, the capsule filter become clogged, so after the field blank was collected, the tubing/filter was purged 

with only 0.5 liters. After the collection of the first sample (dissolved metals 200.8), the filter was changed. The 

tubing/filter was purged for another 0.5 liters and the remaining two samples were collected. On day 2, the 

tubing/filter was purged for 1 litter. After the collection of the first sample (dissolved metals by 200.8) the filter was 

replaced. The tubing/filter was purged briefly and the remaining two samples were collected. On day 3 and 4, the 

filter/tubing was purged for 1.5 and 2.0 litters respectively and there was no need to change the filter. 
3-4

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

Section 3.1: 

 Dissolved metals by 200.8; 

 Dissolved metals by 200.7; and 

 Dissolved hexavalent chromium. 

Hexavalent chromium samples were immediately placed on ice after sample collection. 

3.1.2 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. Belews Creek 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). At the time that sampling occurred, one of the clarifiers was 

out of service. This did not affect normal plant operations because Belews Creek has never 

operated more than one clarifier at a time. 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 
3-5

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. 

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 Belews Creek’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. ERG had planned on using a pH meter to test the pH; however, the 

sampling team could not get the pH meter to calibrate properly. 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 Belews Creek’s representatives; therefore, duplicate samples were collected. 

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

or oxidants were detected during 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. 
3-6

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 Belews Creek’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 and total 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 1-2 liters of sample, samplers 

collected the following samples using a “cleanbox,” as described in Section 3.1: 

 Dissolved metals by 200.8; 

 Dissolved metals by 200.7; and 

 Dissolved hexavalent chromium. 

Hexavalent chromium samples were immediately placed on ice after sample collection. 

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

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

described in Section 3.1: 

 Total metals by 200.8; and 

 Total metals by 200.7. 

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

Teflon® tubing into the other previously filled 20-liter container. 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. 
3-7

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. Belews Creek installed a threeway 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 

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. 
3-8

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 Belews Creek’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. ERG had planned on using a pH meter to test the pH; however, the 

sampling team could not get the pH meter to calibrate properly. 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 Belews Creek’s representatives; therefore, duplicate samples were collected. 

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

or oxidants were detected during this sampling episode at the effluent from the 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 
3-9

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 Belews Creek’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: 

 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 Belews Creek were analyzed for the following pollutants: 
3-10

 Classicals: 

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

— Chemical oxygen demand (COD), 

— Total suspended solids (TSS), 

— Total dissolved solids (TDS), 

— Sulfate, 

— Chloride, 

— Total Kjeldahl nitrogen (TKN), 

— Ammonia as nitrogen, 

— Nitrate/nitrite as nitrogen, 

— Total phosphorus, 

— Total cyanide; 

 Total Metals2

: 

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

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

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

titanium, vanadium, and zinc. 

 Dissolved Metals: 

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

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

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

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

concentrations. 

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

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

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

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

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

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

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

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

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

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

hexavalent chromium samples were preserved with ammonium sulfate buffer solution to a pH 

between 9.3 and 9.5 S.U., although for several of the samples preservation was discontinued 

before this target pH was reached because the sample bottle became too full and additional 

preservative could not be added. See Section 3.4 for more details. The Group II samples were 

preserved with sulfuric acid to a pH of <2 S.U. in the staging area, and the pH was confirmed 

with four-color pH strips. Each total cyanide sample was tested for sulfides and oxidants 

immediately after sample collection. Because sulfides and oxidants were not detected at any of 

the sampling points during the sampling episode, the samplers did not need to dilute the samples 

 

2 In this report, EPA uses the terms “total metals” and “total recoverable metals” interchangeably. 
3-11

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, Belews Creek 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 Routine Hexavalent Chromium. ERG planned to preserve the 

routine hexavalent chromium samples to a pH between 9.3 and 9.7 S.U. using an 

ammonium sulfate buffer solution; however, for several of the samples, 

preservation was discontinued because the sample bottle became too full and 

additional preservative could not be added to the sample bottle. All samples at 

least reached a pH of 8.5 S.U. See Table 3-7 for a list of affected samples. 

 pH field test measurements: The sampling team was unable to calibrate the pH 

meter properly; therefore, only four-color pH strips were used to measure the pH 

of the samples during the field tests. 

 Field blank hexavalent chromium sample at SP-1: Because Belews Creek’s 

representative collected fewer field blank sample volume at SP-1, they collected 

EPA’s hexavalent chromium field blank sample in their clean box while ERG was 

collecting the dissolved metals by 200.7 field blank sample volume. 

 Total mercury grab sample at SP-3 (Day 1): On day 1 of sample collection at 

the effluent from the bioreactor (SP-3), grab one of the four total mercury grab 

sample bottles was filled only three-quarters of the way full. The samplers noted 

this in the traffic report that was sent with the samples to the laboratory. 

 Collection of total metals samples at SP-2 (Day 2): On day 2 of sample 

collection at the influent to the bioreactor system (SP-2), the sampling team 

dropped the end of the tubing set used to fill the sample bottles at the pump-off 

area after the collection of the dissolved hexavalent chromium and before the 

collection of total metals samples. The end of the tubing touched the ground, 

therefore, the samplers purged the tubing with 1 liter of sample while Belews 

Creek’s representatives used their end of the pump-off tubing to rinse the outside 

of ERG’s tubing. 
3-12

 Collection of dissolved mercury samples at SP-2 (Day 3): On day 3 of sample 

collection at the influent to the bioreactor system (SP-2), the sampling team 

dropped the outer bag on the floor and immediately picked it up. The contents of 

the sample and the inner bag were not affected. The outer bag was still used to 

contain the inner bag and bottle after sample collection. 

 Classicals compositor set up at SP-2 (Day 4): On day 4 of sample collection at 

the influent to the bioreactor system (SP-2), the plastic bag covering one of the 

ends of the T-splitter tubing set was dropped on the ground. The sampling team 

used a new plastic bag to re-cover the end of the tubing before proceeding with 

the sample set up. 
3-13

Table 3-1. Sample Collection Information, Belews Creek

Sampling 

Point 

Number Sampling Point Description 

Type of 

Sample 

Sample Collection 

Date 

Sample Collection 

Time 

Influent to FGD Wastewater Treatment 

System – Day 1 

Grab 6/7/10 1109a and 1227b

Influent to FGD Wastewater Treatment 

System – Day 2 

Grab 6/8/10 1246a and 1419 b

Influent to FGD Wastewater Treatment 

System – Day 3 

Grab 6/9/10 0957a and 1224b

SP-1 

Influent to FGD Wastewater Treatment 

System – Day 4 

Grab 6/10/10 1128a and 1300b

Composite 6/7/10 

 6/8/10

0729c 

0945d

Influent to Bioreactor System – Day 1 

Grab 6/7/10 

 6/8/10 

0751e

, 1355f , and 2002 g 

0147 h 

Composite 6/8/10 

 6/9/10 

0729c 

1049d 

Influent to Bioreactor System – Day 2 

Grab 6/8/10 

 6/9/10 

0744e

, 1342f , and 1941 g 

0141 h 

Composite 6/9/10 

 6/10/10 

0731c 

0953d 

Influent to Bioreactor System – Day 3 

Grab 6/9/10 

 6/10/10 

0743e

, 1346f , and 1945 g 

0145 h 

Composite 6/10/10 

 6/11/10 

0728c 

0657d 

SP-2 

Influent to Bioreactor System – Day 4 

Grab 6/10/10 

 6/11/10 

0738e

, 1339f , and 1939 g 

0137 h 

Composite 6/7/10 

 6/8/10 

0928c 

1119d 

Effluent from Bioreactor System – Day 1

Grab 6/7/10 

 6/8/10 

0944e

, 1537f , and 2145 g 

0344 h 

Composite 6/8/10 

 6/9/10 

0912c 

1136d 

Effluent from Bioreactor System – Day 2

Grab 6/8/10 

 6/9/10 

0926e

, 1526f , and 2126 g 

0328h 

Composite 6/9/10 

 6/10/10 

0915c 

1039d 

Effluent from Bioreactor System – Day 3

Grab 6/9/10 

 6/10/10 

0927e

, 1525f , and 2124 g 

0325h 

Composite 6/10/10 

 6/11/10 

0905c 

0835d 

SP-3 

Effluent from Bioreactor System – Day 4

Grab 6/10/10 

 6/11/10 

0915e

, 1518f , and 2113 g 

0313h 
3-14

Table 3-1. Sample Collection Information, Belews Creek

Sampling 

Point 

Number Sampling Point Description 

Type of 

Sample 

Sample Collection 

Date 

Sample Collection 

Time 

Composite 6/9/10 

 6/10/10 

0731c 

0954d 

SP-4 Duplicate of Influent to Bioreactor 

System – Day 3 

Grab 6/9/10 

 6/10/10 

0744e

, 1347f , and 1947 g 

0147 h 

Composite 6/8/10 

 6/9/10 

0912c 

1137d 

SP-5 Duplicate of Effluent from Bioreactor 

System – Day 2 

Grab 6/8/10 

 6/9/10 

0928e

, 1528f , and 2128 g 

0330 h 

SP-6 Influent to FGD Wastewater Treatment 

System Field Blank 

Grab 6/7/10 1049 i and 1219j

Composite 6/7/10 

6/8/10

0638k

1008l

Influent to Bioreactor System Field 

Blank – Day 1 

Grab 6/7/10 0746m

Influent to Bioreactor System Field 

Blank – Day 2 

Grab 6/8/10 0739m

Influent to Bioreactor System Field 

Blank – Day 3 

Grab 6/9/10 0737m

SP-7 

Influent to Bioreactor System Field 

Blank – Day 4 

Grab 6/10/10 0733m

Composite 6/7/10 

6/8/10 

0828k

1107l

Effluent from Bioreactor System Field 

Blank – Day 1 

Grab 6/7/10 0939m

Effluent from Bioreactor System Field 

Blank – Day 2 

Grab 6/8/10 0922m

Effluent from Bioreactor System Field 

Blank – Day 3 

Grab 6/9/10 0922m

SP-8 

Effluent from Bioreactor System Field 

Blank – Day 4 

Grab 6/10/10 0910m

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 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. 
3-15

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.
3-16 

Table 3-2. Sample Collection at Belews Creek 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+1QC 4+SP-3 Effluent from Bioreactor System 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+SP-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+2QC 14

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
3-17 

Table 3-3. Field Measurements, Belews Creek

Sampling 

Point 

Number Sampling Point Description Date Time 

Temperature 

(°C) 

pH 

(S.U.) 

Waste 

Stream Flow 

Rate 

(gpm) 

Influent to FGD Wastewater Treatment System – Day 1

6/7/2010 1124 45 7 554a 

Influent to FGD Wastewater Treatment System – Day 2 

6/8/2010 1301 44 6.3 481b 

Influent to FGD Wastewater Treatment System – Day 3 

6/9/2010 1009 42 6.5 474c 

SP-1 

Influent to FGD Wastewater Treatment System – Day 4 

6/10/2010 1140 46.5 7 483d 

Samplers notdark brown chigh in solidsoxidants in to

6/7/10 0754 40 6.5 5186/7/10 1358 41 6.5 560 6/7/10 2004 40 6.5 531 

Influent to Bioreactor System – Day 1

6/8/10 0149 40 6.5 562 6/8/10 0748 39 6.5 280 6/8/10 1345 39 7 390 6/8/10 1939 39 6.5 375 

Influent to Bioreactor System – Day 2 

6/9/10 0141 38 6.5 504 

6/9/10 0744 38 6.5 264 6/9/10 1348 38 6.5 276 6/9/10 1947 39 6.5 535 

Influent to Bioreactor System – Day 3 

6/10/10 0147 39 6.5 531 

6/10/10 0738 39 6 383 6/10/10 1339 41 6.5 566 6/10/10 1934 41 6.5 419 

SP-2 

Influent to Bioreactor System – Day 4 

6/11/10 0138 41 6.5 506 

Samples were did not have aNo detected stotal cyanide 
3-18 

Table 3-3. Field Measurements, Belews Creek

Sampling 

Point 

Number Sampling Point Description Date Time 

Temperature 

(°C) 

pH 

(S.U.) 

Waste 

Stream Flow 

Rate 

(gpm) 

6/7/10 0948 34 7 4746/7/10 1541 34 7 5626/7/10 2147 34 7 469 

Effluent from Bioreactor System – Day 1

6/8/10 0348 34 7 469 6/8/10 0932 34 7 378 6/8/10 1531 34 7 384 6/8/10 2128 34 7 437 

Effluent from Bioreactor System – Day 2 

6/9/10 0330 34 7 470 

6/9/10 0928 34 7 265 6/9/10 1525 34 7.5 384 6/9/10 2124 34 7.5 481 

Effluent from Bioreactor System – Day 3 

6/10/10 0326 34 7.5 453 

6/10/10 0916 34 7 397 6/10/10 1518 35 6.5 547 6/10/10 2114 34 7.5 346 

SP-3 

Effluent from Bioreactor System – Day 4 

6/11/10 0314 34 7 524 

Samples were did not have aNo detected stotal cyanide 

b Based on average of flow meter measurements collected every minute from 1104 to 1131 on 6/7/10 (time of sample collection). c Based on average of flow meter measurements collected every minute from 1241 to 1308 on 6/8/10 (time of sample collection). d Based on average of flow meter measurements collected every minute from 0952 to 1019 on 6/9/10 (time of sample collection). e Based on average of flow meter measurements collected every minute from 1123 to 1250 on 6/10/10 (time of sample collection). f Based on average of flow meter measurements collected every minute from 1030 to 1115 on 10/23/08 (time of sample collection)
3-19

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

Sample Number Sample Point Sample Description 

71641 SP-1, Day 1 Influent to FGD Wastewater Treatment System - Day 1 

71642 SP-1, Day 2 Influent to FGD Wastewater Treatment System - Day 2 

71643 SP-1, Day 3 Influent to FGD Wastewater Treatment System - Day 3 

71644 SP-1, Day 4 Influent to FGD Wastewater Treatment System - Day 4 

71645 SP-2, Day 1 Influent to Bioreactor System - Day 1 

71646 SP-2, Day 2 Influent to Bioreactor System - Day 2 

71647 SP-2, Day 3 Influent to Bioreactor System - Day 3 

71648 SP-2, Day 4 Influent to Bioreactor System - Day 4 

71649 SP-3, Day 1 Effluent from Bioreactor System - Day 1 

71650 SP-3, Day 2 Effluent from Bioreactor System - Day 2 

71651 SP-3, Day 3 Effluent from Bioreactor System - Day 3 

71652 SP-3, Day 4 Effluent from Bioreactor System - Day 4 

71653 SP-4, Day 3 Duplicate of Influent to Bioreactor System - Day 3 

71654 SP-5, Day 2 Duplicate of Effluent from Bioreactor System - Day 2 

71655 SP-6, Day 1 Influent to FGD Wastewater Treatment System Field Blank - Day 1 

71656 SP-7, Day 1 Influent to Bioreactor System Field Blank - Day 1 

71657 SP-7, Day 2 Influent to Bioreactor System Field Blank - Day 2 

71658 SP-7, Day 3 Influent to Bioreactor System Field Blank - Day 3 

71659 SP-7, Day 4 Influent to Bioreactor System Field Blank - Day 4 

71660 SP-8, Day 1 Effluent from Bioreactor System Field Blank - Day 1 

71661 SP-8, Day 2 Effluent from Bioreactor System Field Blank - Day 2 

71662 SP-8, Day 3 Effluent from Bioreactor System Field Blank - Day 3 

71663 SP-8, Day 4 Effluent from Bioreactor System Field Blank - Day 4 
3-20

Table 3-5. Analytical Methods, Belews Creek

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).
3-21

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

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.
3-22 

Table 3-7. Sample Preservation Summary, Belews Creek

Sampling Point 

Number Analysis Date 

Chemical 

Added 

Initial pH 

(S.U.) 

Final pH 

(S.U.) 

Amount 

Added 

(drops) 

71641 Group II Volume 1 6/7/10 H2SO4 6 2 55 

71641 Group II Volume 2 6/7/10 H2SO4 6 2 55 

71641 Hexavalent Chromium 6/7/10 (NH4)2SO4

Buffer 

6 8.5 a 530 

71655 Hexavalent Chromium Field 

Blank 

6/7/10 (NH4)2SO4

Buffer 

5 9 a 630 

71641 Total Cyanide 6/7/10 NaOH 7 10 25 

71645 Total Cyanide 6/7/10 NaOH 6.5 10.5 25 

71649 Total Cyanide 6/7/10 NaOH 7 10 25 

71642 Group II Volume 1 6/8/10 H2SO4 6 2 55 

71642 Group II Volume 2 6/8/10 H2SO4 6 2 55 

71645 Group II Volume 1 6/8/10 H2SO4 6 2 30 

71645 Group II Volume 2 6/8/10 H2SO4 6 2 30 

71649 Group II Volume 1 6/8/10 H2SO4 6 2 30 

71649 Group II Volume 2 6/8/10 H2SO4 6 2 30 

71642 Hexavalent Chromium 6/8/10 (NH4)2SO4

Buffer 

6.0 8.8 a 700 

71645 Hexavalent Chromium 6/8/10 (NH4)2SO4

Buffer 

6.5 9.3 700 

71649 Hexavalent Chromium 6/8/10 (NH4)2SO4

Buffer 

6.5 8.9 a 735 

71656 Hexavalent Chromium Field 

Blank 

6/8/10 (NH4)2SO4

Buffer 

6.5 9.5 400 

71660 Hexavalent Chromium Field 

Blank 

6/8/10 (NH4)2SO4

Buffer 

6.5 9.5 700 

71642 Total Cyanide 6/8/10 NaOH 6.3 10 25 

71646 Total Cyanide 6/8/10 NaOH 6.5 10 25 

71650 Total Cyanide 6/8/10 NaOH 7 10 25 

71654 Total Cyanide 6/8/10 NaOH 7 10 25 

71643 Group II Volume 1 6/9/10 H2SO4 6.5 2 30 

71643 Group II Volume 2 6/9/10 H2SO4 6.5 2 30 

71646 Group II Volume 1 6/9/10 H2SO4 5.5 2 30 

71646 Group II Volume 2 6/9/10 H2SO4 5.5 2 30 

71650 Group II Volume 1 6/9/10 H2SO4 5.5 2 30 

71650 Group II Volume 2 6/9/10 H2SO4 5.5 2 30 

71654 Group II Volume 1 6/9/10 H2SO4 5.5 2 30 

71654 Group II Volume 2 6/9/10 H2SO4 5.5 2 30 

71643 Hexavalent Chromium 6/9/10 (NH4)2SO4

Buffer 

5.5 9.0 a 500 
3-23 

Table 3-7. Sample Preservation Summary, Belews Creek

Sampling Point 

Number Analysis Date 

Chemical 

Added 

Initial pH 

(S.U.) 

Final pH 

(S.U.) 

