# 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. I NTRODUCTION 

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

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

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

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

2. F ACILITY 

# O VERVIEW 

# ........................................................................................................2-1

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

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. S AMPLE 

# C OLLECTION 

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

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

3.1.1 Influent to FGD Wastewat er Treatment System......................................3-2

3.1.2 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. L ABORATORY 

# A NALYTICAL 

# R ESULTS AND 

# D ISCUSSION 

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

5. D ATA 

# Q UALITY 

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

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

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

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

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

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

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

6. R EFERENCES 

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

Appendix A: A NALYTICAL 

# R ESULTS



# Appendix B: D ATA 

# R EVIEW 

# N ARRATIVES



# Appendix C: P ICTURES 

# F ROM THE 

# S AMPLING 

# E PISODE



# Appendix D: FGD ICP/MS SOP: I NDUCTIVELY 

# C OUPLED 

# P LASMA 

# M ASS 

# S PECTROMETRY FOR



# T RACE 

# E LEMENT 

# A NALYSIS IN 

# F LUE 

# G AS 

# D ESULFURIZATION 

# W ASTEWATERS

# ii LIST OF TABLES

Page

Table 3-1. Sample Collection In formation, Belews Creek........................................................ 3-13

Table 3-2. Sample Collection at Be lews 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 Me thods, Belews Creek .......................................................................... 3-20

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

Table 3-7. Sample Preservati on Summary, Belews Creek ........................................................ 3-22

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

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

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

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

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

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

Table 4-1. Influent to F GD Wastewater Treatment Sy stem, Belews Creek............................... 4-4

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

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

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

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

Table 4-5. Metal Pollutants 4-Day Aver age Data Summary fo r FGD Wastewater

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

Table 5-1. Field Duplicate Re sults – Influent to Bioreacto r System, Belews Creek.................. 5-5

Table 5-2. Field Duplicate Resu lts – 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-1 1

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Belews Creek ................................................................................................................ A-4 1

Table A-15. Bottle Blank and Equipment Bla nk 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-5 1

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

Belews Creek ................................................................................................................ A-5 3

# LIST OF TABLES (Continued)

Page

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

Belews Creek ................................................................................................................ A-5 4

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

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

Table A-21. Effluent from th e Bioreactor System Field Bl ank, Day 1 Analytical Results,

Belews Creek ................................................................................................................ A-5 6

Table A-22. Effluent from th e Bioreactor System Field Bl ank, Day 2 Analytical Results,

Belews Creek ................................................................................................................ A-5 8

Table A-23. Effluent from th e Bioreactor System Field Bl ank, Day 3 Analytical Results,

Belews Creek ................................................................................................................ A-5 9

Table A-24. Effluent from th e Bioreactor System Field Bl ank, Day 4 Analytical Results,

Belews Creek ................................................................................................................ A-6 0

# 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 Sy stem, Belews Creek ................................................................ 2-7

Figure C-1. Sampler Working Inside a “Cleanbox” ....................................................................C-1

Figure C-2. Sample Tap and Tubing at the In fluent to the FGD Wastewater Treatment

System......................................................................................................................... .....C-2

Figure C-3. Sample Collection Set- Up at the Pump-Off Station.................................................C-3

Figure C-4. Sample Collection Set-Up at th e 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. I NTRODUCTION



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

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

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

and evaluate treatment technologi es and best management practic es used to reduce pollutant

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

place June 6 - 11, 2010, at Duke Energy Carolinas’ Belews Creek Steam Station (Belews Creek),

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

was to characterize the purge stream entering th e flue gas desulfuriza tion (FGD) wastewater

treatment system and the influent to and efflue nt from the FGD bioreactor treatment system. The

influent to the bioreactor syst em 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 pr esent in the wastewater discharges from steam

electric power plants that substantially cont ribute to the toxic load ings for the industry.

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

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

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

the untreated FGD wastewaters a nd effluent quality from tec hnologies designed to treat the

wastewater.

1.2 Power Plant Site Selection

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

configurations and characte ristics of the plants.

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

characteristics:

 The plant is a coal-fired pow er 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 commerc ial-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 En ergy 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 sa mpling points, and determine the set-up for the

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

Monday through Friday (June 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 sample s with the Utility

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

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

collected samples on behalf of the plant.

# 2-1 2. F ACILITY 

# O VERVIEW



# Belews Creek operates two steam electric units and each has a coal-f ired 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 facilitie s are located on approximately 700 acres in

Belews Creek, NC, adjacent to Belews Lake. Th e 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 (SO 2 

# ) releases from the plant. The Un it 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 SO 2 

# from the flue gas. With the addition of the

FGD scrubber systems, Belews Creek also instal led an FGD wastewater treatment system to

control the discharges of the wastewater gene rated during the operation of the FGD scrubbers.

Sections 2.1 and 2.2 further discuss the F GD scrubber systems and the FGD wastewater

treatment system, respectively.

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

2004, respectively, to control nitrogen oxide (NO

x 

# ) releases from the plant. Initially, Belews

Creek was only operating the SCRs during ozon e 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 operati ng 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 as h 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 hoppe rs 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 sy stem 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 la rge for use in the FGD

system. The underflow from the hydrocyclones is tr ansferred 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 r eaction tank of the FGD system and the recycle

pumps send the slurry to the vari ous levels of the FGD scrubber (t ypically 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 sl urry falls downward and the flue gas flows

countercurrent to the slurry, the spray droplets of the limestone slurry contact the flue gas and

absorb the SO 2 

# , which reacts with the limestone particle s and produces calcium sulfite. The spray

droplets continue to flow downward in the scr ubber until they reach the reaction tank. Belews

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

gypsum).

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

maintain the solids concentration in the sc rubbers 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 concentra tion of 12,000 ppm. Belews Creek transfers the

blowdown from the scrubber to the gypsum dewatering operations.

The gypsum slurry is pumped to the prim ary 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 wa ter exits the top of the hydrocyclones. The

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

transferred to the vacuum filter belts. Th e 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 th e scrubber or sent to the filter feed tank. The

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

FGD wastewater treatment system.

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

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

approximately 10 percent. Belews Creek transf ers 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 mile s from the plant. Belews Creek generates approximately

500,000 tons of gypsum per year; however, plant pe rsonnel stated that th e gypsum production is

dependent on the coal being burned and sulfur conten t of the coal.

2.2 FGD Wastewater Treatment System

The FGD wastewater treatment system is de signed 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 equali zation tank varies dependi ng on whether one or both

of the scrubbers are purging.

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

installed the wastewater treatment system to treat the FGD scrubbe r 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 c ontains 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 proces s 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 trea tment system, showing

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

biological reactor po rtions of the treatment system.

The secondary hydrocyclone overflow from the scrubbers is transfe rred to the purge tank

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

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

had a pH between 6 and 7 S.U., and a temperatur e 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 biol ogical treatment system, and off-specification

biological treatment effluent.

2.2.1 Physical/Chemical Separation

From the equalization tank, the wastewater enters three reac tion 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 additi on, but which is only used to provide additional

mixing; and reaction tank 3, in which ferric ch loride 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 sp lits and enters two clarifiers in parallel.

Each of the clarifiers is capab le 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 facilita tes removal of the solids in the wa stewater. Hydrochloric acid is

added to the wastewater at a poi nt 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 over flow from the two clarif iers is split and sent

through three sand filters in paralle l. Each of the sand filters can handle 75 percent of the waste

# 2-4 stream capacity. The target maximum TSS level fo r the sand filter effluent is 50 ppm; however,

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

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

to the equalization tank.