Amount 

Added 

(drops) 

71646 Hexavalent Chromium 6/9/10 (NH4)2SO4

Buffer 

5.5 9.0 a 590 

71650 Hexavalent Chromium 6/9/10 (NH4)2SO4

Buffer 

5.5 9.0 a 480 

71654 Hexavalent Chromium 6/9/10 (NH4)2SO4

Buffer 

5.5 9.0 a 515 

71643 Total Cyanide 6/9/10 NaOH 6.5 10 25 

71647 Total Cyanide 6/9/10 NaOH 6.5 10 25 

71651 Total Cyanide 6/9/10 NaOH 7.5 10 25 

71651 Total Cyanide - QC 6/9/10 NaOH 7.5 10 25 

71653 Total Cyanide 6/9/10 NaOH 6.5 10 25 

71644 Group II Volume 1 6/10/10 H2SO4 5.5 2 40 

71644 Group II Volume 2 6/10/10 H2SO4 5.5 2 40 

71647 Group II Volume 1 6/10/10 H2SO4 5.5 2 30 

71647 Group II Volume 2 6/10/10 H2SO4 5.5 2 30 

71651 Group II Volume 1 6/10/10 H2SO4 5.5 2 30 

71651 Group II Volume 2 6/10/10 H2SO4 5.5 2 30 

71651 Group II Volume 1 – QC 6/10/10 H2SO4 5.5 2 30 

71651 Group II Volume 2 – QC 6/10/10 H2SO4 5.5 2 30 

71653 Group II Volume 1 6/10/10 H2SO4 5.5 2 30 

71653 Group II Volume 2 6/10/10 H2SO4 5.5 2 30 

71644 Hexavalent Chromium 6/10/10 (NH4)2SO4

Buffer 

6.0 8.8 a 540 

71647 Hexavalent Chromium 6/10/10 (NH4)2SO4

Buffer 

5.5 9.5 850 

71651 Hexavalent Chromium 6/10/10 (NH4)2SO4

Buffer 

5.5 9 a 415 

71653 Hexavalent Chromium 6/10/10 (NH4)2SO4

Buffer 

5.5 9.5 750 

71644 Total Cyanide 6/10/10 NaOH 6.5 10 25 

71648 Total Cyanide 6/10/10 NaOH 6.5 10 25 

71648 Total Cyanide – QC 6/10/10 NaOH 6.5 10 25 

71652 Total Cyanide 6/10/10 NaOH 7.5 10 25 

71648 Group II Volume 1 6/11/10 H2SO4 6 2 30 

71648 Group II Volume 2 6/11/10 H2SO4 6 2 30 

71648 Group II Volume 1 – QC 6/11/10 H2SO4 6 2 30 

71648 Group II Volume 2 – QC 6/11/10 H2SO4 6 2 30 

71652 Group II Volume 2 6/11/10 H2SO4 6 2 30 

71652 Group II Volume 1 6/11/10 H2SO4 6 2 30 
3-24 

Table 3-7. Sample Preservation Summary, Belews Creek

Sampling Point 

Number Analysis Date 

Chemical 

Added 

Initial pH 

(S.U.) 

Final pH 

(S.U.) 

Amount 

Added 

(drops) 

71648 Hexavalent Chromium 6/11/10 (NH4)2SO4

Buffer 

6.0 9.0 a 730 

71652 Hexavalent Chromium 6/11/10 (NH4)2SO4

Buffer 

6.0 9.0 a 520 

a

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

added to the sample bottle. 
3-25 

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

Creek

Unit ID Boiler Type 

Capacity 

(MW) 

Electricity Production 

(MW) 

(or Percent Capacity %)

SCR 

(No, On, Off) 

Particulate Control System 

(HS/CS ESP, or BH) 

1 Opposed Firing 1200 67.2% On CS ESP 

2 Opposed Firing 1200 64.4% On CS ESP 

CS ESP – Cold-side electrostatic precipitator. 
3-26 

Table 3-9. FGD Scrubber System Operating Characteristics, Belews Creek 

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 Belews Lake 96.22 Yes Spray Yes Limestone None Belews Lake 96.9
3-27

Table 3-10. Coal Usage during Sample Collection, Belews Creek 

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 9,253 WV 1.18 1,453 1 

2 CAPP 8,533 WV 1.18 1,453 

1 CAPP 9,098 WV 0.75 741 2 

2 CAPP 9,325 WV 0.75 741 

1 CAPP 8,392 WV 0.92 1,500 

3 

2 CAPP 8,136 WV 0.92 1,500 

1 CAPP 9,700 WV 0.74 888 

4A 

2 CAPP 9,668 WV 0.74 888 

1 NAPP AT 20% / 

CAPP AT 80% *see note below WV 2.27 861 

4B 

2 NAPP AT 20% / 

CAPP AT 80% *see note below WV 2.27 861 

* Note : Day 4 has two coal entries, 4A from midnight to 15:00 and 4B 15:00 to midnight. Feeder changes were 

made to reclaim the higher sulfur Northern Appalachian Coal (NAPP) at a 20% blend ratio with 80% of Central 

Appalachian Coal ( CAPP). The weight shown for the 4A entry is for the entire 24-hour period. An hourly 

breakdown is not available. 

 

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

Scrubber Slurry 

Blowdown Flow Rate 

Day of 

Sampling 

FGD 

System ID 

Associated 

Unit IDs 

Flow Rate 

(gpm) Duration 

Scrubber 

Slurry 

Percent 

Solids 

Time of 

Dewatering 

During 

Sampling Day 

Percent 

Filtrate 

Recycled 

Back to 

Scrubber 

1 1 297 19 hrs 15-17% dewatered 3 times 100% 

1 

2 2 273 11 hrs 15-17% dewatered 3 times 100% 

1 1 313 12 hrs 15-17% dewatered 5 times 100% 

2 

2 2 265 12 hrs 15-17% dewatered 3 times 100% 

1 1 313 13 hrs 15-17% dewatered 3 times 100% 

3 

2 2 283 12 hrs 15-17% dewatered 3 times 100% 

1 1 310 17 hrs 15-17% dewatered 3 times 100% 

4 

2 2 263 19.5 hrs 15-17% dewatered 3 times 100% 
3-28 

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

Scrubber Purge Chemical Usage 

Day of 

Sampling 

Flow Rate 

(gpm) 

Duration 

(hr) Lime 

35% Ferric 

Chloride 

Organosulfide: 

NA 

Polymer

Nalco 713

1 515 24 pH – 8.5 S.U. 1,400 lbs 25 ppm 20.9 gpd NA 5 ppm 4.2 gpd 2 496 16 pH – 8.5 S.U. 2,200 lbs 25 ppm 17.1 gpd NA 5 ppm 3.4 gpd 3 518 20 pH – 8.5 S.U. 2,200 lbs 25 ppm 16.6 gpd NA 5 ppm 3.3 gpd 4 508 20 pH – 8.5 S.U. 2,900 lbs 25 ppm 19.8 gpd NA 5 ppm 4.0 gpd 

NA – Not applicable
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 room temperature bromine monochloride digestion 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 Belews Creek, 

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 5-2 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 5-3 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 
4-3 

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

the sample collection across the treatment system was not timed to reflect the amount of time it 

takes the wastewater to pass through the system. 

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. 
4-4 

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

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

value. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. ** - The accuracy of the Day 1 dissolved mercury analytical result seems questionable based on the results from the other sampling days. If the Day 1 was excluded from the calculated average, the 4-day average would be 131 ng/L. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria.

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

Influent to FGD Wastewater Treatment System (S

Analyte Units Method Day 1 Day 2 Day 3 Day 

ClassicalsAmmonia mg/L 350.1 1.10 NQ (1.00) NQ (1.00) NQ (1.00Nitrate Nitrite as N mg/L 353.2 20.0 14.0 16.0 15.0 Nitrogen, Total Kjeldahl mg/L 351.2 29.0 B,F 5.70 6.50 5.50 Biochemical Oxygen Demand mg/L 5210B ND (10.0) ND (10.0) ND (10.0) ND (10.0Chemical Oxygen Demand mg/L 410.4 220 250 210 180 Chloride mg/L 300.0 7,700 7,100 7,600 8,000 Sulfate mg/L 300.0 1,600 1,500 1,100 1,500 Cyanide, Total mg/L 4500 CN E ND (0.0100) F NQ (0.100) NQ (0.100) NQ (0.100Total Dissolved Solids mg/L 2540C 17,000 D 14,000 13,000 25,000 Total Suspended Solids mg/L 2540D 3,100 D 4,900 3,300 D 2,500 Phosphorus, Total mg/L 365.1 0.350 B 0.150 B 1.30 B NQ (0.050Total MetalsAluminum ug/L 200.7 92,000 4 97,000 4 83,000 4 82,000 Antimony ug/L 200.8 8.40 10.0 9.60 9.10 Arsenic ug/L 200.8 270 4 230 240 200 Barium ug/L 200.7 1,300 1,200 1,200 1,200 Beryllium ug/L 200.7 8.90 9.70 8.20 8.40 
4-5 

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

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

value. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. ** - The accuracy of the Day 1 dissolved mercury analytical result seems questionable based on the results from the other sampling days. If the Day 1 was excluded from the calculated average, the 4-day average would be 131 ng/L. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria.

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

Influent to FGD Wastewater Treatment System (S

Analyte Units Method Day 1 Day 2 Day 3 Day 

Boron ug/L 200.7 150,000 B,4 140,000 B,4 140,000 B,4 170,000 Cadmium ug/L 200.8 4.10 NQ (4.00) NQ (4.00) NQ (4.00Calcium ug/L 200.7 4,700,000 4 5,300,000 4 4,000,000 4 4,100,00Chromium ug/L 200.8 260 4,^ 250 ^ 250 ^ 250 Cobalt ug/L 200.7 54.0 61.0 56.0 55.0 Copper ug/L 200.8 150 170 160 140 Iron ug/L 200.7 100,000 4 110,000 4 99,000 4 100,000 Lead ug/L 200.8 130 120 130 120 Magnesium ug/L 200.7 830,000 4 760,000 4 670,000 4 710,000 Manganese ug/L 200.7 5,500 4 6,000 4 5,600 4 5,800 Mercury ng/L 1631E 248,000 257,000 291,000 224,000 Molybdenum ug/L 200.7 45.0 47.0 45.0 44.0 Nickel ug/L 200.8 230 4 240 230 220 Selenium ug/L 200.8 6,800 4 6,300 6,600 6,600 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Sodium ug/L 200.7 48,000 46,000 46,000 48,000 Thallium ug/L 200.8 3.70 3.20 3.40 4.00 Tin ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200Titanium ug/L 200.7 1,400 1,500 1,400 1,300 Vanadium ug/L 200.8 190 4 210 200 190 
4-6 

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

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

value. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. ** - The accuracy of the Day 1 dissolved mercury analytical result seems questionable based on the results from the other sampling days. If the Day 1 was excluded from the calculated average, the 4-day average would be 131 ng/L. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria.

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

Influent to FGD Wastewater Treatment System (S

Analyte Units Method Day 1 Day 2 Day 3 Day 

Zinc ug/L 200.8 330 4 290 290 290 Dissolved MetalsAluminum ug/L 200.7 ND (200) F NQ (200) B NQ (200) B ND (200Antimony ug/L 200.8 2.00 2.50 2.00 2.50 Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) 4.80 4.30 Barium ug/L 200.7 650 640 B 660 700 Beryllium ug/L 200.7 ND (2.00) F ND (2.00) ND (2.00) ND (2.00Boron ug/L 200.7 150,000 B,4 140,000 B,4 150,000 B,4 150,000 Cadmium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00Calcium ug/L 200.7 3,200,000 4 3,100,000 B,4 3,600,000 4 3,300,00Chromium ug/L 200.8 8.70 ND (8.00) ND (8.00) ND (8.00Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) T,Est ND (10.0Cobalt ug/L 200.7 NQ (20.0) 28.0 28.0 27.0 Copper ug/L 200.8 NQ (4.00) NQ (4.00) 4.20 NQ (4.00Iron ug/L 200.7 ND (200) F ND (200) ND (200) ND (200Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Magnesium ug/L 200.7 720,000 4 670,000 4 690,000 4 700,000 Manganese ug/L 200.7 2,100 4 5,300 4 5,400 B,4 5,400 Mercury ng/L 1631E 49,300** 119 142 NA Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) NQ (40.0
4-7 

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

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

value. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. ** - The accuracy of the Day 1 dissolved mercury analytical result seems questionable based on the results from the other sampling days. If the Day 1 was excluded from the calculated average, the 4-day average would be 131 ng/L. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria.

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

Influent to FGD Wastewater Treatment System (S

Analyte Units Method Day 1 Day 2 Day 3 Day 

Nickel ug/L 200.8 100 130 140 140 Selenium ug/L 200.8 1,300 4 400 410 550 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Sodium ug/L 200.7 47,000 45,000 47,000 48,000 Thallium ug/L 200.8 3.90 3.90 3.80 4.00 Tin ug/L 200.7 NQ (200) F NQ (200) NQ (200) NQ (200Titanium ug/L 200.7 NQ (20.0) F NQ (20.0) NQ (20.0) NQ (20.0Vanadium ug/L 200.8 NQ (10.0) ND (10.0) NQ (10.0) NQ (10.0Zinc ug/L 200.8 39.0 32.0 32.0 33.0 
4-8 

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 + - The dissolved mercury result for this sample is based on grabs 1 through 3 because the fourth grab was dropped by the laboratory. Each of the thre

individually and a mathematical average was used to calculate the composite sample concentration. < - 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 

^ - 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. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria. 

Table 4-2. Influent to the Bioreactor System, Belews Creek 

Influent to the Bioreactor System (SP-2)

Analyte Units Method Day 1 Day 2 Day 3 Day 4 

ClassicalsAmmonia mg/L 350.1 1.20 1.30 1.05 NQ (1.00) Nitrate Nitrite as N mg/L 353.2 19.0 19.0 20.0 21.0 Nitrogen, Total Kjeldahl mg/L 351.2 NQ (5.00) B NQ (2.50) B < 1.65 2.60 Biochemical Oxygen Demand mg/L 5210B ND (20.0) ND (20.0) ND (20.0) ND (20.0) Chemical Oxygen Demand mg/L 410.4 370 320 230 140 Chloride mg/L 300.0 7,800 8,000 7,400 7,900 Sulfate mg/L 300.0 1,300 1,300 1,700 1,200 Cyanide, Total mg/L 4500 CN E ND (0.100) ND (0.100) ND (0.100) ND (0.100) Total Dissolved Solids mg/L 2540C 16,000 15,000 23,500 26,000 Total Suspended Solids mg/L 2540D 7.60 12.0 NQ (4.00) NQ (4.00) Phosphorus, Total mg/L 365.1 NQ (0.0500) B NQ (0.0500) B NQ (0.0500) NQ (0.0500) Total MetalsAluminum ug/L 200.7 ND (5,000) NQ (200) NQ (200) NQ (200) Antimony ug/L 200.8 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.00) Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) Barium ug/L 200.7 390 380 380 420 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00) 
4-9 

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 + - The dissolved mercury result for this sample is based on grabs 1 through 3 because the fourth grab was dropped by the laboratory. Each of the thre

individually and a mathematical average was used to calculate the composite sample concentration. < - 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 

^ - 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. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria. 

Table 4-2. Influent to the Bioreactor System, Belews Creek 

Influent to the Bioreactor System (SP-2)

Analyte Units Method Day 1 Day 2 Day 3 Day 4 

Boron ug/L 200.7 160,000 B 140,000 B 150,000 150,000 Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00) Calcium ug/L 200.7 3,700,000 3,300,000 3,250,000 3,700,000 Chromium ug/L 200.8 17.0 ^ 18.0 ^ 20.0 20.0 Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) Copper ug/L 200.8 NQ (4.00) ND (4.00) ND (4.00) ND (4.00) Iron ug/L 200.7 NQ (200) ND (200) ND (200) NQ (200) Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Magnesium ug/L 200.7 810,000 740,000 720,000 740,000 Manganese ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0) Mercury ng/L 1631E 46,600 43,000 47,300 53,300 Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) NQ (40.0) Nickel ug/L 200.8 12.0 11.0 7.20 8.70 Selenium ug/L 200.8 1,100 1,200 1,300 1,300 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Sodium ug/L 200.7 48,000 50,000 48,000 50,000 Thallium ug/L 200.8 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.00) Tin ug/L 200.7 ND (200) ND (200) ND (200) NQ (200) Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0) Vanadium ug/L 200.8 NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0) Zinc ug/L 200.8 NQ (10.0) 12.0 ND (10.0) ND (10.0) 
4-10 

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 + - The dissolved mercury result for this sample is based on grabs 1 through 3 because the fourth grab was dropped by the laboratory. Each of the thre

individually and a mathematical average was used to calculate the composite sample concentration. < - 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 

^ - 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. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria. 

Table 4-2. Influent to the Bioreactor System, Belews Creek 

Influent to the Bioreactor System (SP-2)

Analyte Units Method Day 1 Day 2 Day 3 Day 4 

Dissolved MetalsAluminum ug/L 200.7 ND (200) ND (200) ND (200) ND (200) Antimony ug/L 200.8 2.10 NQ (2.00) NQ (2.00) NQ (2.00) Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) Barium ug/L 200.7 410 B 380 375 420 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Boron ug/L 200.7 160,000 B 150,000 B 140,000 150,000 Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00) Calcium ug/L 200.7 3,400,000 B 3,600,000 3,250,000 3,700,000 Chromium ug/L 200.8 17.0 18.0 19.5 20.0 Chromium (VI) ug/L 218.6 13.4 11.7 T,Est 13.2 14.6 Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) Copper ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) ND (4.00) Iron ug/L 200.7 ND (200) ND (200) NQ (200) ND (200) Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Magnesium ug/L 200.7 760,000 730,000 720,000 740,000 Manganese ug/L 200.7 NQ (20.0) NQ (20.0) B NQ (20.0) NQ (20.0) Mercury ng/L 1631E 47,000 49,300+ 44,000 44,400 Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) NQ (40.0) Nickel ug/L 200.8 13.0 10.0 6.40 9.70 Selenium ug/L 200.8 1,100 1,200 1,250 1,300 
4-11 

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 + - The dissolved mercury result for this sample is based on grabs 1 through 3 because the fourth grab was dropped by the laboratory. Each of the thre

individually and a mathematical average was used to calculate the composite sample concentration. < - 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 

^ - 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. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria. 

Table 4-2. Influent to the Bioreactor System, Belews Creek 

Influent to the Bioreactor System (SP-2)

Analyte Units Method Day 1 Day 2 Day 3 Day 4 

Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Sodium ug/L 200.7 49,000 49,000 47,500 50,000 Thallium ug/L 200.8 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.00) Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0) Vanadium ug/L 200.8 NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0) Zinc ug/L 200.8 ND (10.0) ND (10.0) NQ (10.0) ND (10.0) 
4-12 

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. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. ** - The Day 2 duplicate of the effluent from the bioreactor system was detected at a concentration of 6,440 ng/L, which seems like an erroneous resu

original sample concentration and the other three sample days. For presentation purposes in this table, the duplicate result has been removed from the 

and from the calculation of the 4-day average result. 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. H – Sample was prepared/analyzed beyond the specified holding time. 

Table 4-3. Effluent from the Bioreactor System, Belews Creek 

Effluent from the Bioreactor System (SP-3

Analyte Units Method Day 1 Day 2 Day 3 Day 

ClassicalsAmmonia mg/L 350.1 4.50 4.45 4.40 4.50 Nitrate Nitrite as N mg/L 353.2 ND (0.100) F NQ (0.100) ND (0.100) F ND (0.10Nitrogen, Total Kjeldahl mg/L 351.2 6.10 F 5.75 6.30 B,F,H 6.00 Biochemical Oxygen Demand mg/L 5210B ND (10.0) ND (10.0) ND (10.0) ND (10.0Chemical Oxygen Demand mg/L 410.4 240 255 130 F 190 Chloride mg/L 300.0 8,000 7,700 7,000 7,800 Sulfate mg/L 300.0 1,400 1,400 1,300 2,500 Cyanide, Total mg/L 4500 CN E 0.0120 F NQ (0.100) NQ (0.100) F NQ (0.10Total Dissolved Solids mg/L 2540C 16,000 14,000 24,000 B 55,000 Total Suspended Solids mg/L 2540D 6.80 24.0 4.00 NQ (4.00Phosphorus, Total mg/L 365.1 0.120 B 0.130 0.110 B,F ND (0.050Total MetalsAluminum ug/L 200.7 ND (5,000) NQ (200) NQ (200) NQ (200Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00Barium ug/L 200.7 390 380 370 380 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00
4-13 

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. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. ** - The Day 2 duplicate of the effluent from the bioreactor system was detected at a concentration of 6,440 ng/L, which seems like an erroneous resu

original sample concentration and the other three sample days. For presentation purposes in this table, the duplicate result has been removed from the 

and from the calculation of the 4-day average result. 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. H – Sample was prepared/analyzed beyond the specified holding time. 

Table 4-3. Effluent from the Bioreactor System, Belews Creek 

Effluent from the Bioreactor System (SP-3

Analyte Units Method Day 1 Day 2 Day 3 Day 

Boron ug/L 200.7 180,000 B 190,000 170,000 B,4 140,000 Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00Calcium ug/L 200.7 4,000,000 3,300,000 3,300,000 4 3,600,00Chromium ug/L 200.8 ND (8.00) ^ ND (8.00) ND (8.00) ^ ND (8.00Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0Copper ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00Iron ug/L 200.7 NQ (200) NQ (200) 300 NQ (200Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Magnesium ug/L 200.7 890,000 760,000 750,000 4 740,000 Manganese ug/L 200.7 470 320 260 230 Mercury ng/L 1631E 230 247** 346 406 Molybdenum ug/L 200.7 ND (40.0) ND (40.0) NQ (40.0) NQ (40.0Nickel ug/L 200.8 ND (4.00) ND (4.00) NQ (4.00) ND (4.00Selenium ug/L 200.8 7.30 25.5 5.10 25.0 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Sodium ug/L 200.7 51,000 50,000 48,000 49,000 Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0
4-14 

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. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. ** - The Day 2 duplicate of the effluent from the bioreactor system was detected at a concentration of 6,440 ng/L, which seems like an erroneous resu

original sample concentration and the other three sample days. For presentation purposes in this table, the duplicate result has been removed from the 

and from the calculation of the 4-day average result. 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. H – Sample was prepared/analyzed beyond the specified holding time. 

Table 4-3. Effluent from the Bioreactor System, Belews Creek 

Effluent from the Bioreactor System (SP-3

Analyte Units Method Day 1 Day 2 Day 3 Day 

Vanadium ug/L 200.8 ND (10.0) NQ (10.0) ND (10.0) ND (10.0Zinc ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) ND (10.0Dissolved MetalsAluminum ug/L 200.7 NQ (200) B NQ (200) NQ (200) NQ (200Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00Barium ug/L 200.7 370 B 375 370 370 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00Boron ug/L 200.7 160,000 B 160,000 150,000 B,4 140,000 Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00Calcium ug/L 200.7 3,200,000 B 3,600,000 3,300,000 4 3,600,00Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ^ ND (8.00Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10.0Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0Copper ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00Iron ug/L 200.7 NQ (200) < 255 NQ (200) NQ (200Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Magnesium ug/L 200.7 730,000 755,000 740,000 4 730,000 Manganese ug/L 200.7 410 315 260 230 
4-15 

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. ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. ** - The Day 2 duplicate of the effluent from the bioreactor system was detected at a concentration of 6,440 ng/L, which seems like an erroneous resu

original sample concentration and the other three sample days. For presentation purposes in this table, the duplicate result has been removed from the 

and from the calculation of the 4-day average result. 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. H – Sample was prepared/analyzed beyond the specified holding time. 

Table 4-3. Effluent from the Bioreactor System, Belews Creek 

Effluent from the Bioreactor System (SP-3

Analyte Units Method Day 1 Day 2 Day 3 Day 

Mercury ng/L 1631E 23.1 21.3 28.2 36.1 Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) ND (40.0) NQ (40.0Nickel ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00Selenium ug/L 200.8 8.10 23.5 4.90 22.0 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Sodium ug/L 200.7 48,000 49,500 48,000 48,000 Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0Vanadium ug/L 200.8 ND (10.0) NQ (10.0) NQ (10.0) ND (10.0Zinc ug/L 200.8 ND (10.0) ND (10.0) 12.0 F ND (10.0
4-16 

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

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

one result is a J-value. 

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

Analyte Units Method

Influent to FGD 

Wastewater Treatment 

System (SP-1)

4-Day Average

Influent to 

Bioreactor 

System (SP-2

4-Day Averag

ClassicalsAmmonia mg/L 350.1 < 0.650 < 1.01 Nitrate Nitrite as N mg/L 353.2 16.3 19.8 Nitrogen, Total Kjeldahl mg/L 351.2 11.7 < 2.00 Biochemical Oxygen Demand mg/L 5210B ND (10.0) ND (20.0) Chemical Oxygen Demand mg/L 410.4 215 265 Chloride mg/L 300.0 7,600 7,780 Sulfate mg/L 300.0 1,430 1,380 Cyanide, Total mg/L 4500 CN E NQ (0.0775) ND (0.100) Total Dissolved Solids mg/L 2540C 17,300 20,100 Total Suspended Solids mg/L 2540D 3,450 < 5.90 Phosphorus, Total mg/L 365.1 < 0.456 NQ (0.0500) 
4-17 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu* - The 4-day average result includes an analytical result where the accuracy is questionable. If the questionable result was excluded from the calculataverage would be 131 ng/L. ** - The 4-day average result presented has been revised to exclude the Day 2 duplicate result because it is an erroneous result based on the Day 2 origresults from the other sampling days. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. 

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

Influent to FGD 

Wastewater Treatment

System (SP-1)

4-Day Average

Influent to 

Bioreactor 

System (SP-2)

4-Day Average

4

Analyte Units Method Total Dissolved Total Dissolved Tot

MetalsAluminum ug/L 200.7 88,500 NQ (200) NQ (1,400) ND (200) NQ (1Antimony ug/L 200.8 9.28 2.25 NQ (2.00) < 1.28 ND (2Arsenic ug/L 200.8 235 < 3.28 NQ (4.00) NQ (4.00) NQ (4Barium ug/L 200.7 1,230 663 393 396 38Beryllium ug/L 200.7 8.80 ND (2.00) ND (2.00) ND (2.00) ND (2Boron ug/L 200.7 150,000 148,000 150,000 150,000 170,0Cadmium ug/L 200.8 < 2.53 NQ (4.00) ND (4.00) ND (4.00) ND (4Calcium ug/L 200.7 4,530,000 3,300,000 3,490,000 3,490,000 3,550Chromium ug/L 200.8 253 < 5.18 18.8 18.6 ND (8Chromium (VI) ug/L 218.6 NA ND (10.0) NA 13.2 NA Cobalt ug/L 200.7 56.5 < 23.3 ND (20.0) ND (20.0) ND (2Copper ug/L 200.8 155 < 2.55 NQ (4.00) NQ (4.00) ND (4Iron ug/L 200.7 102,000 ND (200) NQ (200) NQ (200) < 1Lead ug/L 200.8 125 ND (2.00) ND (2.00) ND (2.00) ND (2Magnesium ug/L 200.7 743,000 695,000 753,000 738,000 785,0Manganese ug/L 200.7 5,730 4,550 NQ (20.0) NQ (20.0) 32Mercury ng/L 1631E 255,000 16,500* 47,600 46,200 307Molybdenum ug/L 200.7 45.3 NQ (40.0) NQ (40.0) NQ (40.0) NQ (4Nickel ug/L 200.8 230 128 9.73 9.78 NQ (4Selenium ug/L 200.8 6,580 665 1,230 1,210 15.Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) ND (2
4-18 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu* - The 4-day average result includes an analytical result where the accuracy is questionable. If the questionable result was excluded from the calculataverage would be 131 ng/L. ** - The 4-day average result presented has been revised to exclude the Day 2 duplicate result because it is an erroneous result based on the Day 2 origresults from the other sampling days. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. 

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

Influent to FGD 

Wastewater Treatment

System (SP-1)

4-Day Average

Influent to 

Bioreactor 

System (SP-2)

4-Day Average

4

Analyte Units Method Total Dissolved Total Dissolved Tot

Sodium ug/L 200.7 47,000 46,800 49,000 48,900 49,5Thallium ug/L 200.8 3.58 3.90 NQ (2.00) NQ (2.00) ND (2Tin ug/L 200.7 NQ (200) NQ (200) NQ (200) ND (200) ND (2Titanium ug/L 200.7 1,400 NQ (20.0) NQ (20.0) NQ (20.0) NQ (2Vanadium ug/L 200.8 198 NQ (10.0) NQ (10.0) NQ (10.0) ND (1Zinc ug/L 200.8 300 34.0 < 6.75 ND (10.0) ND (1
5-1 

5. DATA QUALITY

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

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

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

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

for this sampling episode include the analysis of matrix spikes, blanks, duplicate samples, and 

QC standard checks. 

5.1 Analytical Quality Control

ERG contracted directly with analytical laboratories for the analysis of samples collected 

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

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

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

this episode. The data review narratives are included in Appendix B. 

5.2 Field Quality Control

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

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

5.2.1 Bottle Blanks 

ERG collects bottle blanks to evaluate possible contamination from the sample collection 

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

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

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

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

analyzed the samples using EPA Method 1638. 

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

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

Frontier then analyzed the samples using EPA Method 1631E. 

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

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

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

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

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

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

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

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

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

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

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

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

collect the metals and mercury samples. 

5.2.2 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 samples3

. 

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

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

ASTM Type 1 water through a precleaned funnel attached to the silicone tubing used for sample 

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

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

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

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

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

 

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

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

filtering the sample, which is assessed as the field blank for the dissolved mercury sample. Mercury was detected at 

a concentration of 0.77 ng/L in the filtration blank performed for the second day of samples, which includes the 

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

bioreactor system (Day 1), the third and fourth grab sample for the effluent from the bioreactor system (Day 1), the 

first and second grab samples for influent to the bioreactor system (Day 2), the first and second grab samples for the 

effluent from the bioreactor system (Day 2), and the first and second grab samples for the duplicate of the FGD 

effluent from the bioreactor system. Mercury was not detected above the method detection limit (0.24 ng/L) in the 

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

as “true” split samples with Belews Creek’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 hexavalant 

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 around 70 minutes, the sampling team began pumping off the ASTM 

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

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

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

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

Creek’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 

Belews Creek’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 
5-4 

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 relative percent difference (RPD) between the two 

sample results is examined to determine the precision of the data. EPA used the following 

equation to calculate the RPD for the duplicate sample results. 

100

2

S D

S D

RPD (%) 





 



 

  (5-1) 

where: 

S = concentration of the analyte from original sample analysis; 

D = concentration of the analyte from the duplicate sample analysis; and 

RPD = relative percent difference between the original and duplicate sample 

result. 

During this sampling episode, EPA collected duplicate samples for the 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). 
5-5 

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

presented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at leas^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 

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

Analyte Method Units 

Original Influent 

to Bioreactor 

System, Day 3 

Concentration (SP-2) 

Duplicate Influent 

to Bioreactor 

System 

Concentration (SP-4) 

Aver

Resu

Classicals Ammonia 350.1 mg/L 1.10 1.00 1.0Nitrate Nitrite as N 353.2 mg/L 20.0 20.0 20.Nitrogen, Total Kjeldahl 351.2 mg/L ND (1.00) 2.80 < 1.Biochemical Oxygen Demand 5210B mg/L ND (20.0) ND (20.0) ND (2Chemical Oxygen Demand 410.4 mg/L 180 280 23Chloride 300.0 mg/L 7,400 7,400 7,40Sulfate 300.0 mg/L 2,200 1,200 1,70Cyanide, Total 4500 CN E mg/L ND (0.100) ND (0.100) ND (0Total Dissolved Solids 2540C mg/L 24,000 B 23,000 B 23,5Total Suspended Solids 2540D mg/L NQ (4.00) NQ (4.00) NQ (4Phosphorus, Total 365.1 mg/L NQ (0.0500) B NQ (0.0500) B NQ (0.0Total Metals Aluminum 200.7 ug/L NQ (200) ND (200) NQ (2Antimony 200.8 ug/L NQ (2.00) NQ (2.00) NQ (2Arsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4Barium 200.7 ug/L 380 380 38Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2Boron 200.7 ug/L 150,000 B 150,000 B 150,0Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND (4Calcium 200.7 ug/L 3,200,000 3,300,000 3,250Chromium 200.8 ug/L 20.0 ^ 20.0 ^ 20.Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (2Copper 200.8 ug/L ND (4.00) ND (4.00) ND (4Iron 200.7 ug/L ND (200) ND (200) ND (2Lead 200.8 ug/L ND (2.00) ND (2.00) ND (2Magnesium 200.7 ug/L 720,000 720,000 720,0Manganese 200.7 ug/L NQ (20.0) NQ (20.0) NQ (2
5-6 

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

presented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at leas^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 

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

Analyte Method Units 

Original Influent 

to Bioreactor 

System, Day 3 

Concentration (SP-2) 

Duplicate Influent 

to Bioreactor 

System 

Concentration (SP-4) 

Aver

Resu

Mercury 1631E ng/L 40,800 53,800 47,3Molybdenum 200.7 ug/L NQ (40.0) NQ (40.0) NQ (4Nickel 200.8 ug/L 7.20 7.20 7.2Selenium 200.8 ug/L 1,300 1,300 1,30Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2Sodium 200.7 ug/L 48,000 48,000 48,0Thallium 200.8 ug/L NQ (2.00) NQ (2.00) NQ (2Tin 200.7 ug/L ND (200) ND (200) ND (2Titanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ (2Vanadium 200.8 ug/L NQ (10.0) NQ (10.0) NQ (1Zinc 200.8 ug/L ND (10.0) ND (10.0) ND (1Dissolved Metals Aluminum 200.7 ug/L ND (200) ND (200) ND (2Antimony 200.8 ug/L NQ (2.00) NQ (2.00) NQ (2Arsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4Barium 200.7 ug/L 390 360 37Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2Boron 200.7 ug/L 140,000 B 140,000 B 140,0Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND (4Calcium 200.7 ug/L 3,400,000 3,100,000 3,250Chromium 200.8 ug/L 20.0 ^ 19.0 ^ 19.Chromium (VI) 218.6 ug/L 12.8 13.5 13.Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (2Copper 200.8 ug/L ND (4.00) NQ (4.00) NQ (4Iron 200.7 ug/L NQ (200) ND (200) NQ (2Lead 200.8 ug/L ND (2.00) ND (2.00) ND (2Magnesium 200.7 ug/L 740,000 700,000 720,0Manganese 200.7 ug/L NQ (20.0) NQ (20.0) NQ (2
5-7 

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

presented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at leas^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. 

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

Analyte Method Units 

Original Influent 

to Bioreactor 

System, Day 3 

Concentration (SP-2) 

Duplicate Influent 

to Bioreactor 

System 

Concentration (SP-4) 

Aver

Resu

Mercury 1631E ng/L 43,500 44,400 44,0Molybdenum 200.7 ug/L NQ (40.0) NQ (40.0) NQ (4Nickel 200.8 ug/L 6.50 6.30 6.4Selenium 200.8 ug/L 1,300 1,200 1,25Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2Sodium 200.7 ug/L 49,000 46,000 47,5Thallium 200.8 ug/L NQ (2.00) NQ (2.00) NQ (2Tin 200.7 ug/L ND (200) ND (200) ND (2Titanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ (2Vanadium 200.8 ug/L NQ (10.0) NQ (10.0) NQ (1Zinc 200.8 ug/L ND (10.0) NQ (10.0) NQ (1
5-8 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quThe total mercury duplicate result seems erroneous based on the Day 2 original sample result and the results from the other sampling days. The duplic

excluded from the presentation of the Day 2 average result in Table 4-3. Additionally, 247 ng/L (instead of 3,340 ng/L) was used in the calculation of 

presented in Table 4-3 and 4-5. NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at leas^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria. 

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

Analyte Method Units 

Original Effluent from 

Bioreactor System, Day 2 

Concentration (SP-3) 

Duplicate Effluent from 

Bioreactor System 

Concentration (SP-5) 

Averag

Result 

Classicals Ammonia 350.1 mg/L 4.30 4.60 4.45 Nitrate Nitrite as N 353.2 mg/L NQ (0.100) ND (0.100) NQ (0.10Nitrogen, Total Kjeldahl 351.2 mg/L 5.80 5.70 F 5.75 Biochemical Oxygen Demand 5210B mg/L ND (10.0) ND (10.0) ND (10.Chemical Oxygen Demand 410.4 mg/L 340 170 255 Chloride 300.0 mg/L 7,600 7,800 7,700 Sulfate 300.0 mg/L 1,400 1,400 1,400 Cyanide, Total 4500 CN E mg/L NQ (0.100) F NQ (0.100) NQ (0.10Total Dissolved Solids 2540C mg/L 14,000 14,000 14,000 Total Suspended Solids 2540D mg/L 22.0 26.0 24.0 Phosphorus, Total 365.1 mg/L 0.130 B 0.130 B 0.130 Total Metals Aluminum 200.7 ug/L NQ (200) NQ (200) NQ (20Antimony 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Arsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.0Barium 200.7 ug/L 380 380 380 Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.0
5-9 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quThe total mercury duplicate result seems erroneous based on the Day 2 original sample result and the results from the other sampling days. The duplic

excluded from the presentation of the Day 2 average result in Table 4-3. Additionally, 247 ng/L (instead of 3,340 ng/L) was used in the calculation of 

presented in Table 4-3 and 4-5. NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at leas^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria. 