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

clarifier sludge is recycled fr om the sludge storage tank to reac tion 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 f ilter 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 th e treatment system, Belews Cree k treats the wastewater in

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

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

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

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

form, while other metals are precipitated as su lfide 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 110 o 

# F to 95 o 

# F. As the wastewater flows from the heat exchanger to the first

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

of carbon to feed the bacteria. Th e wastewater is divided evenly among the eight first-stage cells.

The flow to each cell is sent to 16 distribution pi pes to create an even di stribution of flow into

the top of the cell. The water le vel in the cells is approximately three feet above the activated

carbon bed.

Belews Creek operates the biore actors 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 a ffect the performance of the microbes and potentially allow for

nondesirable microbes to propagate.

The effluent from all eight of the first-stage bi oreactor 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 adde d to the wastewater as feed for the microbes as

the wastewater is transferred. As in the first stage, the wastew ater is divided evenly among the

eight second-stage cells and each cell has 16 distri butor pipes to evenly distribute the flow into

the cell.

Occasionally the bioreactor ce lls need to be backflushed to remove accumulated solids.

The plant pumps the effluent from the first-st age bioreactor cells b ackwards 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 th e FGD wastewater treatment system.

# 2-5 Because the first-stage bioreac tor cells denitrify the waste stream, they produce nitrogen

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

degassing operation where water is sent backward s 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 treatm ent system, wastewater is transferred to

two wetland supply tanks, which is then transferre d directly to the ash ba sin. According to plant

personnel, the treated FGD wastew ater, excluding cooling water, represents approximately seven

percent of the total flow discha rge 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 upstr eam of the equalization tank (i.e., the

sample was collected prior to any chem ical 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 bi oreactor 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.

# 2-6Figure 2-1. Simplified Diagramof the FGD Wastewater Treatment System, Belews Creek

# 2-7FGD Scrubber Purge(from Purge Tank)LimePolymerEqualizationTankReaction Tank 1ReactionTank 2ReactionTank 3SP-1SP-2Indicates a Sampling PointFerricChlorideFilter2HoldingTankClarifier 1SludgeStorageTankFilter PressSumpFilterBackwashFilter1Solids to FlyAsh LandfillWastewater FlowSludge FlowIntermittent Wastewater FlowClarifierSludgeMixChamberClarifier 2Filter3Cooling WaterNutrientFirst-StageBioreactors(8)First-StageEffluentStorageSecond-StageBioreactors(8)Second-StageEffluentStorageTo Ash BasinBio Reactor BackflushHydrochloricAcidSP-3Figure 2-2. Physical/Chemical Separation and Biological Reactor Portion of FGD Wastewater Treatment System, BelewsCreek

# 3-1 3. S AMPLE 

# C OLLECTION



# During the Belews Creek sampling episode, the sampling team followed the collection

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

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

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

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

activities.

3.1 Sampling Points, Sample Collectio n Methods, and Field Measurements

This section describes the sampling point s, sample collection methods, and field

measurements. Additional details are available in Section 3 of the Sampling Plan. 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, sampli ng point descriptions, type of sample

collection, and sample collection dates and times. Table 3-2 list s the sampling point numbers and

descriptions, the number of samples collected, and the pollutant parameters for which the

samples were analyzed. Table 3-3 presents th e field measurement data collected from each

sampling point. Table 3-4 presents a crosswalk be tween the sample numbers used for laboratory

sample identification and the sample points for each day.

The sampling points for this episode were:

 SP-1 Influent to FGD Wastewater Treatment System;

 SP-2 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 fr om Bioreactor System (SP-3);

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

 SP-7 Influent to Bioreactor Syst em (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 tubi ng configuration at each sampling

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

cyanide) at all sampling points as “true” splits (i.e., samples for the same analyte were collected

simultaneously). The mercury and cyanide samples were collected directly from a sample tap;

therefore, for these samples, EPA and Belews Creek’s representative collected duplicate

samples, with one filling the bot tle immediately after the other.

At each of the sampling points, EPA collected metals sample fractions following EPA

Method 1669 collection protocols. To collect these samples, EPA samplers donned Tyvek®

coveralls and dust masks (dust masks were worn until all mercury samples had been collected).

In addition, EPA set up a “cleanbox,” which consists of a portable plastic rectangular box with a

shallow lip and a flip-top lid th at secures itself ope n with clips. The “cleanbox” is double-bagged

with a clear inner bag, enclosed in a translu cent outer bag. The “cleanbo x” is handled using

# 3-2 “clean hands / dirty hands” techniques, where by the inner bag is ha ndled only by the “clean

hands” sampler. When the “cleanbox” is opened, the sampler is able to position his/her hands in

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

tubing. The “cleanbox” minimizes potential at mospheric contamination during sample

collection. Figure C-1, in Appendix C, is a pictur e of a sampler working inside a “cleanbox.”

The metals sample bottles were also double-bagged. To collect the metals samples, EPA

placed the sample bottles (while still in its seal ed inner bag) into the “cleanbox” following the

protocols specified in Method 1669, also referred to as “clean hands / dirty hands” protocols.

Sampling staff filled the sample container, then cl osed the sample bottle lid and sealed the inner

bag as quickly as possible with in the “cleanbox.” The bagged sample bottles were then removed

from the “cleanbox” and placed into the outer bag following the “clean hands / dirty hands”

protocols.

3.1.1 Influent to FGD Wastewater Treatment System

The influent to FGD wastewater treatment syst em (SP-1) was collected from a sample tap

located on the 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 cons istent 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 usi ng 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 sample s 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 th e silicone tubing was fitted w ith a “Y” splitter, with two

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

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

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

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

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

dissolved metals samples).

# 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 containe rs for biochemical oxygen demand (BOD 5 

# ), Group I,

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

Table 3-6 for a list of Group I and Group II analytes. BOD 5 

# , Group I, Group II, and total cyanide

samples were immediately placed on ice after sa mple collection.

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

potassium-iodide starch test stri ps were used to measure for su lfides and oxidants, respectively.

No sulfides or oxidants were detected during th e sampling episode. The samplers then preserved

the total cyanide sample with sodium hydroxide to a pH >10 S.U. and placed it on ice.

Samples for the dissolved metals analyses we re pumped from the previously filled 10-

liter container. The pump-off station consisted of a length of Teflon® tubing attached to a length

of silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team

attached a capsule filter to th e silicone tubing, which was a s hort distance downstream of the

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

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

to collect “true” split samples with Belews Cree k’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-lit er container filled

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

solids in the wastewater had b een settling for approximately 70 minutes. Approximately 0.5 - 2

liters 1 

# 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 th e 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 respec tively and there was no need to change the filter.

# 3-4 Samplers collected the following dissolved sa mples using a “cleanbox,” as described in

Section 3.1:

 Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

Hexavalent chromium samples were immedi ately placed on ice after sample collection.

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 th ree 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 separa te taps to collect samples from the sampling

point. The sample tap was located inside the F GD wastewater treatment building (see Figure 2-2

for the sampling location for SP-2). At the time th at sampling occurred, one of the clarifiers was

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

operated more than one clarifier at a time. Becau se the sampling point was located inside, there

were no wind or rain concerns during the sample collection.

ERG collected the influent from the biorea ctor system composite samples using two

automatic compositors which were programmed to collect individual samp le volumes into two

20-liter containers. The compositors were progr ammed to collect 830 mL every hour during the

24-hour composite period. Following the composite period, ERG pumped off the specific sample

volumes into the individual sample containers.

ERG used one automatic compositor to collect sample volume for the metals analyses

(excluding mercury) and another automatic compos itor to collect sample volume for all classical

analytes (i.e., BOD 5 

# , Group I, and Group II, excluding cy anide). In addition to collecting

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

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

grab sample for cyanide during each compositing period.