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

Analyte Method Units 

Original Effluent from 

Bioreactor System, Day 2 

Concentration (SP-3) 

Duplicate Effluent from 

Bioreactor System 

Concentration (SP-5) 

Averag

Result 

Boron 200.7 ug/L 190,000 B 190,000 B 190,00Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND (4.0Calcium 200.7 ug/L 3,300,000 3,300,000 3,300,00Chromium 200.8 ug/L ND (8.00) ^ ND (8.00) ^ ND (8.0Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20.Copper 200.8 ug/L ND (4.00) ND (4.00) ND (4.0Iron 200.7 ug/L NQ (200) NQ (200) NQ (20Lead 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Magnesium 200.7 ug/L 760,000 760,000 760,00Manganese 200.7 ug/L 320 320 320 Mercury 1631E ng/L 247 6,440* 3,340* Molybdenum 200.7 ug/L ND (40.0) ND (40.0) ND (40.Nickel 200.8 ug/L ND (4.00) ND (4.00) ND (4.0Selenium 200.8 ug/L 26.0 25.0 25.5 Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Sodium 200.7 ug/L 50,000 50,000 50,000 Thallium 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Tin 200.7 ug/L ND (200) ND (200) ND (20Titanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.
5-10 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quThe total mercury duplicate result seems erroneous based on the Day 2 original sample result and the results from the other sampling days. The duplic

excluded from the presentation of the Day 2 average result in Table 4-3. Additionally, 247 ng/L (instead of 3,340 ng/L) was used in the calculation of 

presented in Table 4-3 and 4-5. NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at leas^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria. 

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

Analyte Method Units 

Original Effluent from 

Bioreactor System, Day 2 

Concentration (SP-3) 

Duplicate Effluent from 

Bioreactor System 

Concentration (SP-5) 

Averag

Result 

Vanadium 200.8 ug/L ND (10.0) NQ (10.0) NQ (10.Zinc 200.8 ug/L ND (10.0) ND (10.0) ND (10.Dissolved Metals Aluminum 200.7 ug/L NQ (200) B NQ (200) B NQ (20Antimony 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Arsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.0Barium 200.7 ug/L 370 380 375 Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.0Boron 200.7 ug/L 160,000 B 160,000 B 160,00Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND (4.0Calcium 200.7 ug/L 3,600,000 3,600,000 3,600,00Chromium 200.8 ug/L ND (8.00) ND (8.00) ND (8.0Chromium (VI) 218.6 ug/L ND (10.0) T,Est ND (10.0) T,Est ND (10.Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20.Copper 200.8 ug/L ND (4.00) ND (4.00) ND (4.0Iron 200.7 ug/L NQ (200) 410 < 255 Lead 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Magnesium 200.7 ug/L 750,000 760,000 755,00Manganese 200.7 ug/L 310 B 320 B 315 
5-11 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quThe total mercury duplicate result seems erroneous based on the Day 2 original sample result and the results from the other sampling days. The duplic

excluded from the presentation of the Day 2 average result in Table 4-3. Additionally, 247 ng/L (instead of 3,340 ng/L) was used in the calculation of 

presented in Table 4-3 and 4-5. NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

presented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at leas^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. T – Temperature at time of receipt was above the method control criteria. 

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

Analyte Method Units 

Original Effluent from 

Bioreactor System, Day 2 

Concentration (SP-3) 

Duplicate Effluent from 

Bioreactor System 

Concentration (SP-5) 

Averag

Result 

Mercury 1631E ng/L 23.4 19.2 21.3 Molybdenum 200.7 ug/L ND (40.0) NQ (40.0) NQ (40.Nickel 200.8 ug/L ND (4.00) ND (4.00) ND (4.0Selenium 200.8 ug/L 24.0 23.0 23.5 Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Sodium 200.7 ug/L 49,000 50,000 49,500 Thallium 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Tin 200.7 ug/L ND (200) ND (200) ND (20Titanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.Vanadium 200.8 ug/L ND (10.0) NQ (10.0) NQ (10.Zinc 200.8 ug/L ND (10.0) ND (10.0) ND (10.
6-1

6. REFERENCES

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

Creek Steam Station. May 27. DCN SE00502. 

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

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

ANALYTICAL RESULTS 
A-1 

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. D – Laboratory duplicate RPD greater than method-specified criteria. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL Con

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 4 0.076 0.4 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.38 5 Biochemical Oxygen Demand 5210B mg/L 5 1.2 10 ND Chemical Oxygen Demand 410.4 mg/L 5 20 100 2Chloride 300.0 mg/L 500 130 1,500 7Sulfate 300.0 mg/L 100 23 500 1Cyanide, Total 4500 CN E mg/L 1 0.002 0.01 ND Total Dissolved Solids 2540C mg/L 1 47 100 17Total Suspended Solids 2540D mg/L 1 11 40 3Phosphorus, Total 365.1 mg/L 1 0.005 0.05 0Total MetalsAluminum 200.7 ug/L 50 240 5,000 92Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 10 6.1 20 2Barium 200.7 ug/L 2 2.5 20 1Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 150Cadmium 200.8 ug/L 2 1.2 4 4Calcium 200.7 ug/L 50 1,700 10,000 4,70
A-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. D – Laboratory duplicate RPD greater than method-specified criteria. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL Con

Chromium 200.8 ug/L 10 16 40 2Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 10 4.8 20 1Iron 200.7 ug/L 2 32 200 100Lead 200.8 ug/L 2 0.73 2 1Magnesium 200.7 ug/L 50 540 10,000 830Manganese 200.7 ug/L 2 0.51 20 5Mercury 1631E ng/L 20,000 4,830 10,100 24Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 2Selenium 200.8 ug/L 10 3.1 20 6Silver 200.8 ug/L 2 0.59 2 ND Sodium 200.7 ug/L 2 180 10,000 48Thallium 200.8 ug/L 2 0.47 2 3Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 1Vanadium 200.8 ug/L 10 8.4 50 1Zinc 200.8 ug/L 2 4.1 10 3Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 2
A-3 

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. D – Laboratory duplicate RPD greater than method-specified criteria. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL Con

Barium 200.7 ug/L 2 2.5 20 6Beryllium 200.7 ug/L 2 0.71 2 ND Boron 200.7 ug/L 50 170 5,000 150Cadmium 200.8 ug/L 2 1.2 4 3Calcium 200.7 ug/L 50 1,700 10,000 3,20Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 ND Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 ND Lead 200.8 ug/L 2 0.73 2 ND Magnesium 200.7 ug/L 2 21 400 720Manganese 200.7 ug/L 2 0.51 20 2Mercury 1631E ng/L 4,000 965 2,020 49Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 1Selenium 200.8 ug/L 2 0.62 4 1Silver 200.8 ug/L 2 0.59 2 ND Sodium 200.7 ug/L 2 180 10,000 47Thallium 200.8 ug/L 2 0.47 2 3Tin 200.7 ug/L 2 4.8 200 5Titanium 200.7 ug/L 2 1.6 20 7
A-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. D – Laboratory duplicate RPD greater than method-specified criteria. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL Con

Vanadium 200.8 ug/L 2 1.7 10 3Zinc 200.8 ug/L 2 4.1 10 
A-5 

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. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 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 5 1.2 10 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 11 40 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 50 240 5,000 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 5 3.1 10 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 5 8.2 20 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
A-6 

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. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

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 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20,000 4,830 10,100 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 5 2.2 10 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 5 4.2 25 Zinc 200.8 ug/L 5 10 25 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 
A-7 

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. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 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 
A-8 

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. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 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 5 1.2 10 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 11 40 Phosphorus, Total 365.1 mg/L 5 0.025 0.25 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 5 3.1 10 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 4Chromium 200.8 ug/L 5 8.2 20 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
A-9 

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. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

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 20,000 4,830 10,100 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 5 2.2 10 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 5 10 25 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 3
A-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. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 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 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 
A-11 

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 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 5 1.2 10 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 11 40 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 10 6.1 20 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 10 16 40 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 
A-12 

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

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 20,000 4,830 10,100 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 10 4.5 20 Selenium 200.8 ug/L 10 3.1 20 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 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 10 20 50 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 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
A-13 

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

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 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-14 

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-5. Influent to the Bioreactor System, Day 1 Analytical Results, Belews Creek 

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 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 10 2.4 20 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 50 240 5,000 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 
A-15 

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-5. Influent to the Bioreactor System, Day 1 Analytical Results, Belews Creek 

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 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
A-16 

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-5. Influent to the Bioreactor System, Day 1 Analytical Results, Belews Creek 

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 
A-17 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-6. Influent to the Bioreactor System, Day 2 Analytical Results, Belews Creek 

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 2 0.038 0.2 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.19 2.5 Biochemical Oxygen Demand 5210B mg/L 10 2.4 20 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 
A-18 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-6. Influent to the Bioreactor System, Day 2 Analytical Results, Belews Creek 

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 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 1 1.96 10 
A-19 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-6. Influent to the Bioreactor System, Day 2 Analytical Results, Belews Creek 

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 2,000 483 1,010 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-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). 

Table A-7. Influent to the Bioreactor System, Day 3 Analytical Results, Belews Creek 

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample-Specific QL Co

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 5 0.095 0.5 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 NBiochemical Oxygen Demand 5210B mg/L 10 2.4 20 ND Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 7Sulfate 300.0 mg/L 100 23 500 2Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 ND Total Dissolved Solids 2540C mg/L 1 47 100 24Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 0Total 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 NBoron 200.7 ug/L 50 170 5,000 15Cadmium 200.8 ug/L 2 1.2 4 NCalcium 200.7 ug/L 50 1,700 10,000 3,2Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 ND Copper 200.8 ug/L 2 0.96 4 N
A-21 

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-7. Influent to the Bioreactor System, Day 3 Analytical Results, Belews Creek 

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample-Specific QL Co

Iron 200.7 ug/L 2 32 200 ND Lead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 2 21 400 72Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 4,000 965 2,020 40Molybdenum 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 1Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 4Thallium 200.8 ug/L 2 0.47 2 0Tin 200.7 ug/L 2 4.8 200 ND Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 ND Dissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND 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 NBoron 200.7 ug/L 50 170 5,000 14Cadmium 200.8 ug/L 2 1.2 4 NCalcium 200.7 ug/L 50 1,700 10,000 3,4
A-22 

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-7. Influent to the Bioreactor System, Day 3 Analytical Results, Belews Creek 

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample-Specific QL Co

Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 ND Copper 200.8 ug/L 2 0.96 4 NIron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 2 21 400 74Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 4,000 965 2,020 43Molybdenum 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 1Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 49Thallium 200.8 ug/L 2 0.47 2 0Tin 200.7 ug/L 2 4.8 200 ND Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.8 ug/L 2 4.1 10 ND 
A-23 

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. 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-8. Influent to the Bioreactor System, Day 4 Analytical Results, Belews Creek 

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 5 0.095 0.5 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 Biochemical Oxygen Demand 5210B mg/L 10 2.4 20 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 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 
A-24 

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. 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-8. Influent to the Bioreactor System, Day 4 Analytical Results, Belews Creek 

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 2,000 483 1,010 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 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 
A-25 

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. 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-8. Influent to the Bioreactor System, Day 4 Analytical Results, Belews Creek 

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 
A-26 

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. 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). 

Table A-9. Effluent from the Bioreactor System, Day 1 Analytical Results, Belews Cree

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 Biochemical Oxygen Demand 5210B mg/L 5 1.2 10 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.002 0.01 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 50 240 5,000 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
A-27 

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. 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). 

Table A-9. Effluent from the Bioreactor System, Day 1 Analytical Results, Belews Cree

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 200 48.3 101 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 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 
A-28 

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. 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). 

Table A-9. Effluent from the Bioreactor System, Day 1 Analytical Results, Belews Cree

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 
A-29 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-10. Effluent from the Bioreactor System, Day 2 Analytical Results, Belews Cre

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 Biochemical Oxygen Demand 5210B mg/L 5 1.2 10 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 3Chromium 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 
A-30 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-10. Effluent from the Bioreactor System, Day 2 Analytical Results, Belews Cre

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 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 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 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 3Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 
A-31 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-10. Effluent from the Bioreactor System, Day 2 Analytical Results, Belews Cre

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 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 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-32 

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. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-11. Effluent from the Bioreactor System, Day 3 Analytical Results, Belews Cre

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 Biochemical Oxygen Demand 5210B mg/L 5 1.2 10 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 
A-33 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 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. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-11. Effluent from the Bioreactor System, Day 3 Analytical Results, Belews Cre

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 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 1 1.96 10 
A-34 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. 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. H – Sample was prepared/analyzed beyond the specified holding time. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-11. Effluent from the Bioreactor System, Day 3 Analytical Results, Belews Cre

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 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 
A-35 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-12. Effluent from the Bioreactor System, Day 4 Analytical Results, Belews Cre

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 Biochemical Oxygen Demand 5210B mg/L 5 1.2 10 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 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 
A-36 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-12. Effluent from the Bioreactor System, Day 4 Analytical Results, Belews Cre

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 2 0.51 20 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 1 1.96 10 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
A-37 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-12. Effluent from the Bioreactor System, Day 4 Analytical Results, Belews Cre

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 
A-38 

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-13. Duplicate of Influent to the Bioreactor System Analytical Results, Belews Cr

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 5 0.095 0.5 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 Biochemical Oxygen Demand 5210B mg/L 10 2.4 20 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 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 
A-39 

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-13. Duplicate of Influent to the Bioreactor System Analytical Results, Belews Cr

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 2,000 483 1,010 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 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 
A-40 

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-13. Duplicate of Influent to the Bioreactor System Analytical Results, Belews Cr

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 
A-41 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-14. Duplicate of Effluent from the Bioreactor System Analytical Results, Belews C

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

ClassicalsAmmonia 350.1 mg/L 1 0.47 1 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 NNitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 Biochemical Oxygen Demand 5210B mg/L 5 1.2 10 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 47 100 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 3Chromium 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 
A-42 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-14. Duplicate of Effluent from the Bioreactor System Analytical Results, Belews C

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 2,000 483 1,010 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 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 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 3Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 1.96 10 
A-43 

ND – Not detected (number in parentheses is the quantitation limit). ^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. T – Temperature at time of receipt was above the method control criteria. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-14. Duplicate of Effluent from the Bioreactor System Analytical Results, Belews C

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 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 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

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

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

A-44 

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

Analyte Method Process Units Concentration 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

HDPE 500 ml Plastic Bottles – Bottle Blank (for metals samples) 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

A-45 

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

Analyte Method Process Units Concentration 

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

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

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

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

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

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

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

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

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

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

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

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

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

125 ml Glass Bottles – Bottle Blank (for mercury composite samples)

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

250 ml Glass Bottles – Bottle Blank (for mercury grab samples)

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

LDPE 10 L Composite Bottles – Bottle Blank (sample composite bottle for dissolved/filtration pump-off)

Aluminuma EPA 1638 Dissolved ug/L 4.71 

Antimony EPA 1638 Dissolved ug/L ND (0.50) 

Arsenic EPA 1638 Dissolved ug/L ND (0.50) 

Barium EPA 1638 Dissolved ug/L ND (0.10) 

Beryllium EPA 1638 Dissolved ug/L ND (0.10) 

Cadmium EPA 1638 Dissolved ug/L ND (0.10) 

Chromium EPA 1638 Dissolved ug/L ND (1.0) 

Cobalt EPA 1638 Dissolved ug/L ND (0.10) 

Copper EPA 1638 Dissolved ug/L ND (0.30) 

Lead EPA 1638 Dissolved ug/L ND (0.050) 

Manganese EPA 1638 Dissolved ug/L ND (0.50) 

Molybdenum EPA 1638 Dissolved ug/L ND (0.50) 

Nickel EPA 1638 Dissolved ug/L ND (0.50) 

Selenium EPA 1638 Dissolved ug/L ND (2.0) 

Silver EPA 1638 Dissolved ug/L ND (0.10) 

Thallium EPA 1638 Dissolved ug/L ND (0.050) 

Vanadium EPA 1638 Dissolved ug/L ND (1.0) 

Zinc EPA 1638 Dissolved ug/L ND (0.50) 

LDPE 20 L Composite Bottles – Bottle Blank (sample composite bottle for dissolved/filtration pump-off)

Aluminum EPA 1638 Dissolved ug/L ND (2.0) 

Antimony EPA 1638 Dissolved ug/L ND (0.50) 
a

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

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

A-46 

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

Analyte Method Process Units Concentration 

Arsenic EPA 1638 Dissolved ug/L ND (0.50) 

Barium EPA 1638 Dissolved ug/L ND (0.10) 

Beryllium EPA 1638 Dissolved ug/L ND (0.10) 

Cadmium EPA 1638 Dissolved ug/L ND (0.10) 

Chromium EPA 1638 Dissolved ug/L ND (1.0) 

Cobalt EPA 1638 Dissolved ug/L ND (0.10) 

Copper EPA 1638 Dissolved ug/L ND (0.30) 

Lead EPA 1638 Dissolved ug/L ND (0.050) 

Manganese EPA 1638 Dissolved ug/L ND (0.50) 

Molybdenum EPA 1638 Dissolved ug/L ND (0.50) 

Nickel EPA 1638 Dissolved ug/L ND (0.50) 

Selenium EPA 1638 Dissolved ug/L ND (2.0) 

Silver EPA 1638 Dissolved ug/L ND (0.10) 

Thallium EPA 1638 Dissolved ug/L ND (0.050) 

Vanadium EPA 1638 Dissolved ug/L ND (1.0) 

Zinc EPA 1638 Dissolved ug/L ND (0.50) 

Sample Tap Tubing Set – Equipment Blank (seven feet of #73 silicone tubing, Y-splitter, and two pieces of 5 

feet of #24 silicone tubing for sample collection for mercury and metals from sample taps) 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

A-47 

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

Analyte Method Process Units Concentration 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

T-Splitter Tubing Set – Equipment Blank (Ten feet of #73 silicone tubing, T-splitter, six feet of #73 silicone 

tubing, and 15 feet of #73 silicone tubing for total and dissolved sample collection for metal composites)

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

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

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

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

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

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

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

A-48 

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

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-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 Results, 

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 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-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-16. Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, 

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 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 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-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 the Bioreactor System Field Blank, Day 1 Analytical Results, Belews 

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 NCadmium 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 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-52 

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 the Bioreactor System Field Blank, Day 1 Analytical Results, Belews 

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 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 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-53 

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-18. Influent to the Bioreactor System Field Blank, Day 2 Analytical Results, Belews 

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-19. Influent to the Bioreactor System Field Blank, Day 3 Analytical Results, Belews 

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
A-55 

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

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

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
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 the Bioreactor System Field Blank, Day 1 Analytical Results, Belew

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 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 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-57 

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 the Bioreactor System Field Blank, Day 1 Analytical Results, Belew

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 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-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-22. Effluent from the Bioreactor System Field Blank, Day 2 Analytical Results, Belew

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-23. Effluent from the Bioreactor System Field Blank, Day 3 Analytical Results, Belew

Analyte Method Units

Dilution 

Factor

SampleSpecific MDL Sample- Specific QL 

Total MetalsMercury 1631E ng/L 1 0.24 0.5 
A-60 

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 the Bioreactor System Field Blank, Day 4 Analytical Results, Belew

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 
MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD 

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

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Randy Mercurio, ERG. 

 Donna Tedder, ERG 

Date: 2/2/2011 

Subject: FGS Data Review Narrative for Total Mercury – Episode 6558 

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

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

Atomic Fluorescence Spectrometry (CVAFS) analysis. 

Table 1 summarizes the 38 samples (excluding laboratory filter blanks) FGS extracted 

and analyzed for total mercury. 