On day 1 only, ERG collected field blank samp les (SP-7) for hexavalent chromium, total

and dissolved metals by 200.7, and total and di ssolved metals by 200.8. See Section 5.2.3 for a

description of the field blank sa mple collection procedures at th e influent to the bioreactor

system.

Samplers set up the compositors by attaching tw o T-splitter tubing sets to two of the taps

on the three-way splitter. The T-splitter tubing set consisted of three silicone tubes attached to a

T-splitter. The tubing configura tion was set up such that one e nd was connected to the sample

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

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

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

flow through both sets of tubing before calibrati ng either of the automatic compositors. This

ensured that the flow through the tubing during calibration would be the expected flow through

the tubing during sample collection. The automatic compositors were calibrated such that they

# 3-5 collected 830 mL every hour, so that the project ed complete volume would be 20 liters. After

calibration, the tubing was attached to a vented cap on a 20-liter composite container. The

sample tap was left open during the entire sample collection time period a nd flowed directly to

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

the sampling program and was capable of purging th e line back to the flowing stream between

each individual sample aliquot.

Both 20-liter composite containers were placed into plastic trash cans, and maintained on

ice for the entire 24-hour compositing period. A plas tic bag was placed on 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 gr ab sample every day, ERG collected field blanks

for total mercury samples. See Section 5.2.3 for a de scription of the field blank sample collection

procedures at the 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 pur ging the tap for two minutes, the samples were collected directly from the

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

directly from the tap, ERG was not able to collect split samples with Belews Creek’s

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

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

shroud was replaced for each set of mercury grab samples. After collecti ng 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 us ing a pH meter to test the pH; however, the

sampling team could not get the pH meter to ca librate properly. Table 3-3 presents the field

measurement data for the influe nt to the bioreactor system.

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

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

Because total cyanide samples were collected directly from the ta p, ERG was not able to collect

split samples with Belews Creek’s representative s; 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 influe nt to the bioreactor system.

ERG samplers then preserved the total cyanide sa mples with sodium hydroxide to a pH >10 S.U.

and placed the samples on ice.

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

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

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

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

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

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

was programmed to collect the same volum e 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 coll ected in the 20-liter containe rs into the individual sample

containers at the pump-off area. For this samp ling point, ERG used a sample pump-off approach

to transfer the composite samples to the individual sample bottles. For this sample pump-off

procedure, the dissolved metals samples were collected before the total metals and classical

samples to prevent cross-contamination with in the tubing, which could lead to greater

concentrations in the dissolved metals fractions.

Samples for the dissolved and total metals analyses were pumped from one of the

previously filled 20-liter cont ainers. The pump-off station cons isted of a length of Teflon®

tubing attached to a length of silicone tubing, which was threaded throu gh an ISCO peristaltic

pump. The sampling team attached a capsule fi lter to the silicone t ubing, which was a short

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

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

tubing. This set-up allowed EPA to collect “true” split samples w ith 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 collec ting 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 “cl eanbox,” as described in Section 3.1:

 Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

Hexavalent chromium samples were immediat ely placed on ice after sample collection.

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

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

described in Section 3.1:

 Total metals by 200.8; and

 Total metals by 200.7.

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

Teflon® tubing into the other pr eviously filled 20-liter cont ainer. Once the tubing was purged

with 1-2 liters of sample, samplers fille d containers for biochemical oxygen demand (BOD 5 

# ),

Group I, and Group II samples directly from the tubing without using a “cleanbox.” See Table 3-

6 for a list of Group I and Group II analytes. BOD 5 

# , Group I, and Group II samples were

immediately placed on ice af ter sample collection.

# 3-7 For all analytes, ERG collected QC samples at the influent to the bi oreactor system (SP2) on Day 4 of the sampling episode. In additi on, 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 F GD 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 biorea ctor system composite samples using two

automatic compositors which were programmed to collect individual samp le volumes into two

20-liter containers. The compositors were progr ammed to collect 830 mL every hour during the

24-hour composite period. Following the composite period, ERG pumped off the specific sample

volumes into the individual sample containers.

ERG used one automatic compositor to collect sample volume for the metals analyses

(excluding mercury) and another automatic compos itor to collect sample volume for all classical

analytes (i.e., BOD 5 

# , Group I, and Group II, excluding cy anide). In addition to collecting

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

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

grab sample for cyanide during each compositing period.

On day 1 only, ERG collected field blank samp les (SP-8) for hexavalent chromium, total

and dissolved metals by 200.7, and total and di ssolved metals by 200.8. See Section 5.2.3 for a

description of the field blank sa mple collection procedures at th e effluent from the bioreactor

system.

Samplers set up the compositors by attaching tw o T-splitter tubing sets to two of the taps

on the three-way splitter. The T-splitter tubing set consisted of three silicone tubes attached to a

T-splitter. The tubing configura tion was set up such that one e nd was connected to the sample

tap, one end was threaded through the 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 samp le tap, opened the valve, and allowed sample to

flow through both sets of tubing before calibrati ng either of the automatic compositors. This

ensured that the flow through the tubing during calibration would be the expected flow through

the tubing during sample collection. The automatic compositors were calibrated such that they

collected 830 mL every hour, so that the project ed complete volume would be 20 liters. After

calibration, the tubing was attached to a vented cap on a 20-liter composite container. The

sample tap was left open during the entire sample collection time period a nd flowed directly to

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

the sampling program and was capable of purging th e line back to the flowing stream between

each individual sample aliquot.

# 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 plas tic bag was placed on top of the trash cans

to minimize contamination. Figure C-5, in Appendi x 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 gr ab sample every day, ERG collected field blanks

for total mercury samples. See Section 5.2.3 for a de scription of the field blank sample collection

procedures at the effluent from the 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 ta p for two minutes, the samples were collected directly from the

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

directly from the tap, ERG was not able to collect split samples with Belews Creek’s

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

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

shroud was replaced for each set of mercury grab samples. After collecti ng 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 us ing a pH meter to test the pH; however, the

sampling team could not get the pH meter to ca librate properly. Table 3-3 presents the field

measurement data for the effluent from the bioreactor system.

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

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

Because total cyanide samples were collected directly from the ta p, ERG was not able to collect

split samples with Belews Creek’s representative s; 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 duri ng 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 coll ected in the two composite containers, ERG

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

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

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

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

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

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

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

transferred the wastewater coll ected in the 20-liter containe rs into the individual sample

containers at the pump-off area. For this samp ling point, ERG used a sample pump-off approach

to transfer the composite samples to the individual sample bottles. For this sample pump-off

procedure, the dissolved metals samples were collected before the total metals and classical

# 3-9 samples to prevent cross-contamination with in the tubing, which could lead to greater

concentrations in the dissolved metals fractions.

Samples for the dissolved and total metals analyses were pumped from one of the

previously filled 20-liter cont ainers. The pump-off station cons isted of a length of Teflon®

tubing attached to a length of silicone tubing, which was threaded throu gh an ISCO peristaltic

pump. The sampling team attached a capsule fi lter to the silicone t ubing, which was a short

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

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

tubing. This set-up allowed EPA to collect “true” split samples w ith 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 collec ting 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 fiel d 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 “cl eanbox,” as described in Section 3.1:

 Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

Hexavalent chromium samples were immedi ately placed on ice after sample collection.

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

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

described in Section 3.1:

 Total metals by 200.8; and

 Total metals by 200.7.

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

Teflon® tubing into the other prev iously filled 20-liter contai ner. After the tubing was purged

with 1-2 liters of sample, samplers fille d containers for biochemical oxygen demand (BOD 5 

# ),

Group I, and Group II samples directly from the tubing without using a “cleanbox.” See Table 3-

6 for a list of Group I and Group II analytes. BOD 5 

# , Group I, and Group II samples were

immediately placed on ice af ter sample collection.