Table 1. EPA Episode 6558 Total Mercury–Sample Identification 

EPA 

Sample # 

Lab Sample 

ID # 

Sample 

Matrix Sample Description Sampling Date 

71641 1006065-01 Aqueous FGD Influent Day 1 6/7/2010 

71641 1006065-02 Aqueous Dissolved FGD Influent Day 1 6/7/2010 

71642 1006085-01 Aqueous FGD Influent Day 2 6/8/2010 

71642 1006085-02 Aqueous Dissolved FGD Influent Day 2 6/8/2010 

71643 1006092-01 Aqueous FGD Influent Day 3 6/9/2010 

71643 1006092-02 Aqueous Dissolved FGD Influent Day 3 6/9/2010 

71644 1006109-07 Aqueous FGD Influent Day 4 6/10/2010 

71645 1006085-03 Aqueous FGD Bioreactor Influent Day 1 6/7/2010 

71645 1006085-04 Aqueous Dissolved FGD Bioreactor Influent Day 1 6/7/2010 

71646 1006085-14 Aqueous Dissolved FGD Bioreactor Influent Day 2 6/8/2010 

71646 1006092-04 Aqueous Dissolved FGD Bioreactor Influent Day 2 6/9/2010 

71646 1006092-21 Aqueous Dissolved FGD Bioreactor Influent Day 2 6/9/2010 

71646 1006092-03 Aqueous FGD Bioreactor Influent Day 2 6/9/2010 

71647 1006109-09 Aqueous FGD Bioreactor Influent Day 3 6/10/2010 

71647 1006109-10 Aqueous Dissolved FGD Bioreactor Influent Day 3 6/10/2010 

71648 1006118-01 Aqueous FGD Bioreactor Influent Day 4 6/11/2010 

71648 1006118-02 Aqueous Dissolved FGD Bioreactor Influent Day 4 6/11/2010 

71649 1006085-05 Aqueous FGD Bioreactor Effluent Day 1 6/8/2010 

71649 1006085-06 Aqueous Dissolved FGD Bioreactor Effluent Day 1 6/8/2010 

1
Table 1. EPA Episode 6558 Total Mercury–Sample Identification 

EPA Lab Sample Sample 

Sample # ID # Matrix Sample Description Sampling Date 

71650 1006092-05 Aqueous FGD Bioreactor Effluent Day 2 6/9/2010 

71650 1006092-06 Aqueous Dissolved FGD Bioreactor Effluent Day 2 6/9/2010 

71651 1006109-11 Aqueous FGD Bioreactor Effluent Day 3 6/10/2010 

71651 1006109-12 Aqueous Dissolved FGD Bioreactor Effluent Day 3 6/10/2010 

71652 1006118-03 Aqueous FGD Bioreactor Effluent Day 4 6/11/2010 

71652 1006118-04 Aqueous Dissolved FGD Bioreactor Effluent Day 4 6/11/2010 

71653 1006109-13 Aqueous FGD Bioreactor Influent Duplicate 6/10/2010 

71653 1006109-14 Aqueous 

Dissolved FGD Bioreactor Influent 

Duplicate 6/10/2010 

71654 1006092-07 Aqueous FGD Bioreactor Effluent Duplicate 6/9/2010 

71654 1006092-08 Aqueous 

Dissolved FGD Bioreactor Effluent 

Duplicate 6/9/2010 

71655 1006065-03 Aqueous FGD Influent Field Blank (FB) Day 1 6/7/2010 

71656 1006065-06 Aqueous FGD Bioreactor Influent FB Day 1 6/7/2010 

71657 1006085-07 Aqueous FGD Bioreactor Influent FB Day 2 6/8/2010 

71658 1006092-19 Aqueous FGD Bioreactor Influent FB Day 3 6/9/2010 

71659 1006109-05 Aqueous FGD Bioreactor Influent FB Day 4 6/10/2010 

71660 1006065-09 Aqueous FGD Bioreactor Effluent FB Day 1 6/7/2010 

71661 1006085-19 Aqueous FGD Bioreactor Effluent FB Day 2 6/8/2010 

71662 1006092-20 Aqueous FGD Bioreactor Effluent FB Day 3 6/9/2010 

71663 1006109-06 Aqueous FGD Bioreactor Effluent FB Day 4 6/10/2010 

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. The following summarizes the findings from the data review: 

 One filter blank (lab sample number 1006085-20) exceeded the method detection 

level (MDL). The samples associated with this filter blank do not require 

qualification. All of the detected values for these samples were at least 30 times 

the level found in the blank. 

 The MDL provided by the laboratory is above the MDL requirement for EPA 

Method 1631E; however, the MDL used for this sampling program is based on 

analyses in the synthetic matrix and not based on blank water. 

 One set of field duplicates was out of the method-suggested relative percent 

difference (RPD) criteria. 

2
SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES 

As discussed in the case narrative provided by FGS, “One (1) of the 250 mL glass bottles 

submitted for grab sample 71646 FGD Bioreactor Influent Day 2 was dropped and 

broken during filtration. Per the client's request, the remaining grab aliquots for sample 

71646 Dissolved FGD Bioreactor Influent Day 2 were not composited and run as discrete 

samples. 

Also discussed in the FGS narrative, “Two (2) of the 250 mL glass bottles submitted for 

sample 71644 FGD Influent Day 4 were dropped and broken during preservation. The 

two bottles that were broken contained the dissolved mercury aliquot (lab-filtered) and 

total mercury aliquot. Only one total mercury aliquot remained for the sample; therefore 

no dissolved mercury results were available for sample 71644 FGD Influent Day 4.” 

ONGOING PRECISION AND ACCURACY/RECOVERY 

The results for all ongoing precision and recovery (OPR) samples, in the form of blank 

spike/blank spike duplicates (BS/BSDs), fell within the method criteria of 77-123% 

recovery. 

INITIAL CALIBRATION 

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

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

factor ≥0.995. 

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

of true value. 

CONTINUING CALIBRATION VERIFICATION (CCV) 

All CCVs met method-specified criteria. 

BLANKS 

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

calibration blanks (CCBs) met method-specified requirements. 

FGS analyzed a total of five filter blanks. One filter blank, Sample 1006085-20, 

exceeded the MDL (0.239 ng/L) at 0.77 ng/L. The samples associated with this filter 

blank, 71642, 71645, 71646 (Dissolved FGD Bioreactor Influent Day 2 only), 71649, 

71657, and 71661, do not require qualification. All of the detected values for these 

samples were at least 30 times the level found in the blank. 

3
4

DETECTION LIMITS 

The laboratory MDL in the synthetic matrix was 0.239 ng/L. Results below this MDL 

were reported as not detected (ND). 

DUPLICATES 

Field duplicates, Samples 71654 and 71653, were collected on Samples 71650 and 

71647, respectively. The 71654/71650 RPD was 185% for total mercury and 20% for 

dissolved mercury. The 71653/71647 RPD was 27% for total mercury and 2% for 

dissolved mercury. The method-suggested RPD criteria between field duplicates is 20%. 

Laboratory duplicates were performed in this episode on Samples 71645, 71643, 71646, 

and they all met method-specified criteria. 

MATRIX SPIKE AND MATIX SPIKE DUPLICATES 

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on Samples 

71645, 71646, 71648, 71651, and 71654. All recoveries were within method 

specifications of 71-125%. The RPDs were 0.00, 4.24, 5.26, 2.40, and 16.7%, 

respectively. 
MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD 

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

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Randy Mercurio, ERG 

Date: 3/29/2011 

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

Episode 6558 

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 6558. 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. 

EPA 

Sample # EPA Sample Description 

Lab Sample 

ID # 

Sample 

Matrix 

Sampling 

Date 

Receipt 

Date 

71641 FGD Influent, Day 1 280-4226-1 Aqueous 6/7/2010 6/8/2010 

71642 FGD Influent, Day 2 280-4279-1 Aqueous 6/8/2010 6/9/2010 

71643 FGD Influent, Day 3 280-4337-1 Aqueous 6/9/2010 6/10/2010 

71644 FGD Influent, Day 4 280-4376-1 Aqueous 6/10/2010 6/11/2010 

71645 FGD Bioreactor Influent, Day 1 280-4279-2 Aqueous 6/8/2010 6/9/2010 

71646 FGD Bioreactor Influent, Day 2 280-4337-2 Aqueous 6/9/2010 6/10/2010 

71647 FGD Bioreactor Influent, Day 3 280-4376-2 Aqueous 6/10/2010 6/11/2010 

71648 FGD Bioreactor Influent, Day 4 280-4415-1 Aqueous 6/11/2010 6/12/2010 

71649 FGD Bioreactor Effluent, Day 1 280-4279-3 Aqueous 6/8/2010 6/9/2010 

71650 FGD Bioreactor Effluent, Day 2 280-4337-3 Aqueous 6/9/2010 6/10/2010 

71651 FGD Bioreactor Effluent, Day 3 280-4376-3 Aqueous 6/10/2010 6/11/2010 

71652 FGD Bioreactor Effluent, Day 4 280-4415-2 Aqueous 6/11/2010 6/12/2010 

71653 

FGD Bioreactor Influent - 

Duplicate 280-4376-4 Aqueous 6/10/2010 6/11/2010 

71654 

FGD Bioreactor Effluent - 

Duplicate 280-4337-4 Aqueous 6/9/2010 6/10/2010 

71655 FGD Influent Field Blank, Day 1 280-4226-2 Aqueous 6/7/2010 6/8/2010 

71656 

FGD Bioreactor Influent, Field 

Blank Day 1 280-4279-4 Aqueous 6/8/2010 6/9/2010 

71660 

FGD Bioreactor Effluent, Field 

Blank Day 1 280-4279-5 Aqueous 6/8/2010 6/9/2010 

1
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 Element 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. 

INSTRUMENT TUNE CONDITIONS 

The tune report for each day of analysis consistently failed the required <5% relative 

standard deviation (RSD) for beryllium. According to Section 10.3.2 of TestAmerica’s 

SOP, “The relative standard deviations must be less than 5% for a minimum of 4 

integrations of the solution.” 

INTERNAL STANDARDIZATION 

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

 

INITIAL CALIBRATION 

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

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

INITIAL AND CONTINUING CALIBRATION VERIFICATION 

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

performed by TestAmerica all had recoveries within the method criteria. 

BLANKS 

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

were found above 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 were above the MDL and were 

flagged with the “J” qualifier. 

REPORTING LIMIT VERIFICATION STANDARD (CRI) 

All CRI samples passed Test America’s 50-150% recovery limits. 

2
3

LABORATORY CONTROL SAMPLE (LCS) 

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

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION 

Chromium in the ICSA solution was always above the RL of 4 ug/L, indicating 

interferents were not being removed effectively. Therefore, all sample results for 

chromium, including QC samples, from this episode have been flagged with the “^” 

qualifier. 

SERIAL DILUTION 

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

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

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

calculated; however, those samples with significant concentrations did have percent 

differences calculated and met the typical <10% criterion, with the exception of dissolved 

Selenium in Sample 71649. 

FIELD/LABORATORY DUPLICATES 

The relative percent difference (RPD) of the field duplicates 71650/71654 and 

71647/71653 were less than 20% for all values equal to or greater than the reporting 

limit. 

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

Matrix spikes and matrix spike duplicates were performed on Samples 71641, 71648, 

71649, 71650 and 71651. Many spike recoveries were outside the method control limits 

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

four or more, which have been flagged “4”. Otherwise, the MS/MSD spike recoveries 

were always within the control limits of 70-130% with the exception of the dissolved zinc 

(MS Sample 71651). The RPD for all MS/MSD passed the method-specified criteria of 

20 percent. 

POST SPIKE 

Post spikes passed Test America’s 85-115% recovery with the exception of total and 

dissolved Selenium for sample 71648. 

DETECTION LIMITS 

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

of reagent water. 
MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD 

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

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Randy Mercurio, ERG 

Date: 3/29/2011 

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

Episode 6558 

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

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

manganese) for Sample Episode 6558. 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 6558 Total & Dissolved Metals – Sample Identification 

EPA 

Sample 

# EPA Sample Description 

Lab Sample 

ID # 

Sample 

Matrix 

Sampling 

Date 

Receipt 

Date 

71641 FGD Influent, Day1 280-4226-1 Aqueous 6/7/2010 6/8/2010 

71642 FGD Influent, Day 2 280-4279-1 Aqueous 6/8/2010 6/9/2010 

71643 FGD Influent, Day 3 280-4337-1 Aqueous 6/9/2010 6/10/2010 

71644 FGD Influent, Day 4 280-4376-1 Aqueous 6/10/2010 6/11/2010 

71645 FGD Bioreactor Influent, Day 1 280-4279-2 Aqueous 6/8/2010 6/9/2010 

71646 FGD Bioreactor Influent, Day 2 280-4337-2 Aqueous 6/9/2010 6/10/2010 

71647 FGD Bioreactor Influent, Day 3 280-4376-2 Aqueous 6/10/2010 6/11/2010 

71648 FGD Bioreactor Influent, Day 4 280-4415-1 Aqueous 6/11/2010 6/12/2010 

71649 FGD Bioreactor Effluent, Day 1 280-4279-3 Aqueous 6/8/2010 6/9/2010 

71650 FGD Bioreactor Effluent, Day 2 280-4337-3 Aqueous 6/9/2010 6/10/2010 

71651 FGD Bioreactor Effluent, Day 3 280-4376-3 Aqueous 6/10/2010 6/11/2010 

71652 FGD Bioreactor Effluent, Day 4 280-4415-2 Aqueous 6/11/2010 6/12/2010 

71653 

FGD Bioreactor Influent - 

Duplicate 280-4376-4 Aqueous 6/10/2010 6/11/2010 

71654 

FGD Bioreactor Effluent - 

Duplicate 280-4337-4 Aqueous 6/9/2010 6/10/2010 

71655 FGD Influent Field Blank, Day 1 280-4226-2 Aqueous 6/7/2010 6/8/2010 

71656 

FGD Bioreactor Influent, Field 

Blank Day 1 280-4279-4 Aqueous 6/8/2010 6/9/2010 

1
Table 1. EPA Episode 6558 Total & Dissolved Metals – Sample Identification 

EPA 

Sample Lab Sample Sample Sampling Receipt 

# EPA Sample Description ID # Matrix Date Date 

71660 

FGD Bioreactor Effluent, Field 

Blank Day 1 280-4279-5 Aqueous 6/8/2010 6/9/2010 

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. The following summarizes the findings 

from the data review: 

The serial dilution of sample 71641 failed the required ±10% difference for calcium 

(24%), cobalt (15%) and magnesium (12%) and sample 71643 failed for aluminum 

(12%); these elements were flagged “V” as failing the QC criteria. These dilution tests 

indicate there may be a chemical or physical interference. 

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES 

There were no sample receipt issues in this data package. 

INTERNAL STANDARDIZATION 

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

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

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

INITIAL CALIBRATION 

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

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

INITIAL AND CONTINUING CALIBRATION VERIFICATION 

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

performed by TestAmerica all had recoveries within the method criteria. 

BLANKS 

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

were found above the method detection limit (MDL) and were flagged with the “J” 

qualifier. 

2
All instrument blanks (ICB and CCB) were less than the RL; however, some elements 

were above the MDL and were flagged with the “J” qualifier. 

RL VERIFICATION STANDARD (CRI) 

All CRI samples passed TestAmerica’s control limits of 50 – 150%. 

LABORATORY CONTROL SAMPLE (LCS) 

All LCS passed the method 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. Sample 

71641 failed the required ±10% difference for calcium (24%), cobalt (15%), but the 

concentration was less than the RL, and magnesium (12%), and Sample 71643 failed for 

aluminum (12%); these elements were flagged “V” as failing the QC criteria. These 

dilution tests indicate there may be a chemical or physical interference according to 

Section 9.5.2 of the 200.7 Method. 

FIELD/LABORATORY DUPLICATES 

The RPD of the field duplicates were less than 20% for all concentrations greater than the 

reporting limit, with the exception of iron for the dissolved samples 71650 and 71654. 

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

Matrix spike and matrix spike duplicates were performed on samples 71641, 71642, 

71643, 71648 and 71651. Many elements with high concentrations frequently failed the 

spike recovery and were flagged with a “4” qualifier indicating that concentrations in the 

parent sample was greater than four times the spike. In many cases, the MS/MSD spike 

recoveries failed TestAmerica’s SOP requirements and were flagged with the “F” 

qualifier. Otherwise, the MS/MSD spike recoveries were always within the control limits 

of 70–130% with the exception of dissolved aluminum (MS Sample 71641), which was 

recovered at 68%. The RPD between the MS and MSD for dissolved beryllium, iron, tin 

& titanium for Sample 71641 was greater than 20%, which fails TestAmerica’s RPD 

requirement; therefore, the results for these dissolved analytes for Sample 71641 were 

flagged with the “F” qualifier. 

3
4

DETECTION LIMITS 

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

of reagent water. 
MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD 

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

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Randy Mercurio, ERG 

 Donna Tedder, ERG 

Date: 2/2/2011 

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

6558 

Frontier Global Sciences (FGS) generated analytical data for dissolved hexavalent 

chromium for Sample Episode 6558. 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 17 samples FGS extracted and analyzed for dissolved hexavalent 

chromium. 

Table 1. EPA Episode 6558 Dissolved Hexavalent Chromium–Sample Identification 

EPA 

Sample # 

Sample 

Matrix Sample Description 

Sampling 

Date 

Analysis 

Date 

71641 Aqueous FGD Influent Day 1 6/7/10 6/21/10 

71642 Aqueous FGD Influent Day 2 6/8/10 6/21/10 

71643 Aqueous FGD Influent Day 3 6/9/10 6/22/10 

71644 Aqueous FGD Influent Day 4 6/10/10 6/22/10 

71645 Aqueous FGD Bioreactor Influent Day 1 6/8/10 6/21/10 

71646 Aqueous FGD Bioreactor Influent Day 2 6/9/10 6/22/10 

71647 Aqueous FGD Bioreactor Influent Day 3 6/10/10 6/22/10 

71648 Aqueous FGD Bioreactor Influent Day 4 6/11/10 6/22/10 

71649 Aqueous FGD Bioreactor Effluent Day 1 6/8/10 6/22/10 

71650 Aqueous FGD Bioreactor Effluent Day 2 6/9/10 6/22/10 

71651 Aqueous FGD Bioreactor Effluent Day 3 6/10/10 6/22/10 

71652 Aqueous FGD Bioreactor Effluent Day 4 6/11/10 6/22/10 

71653 Aqueous FGD Bioreactor Influent Duplicate 6/10/10 6/22/10 

71654 Aqueous FGD Bioreactor Effluent Duplicate 6/9/10 6/22/10 

71655 Aqueous FGD Influent Field Blank (FB) Day 1 6/7/10 6/21/10 

71656 Aqueous FGD Bioreactor Influent FB Day 1 6/8/10 6/21/10 

71660 Aqueous FGD Bioreactor Effluent FB Day 1 6/8/10 6/22/10 

1
SUMMARY 

Samples 71643, 71646, 71650, and 71654 arrived with temperatures above the required 

≤4°C. 

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 (71641, 71642, 71644, 71649, 71650, 71651, 71652, 71654, and 71660) 

were diluted prior to analysis due to the presence of high levels of nontarget chloride 

interferences. 

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES 

Samples 71643, 71646, 71650, and 71654 arrived at the laboratory at 12.2°C, higher than 

the required temperature of ≤4°C (see Table 2 below). 

INITIAL PRECISION AND ACCURACY/RECOVERY 

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

method criteria. 

ONGOING PRECISION AND ACCURACY/RECOVERY 

The analytical method did not require the analysis of an ongoing 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 analytical method. 

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

of true value required by the analytical method. 

CONTINUING CALIBRATION VERIFICATION (CCV) 

All CCVs met method-specified criteria except the following: CCV2 and CCV3 had high 

recoveries in the initial analysis sequence on 6/21/10. All samples affected by these 

failing CCVs were successfully reanalyzed with acceptable CCVs. 

BLANK 

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

calibration blanks (CCBs) met method-specified requirements. 

2
3

OTHER CHECKS 

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

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. Samples 71653 and 71654 were 

duplicates of Samples 71647 and 71650, respectively. Sample 71647 and its duplicate 

had an RPD of 5%. Sample 71650 and its duplicate were nondetects (NDs), indicating 

the analyte was not detected at or above the reporting limit. 

MATRIX SPIKE AND MATIX SPIKE DUPLICATES 

The MSs and matrix spike duplicates (MSDs) were performed using a secondary source 

spike on Samples 71650 and 71648. All MS/MSD recoveries were within 75-125%, with 

an RPD of 0.737 and 3.06%, respectively. 

Table 2. Data Review Summary Table

Sample Analyte Qualifier Reason Level Detected 

71643 Chromium (VI) Estimated value 

Receipt 

temperature of 

12.2°C 

ND 

71646 Chromium (VI) Estimated value 

Receipt 

temperature of 

12.2°C 

11.7 μg/L 

71650 Chromium (VI) Estimated value 

Receipt 

temperature of 

12.2°C 

ND 

71654 Chromium (VI) Estimated value 

Receipt 

temperature of 

12.2°C 

ND 

ND - Not detected. 
MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD 

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

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Becky Schwantes, ERG 

Date: 2/2/2011 

Subject: TestAmerica Data Review Narrative for Classicals Analyses – Episode 6558 

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry 

analyses for Sample Episode 6558. 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 6558 Classical Analytes – Sample Identification 

EPA 

Sample # 

Sample 

Matrix Sample Description 

Sampling 

Date 

71641 Water FGD Influent, Day 1 06/07/10 

71642 Water FGD Influent, Day 2 06/08/10 

71643 Water FGD Influent, Day 3 06/09/10 

71644 Water FGD Influent, Day 4 06/10/10 

71645 Water FGD Bioreactor Influent, Day 1 06/08/10 

71646 Water FGD Bioreactor Influent, Day 2 06/09/10 

71647 Water FGD Bioreactor Influent, Day 3 06/10/10 

71648 Water FGD Bioreactor Influent, Day 4 06/11/10 

71649 Water FGD Bioreactor Effluent, Day 1 06/08/10 

71650 Water FGD Bioreactor Effluent, Day 2 06/09/10 

71651 Water FGD Bioreactor Effluent, Day 3 06/10/10 

1 
Table 1. EPA Episode 6558 Classical Analytes – Sample Identification 

EPA 

Sample # 

Sample 

Matrix 

Sampling 

Sample Description Date 

71652 Water FGD Bioreactor Effluent, Day 4 06/11/10 

71653 Water FGD Bioreactor Influent - Duplicate 06/10/10 

71654 Water FGD Bioreactor Effluent - Duplicate 06/09/10 

SUMMARY 

Unless otherwise noted below, 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. 

If required by the method, a matrix spike (MS) sample was analyzed. Unless noted 

below, two MS samples were run on samples 71648 (FGD bioreactor influent) and 71651 

(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 data reviewer identified no issues. All QC samples met the criteria specified in EPA 

Method 350.1. 

2 
BOD5 

Even though TestAmerica ran at least five dilutions on every sample, no dilutions had a 

dissolved oxygen (DO) depletion greater than 2.0 mg/L. Therefore, BOD5 was reported 

as nondetect for all samples. All glucose-glutamic acid standards, water blanks, and 

laboratory duplicates were analyzed appropriately and met the criteria specified in SM 

5210B. 

Chloride and Sulfate 

TestAmerica was required by the SOW to run a matrix spike and matrix spike duplicate 

(MS/MSD) analysis on sample 71648 (FGD bioreactor influent) and sample 71651 (FGD 

bioreactor effluent). However, the MS/MSD analysis for both chloride and sulfate was 

only run on sample 71648. The MS/MSD results for sample 71648 met the criteria of 80-

120% specified in EPA Method 300.0 indicating matrix interferences were not interfering 

with the results for samples with the same matrix (i.e., FGD bioreactor influent). The 

percent recoveries for chloride were 98% (MS) and 99% (MSD) and the percent recovery 

for both the MS and MSD samples for sulfate was 100%. Because an MS was not run on 

sample 71651, the data reviewer could not determine whether matrix interferences were 

disrupting results in FGD bioreactor effluent samples. The LFBs associated with all 

samples met the method criteria. 

The RPD between sample 71647 and its field duplicate 71653 for sulfate was 58.8%. 

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 300.0. 

COD 

The percent recoveries for the MS/MSD analysis for sample 71648 (FGD bioreactor 

influent) were below the control limits of 90-110% required by EPA Method 410.4. The 

percent recoveries for the MS and MSD analyses were 86% and 87%, respectively. The 

low percent recovery could indicate that results for samples with the same matrix (FGD 

bioreactor influent) could be biased low. Sample 71648 was flagged as a minimum value. 

The LFBs associated with all samples met the method criteria. 

The percent recoveries for the MS and MSD analyses for sample 71651 (FGD bioreactor 

effluent) were 92% and 86%, respectively. These MS/MSD percent recoveries indicate 

that results for samples with the same matrix (FGD bioreactor effluent) could be biased 

low. However, EPA Method 410.4 only requires that the result for the MS analysis be 

within 90-110%, so sample 71651 was not flagged. 

The RPD between sample 71647 and its field duplicate 71653 was 43.5% and between 

sample 71654 and its field duplicate 71650 was 66.7%. 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.

3 
Cyanide 

Samples 71642, 71643, 71644, 71645, 71646, 71647, 71648, 71650, 71651, 71652, 

71653, and 71654 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 were diluted. 

The results of the diluted sample for 71642, 71643, 71644, 71650, 71651, 71652, and 

71654 were below the lowest calibration standard used by the laboratory (0.01 mg/L). 

These samples were already qualified by the laboratory with a “J” indicating that the 

result was below the RL, so no further qualification was necessary. 

SM 4500 CN-

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

no control limits specified in the method. The laboratory ran MS/MSD analysis on 

samples 71641, 71648, 71649, 71650, and 71651. As shown by Table 2 below, nearly all 

of the MS/MSD percent recoveries were below the laboratory control limits (90-110%). 

It should be noted that samples 71641, 71648, 71650, and 71651 were all either ND or 

qualified by the laboratory with a “J” because the result was less than the RL; these low 

results may have impacted the MS/MSD percent recoveries. The low MS/MSD percent 

recoveries for sample 71649 suggest that cyanide results for sample 71649 and samples 

with a similar matrix (FGD bioreactor effluent) could be biased low because of matrix 

interferences. Because SM 4500 CN-

 E does not require MS/MSD analysis, the data were 

not qualified. 

Table 2. MS/MSD Results for Total Cyanide Analysis 

Sample 

Number Type 

Result 

(mg/L) 

Spike 

Amount 

(mg/L) 

Spike Result 

(mg/L) 

Percent 

Recovery 

71641 MS ND 0.100 mg/L ND 0% 

71641 MSD ND 0.100 mg/L ND 0% 

71649 MS 0.012 0.100 mg/L 0.0956 84% 

71649 MSD 0.012 0.100 mg/L 0.0972 85% 

71650 MS 0.057 1.0 mg/L 0.959 90% 

71650 MSD 0.057 1.0 0.944 89% 

71651 MS 0.039 1.0 0.903 86% 

71651 MSD 0.039 1.0 0.916 88% 

71648 MS ND 1.0 ND 0% 

71648 MSD ND 1.0 ND 0% 

ND – Not detected. 

Nitrate/Nitrite 

The percent recoveries for the MS/MSD analysis for samples 71649 and 71651 (FGD 

bioreactor effluent) were above the control limits of 90-110% required by EPA Method 

353.2 and above the laboratory control limits of 72-113%. The percent recovery was 

4 
118% for both the MS and MSD samples for 71651 and 119% for both the MS and MSD 

samples for 71649. Because nitrate/nitrite was not detected in sample 71649 or 71651, 

there was no need to qualify either sample as a maximum value. 

Furthermore, the percent recoveries for the MS analysis for sample 71648 (FGD 

bioreactor influent) was above the control limits required by the method, but within the 

laboratory control limits. The MSD analysis for sample 71648 was within both the 

method and laboratory control limits. The MS and MSD percent recoveries were 111% 

and 110%, respectively. Sample 71648 was qualified as a maximum value. 

The result for sample 71650 with a concentration of 0.019 mg/L was below the lowest 

standard (0.05 mg/L) used to create the calibration curve. However, because this sample 

was already qualified by the laboratory with a “J” because the result was below the RL, 

no further qualification was necessary. 

Phosphorus 

Phosphorus was detected at 0.00790 mg/L in the LRB associated with all samples. 

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

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

based on LRB result. 

The percent recoveries for the MS and MSD analyses for samples 71648 and 71651 were 

not within the control limits of 90-110% specified in EPA Method 365.1. The MS and 

MSD percent recoveries for sample 71648 (FGD bioreactor influent) were within the 

laboratory control limits of 71-128%, but the MS and MSD percent recoveries for sample 

71651 were not. The percent recoveries for MS and MSD analyses on sample 71648 were 

both 75%. The percent recoveries for MS and MSD analyses on sample 71651 were 60% 

and 58%, respectively. Sample 71651 was qualified as a minimum value because the MS 

percent recovery was below the method specified criteria. The results also may be biased 

low for samples with a similar matrix (i.e., FGD bioreactor effluent) because of matrix 

interferences. Sample 71648 was already qualified by the laboratory with a “J” because 

the result was below the RL, so no further qualification was necessary. 

The results for the following samples were less than the lowest calibration standard 

(0.025 mg/L): 71644, 71645, 71646, 71647, 71648, and 71653. However, these samples 

were already qualified by the laboratory with a “J”, so no further action was taken. 

TDS 

The RPDs for laboratory duplicates from samples 71642, 71643, 71644, and 71648 were 

less than 10% as required by SM 2540C. However, the RPD for sample 71641 and its 

laboratory duplicate was 15%. Because the RPD was greater than the method control 

limits, sample 71641 was qualified as an estimated value. 

5 
TDS was detected at 8.0 mg/L, which is above the MDL (4.7 mg/L), but below the RL 

(10 mg/L), in two of the LRBs. Because the blank result was less than the RL, no samples 

were qualified based on LRB analyses. Furthermore, the TDS concentration in all 

samples was at least 1000 times greater than the concentration of TDS detected in the 

LRB, so sample results are unlikely to be affected by the TDS contamination in the LRB. 

All 14 samples analyzed for TDS did not achieve a constant weight after three drying 

cycles. In all cases, the weight increased from the first weighing to the second weighing. 

SM 2540C warns that samples that contain high levels of calcium, magnesium, chloride, 

and sulfate may be hygroscopic, meaning they absorb moisture from the air. FGD 

wastewater contains high concentrations of all of these species, so this was likely the 

cause for the inconsistent weight calculations. The samples were not qualified, but results 

may be biased high. 

TKN 

TKN was detected in the LRBs associated with samples 71641, 71645, 71646, and 71651 

at 0.894 mg/L, 0.645 mg/L, and 0.108 mg/L. These results were greater than the MDL 

(0.077 mg/L), but less than the RL (1.0 mg/L). Because these blank results were all less 

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

The RPD between sample 71647 and its field duplicate 71653 could not be reliably 

determined because the result for sample 71647 was ND and the result for sample 71653 

was 2.8 mg/L. 

The percent recoveries for the MS/MSD analysis for samples 71641 (FGD influent) and 

71654 (FGD bioreactor effluent) did not meet the control limits (90-110%) specified in 

EPA Method 351.2. The MS analysis for sample 71649 (FGD bioreactor influent) and 

71651 (FGD bioreactor effluent) also did not meet the control limits specified in the 

method. Furthermore, the MS/MSD percent recoveries for sample 71641 did not meet the 

laboratory criteria of 54-131%. Table 3 presents the percent recoveries of TKN for the 

MS/MSD analysis. 

TestAmerica appropriately analyzed sample 71641 with a 5 fold dilution, but due to 

analyst error analyzed the MS/MSD samples with only a 2.5 fold dilution. This was likely 

the reason for the very negative percent recovery for the MS/MSD samples associated 

with 71641. Also, sample 71651 was analyzed again in another batch because the TKN 

and ammonia results did not agree. However, TestAmerica did not reanalyze the 

MS/MSD analysis. Thus, the MS/MSD samples and the final sample result for 71651 

were analyzed in different batches. Samples of the same matrix did not appear to have 

correlating percent recoveries. For example, 71651 and 71654 both had similar matrices 

being FGD bioreactor effluent samples, but one sample had percent recoveries below the 

control limits and the other had percent recoveries above the control limits. Sample 

71641 was qualified as a minimum value while samples 71649 and 71654 were qualified 

as maximum values. 

6 
Table 3. MS/MSD Results for TKN Analysis 

Sample 

Number Type 

Result 

(mg/L) 

Spike 

Amount 

(mg/L) 

Spike Result 

(mg/L) 

Percent 

Recovery 

71641 MS 29 7.50 12.0 -229% 

71641 MSD 29 7.50 9.74 -259% 

71648 MS 2.6 3.00 5.49 96% 

71648 MSD 2.6 3.00 5.86 108% 

71649 MS 6.1 3.00 9.56 115% 

71649 MSD 6.1 3.00 9.42 110% 

71651 MS 6.3 3.00 8.49 74% 

71651 MSD 6.3 3.00 9.12 95% 

71654 MS 5.7 3.00 8.99 111% 

71654 MSD 5.7 3.00 9.06 114% 

Sample 71651 should also be qualified as a minimum value because the percent recovery 

of the MS sample was below the control limits specified in the method. However, this 

sample was also analyzed outside of the hold time. The ammonia and TKN results did not 

agree in the first analysis, so the sample had to be reanalyzed in another batch. The 

reanalysis of the sample was done one day outside of the 28-day hold time. The sample 

result was qualified by the laboratory as being analyzed outside of hold time; however, it 

was not qualified as an estimated value. Thus, sample 71651 was reported as an estimated 

value. 

TSS 

The RPDs for laboratory duplicates for samples 71642, 71644, and 71648 were less than 

10% as required by SM 2540D. However, the RPDs for samples 71641 and 71643 were 

15% and 13%, respectively. Because the laboratory duplicate RPDs for samples 71641 

and 71643 were above the method criteria, these two samples were qualified as estimated 

values. 

7 
8 

Table 4. Data Review Summary Table 

Sample Analyte Qualifier/Action Reason Level Detected

71648 COD Minimum value MS % recovery 

below methodspecified criteria 

140 mg/L 

71648 Nitrate/Nitrite Maximum value MS % recovery 

above methodspecified criteria 

21 mg/L 

71651 Total 

Phosphorus 

Minimum value MS % recovery 

below methodspecified criteria 

0.11 mg/L 

71641 TDS Estimated value Lab duplicate 

RPD > methodspecified criteria 

17000 mg/L 

71641 TKN Minimum value MS % recovery 

below methodspecified criteria 

29 mg/L 

71649 TKN Maximum value MS % recovery 

above methodspecified criteria 

6.1 mg/L 

71651 TKN Estimated value Analyzed one day 

past holding time, 

MS % recovery 

below methodspecified criteria 

6.3 mg/L 

71654 TKN Maximum value MS % recovery 

above methodspecified criteria 

5.7 mg/L 

71641 TSS Estimated value Lab duplicate 

RPD > methodspecified criteria 

3,100 mg/L 

71643 TSS Estimated value Lab duplicate 

RPD > methodspecified criteria 

3,300 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 
D-2 

3.2 Dissolved Metals - Those elements which pass through a 0.45-m membrane 

filter (sample is acidified after filtration). 

3.3 Suspended Metals - Those elements which are retained by a 0.45-m 

membrane filter. 

3.4 Total Recoverable Metals - The concentration determined on an unfiltered 

sample following treatment with hot, diluted mineral acids, as described in this 

procedure 

3.5 Instrument Detection Limit (IDL) - See Section 12.2 

3.6 Sensitivity - The slope of the analytical curve (i.e., the functional relationship 

between raw instrument signal and the concentration). 

3.7 Tuning Solution - This is a multi-element solution containing analytes which are 

representative of the entire mass range capable of being scanned by the 

instrument. It is used to optimize the sensitivity of the instrument and to verify 

the mass resolution meets method criteria. 

3.8 Initial Calibration Verification / Quality Control Standard (ICV/QCS) - A multielement standard of known concentrations prepared to verify instrument 

calibration. This solution must be an independent standard prepared near the 

mid-point of the calibration curve, and at a concentration other than that used for 

instrument calibration. 

3.9 Continuing Calibration Verification (CCV) - A multi-element standard of known 

concentrations prepared to monitor and verify the instrument daily continuing 

performance. 

3.10 Laboratory Control Sample / Laboratory Fortified Blank (LCS/LFB) - A multielement standard of known concentrations that is carried through the entire 

sample preparation and analysis procedure. This solution is used to verify 

method performance in an ideal sample matrix. 

3.11 Reagent Blank - High purity (> 18 megohm-cm) water containing the same acid 

matrix as the calibration standards that is carried through the entire digestion 

process. The reagent blank is used to determine the concentrations of trace 

metals in the reagents used to prepare and analyze the samples. 

3.12 Calibration Blank - High purity (> 18 megohm- cm) water acidified with the 

same acid concentrations present in the standards and samples. Also referred to 

as the Initial Calibration Blank (ICB) and Continuing Calibration Blank (CCB). 

3.13 Method Detection Limit (MDL) – Refers to the instructions in Appendix B to 40 

CFR Part 136. Also see Section 12.1 of this document. The MDL is determined 

from analysis of a sample in a given matrix containing the analyte. 

3.14 Individual FGD Interference Check solutions – Single element solutions at 

concentrations similar to those found in flue gas desulfurization wastewaters. 

3.15 Synthetic FGD wastewater – A mixed solution of elements at typical 

concentrations found in flue gas desulfurization wastewaters. 
D-3 

4.0 Interferences

4.1 Isobaric Interferences 

Isobaric interferences in the ICP/MS are caused by isotopes of different elements 

forming ions with the same nominal mass-to-charge ratio (m/z). The 

recommended ions used for the elements in this procedure do not have 

elemental isobaric interferences, except for a very small interference from 

krypton on 78Se, which can be avoided by using argon free of krypton. 