For all analytes, ERG collected QC samples at the effluent from th e bioreactor system

(SP-3) on Day 3 of the sampling episode. In add ition, for all analytes, ER G collected a duplicate

sample of the effluent from bioreactor syst em (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 (BOD 5 

# ),

— Chemical oxygen demand (COD),

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus,

— Total cyanide;

 Total Metals 2 

# :

— 

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

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

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

titanium, vanadium, and zinc.

 Dissolved Metals:

— 

# Same parameters as listed for tota l metals, plus hexavalent chromium.

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

pollution control wastewaters, in cluding contributions from coal , scrubber sorb ents, treatment

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

concentrations.

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

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

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

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

collection, the samplers placed the BOD 5 

# , Group I, Group II, dissolved hexavalent chromium,

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

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

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

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

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

hexavalent chromium samples were preserved w ith 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 adde d. 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. E ach total cyanide sample was tested for sulfides and oxidants

immediately after sample collection. Because sulf ides 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 te sting for sulfides and oxi dants, the total cyanide

samples were preserved with sodium hydroxi de to a pH >10 S.U. and placed on ice.

3.3 Plant Operational Data

During the EPA sampling episode, Belews Cr eek plant personnel pr ovided the sampling

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

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

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

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

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

episode, and Table 3-12 presents th e FGD wastewater treatment syst em operating characteristics.

3.4 Deviations from the Sampling and Analysis Plan

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

described below:

 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; howe ver, 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 Tabl e 3-7 for a list of affected samples.

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

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

of the samples duri ng the field tests.

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

representative collected fewer field bla nk 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), gr ab 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 se nt 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 biorea ctor 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 collect ion of the dissolved hexavalent chromium and before the

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

therefore, the samplers pur ged 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 biorea ctor system (SP-2), the sampling team

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

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

contain the inner bag and bo ttle 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 befo re 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 Wa stewater Treatment

System – Day 1 Grab 6/7/10 1109 a 

# and 1227 b



# Influent to FGD Wa stewater Treatment

System – Day 2 Grab 6/8/10 1246 a 

# and 1419 b



# Influent to FGD Wa stewater Treatment

System – Day 3 Grab 6/9/10 0957 a 

# and 1224 b 

# SP-1

Influent to FGD Wa stewater Treatment

System – Day 4 Grab 6/10/10 1128 a 

# and 1300 b



# Composite 6/7/10

6/8/10 0729 c



# 0945 d 

# Influent to Bioreact or System – Day 1

Grab 6/7/10

6/8/10 0751 e 

# , 1355 f 

# , and 2002 g



# 0147 h



# Composite 6/8/10

6/9/10 0729 c



# 1049 d 

# Influent to Bioreact or System – Day 2

Grab 6/8/10

6/9/10 0744 e 

# , 1342 f 

# , and 1941 g



# 0141 h



# Composite 6/9/10

6/10/10 0731 c



# 0953 d 

# Influent to Bioreact or System – Day 3

Grab 6/9/10

6/10/10 0743 e 

# , 1346 f 

# , and 1945 g



# 0145 h



# Composite 6/10/10

6/11/10 0728 c



# 0657 d 

# SP-2

Influent to Bioreact or System – Day 4

Grab 6/10/10

6/11/10 0738 e 

# , 1339 f 

# , and 1939 g



# 0137 h



# Composite 6/7/10

6/8/10 0928 c



# 1119 d 

# Effluent from Bioreactor System – Day 1

Grab 6/7/10

6/8/10 0944 e 

# , 1537 f 

# , and 2145 g



# 0344 h



# Composite 6/8/10

6/9/10 0912 c



# 1136 d 

# Effluent from Bioreactor System – Day 2

Grab 6/8/10

6/9/10 0926 e 

# , 1526 f 

# , and 2126 g



# 0328 h



# Composite 6/9/10

6/10/10 0915 c



# 1039 d 

# Effluent from Bioreactor System – Day 3

Grab 6/9/10

6/10/10 0927 e 

# , 1525 f 

# , and 2124 g



# 0325 h



# Composite 6/10/10

6/11/10 0905 c



# 0835 d 

# SP-3

Effluent from Bioreactor System – Day 4

Grab 6/10/10

6/11/10 0915 e 

# , 1518 f 

# , and 2113 g



# 0313 h

# 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 0731 c



# 0954 d 

# SP-4 Duplicate of Influent to Bioreactor

System – Day 3

Grab 6/9/10

6/10/10 0744 e 

# , 1347 f 

# , and 1947 g



# 0147 h



# Composite 6/8/10

6/9/10 0912 c



# 1137 d 

# SP-5 Duplicate of Effl uent from Bioreactor

System – Day 2

Grab 6/8/10

6/9/10 0928 e 

# , 1528 f 

# , and 2128 g



# 0330 h



# SP-6 Influent to FGD Wastewater Treatment

System Field Blank Grab 6/7/10 1049 i 

# and 1219 j



# Composite 6/7/10

6/8/10 0638 k



# 1008 l 

# Influent to Bioreact or System Field

Blank – Day 1

Grab 6/7/10 0746 m



# Influent to Bioreact or System Field

Blank – Day 2 Grab 6/8/10 0739 m



# Influent to Bioreact or System Field

Blank – Day 3 Grab 6/9/10 0737 m 

# SP-7

Influent to Bioreact or System Field

Blank – Day 4 Grab 6/10/10 0733 m



# Composite 6/7/10

6/8/10 0828 k



# 1107 l 

# Effluent from Bior eactor System Field

Blank – Day 1

Grab 6/7/10 0939 m



# Effluent from Bior eactor System Field

Blank – Day 2 Grab 6/8/10 0922 m



# Effluent from Bior eactor System Field

Blank – Day 3 Grab 6/9/10 0922 m 

# SP-8

Effluent from Bior eactor System Field

Blank – Day 4 Grab 6/10/10 0910 m

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 (BOD 5 

# , 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 (BOD 5 

# , Group I, and Group II).

e 

# Start time for the collection of the total and dissolved mercury Grab 1 samples.

f 

# Start time for the collection of the total and dissolved mercury Grab 2 samples.

g 

# Start time for the collection of the total and di ssolved mercury Grab 3 and total cyanide samples.

h 

# Start time for the collection of the total and dissolved mercury Grab 4 samples.

i 

# Start time for the collection of total 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.

# 3-16Table 3-2. Sample Collection at Belews Creek Steam StationSamplingPoint NumberSampling Point Name Total Metals (EPA Method 200.8 with collision cell) Total Metals (EPA Method 200.7) Dissolved Metals (EPA Method 200.8 with collision cell) Dissolved Metals (EPA Method 200.7) Total Mercury Dissolved Mercury Hexavalent Chromium BOD 5 Group I

a Group II

b Total CyanideSP-1 Influent to FGD Wastewater TreatmentSystem4 4 4 4 4 4 4 4 4 4 4SP-2 Influent to Bioreactor System4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-3 Effluent from Bioreactor System 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-4 Duplicate of Influent to Bioreactor System 1 1 1 1 1 1 1 1 1 1 1SP-5 Duplicate of Effluent from BioreactorSystem1 1 1 1 1 1 1 1 1 11SP-6 Influent to FGD Wastewater TreatmentSystem Field Blank1 1 1 1 1 1SP-7 Influent to Bioreactor SystemField Blank 1 1 1 1 4 1SP-8 Effluent from Bioreactor System FieldBlank1 1 1 1 4 1Total Number of Samples 17+2QC17+2QC 17+2QC 17+2QC 23+2QC 14+2QC 17+2QC 14+2QC 14+2QC 14+2QC 14+2QCaGroup I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate, and chloride.bGroup II includes ammonia as nitrogen, nitrate/nitrite as nitrogen, total Kjeldahlnitrogen (TKN), chemical oxygen demand (COD), and total phosphorus.