4.2 Isobaric Molecular 

Isobaric molecular interferences are caused by ions consisting of more than one 

atom. These molecular interferences are minimized by use of the collision cell 

utilizing He and/or H2 gases. Common examples are potential interferences from 

40Ar35Cl or 40Ca35Cl on 75As, or 35Cl16O on 51V, or 40Ar12C on 52Cr. Collision cell 

interference removal works both by causing the interfering molecular ion to 

dissociate and by reducing the kinetic energy of the ion. The latter is termed 

Kinetic Energy Discrimination (KED), and is the primary mechanism for 

interference removal. Polyatomic ions are larger than elemental ions and so 

collide with the helium atoms in the collision cell more frequently than the smaller 

elemental ions. Each collision reduces the energy of the ion, so the molecular 

ions lose energy more quickly. At the end of the collision cell a positive voltage 

plate prevents passage of the now low energy molecular ions. Thus, the 

interference is eliminated because the molecular ions do not reach the detector. 

4.3 Doubly Charged Ion Interferences 

Doubly charged elemental ions are possible in cases where the second 

ionization potential of the element is significantly below the fist ionization 

potential for argon (15.7eV). If a doubly charged ion is formed, it will cause a 

response at half of its elemental mass, potentially causing an interference. 

Fortunately, most elements have high enough second ionization potentials that 

formation of doubly charged ions is not an issue. For the target analytes in this 

procedure, a significant potential for interference is from 150Nd and 150Dy 

(potential interference on 75As and from 156Gd (potential interference on 78Se). To 

check for these potential interferences, monitor the response for mass 150 and 

156. If the cps for these masses is > 5 times the cps for the quantitation limit for 

arsenic (in the case of mass 150) or selenium (in the case of mass 156) an 

interference is possible. In this case analyze a 100ppb standard of Nd and Dy (if 

mass 150 is observed) or Gd (if mass 156 is observed) and measure the 

response at 150 and 75 (or 156 and 78). This ratio can then be used to create an 

interference correction equation. For example, if the response for a 100ppb Gd 

standard at mass 156 is 10,000 cps, and the observed response for the same 

standard at mass 78 is 1,000 counts, then the equation for 78Se would be: 

78Se = 78Se – (156Gd/10) 

4.4 Physical Interferences 

 Physical interferences are associated with the transport and nebulization 

process. Internal standards are used to compensate for these types of 

interferences. 

 Internal standards should be added at a level to give approximately 

50,000 - 800,000 counts of raw signal intensity. The mass of the internal 

standard should ideally be within 50 amu of the mass of the measured 
D-4 

analyte. Consideration should also be given to matching internal 

standards to analytes with similar ionization potentials. 

 Matrix effects are monitored by comparing the internal standard intensity 

in the sample to the internal standard intensity of the calibration blank. 

The internal standards must be between 60% and 125% of the calibration 

blank. If they are outside this window the sample is diluted by a factor of 

2 (1:1) and is reanalyzed. 

 Memory effects are dependent on the relative concentration differences 

between samples and/or standards which are analyzed sequentially. The 

rinse period between samples must be long enough to eliminate 

significant memory interference (see section 10.3.6). 

5.0 Safety 

This procedure may involve hazardous material, operations and equipment. This 

procedure does not purport to address all of the safety problems associated with its use. 

It is the responsibility of the user of the method to follow appropriate safety, waste 

disposal and health practices under the assumption that all samples and reagents are 

potentially hazardous. Safety glasses, gloves, lab coats and closed-toe, nonabsorbent 

shoes are required. 

5.1 Specific Safety Concerns or Requirements 

5.1.1 Eye protection that satisfies ANSI Z87.1, laboratory coat, and 

nonpowdered nitrile or latex gloves must be worn while handling 

samples, standards, solvents, and reagents. Disposable gloves that 

have been contaminated must be removed and discarded; nondisposable gloves must be cleaned immediately. 

5.1.2 The ICP plasma emits strong UV light and is harmful to vision. All 

analysts must avoid looking directly at the plasma. The RF Generator 

produces strong radio frequency waves, most of which are unshielded. 

People with pacemakers should not go near the instrument while in 

operation. 

5.2 Primary Materials Used 

The following is a list of the materials used in this method, which have a serious 

or significant hazard rating. Note: This list does not include all materials 

used in the method. The table contains a summary of the primary hazards 

listed in the MSDS for each of the materials listed in the table. 
D-5 

Material (1) Hazards Exposure 

Limit (2) Signs and Symptoms of Exposure 

Nitric Acid Corrosive 

Oxidizer 

Poison 

2 ppmTWA 

4 ppmSTEL 

Nitric acid is extremely hazardous; it is corrosive, reactive, 

an oxidizer, and a poison. Inhalation of vapors can cause 

breathing difficulties and lead to pneumonia and pulmonary 

edema, which may be fatal. Other symptoms may include 

coughing, choking, and irritation of the nose, throat, and 

respiratory tract. Can cause redness, pain, and severe skin 

burns. Concentrated solutions cause deep ulcers and stain 

skin a yellow or yellow-brown color. Vapors are irritating and 

may cause damage to the eyes. Contact may cause severe 

burns and permanent eye damage. 

Material (1) Hazards Exposure 

Limit (2) Signs and Symptoms of Exposure 

Hydrochloric 

Acid

Corrosive 

Poison 

5 ppmCeiling Inhalation of vapors can cause coughing, choking, 

inflammation of the nose, throat, and upper respiratory tract, 

and in severe cases, pulmonary edema, circulatory failure, 

and death. Can cause redness, pain, and severe skin burns. 

Vapors are irritating and may cause damage to the eyes. 

Contact may cause severe burns and permanent eye 

damage. 

1 – Always add acid to water to prevent violent reactions. 

2 – Exposure limit refers to the OSHA regulatory exposure limit. 

6.0 Equipment and Supplies

6.1 Instrumentation 

 Inductively Coupled Plasma Mass Spectrometer (ICP/MS) capable of providing 

resolution, less than or equal to 0.9 amu at 10% peak height from 6-253 amu 

and 1.0 amu at 5% peak height from 6-253 amu with a data system that allows 

corrections for isobaric interferences and the application of the internal standard 

technique. The ICP/MS must be equipped with a collision cell for the removal of 

molecular interferences. This procedure was developed using an Agilent 7500 

or 7700 instrument equipped with a high matrix interface. The interface extends 

the amounts of total dissolved solids that may be measured into the percent 

concentration range. Any collision cell instrumentation that meets the 

specifications in this procedure may be used. 

 A discrete sample introduction system enables the use of only the exact amount 

of sample volume required for data acquisition. 

 Accessories and configuration that are designed to accommodate samples with 

high levels of dissolved solids should be used. 

 This sampling system results in less matrix being deposited in the system 

during analysis and minimizes the rinse times normally needed for difficult 

matrices. 

 Autosampler with autosampler tubes. 

 Appropriate water cooling device. 

 Block digester with tubes. 

6.2 Supplies 

 Argon gas: High purity grade (99.99%). 
D-6 

 Helium gas: High purity grade (99.99%). 

 Hydrogen gas: High purity grade (99.99%). 

 Calibrated automatic pipettes or Class A glass volumetric pipettes. 

7.0 Reagents and Standards

7.1 Storage and Shelf-Life 

7.1.1 All standards must be stored in glass, FEP fluorocarbon or previously 

unused polyethylene or polypropylene bottles. Standards stored at 

concentrations as received from the vendor and mid-level dilutions must 

be replaced prior to the expiration date assigned by the vendor. If no 

expiration date is provided, the stocks and mid-level standards may be 

stored for up to one year. They must be replaced sooner if verification 

from an independent source indicates a problem (See section 10.3.5 for 

initial calibration verification acceptance criteria). 

7.1.2 Working standards, i.e., all standards at concentrations ready to 

analyze on the ICP/MS (all except tuning mixes, ICSA and ICSAB 

mixes, which are received at ready-to-use concentrations), are prepared 

fresh daily. 

7.2 Standards

7.2.1 Tuning Solution, 10 ppb 

The tuning solution stock is purchased as a custom multi-element mix. 

The concentrations of the constituents are shown in Attachment 5. 

Prepare the Tuning Solution as detailed below. 

 Obtain a clean 100 mL volumetric flask. 

 Place 50 mL of reagent water and 2 mL of conc. HNO3 and 0.5 

mL of conc. HCl in the flask. 

 Swirl to mix. 

 Pipet 0.1mL of the Tuning Solution Stock into the flask. 

 Dilute to volume with reagent water. Stopper and mix. 

7.2.2 PA Tuning Solution 

The dual detector solution may be commercially purchased as a custom 

multi-element mix. 

Prepare the PA Tuning Solution as detailed below. 

 Add approximately 50 mL of the 2% HNO3 / 0.5% HCl to a 100 

mL volumetric flask. 

 Prepare at a concentration recommended by the instrument 

manufacturer. 

7.2.3 Calibration Standards 

Stock calibration standards are purchased as custom multi-element 

mixes or as single element solutions. Each day of analysis, the 

standards are diluted to working levels using 2% nitric acid and 0.5% 

HCl acid matrix. Suggested concentrations are given in Attachment 8, 

but the laboratory may adjust calibration standard concentrations as 
D-7 

appropriate for the instrument and samples. At a minimum, a 3 point 

curve must be used. 

7.2.4 Individual FGD Interference check solutions. 

7.2.4.1 All individual FGD interference check solutions should be 

made up in the same acid matrix as the calibration standards. 

7.2.4.2 Chloride, 10,000 mg/L 

7.2.4.3 Calcium, 5,000 mg/L 

7.2.4.4 Sulfate, 4,000 mg/L 

7.2.4.5 Magnesium, 3,000 mg/L 

7.2.4.6 Sodium, 2,000 mg/L 

7.2.4.7 Boron, 500 mg/L 

7.2.4.8 Iron, 500 mg/L

7.2.4.9 Nitrate, 250 mg/L 

7.2.4.10 Manganese, 200 mg/L 

7.2.4.11 Bromide, 100 mg/L 

7.2.4.12 Fluoride, 100 mg/L 

7.2.4.13 Selenium, 20 mg/L

7.2.4.14 Vanadium, 10 mg/L

7.2.4.15 Zinc, 2 mg/L

7.2.4.16 Chromium, 1 mg/L

7.2.4.17 Copper, 1 mg/L

7.2.5 Mixed Interference Check Solution (Synthetic FGD Wastewater) 

7.2.5.1 Chloride, 5,000 mg/L 

7.2.5.2 Calcium, 2,000 mg/L 

7.2.5.3 Magnesium, 1,000 mg/L 

7.2.5.4 Sulfate, 2,000 mg/L 

7.2.5.5 Sodium, 1,000 mg/L 

7.2.5.6 Butanol, 2000ppm 

7.2.6 Initial Calibration Verification (ICV) Standard 

The ICV stock is from a source different than the source for the 

calibration standards. Each day of analysis, the ICV standard is 

prepared in 2% HNO3 and 0.5 % HCl acid to the concentrations shown 

in Attachment 8. 
D-8 

7.2.7 Continuing Calibration Verification (CCV) Standard 

The CCV is prepared from the same source as the calibration 

standards. The CCV standards are prepared fresh each day of analysis 

in 2% HNO3/0.5% HCl. The concentrations are shown in Attachment 8. 

Prepare the Working CCV as detailed below. 

 Dilute by 2X a known volume of the Working Calibration 

Standard in the 2% HNO3 / 0.5% HCl acid matrix. 

7.2.8 Spiking Stock Solution 

The spike stock solution is prepared from the same stocks as the 

calibration standards using the 2% HNO3 / 0.5% HCl acid matrix. Spike 

concentrations are listed in Attachment 8. 

7.3 Reagents

7.3.1 Reagent Water - ASTM Type I or equivalent for the elements of 

interest, generated using an ion-exchange water polishing system 

capable of achieving 18.0 megohm-cm.

7.3.2 Blank Matrix 2% HNO3 and 0.5% HCl. 

8.0 Sample Collection, Preservation, Shipment and Storage

Sample container, preservation techniques and holding times may vary and are 

dependent on sample matrix, method of choice, regulatory compliance, and/or specific 

contract or client requests. Listed below are the holding times and the references that 

include preservation requirements. 

Matrix Sample 

Container 

Min. Sample 

Size Preservation Holding Time Reference 

Waters HDPE 50 mLs HNO3, pH < 2 180 Days 40 CFR Part 136.3

Soils Glass or 

HDPE 

4 oz Cool 4 + 2oC 180 Days N/A 

9.0 Quality Control 

9.1 Quality control requirements are also summarized in Attachment 7. 

9.2 Ongoing data quality checks are compared with established performance criteria 

to determine if the results of analyses meet the performance characteristics of 

the method. Any QC result that fails to meet control criteria must be 

documented. 

9.3 Individual interference check solutions 

The individual interference check solutions listed in section 7.2.6 are analyzed 

prior to initiating sample analysis, and at least once per quarter while FGD 

wastewaters are being analyzed, and after any major changes to instrument 

operating conditions. Concentrations of target elements observed should be less 

than their reporting limits. In some cases it may not be possible to obtain 

interference check solutions that are completely free of contamination. In this 
D-9 

case, results up to 5X the reporting limit are acceptable if it is possible to 

demonstrate that the isotopic ratios correspond to natural abundances. For 

example, the natural abundances of zinc isotopes are Zn64 48.6%; Zn66 27.9%; 

Zn67 4.1%; Zn68 18.8%; Zn70 0.6%. The measured ratios are not expected to be 

exact, especially for low abundance isotopes, and some isotope may be masked 

by other elements in the solution, (for example Zn70 in the above example will be 

masked by Ge70) but it must be possible to explain the observed ratios. 

Because Arsenic, Manganese and Aluminum are monoisotopic, this 

demonstration is not possible and the level of interference observed must be less 

than the reporting limit. 

9.4 Synthetic FGD interference check solution 

The synthetic FGD matrix solution listed in section 7.2.7 is analyzed prior to 

initiating sample analysis, and at least once per day (immediately after 

calibration) while FGD wastewaters are being analyzed, and after any major 

changes to instrument operating conditions. Internal standard recovery must 

meet method criteria (Section 9.9) and concentrations of target elements 

observed should be less than their reporting limits. In some cases it may not be 

possible to obtain interference check solutions that are completely free of 

contamination. In this case, results up to 5X the reporting limit are acceptable if it 

is possible to demonstrate that the isotopic ratios correspond to natural 

abundances. For example, the natural abundances of zinc isotopes are Zn64

48.6%; Zn66 27.9%; Zn67 4.1%; Zn68 18.8%; Zn70 0.6%. The measured ratios are 

not expected to be exact, and some isotopes may be masked by other elements 

in the solution, (for example Zn70 in the above example will be masked by Ge70) 

but it must be possible to explain the observed ratios. Because Arsenic, 

Manganese and Aluminum are monoisotopic, this demonstration is not possible, 

and the level of interference observed must be less than the reporting limit. 

If the Synthetic FGD solution has to be diluted in order to analyze it 

effectively on the ICP/MS, then all samples and QC (including the MDL 

replicates) must be diluted by at least the same factor. 

9.4.1 Laboratory fortified Synthetic FGD solution 

The synthetic FGD solution is spiked with 40ppb of each of the target 

elements (400ppb for zinc and 4000ppb for aluminum) and analyzed 

once per day, immediately after the synthetic FGD check in section 9.4. 

All target elements must be recovered within 70-130% of the true value. 

If the Laboratory Fortified Synthetic FGD solution has to be diluted 

in order to analyze it effectively on the ICP/MS, then all samples 

and QC (including the MDL replicates) must be diluted by at least 

the same factor. 

9.5 Linear range determination 

The linear range for each element is determined prior to initiating sample 

analysis and at least once per year thereafter. The linear range must also be 

determined subsequent to changes that will have a major effect on instrument 

sensitivity, such as changing the detector. The linear range is established using a 

single element standard at the desired linear range. The result of the analysis 

must be within 10% of the true value. 
D-10 

9.6 Method Blank / Laboratory Reagent Blank (MB/LRB) 

The method blank consists of reagent water that has been processed in 

the same manner as the samples. One method blank must be processed with 

each preparation batch. 

Acceptance Criteria: Method blank results are acceptable if the concentration 

for each analyte of interest is less than the reporting limit. 

Corrective Action: If the method blank does not meet the acceptance 

criteria, the source of contamination should be 

investigated to determine if the problem can be 

minimized or eliminated. Samples associated with the 

contaminated blank shall be reprocessed for analysis, or 

under the following circumstances, may be reported as 

qualified (qualifier flags or narrative comments must be 

included on report): 

 The same analyte was not detected in the 

associated samples; 

 The method blank concentration is less than 1/10 of 

the measured concentration of any sample in the 

batch; 

 The method blank concentration is less than 1/10 

the specified regulatory limit; or 

 The analyte is a common laboratory contaminant 

(copper, iron, lead, calcium, magnesium, 

potassium, sodium, or zinc) less than 2 times the 

RL. Note that some programs do not recognize 

common lab contaminants. 

If the above criteria are not met and reanalysis is not 

possible, then the sample data must be qualified. This 

anomaly must be addressed in the project narrative 

and the client must be notified. 

9.7 Laboratory Control Sample / Laboratory Fortified Blank (LCS/LFB) 

The LCS consists of reagent water that is spiked with the analytes of 

interest as summarized in Attachment 8. One LCS must be processed (digestion 

and analysis) for each preparation batch. 

Acceptance Criteria: LCS control limits are based on three standard 

deviations of past laboratory results. These limits are not 

to exceed 85-115% recovery. The control limits are 

maintained in a LIMS or other appropriate system. 

Corrective Action: If the LCS % recovery falls outside of the control limits for 

any analyte, that analyte is judged to be out of control. 

All associated samples must be reprocessed for 

analysis. One possible exception is a recovery for a 

given element above the upper control limit with no 

detection for the same element in the samples. 

9.8 Matrix Spike / Matrix Spike Duplicate / Laboratory Fortified Sample Matrix / 

Laboratory Fortified Matrix Duplicate (MS/MSD/LFSM/LFMD) 
D-11 

MS is prepared by taking a second aliquot of a selected sample and spiking it 

with the analytes of interest as summarized in Attachment 8. An MSD is 

prepared by taking a third aliquot of a selected sample and spiking it with the 

analytes of interest as summarized in Attachment 8. The MS and MSD are 

processed in the same manner as the samples. One MS/MSD pair must be 

processed every 10 samples. 

Acceptance Criteria: Control limits are based on three standard deviations of 

past laboratory results. These limits are not to exceed 

70-130% recovery, and 20% relative percent difference 

(RPD). The control limits are maintained in the LIMS 

system. If the sample concentration for a specific analyte 

in the sample selected for spiking is greater than the 

concentration added by the spike, then recovery 

accuracy will be reduced. In this case a dilution test may 

be performed. A 1:5 dilution should agree within 20% of 

the original determination. If not, a physical or chemical 

interference is suspected, and must be discussed in the 

sample narrative. 

Corrective Action: If MS/MSD results and any applicable dilution tests do 

not meet the acceptance criteria and all other quality 

control criteria have been met, then a matrix interference 

is suspected. Failed matrix spikes are flagged, and are 

discussed in the final report case narrative. 