# 3-17Table 3-3. Field Measurements, Belews CreekSamplingPointNumberSampling Point DescriptionDateTimeTemperature(°C)pH(S.U.)WasteStream FlowRate(gpm)NotesInfluent to FGD WastewaterTreatment System – Day 16/7/2010 1124457 554aInfluent to FGD WastewaterTreatment System – Day 26/8/2010 1301446.3 481bInfluent to FGD WastewaterTreatment System – Day 36/9/2010 1009426.5 474cSP-1Influent to FGD WastewaterTreatment System – Day 46/10/2010 114046.57 483dSamplers noted that the samples had adark brown color and appeared to behigh in solids. No detected sulfides oroxidants in total cyanide grab.6/7/10 0754406.5 5186/7/10 1358416.5 5606/7/10 2004406.5 531Influent to Bioreactor System– Day 16/8/10 0149406.5 5626/8/10 0748396.5 2806/8/10 1345397 3906/8/10 1939396.5 375Influent to Bioreactor System– Day 26/9/10 0141386.5 5046/9/10 0744386.5 2646/9/10 1348386.5 2766/9/10 1947396.5 535Influent to Bioreactor System– Day 36/10/10 0147396.5 5316/10/10 0738396 3836/10/10 1339416.5 5666/10/10 1934416.5 419SP-2Influent to Bioreactor System– Day 46/11/10 0138416.5 506Samples were clear and colorless anddid not have any observed particulates.No detected sulfides or oxidants intotal cyanide grab.

# 3-18Table 3-3. Field Measurements, Belews CreekSamplingPointNumberSampling Point DescriptionDateTimeTemperature(°C)pH(S.U.)WasteStream FlowRate(gpm)Notes6/7/10 0948347 4746/7/10 1541347 5626/7/10 2147347 469Effluent from BioreactorSystem – Day 16/8/10 0348347 4696/8/10 0932347 3786/8/10 1531347 3846/8/10 2128347 437Effluent from BioreactorSystem – Day 26/9/10 0330347 4706/9/10 0928347 2656/9/10 1525347.5 3846/9/10 2124347.5 481Effluent from BioreactorSystem – Day 36/10/10 0326347.5 4536/10/10 0916347 3976/10/10 1518356.5 5476/10/10 2114347.5 346SP-3Effluent from BioreactorSystem – Day 46/11/10 0314347 524Samples were clear and colorless anddid not have any observed particulates.No detected sulfides or oxidants intotal cyanide grab.bBased on average of flow meter measurements collected every minute from 1104 to 1131 on 6/7/10 (time of sample collection).cBased on average of flow meter measurements collected every minute from1241 to 1308 on 6/8/10 (time of sample collection).dBased on average of flow meter measurements collected every minute from 0952 to 1019 on 6/9/10 (time of sample collection).eBased on average of flow meter measurements collected every minute from 1123 to 1250 on 6/10/10 (time of sample collection).fBased on average of flow meter measurements collected everyminute 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 fr om Bioreactor System - Day 1

71650 SP-3, Day 2 Effluent fr om Bioreactor System - Day 2

71651 SP-3, Day 3 Effluent fr om Bioreactor System - Day 3

71652 SP-3, Day 4 Effluent fr om Bioreactor System - Day 4

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

71654 SP-5, Day 2 Duplicate of Efflue nt 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 Bior eactor System Fiel d Blank - Day 1

71657 SP-7, Day 2 Influent to Bior eactor System Fiel d Blank - Day 2

71658 SP-7, Day 3 Influent to Bior eactor System Fiel d Blank - Day 3

71659 SP-7, Day 4 Influent to Bior eactor System Fiel d Blank - Day 4

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

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

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

71663 SP-8, Day 4 Effluent from Bi oreactor System Field Blank - Day 4

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

Parameter Method Number

Classicals

Biochemical oxygen demand (BOD 5 

# ) SM 5210 B

Chemical oxygen demand (COD) EPA 410.4

Total suspended solids (TSS) SM 2540 D

Total dissolved solids (TDS) SM 2540 C

Sulfate EPA 300.0

Chloride EPA 300.0

Ammonia as nitrogen EPA 350.1

Nitrate/nitrate as nitrogen EPA 353.2

Total Kjeldahl nitrogen (TKN) EPA 351.2

Total phosphorus EPA 365.1

Total cyanide SM 4500 CN E

Total and Dissolved Metals

Mercury EPA 1631E

Hexavalent chromium (dissolved only) EPA 218.6

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

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



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

molybdenum, sodium, tin, and titanium EPA 200.7

1 

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

# 3-21 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

BOD 5 

# One 1-L plastic

bottle One 1-L plastic

bottle ≤ 6  C

Group I a 

# One 1-L plastic

bottles One 1-L plastic

bottles ≤ 6  C

Group II b 

# Two 1-L plastic

bottles Two 1-L plastic

bottles H 2 

# SO 4 

# to pH <2 S.U., ≤ 6  C

Total cyanide One 1-L plastic

bottle One 1-L plastic

bottles Dilution until sulfide is not detected,

NaAsO 2 

# until total chlorine is not

present, NaOH to pH >10 S.U.,

≤ 6  C

Metals

Total metals (EPA Method 200.8 with

collision cell) One 500-mL

plastic bottle No additional

volume needed None

(acid preserve at laboratory)

Total metals (EPA Method 200.7) One 500-mL

plastic bottle No additional

volume needed None

(acid preserve at laboratory)

Dissolved metals (EPA Method 200.8

with collision cell) One 500-mL

plastic bottle No additional

volume needed 0.45-μm filter (performed in field)

(acid preserve at laboratory)

Dissolved metals (EPA Method 200.7) One 500-mL

plastic bottle No additional

volume needed 0.45-μm filter (performed in field)

(acid preserve at laboratory)

Total mercury:

Manual composite grab samples Four 125-mL

glass bottle No additional

volume needed

Influent samples and field blank

samples Two 250-mL

glass bottle No additional

volume needed None

(acid preserve at laboratory)

Dissolved mercury:

Manual composite grab samples Four 125-mL

glass bottle No additional

volume needed

Influent samples One 250-mL

glass bottle No additional

volume needed None

(filter and acid preserve at

laboratory)

Hexavalent chromium One 250-mL

plastic bottle No additional

volume needed 0.45-μm filter (performed in field)

Ammonium sulfate buffer to

pH 9.3 – 9.7 S.U., ≤ 6  C

(a) Group I includes TSS, TD S, sulfate, and chloride.

(b) Group II includes ammonia as nitrogen, COD, nitr ate/nitrite as nitrogen, TKN, and total phosphorus.