9.9 Internal Standards Evaluation for Samples 

The internal standards in samples must be between 60 and 125% of the intensity 

in the calibration blank. If the sample intensities fall outside this range, the 

calibration blank is reanalyzed to confirm the instrument has not drifted out of 

control. If the criteria is met, the sample is diluted by a factor of 2 (1:1) and 

reanalyzed. IS limits and corrective actions for standards and blanks are 

described in Section 10. 

10.0 Procedure

10.1 One-time procedural variations are allowed only if deemed necessary in the 

professional judgment of the supervisor to accommodate variation in sample 

matrix, radioactivity, chemistry, sample size, or other parameters. Any variation 

in procedure shall be completely documented. Any unauthorized deviations from 

this procedure must also be documented as a nonconformance, with a cause 

and corrective action described. 

10.2 Sample Preparation 

10.2.1 EPA Method 1638 was used as the reference for the digestion of the 

samples in which Section 12.2.8 describes Closed Vessel digestion. 

10.2.2 Transfer a 50mL (+/- 0.5mL) aliquot from a well mixed acid preserved 

sample to a 50mL digestion tube. 

10.2.3 Add 0.5mL of concentrated nitric acid and 0.25 mL hydrochloric acid. 

10.2.4 Spike the LCS and MS/MSD samples per spiking protocols. 
D-12 

10.2.5 The total volume of the solution in the tube is now greater than 50 mLs. 

The final volume will be 50 ml following the procedure to eliminate the 

discrepancy in the initial and final volumes. 

10.2.6 Tightly cap each digestion vessel. 

10.2.7 Place the digestion tube into a block digester adjusted to achieve a 

temperature of approximately 85o

C. 

10.2.8 Heat for 2 hours after 85o

C is obtained. 

10.2.9 Remove from the block and allow to cool. 

10.3 Calibration 

10.3.1 Instrument Start Up 

Set up the instrument according to manufacturer’s operating instructions. 

Allow the instrument to become thermally stable for at least 30 minutes 

before tuning. 

10.3.2 Instrument Tuning / Mass Calibration 

Tune the instrument with a solution containing elements representing all 

of the mass regions of interest. The relative standard deviations must be 

less than 5% for a minimum of 4 integrations of the solution. Mass 

calibration and resolution checks using the tuning solution must be 

completed at the beginning of every day. 

Mass Calibration Check – The mass calibration results must be within 

0.1 amu from the true value. If this criterion 

is not met, the mass calibration must be 

adjusted before running samples. 

Mass Resolution Check - The resolution must be verified to be less 

than 0.9 amu full width at 10% peak height. 

10.3.3 Mass 75 interference check 

The concentration determined for arsenic (mass 75) must be less than 

0.25 x the reporting limit when the blank matrix (2% nitric acid / 0.5% 

hydrochloric acid) is infused (using the collision gas mode used for 

arsenic). 

10.3.4 Initial Calibration 

The ICP/MS is calibrated each day of operation using a blank and at 

least 3 standards (see Section 7.2.3). Report the average of at least 

three integrations. 

The validity of the calibration is determined by the subsequent 

calibration verifications, which are performed at concentrations as 

described in the next sections. 

10.3.5 Second-Source Initial Calibration Verification (ICV) 

A 40 g/L / 4,000 ug/L ICV standard (see Section 7.2.8) is analyzed 

immediately after the initial calibration. This is a standard obtained from 

a different vendor than the standard used for calibration. This analysis 

also satisfies the Method 200.8 requirement for a Quality Check 

Standard (QCS). 
D-13 

Acceptance Criteria: The ICV recovery must be within 90-110%. 

Additionally, the internal standard recoveries for 

200.8 must fall between 60 and 125% of true 

values. The ICV can be reanalyzed, but must 

be successful twice in succession or corrective 

action must be taken. 

Corrective Action: If the ICV results are outside of the acceptance 

limits, investigate the accuracy of the 

standards, correct as necessary, and 

recalibrate. 

10.3.6 Calibration Blank 

Checks for the memory effects described at Section 4.4 may be 

accomplished by analysis of an initial calibration blank (ICB) after the 

ICV. Continuing calibration blanks (CCBs) are analyzed after each 

continuing calibration verification. 

Acceptance Criteria: Results for the calibration blanks must be less 

than the RL. 

Corrective Action: If the calibration blank exceeds acceptance 

limits, then the possibility of instrument 

contamination should be examined, particularly 

the possibility of carry-over from high level 

samples. The blank can be reanalyzed, and if 

successful, analysis can continue. However, 

samples tested after high-level samples should 

be retested. If the reanalysis is not successful, 

then the analysis should be terminated. After 

the problem is corrected, recalibrate and 

reanalyze all samples tested since the last 

acceptable CCB. 

10.3.7 Reporting Limit (RL) Verification Standard 

An independent standard is analyzed after the ICV to monitor the lab’s 

ability to produce reliable results at RL-level concentrations. The RL 

verification standard is analyzed after the daily ICB. 

Acceptance Criteria: For project reporting limits at or above two 

times the MDL, the results should be within 

50% of the expected value. Some programs 

may require tighter control, in which case the 

RLs will need to be three or more times the 

MDL concentration. 

Corrective Action: If the RL verification fails to meet acceptance 

limits, data for the associated samples must be 

assessed. For example, if the results are high, 

consider blank contamination, and if the results 

are low, consider MDL verifications. At a 

minimum, sample results must be qualified in 

the final report. 

10.3.8 Continuing Calibration Verification (CCV) Standard 
D-14 

A 50 g/L CCV standard is analyzed after every set of ten samples and 

at the end of the analytical sequence. 

Acceptance Criteria: The CCV recovery must be within 85-115%. In 

addition, the IS recovery must be within 60-

125%. If CCV results are not within these 

limits, the CCV can be reanalyzed, but it must 

be successful twice in succession or further 

corrective action must be taken. 

Corrective Action: If the CCV fails acceptance criteria, then the 

analysis should be terminated. Recalibrate and 

reanalyze all samples tested since the last 

acceptable CCB. 

10.4 Sample Analysis 

10.4.1 Report the average of at least three integrations for all field and QC 

samples analyzed. 

10.4.2 Flush the system with the rinse blank for at least 30 seconds between 

samples and standards during the analytical run. Evaluate the 

effectiveness of this time and increase the flush time, if needed. 

10.4.3 It may be valuable to monitor additional isotopes for elements that are 

potentially susceptible to interferences. In particular, monitoring 

additional isotopes for selenium may help data analysis. 

10.4.4 Dilute and reanalyze samples that are more concentrated than the 

highest calibration standard for an analyte or specific isotope of interest. 

No analyte may be reported from an analysis of a diluted sample in 

which the analyte concentration is less than 5 times the RL. 

The analytical run sequence should be performed as follows to meet all 

quality control criteria: 

Instrument initialization 

Warm-up 

Tune instrument 

Perform mass calibration 

Perform resolution check 

Validate tuning criteria 

Calibration blank 

Calibration standard 1 

Calibration standard 2 

Calibration standard 3 

ICV 

ICB 

RL verification standard 

Synthetic FGD matrix 

Spiked synthetic FGD matrix 

Carryover check 

CCV 

CCB 

10 Samples (which can include all sample types) 

CCV 

CCB 
D-15 

11.0 Calculations / Data Reduction

11.1 LCS percent recoveries are calculated according to the equation:

11.2 ICV percent recoveries are calculated according to the equation:

11.3 CCV percent recoveries are calculated according to the equation:

11.4 Matrix Spike Recoveries are calculated according to the following equation:

Where: 

SSR = Spike Sample Result 

SR = Sample Result 

SA = Spike Added 

NOTE: When the sample concentration is less than the detection limit, use SR = 0 

for the purpose of calculating %R. 

11.5 The relative percent difference (RPD) between sample duplicates is 

calculated according to the following equation:

Where: 

DU1 = Sample result 

DU2 = Sample duplicate result 

100%

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

100%

LCSTrue Value

LCS Found Value - LRB Found Value % 



 



 R 
D-16 

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

2

1 Result ( g/L) V

C V  D

 

Where: 

C = Concentration from instrument readout, ppb 

D = Instrument dilution factor 

V1 = Final volume in liters after sample preparation 

V2 = Initial volume of sample digested in liters 

12.0 Method Performance 

12.1 Method Detection Limit Study (MDL) 

An initial method detection limit study must be performed on each instrument 

before samples can be analyzed. MDL studies are conducted annually as 

follows: 

 Prepare seven samples at three to five times the estimated MDL 

concentration. The MDL samples are prepared in the Synthetic FGD 

wastewater matrix and in reagent water. 

 Prepare and analyze the MDL standards as described in Section 10. 

 Calculate the average concentration found in μg/L, and the standard 

deviation of the concentration(s) in μg/L, for each analyte. 

 The MDL is calculated as Students t for the 99th percentile times the standard 

deviation of the MDL replicate results, following the procedure at 40CFR Part 

136, Appendix B. 

NOTE1: Perform the MDL study in the synthetic FGD 

wastewater matrix. Spiking this matrix provides detection 

limits that are better matched to the complex matrix 

typical of FGD wastewater. These limits can be 

significantly higher than those obtained in a reagent water 

matrix. In some cases (zinc in particular), the level of 

contamination in the synthetic FGD solution may be high 

enough to result in somewhat elevated MDLs. 

NOTE2: An FGD-MDL may be less than the MDL observed in 

method blanks. If this occurs frequently, the FGD-MDL 

should be elevated to the mean of the method blanks plus 

the Student t factor times the standard deviation of the 

method blanks. 

12.2 Instrument Detection Limit Study 

Instrument detection limit (IDL) studies are conducted quarterly for each 

instrument and each mass used for analysis. 

 Prepare ten blanks. 

 Analyze the IDL blanks on three non-consecutive days. 

 The IDL is equal to three times the standard deviation of the blank results.
D-17 

12.3 Demonstration of Capabilities

All personnel are required to perform an initial demonstration of proficiency 

(IDOC) on the instrument they will be using for analysis prior to testing samples. 

On-going proficiency must be demonstrated annually. IDOCs and on-going 

proficiency demonstrations are conducted as follows. 

Four aliquots of the ICV are analyzed using the same instrumental conditions 

and procedures used to analyze samples. The analyst must employ ICV’s from 

four distinct analytical sequences. Using these four ICV’s demonstrates the 

analyst’s ability to optimize and calibrate the instrument and to prepare analytical 

solutions. Calculate the average recovery and standard deviation of the recovery 

for each analyte of interest. 

 If any analyte does not meet the acceptance criteria, (85-115% recovery, 

unless other criteria are established) the test must be repeated. Only those 

analytes that did not meet criteria in the first test need to be evaluated. 

Repeated failure for any analyte indicates the need for the laboratory to 

evaluate the analytical procedure and take corrective action. 

12.4 Training Requirements 

12.4.1 Each analyst performing the method must complete a demonstration of 

capability (DOC) by successfully preparing and/or analyzing four 

consecutive LCSs, or a blind performance evaluation (PE) sample, or 

other acceptable QC samples. Analysts who continue to perform the 

method must successfully complete a demonstration of capability 

annually. 

13.0 Pollution Control 

13.1.1 For information about pollution prevention that may be applicable to 

laboratory operations, consult “Less is Better: Laboratory Chemical 

Management for Waste Reduction” available from the American 

Chemical Society’s Department of Government Relations and Science 

Policy, 1155 16th Street N.W., Washington, D.C., 20036, or online at 

http://www.ups.edu/x7432.xml. 

14.0 Waste Management

All waste must be disposed of in accordance with Federal, State, and local 

regulations. 

15.0 References / Cross-References

15.1 EPA Method 200.8, “Determination of Trace Elements in Waters and Wastes 

by Inductively Coupled Plasma - Mass Spectrometry”, Revision 5.4, EMMC 

Version. 

15.2 EPA Method 1638, “Determination of Trace Elements in Ambient Waters by 

Inductively Coupled Plasma – Mass Spectrometry, January 1996 
D-18 

16.0 Attachments

Attachment 1: Recommended Elemental Equations 

Attachment 2: Internal Standards and Corresponding Metals 

Attachment 3: Sample Preservation and Holding Times 

Attachment 4: Suggested Mass Choices 

Attachment 5: Tuning Solution 

Attachment 6: Suggested Tuning and Response Factor Criteria 

Attachment 7: Summary of Quality Control Requirements 

Attachment 8: Calibration, Calibration Verification, and Spike Concentrations
D-19 

Attachment 1 

Recommended Elemental Equations 

Element 

Isobaric 

Correction Mathematical Equation 

Pb None (1.0000)(208M) + (1.0000)(207M) + (1.0000)(206M) 

6Li Li (natural) (1.0000)(6M) - (0.0813)(7M) 

In Sn (1.0000)(115M) - (0.0149)(118M) 

The 6

Li correction equation is only needed if 6Li is used as an internal standard for low mass elements. 

Attachment 2: Internal Standards and Corresponding Metals 

Internal Std. Associated elements1,2

Sc Na, Mg, Al, K, Ca, V, Cr, Mn 

Ge Fe, Ni, Cu, Zn, As, Se 

In Ag, Cd 

Ho Tl, Pb 

Footnote: (1) Na, Mg, K, Ca and Fe are included in the synthetic FGD wastewater but their 

analytical determination is optional – the interferences caused by these elements are more 

important than the determination of their exact concentration. 

(2) Other internal standards may be used. For example, 6

Li, Ga, Rh, Bi, Ho and Tb may be 

considered for use as internal standards. 
D-20 

Attachment 3: Sample Preservation and Holding Times 

Measurement 

Parameter

Container (1) Preservative (2) Maximum Holding 

Time (3)

Waters: 

Metals (4) P,G HNO3 to pH < 2 6 months 

Soils/Sediments/Wastes: 

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

digestion. 

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

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

collection or shipped to the laboratory unpreserved for preservation at the 

laboratory. 

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

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

considered valid. Holding times are calculated from the date when the sample 

was collected. 

 (4) Samples are filtered immediately on-site by the sampler before adding 

preservative for dissolved elements. 
D-21 

Attachment 4: Suggested Mass Choices 

Masses listed indicate the masses which have the most impact on data quality and the elemental 

equations used to collect the data. 

Mass Element of Interest Analysis mode 

27 Aluminum No gas 

75 Arsenic He 

111 Cadmium He 

52 Chromium He 

63 Copper He 

208, 207, 206 Lead No gas or He 

24 Magnesium No gas 

55 Manganese He 

60 Nickel He 

39 Potassium No gas or He 

78 Selenium He (H2) 

107 Silver He 

23 Sodium No gas or He 

205 Thallium No gas or He 

51 Vanadium He 

66 Zinc He 

NOTE: It is strongly recommended that elements other than those of interest be 

monitored to indicate other potential molecular interferences which could 

affect the data quality. 
D-22 

Attachment 5: Tuning Solution 

A tuning solution containing elements representing all of the mass regions of interest must be analyzed. 

Below are two groups of suggested solutions which cover a typical mass calibration range. 

Method 200.8 

Element Concentration (g/L) 

Mg 10 

Rh 10 

Ba 10 

Be 10 

U 10 

Ce 10 

Y 10 

Pb 10 

Li 10 

Co 10 

In 10 

Tl 10 
D-23 

Attachment 6: Suggested Tuning and Response Factor Criteria 

No Gas Mode

Li7 >2000cps 

Tl205 >3000cps 

CeO/Ce 156/140 1% 

Ce++/Ce+ 70/140 <3% 

He Mode:

ArAr 78 2-3 counts/sec 

ArCl 75 2-3 counts/sec 
D-24 

Attachment 7: Summary of Quality Control Requirements 

QC Parameter Frequency Acceptance Criteria Corrective Action 

ICV/QCS Beginning of every 

analytical run. 

90 - 110% recovery. 

200.8 IS, 60-125% rec. 

Terminate analysis; 

correct the problem; 

recalibrate. 

ICB/CCB Immediately after each 

ICV. 

The result is < RL 

200.8 IS, 60-125% rec. 

Terminate analysis; 

correct the problem; 

recalibrate. 

Synthetic FGD 

interference check 

Prior to initiating 

analysis and at least 

quarterly. 

Result for target elements 

is < RL, unless actual 

presence of target 

element can be 

demonstrated, in which 

case result is < 5X RL. 

Correct the problem prior 

to sample analysis. 

Individual element 

interference checks 

Prior to initiating 

analysis and at least 

quarterly. 

Result for target elements 

is < RL, unless actual 

presence of target 

element can be 

demonstrated, in which 

case result is < 5X RL. 

Correct the problem prior 

to sample analysis. 

CCV Beginning and end of run 

and every 10 samples OR

every 2 hours, whichever 

is more frequent. 

Beginning and end of 

each lot. 

90 - 110% recovery. 

IS, 60-125% rec. 

If unacceptable, 

terminate analysis; 

correct the problem; 

recalibrate the 

instrument, reverify 

calibration and rerun all 

samples since the last 

acceptable CCV. 

CCB Immediately following 

each CCV. 

The result must be < RL 

200.8 IS, 60-125% rec. 

If unacceptable, 

terminate analysis; 

correct the problem, 

recalibrate the 

instrument, reverify 

calibration and rerun 

all samples since the 

last acceptable CCB. 
D-25 

Attachment 7: Summary of Quality Control Requirements (continued) 

QC Parameter Frequency Acceptance Criteria Corrective Action 

Method 

Blank/Laboratory 

Reagent Blank 

One per lot of 20 field 

samples or fewer. 

The result must be less 

than the RL. 

Sample results greater 

than 10x the blank 

concentration or samples 

for which the 

contaminant is < RL, do 

not require redigestion or 

reanalysis. 

Re-run once. If > than 

the RL, Redigest and 

reanalyze samples. 

Note exceptions under 

criteria section. 

See Section 9.4 for 

additional requirements. 

Matrix Spike/Laboratory 

Fortified Matrix 

One every ten samples or 

fewer. 

Must be within 

laboratory control limits. 

See section 9.6 for 

additional requirements. 
D-26 

Attachment 8: Calibration, Calibration Verification, and Spike Concentrations 

Element 

Initial Calibration 

(g/L) 

ICV 

(g/L)

CCV 

(g/L)

LCS

(g/L)

MS/MSD 

(g/L)

Aluminum 100, 1,000, 10,000 4000 5000 4000 4000 

Arsenic 1, 10, 100 40 50 40 40 

Cadmium 1, 10, 100 40 50 40 40 

Chromium 1, 10, 100 40 50 40 40 

Copper 1, 10, 100 40 50 40 40 

Lead 1, 10, 100 40 50 40 40 

Manganese 1, 10, 100 40 50 40 40 

Nickel 1, 10, 100 40 50 40 40 

Selenium 1, 10, 100 40 50 40 40 

Silver 1, 10, 100 40 50 40 40 

Thallium 1, 10, 100 40 50 40 40 

Vanadium 1, 10, 100 40 50 40 40 

Zinc 1, 10, 100 40 50 40 40 

Additional elements may be included in the calibration solution at the above levels. Levels 

may be adjusted to meet specific requirements. 

####