# 3-22 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 H 2 

# SO 4 

# 6 2 55

71641 Group II Volume 2 6/7/10 H 2 

# SO 4 

# 6 2 55

71641 Hexavalent Chromium 6/7/10 (NH 4 

# ) 2 

# SO 4



# Buffer 6 8.5 a 

# 530

71655 Hexavalent Chromium Field

Blank 6/7/10 (NH 4 

# ) 2 

# SO 4



# 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 H 2 

# SO 4 

# 6 2 55

71642 Group II Volume 2 6/8/10 H 2 

# SO 4 

# 6 2 55

71645 Group II Volume 1 6/8/10 H 2 

# SO 4 

# 6 2 30

71645 Group II Volume 2 6/8/10 H 2 

# SO 4 

# 6 2 30

71649 Group II Volume 1 6/8/10 H 2 

# SO 4 

# 6 2 30

71649 Group II Volume 2 6/8/10 H 2 

# SO 4 

# 6 2 30

71642 Hexavalent Chromium 6/8/10 (NH 4 

# ) 2 

# SO 4



# Buffer 6.0 8.8 a 

# 700

71645 Hexavalent Chromium 6/8/10 (NH 4 

# ) 2 

# SO 4



# Buffer 6.5 9.3 700

71649 Hexavalent Chromium 6/8/10 (NH 4 

# ) 2 

# SO 4



# Buffer 6.5 8.9 a 

# 735

71656 Hexavalent Chromium Field

Blank 6/8/10 (NH 4 

# ) 2 

# SO 4



# Buffer 6.5 9.5 400

71660 Hexavalent Chromium Field

Blank 6/8/10 (NH 4 

# ) 2 

# SO 4



# 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 H 2 

# SO 4 

# 6.5 2 30

71643 Group II Volume 2 6/9/10 H 2 

# SO 4 

# 6.5 2 30

71646 Group II Volume 1 6/9/10 H 2 

# SO 4 

# 5.5 2 30

71646 Group II Volume 2 6/9/10 H 2 

# SO 4 

# 5.5 2 30

71650 Group II Volume 1 6/9/10 H 2 

# SO 4 

# 5.5 2 30

71650 Group II Volume 2 6/9/10 H 2 

# SO 4 

# 5.5 2 30

71654 Group II Volume 1 6/9/10 H 2 

# SO 4 

# 5.5 2 30

71654 Group II Volume 2 6/9/10 H 2 

# SO 4 

# 5.5 2 30

71643 Hexavalent Chromium 6/9/10 (NH 4 

# ) 2 

# SO 4



# 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 (NH 4 

# ) 2 

# SO 4



# Buffer 5.5 9.0 a 

# 590

71650 Hexavalent Chromium 6/9/10 (NH 4 

# ) 2 

# SO 4



# Buffer 5.5 9.0 a 

# 480

71654 Hexavalent Chromium 6/9/10 (NH 4 

# ) 2 

# SO 4



# 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 H 2 

# SO 4 

# 5.5 2 40

71644 Group II Volume 2 6/10/10 H 2 

# SO 4 

# 5.5 2 40

71647 Group II Volume 1 6/10/10 H 2 

# SO 4 

# 5.5 2 30

71647 Group II Volume 2 6/10/10 H 2 

# SO 4 

# 5.5 2 30

71651 Group II Volume 1 6/10/10 H 2 

# SO 4 

# 5.5 2 30

71651 Group II Volume 2 6/10/10 H 2 

# SO 4 

# 5.5 2 30

71651 Group II Volume 1 – QC 6/10/10 H 2 

# SO 4 

# 5.5 2 30

71651 Group II Volume 2 – QC 6/10/10 H 2 

# SO 4 

# 5.5 2 30

71653 Group II Volume 1 6/10/10 H 2 

# SO 4 

# 5.5 2 30

71653 Group II Volume 2 6/10/10 H 2 

# SO 4 

# 5.5 2 30

71644 Hexavalent Chromium 6/10/10 (NH 4 

# ) 2 

# SO 4



# Buffer 6.0 8.8 a 

# 540

71647 Hexavalent Chromium 6/10/10 (NH 4 

# ) 2 

# SO 4



# Buffer 5.5 9.5 850

71651 Hexavalent Chromium 6/10/10 (NH 4 

# ) 2 

# SO 4



# Buffer 5.5 9 a 

# 415

71653 Hexavalent Chromium 6/10/10 (NH 4 

# ) 2 

# SO 4



# 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 H 2 

# SO 4 

# 6 2 30

71648 Group II Volume 2 6/11/10 H 2 

# SO 4 

# 6 2 30

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

# SO 4 

# 6 2 30

71648 Group II Volume 2 – QC 6/11/10 H 2 

# SO 4 

# 6 2 30

71652 Group II Volume 2 6/11/10 H 2 

# SO 4 

# 6 2 30

71652 Group II Volume 1 6/11/10 H 2 

# SO 4 

# 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 (NH 4 

# ) 2 

# SO 4



# Buffer 6.0 9.0 a 

# 730

71652 Hexavalent Chromium 6/11/10 (NH 4 

# ) 2 

# SO 4



# Buffer 6.0 9.0 a 

# 520

a 

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

added to the sample bottle.

# 3-25 Table 3-8. Generating Unit Operating Charac teristics 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 elect rostatic precipitator.

# 3-26Table 3-9. FGD Scrubber System Operating Characteristics, Belews CreekUnit IDWet FGDSystem (Yes/No)Type ofScrubberForcedOxidation(Yes/No)SorbentAdditives (DBA,formic acid, etc.)FGD Make-upWater SourceSO2RemovalPercentageType of SolidsSeparation1 Yes Spray Yes LimestoneNone Belews Lake 96.2%SecondaryHydrocyclones2 Yes Spray Yes LimestoneNone Belews Lake 96.9%SecondaryHydrocyclones

# 3-27 Table 3-10. Coal Usage during Samp le 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 dur ing 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%

# 3-28Table 3-12. FGD Wastewater Treatment SystemOperation Information, Belews CreekScrubber PurgeChemical UsageDay ofSamplingFlow Rate(gpm)Duration(hr)Lime35% FerricChlorideOrganosulfide:NAPolymer:Nalco 7130730 % HCl1 515 24pH – 8.5 S.U.1,400 lbs25 ppm20.9 gpdNA5 ppm4.2 gpdpH – 6.5 S.U.505 gpd2 496 16pH – 8.5 S.U.2,200 lbs25 ppm17.1 gpdNA5 ppm3.4 gpdpH – 6.5 S.U.486 gpd3 518 20pH – 8.5 S.U.2,200 lbs25 ppm16.6 gpdNA5 ppm3.3 gpdpH – 6.5 S.U.579 gpd4 508 20pH – 8.5 S.U.2,900 lbs25 ppm19.8 gpdNA5 ppm4.0 gpdpH – 6.5 S.U.677 gpdNA – Not applicable

# 4-1 4. L ABORATORY 

# A NALYTICAL 

# R ESULTS AND 

# D ISCUSSION



# This section summarizes the laboratory results of analyses of samples for the influent to

the FGD wastewater treatment system and the in fluent to and effluent from the bioreactor

system.

The total and dissolved mercury samples we re analyzed by Frontier Global Sciences

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

nitrate membrane filters contained in disposab le polystyrene filtration units at the Frontier

laboratory under clean room conditions on the day of sample receipt. Samples with elevated

solids were filtered through multiple filtration units until the entire sample was filtered. The

mercury samples were subjected to a room temp erature bromine monochlor ide digestion prior to

analysis using a method-compliant bubbler system.

For the total and dissolved mercury sample s 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 describe d in Section 3, the dissolved metals samples

were filtered in the field. The dissolved metals samples were preserved to a pH <2 at least 24

hours prior to being subjected to a heated ni tric acid digestion according to SW846 Method

3005A. The total metals samples were preserved to a pH <2 at least 24 hours prior to being

subjected to a heated nitric acid dige stion according to SW846 Method 3010A.

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

TestAmerica. Similar to the metals anal yzed by EPA Method 200.7, the dissolved metals

analyzed by EPA Method 200.8 were also filtered in the field. The total and dissolved metals

samples were preserved to a pH <2 at least 24 hou rs prior to being subjected to a closed vessel,

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

The classical analytes were analyzed by Te stAmerica and were di gested, prepared, and

analyzed according to the me thods specified in Table 3-5.

Appendix A provides all analytical results fo r all samples collected at Belews Creek,

including all qualified results a nd all results that were measur ed above the method detection

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

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

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

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

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

TestAmerica’s long term blank st udies. If the typical back ground blank levels for a given

element are variable or frequently elevated, th en the quantitation limit may be raised to prevent

# 4-2 the reporting of false positives. This resulted in some analytes (e.g., manganese, sodium) having

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

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

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

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

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

the influent to the bioreactor system (SP-2) and the effluent from the bi oreactor 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 thre e 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 parenthe ses. 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 result s 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 re lative percent difference (RPD). For Table 4-3

(effluent from the bioreactor system), a duplicat e 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 quantitati on limit, then all results were averaged

together;

 If at least one result was above the quan titation limit, then 1⁄2 the quantitation limit

was used in the average calculation for all results that were less than the

quantitation limit and the result is repo rted with a less than sign (“<”);

 If all results were below the quantitation limit, but at least one result was above

the method detection limit (i.e., J-value), then the sample-specific quantitation

limits for all results were averaged and the result is reported as “NQ” followed by

the average of the sample-specific quantitation limits; and

 If all results were below the method de tection limit, then the sample-specific

quantitation limits for all results were aver aged and the result is reported as “ND”

followed by the average of the sample-specific quantitation limits.

Table 4-4 presents the 4-day average results fo r all classical analytes for the influent to

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

the effluent from the bioreactor system (SP-3). Table 4-5 presen ts the 4-day average results for

all metal analytes, including total and dissolved an alyses, for the influent to the FGD wastewater

treatment system (SP-1), the influent to the bior eactor system (SP-2), and the effluent from the

# 4-3 bioreactor system (SP-3). The re sults 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 bioreact or system (SP-2), the

effluent from the bioreactor syst em (SP-3), the duplicate of the in fluent to the bioreactor system

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

including J-values.

# 4-4< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - 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 dissolved mercury resultwas excluded from the calculated average, the 4-day average would be 131 ng/L.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 receiptwas above the method control criteria.Table 4-1. Influent to FGD Wastewater Treatment System, Belews CreekInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageClassicalsAmmoniamg/L350.11.10NQ (1.00)NQ (1.00)NQ (1.00)< 0.650Nitrate Nitrite as Nmg/L353.220.014.016.015.016.3Nitrogen, TotalKjeldahlmg/L351.229.0B,F5.706.505.5011.7Biochemical OxygenDemandmg/L5210BND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Chemical OxygenDemandmg/L410.4220250210180215Chloridemg/L300.07,7007,1007,6008,0007,600Sulfatemg/L300.01,6001,5001,1001,5001,430Cyanide, Totalmg/L4500 CN END (0.0100)FNQ (0.100)NQ (0.100)NQ (0.100)NQ (0.0775)Total Dissolved Solidsmg/L2540C17,000D14,00013,00025,000B17,300Total Suspended Solidsmg/L2540D3,100D4,9003,300D2,5003,450Phosphorus, Totalmg/L365.10.350B0.150B1.30BNQ (0.0500)B< 0.456Total MetalsAluminumug/L200.792,000497,000483,000482,00088,500Antimonyug/L200.88.4010.09.609.109.28Arsenicug/L200.82704230240200235Bariumug/L200.71,3001,2001,2001,2001,230Berylliumug/L200.78.909.708.208.408.80

# 4-5< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - 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 dissolved mercury resultwas excluded from the calculated average, the 4-day average would be 131 ng/L.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 receiptwas above the method control criteria.Table 4-1. Influent to FGD Wastewater Treatment System, Belews CreekInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageBoronug/L200.7150,000B,4140,000B,4140,000B,4170,000B150,000Cadmiumug/L200.84.10NQ (4.00)NQ (4.00)NQ (4.00)< 2.53Calciumug/L200.74,700,00045,300,00044,000,00044,100,0004,530,000Chromiumug/L200.82604,^250^250^250^253Cobaltug/L200.754.061.056.055.056.5Copperug/L200.8150170160140155Ironug/L200.7100,0004110,000499,0004100,000102,000Leadug/L200.8130120130120125Magnesiumug/L200.7830,0004760,0004670,0004710,000743,000Manganeseug/L200.75,50046,00045,60045,8005,730Mercuryng/L1631E248,000257,000291,000224,000255,000Molybdenumug/L200.745.047.045.044.045.3Nickelug/L200.82304240230220230Seleniumug/L200.86,80046,3006,6006,6006,580Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.748,00046,00046,00048,00047,000Thalliumug/L200.83.703.203.404.003.58Tinug/L200.7NQ (200)NQ (200)NQ (200)NQ (200)NQ (200)Titaniumug/L200.71,4001,5001,4001,3001,400Vanadiumug/L200.81904210200190198

# 4-6< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - 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 dissolved mercury resultwas excluded from the calculated average, the 4-day average would be 131 ng/L.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 receiptwas above the method control criteria.Table 4-1. Influent to FGD Wastewater Treatment System, Belews CreekInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageZincug/L200.83304290290290300Dissolved MetalsAluminumug/L200.7ND (200)FNQ (200)BNQ (200)BND (200)NQ (200)Antimonyug/L200.82.002.502.002.502.25Arsenicug/L200.8NQ (4.00)NQ (4.00)4.804.30< 3.28Bariumug/L200.7650640B660700663Berylliumug/L200.7ND (2.00)FND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7150,000B,4140,000B,4150,000B,4150,000B148,000Cadmiumug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Calciumug/L200.73,200,00043,100,000B,43,600,00043,300,0003,300,000Chromiumug/L200.88.70ND (8.00)ND (8.00)ND (8.00)^< 5.18Chromium (VI)ug/L218.6ND (10.0)ND (10.0)ND (10.0)T,EstND (10.0)ND (10.0)Cobaltug/L200.7NQ (20.0)28.028.027.0< 23.3Copperug/L200.8NQ (4.00)NQ (4.00)4.20NQ (4.00)< 2.55Ironug/L200.7ND (200)FND (200)ND (200)ND (200)ND (200)Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.7720,0004670,0004690,0004700,000695,000Manganeseug/L200.72,10045,30045,400B,45,4004,550Mercuryng/L1631E49,300**119142NA16,500**Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)

# 4-7< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - 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 dissolved mercury resultwas excluded from the calculated average, the 4-day average would be 131 ng/L.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 receiptwas above the method control criteria.Table 4-1. Influent to FGD Wastewater Treatment System, Belews CreekInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageNickelug/L200.8100130140140128Seleniumug/L200.81,3004400410550665Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.747,00045,00047,00048,00046,800Thalliumug/L200.83.903.903.804.003.90Tinug/L200.7NQ (200)FNQ (200)NQ (200)NQ (200)NQ (200)Titaniumug/L200.7NQ (20.0)FNQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Vanadiumug/L200.8NQ (10.0)ND (10.0)NQ (10.0)NQ (10.0)NQ (10.0)Zincug/L200.839.032.032.033.034.0

# 4-8Note: The Day 3 results represent the average of the original sample and the field duplicate (SP-4). See Section 5.2.4 for theanalytical results for the individual samples.+- 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 three grabs was analyzedindividually and a mathematical average was used tocalculate the composite sample concentration.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekInfluent to the Bioreactor System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageClassicalsAmmoniamg/L350.11.201.301.05NQ (1.00)< 1.01Nitrate Nitrite as Nmg/L353.219.019.020.021.0F19.8Nitrogen, TotalKjeldahlmg/L351.2NQ (5.00)BNQ (2.50)B< 1.652.60< 2.00Biochemical OxygenDemandmg/L5210BND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Chemical OxygenDemandmg/L410.4370320230140F265Chloridemg/L300.07,8008,0007,4007,9007,780Sulfatemg/L300.01,3001,3001,7001,2001,380Cyanide, Totalmg/L4500 CN END (0.100)ND (0.100)ND (0.100)ND (0.100)FND (0.100)Total Dissolved Solidsmg/L2540C16,00015,00023,50026,000B20,100Total Suspended Solidsmg/L2540D7.6012.0NQ (4.00)NQ (4.00)< 5.90Phosphorus, Totalmg/L365.1NQ (0.0500)BNQ (0.0500)BNQ (0.0500)NQ (0.0500)BNQ (0.0500)Total MetalsAluminumug/L200.7ND (5,000)NQ (200)NQ (200)NQ (200)NQ (1,400)Antimonyug/L200.8NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)Arsenicug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7390380380420B393Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)

# 4-9Note: The Day 3 results represent the average of the original sample and the field duplicate (SP-4). See Section 5.2.4 for theanalytical results for the individual samples.+- 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 three grabs was analyzedindividually and a mathematical average was used tocalculate the composite sample concentration.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekInfluent to the Bioreactor System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageBoronug/L200.7160,000B140,000B150,000150,000B,4150,000Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.73,700,0003,300,0003,250,0003,700,00043,490,000Chromiumug/L200.817.0^18.0^20.020.018.8Cobaltug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Copperug/L200.8NQ (4.00)ND (4.00)ND (4.00)ND (4.00)NQ (4.00)Ironug/L200.7NQ (200)ND (200)ND (200)NQ (200)NQ (200)Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.7810,000740,000720,000740,0004753,000Manganeseug/L200.7NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Mercuryng/L1631E46,60043,00047,30053,30047,600Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)Nickelug/L200.812.011.07.208.709.73Seleniumug/L200.81,1001,2001,3001,30041,230Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.748,00050,00048,00050,00049,000Thalliumug/L200.8NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)Tinug/L200.7ND (200)ND (200)ND (200)NQ (200)NQ (200)Titaniumug/L200.7NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Vanadiumug/L200.8NQ (10.0)NQ (10.0)NQ (10.0)NQ (10.0)NQ (10.0)Zincug/L200.8NQ (10.0)12.0ND (10.0)ND (10.0)< 6.75

# 4-10Note: The Day 3 results represent the average of the original sample and the field duplicate (SP-4). See Section 5.2.4 for theanalytical results for the individual samples.+- 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 three grabs was analyzedindividually and a mathematical average was used tocalculate the composite sample concentration.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekInfluent to the Bioreactor System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageDissolved MetalsAluminumug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Antimonyug/L200.82.10NQ (2.00)NQ (2.00)NQ (2.00)< 1.28Arsenicug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7410B380375420396Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7160,000B150,000B140,000150,000B,4150,000Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.73,400,000B3,600,0003,250,0003,700,00043,490,000Chromiumug/L200.817.018.019.520.0^18.6Chromium (VI)ug/L218.613.411.7T,Est13.214.613.2Cobaltug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Copperug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)ND (4.00)NQ (4.00)Ironug/L200.7ND (200)ND (200)NQ (200)ND (200)NQ (200)Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.7760,000730,000720,000740,0004738,000Manganeseug/L200.7NQ (20.0)NQ (20.0)BNQ (20.0)NQ (20.0)NQ (20.0)Mercuryng/L1631E47,00049,300+44,00044,40046,200Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)Nickelug/L200.813.010.06.409.709.78Seleniumug/L200.81,1001,2001,2501,30041,210

# 4-11Note: The Day 3 results represent the average of the original sample and the field duplicate (SP-4). See Section 5.2.4 for theanalytical results for the individual samples.+- 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 three grabs was analyzedindividually and a mathematical average was used tocalculate the composite sample concentration.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekInfluent to the Bioreactor System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageSilverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.749,00049,00047,50050,00048,900Thalliumug/L200.8NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)Tinug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Titaniumug/L200.7NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Vanadiumug/L200.8NQ (10.0)NQ (10.0)NQ (10.0)NQ (10.0)NQ (10.0)Zincug/L200.8ND (10.0)ND (10.0)NQ (10.0)ND (10.0)ND (10.0)

# 4-12Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-5). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - 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 seemslike an erroneous result compared to the Day 2original sample concentration and the other three sample days.For presentation purposes in this table, the duplicate result has been removed from the average of the Day 2 resultand from the calculation of the 4-day average result.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.Table 4-3. Effluent from the Bioreactor System, Belews CreekEffluent from the Bioreactor System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageClassicalsAmmoniamg/L350.14.504.454.404.504.46Nitrate Nitrite as Nmg/L353.2ND (0.100)FNQ (0.100)ND (0.100)FND (0.100)NQ (0.100)Nitrogen, Total Kjeldahlmg/L351.26.10F5.756.30B,F,H6.006.04Biochemical Oxygen Demandmg/L5210BND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Chemical Oxygen Demandmg/L410.4240255130F190204Chloridemg/L300.08,0007,7007,0007,8007,630Sulfatemg/L300.01,4001,4001,3002,5001,650Cyanide, Totalmg/L4500 CN E0.0120FNQ (0.100)NQ (0.100)FNQ (0.100)< 0.0405Total Dissolved Solidsmg/L2540C16,00014,00024,000B55,000B27,300Total Suspended Solidsmg/L2540D6.8024.04.00NQ (4.00)< 9.20Phosphorus, Totalmg/L365.10.120B0.1300.110B,FND (0.0500)< 0.0963Total MetalsAluminumug/L200.7ND (5,000)NQ (200)NQ (200)NQ (200)NQ (1,400)Antimonyug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Arsenicug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7390380370380B380Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)

# 4-13Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-5). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - 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 seemslike an erroneous result compared to the Day 2original sample concentration and the other three sample days.For presentation purposes in this table, the duplicate result has been removed from the average of the Day 2 resultand from the calculation of the 4-day average result.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.Table 4-3. Effluent from the Bioreactor System, Belews CreekEffluent from the Bioreactor System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageBoronug/L200.7180,000B190,000170,000B,4140,000B170,000Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.74,000,0003,300,0003,300,00043,600,0003,550,000Chromiumug/L200.8ND (8.00)^ND (8.00)ND (8.00)^ND (8.00)ND (8.00)Cobaltug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Copperug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Ironug/L200.7NQ (200)NQ (200)300NQ (200)< 150Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.7890,000760,000750,0004740,000785,000Manganeseug/L200.7470320260230320Mercuryng/L1631E230247**346406307**Molybdenumug/L200.7ND (40.0)ND (40.0)NQ (40.0)NQ (40.0)NQ (40.0)Nickelug/L200.8ND (4.00)ND (4.00)NQ (4.00)ND (4.00)NQ (4.00)Seleniumug/L200.87.3025.55.1025.015.7Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.751,00050,00048,00049,00049,500Thalliumug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Tinug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Titaniumug/L200.7NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)

# 4-14Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-5). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - 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 seemslike an erroneous result compared to the Day 2original sample concentration and the other three sample days.For presentation purposes in this table, the duplicate result has been removed from the average of the Day 2 resultand from the calculation of the 4-day average result.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.Table 4-3. Effluent from the Bioreactor System, Belews CreekEffluent from the Bioreactor System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageVanadiumug/L200.8ND (10.0)NQ (10.0)ND (10.0)ND (10.0)ND (10.0)Zincug/L200.8ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Dissolved MetalsAluminumug/L200.7NQ (200)BNQ (200)NQ (200)NQ (200)NQ (200)Antimonyug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Arsenicug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7370B375370370371Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7160,000B160,000150,000B,4140,000B153,000Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.73,200,000B3,600,0003,300,00043,600,0003,430,000Chromiumug/L200.8ND (8.00)ND (8.00)ND (8.00)^ND (8.00)^ND (8.00)Chromium (VI)ug/L218.6ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Cobaltug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Copperug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Ironug/L200.7NQ (200)< 255NQ (200)NQ (200)< 139Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.7730,000755,000740,0004730,000739,000Manganeseug/L200.7410315260230304

# 4-15Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-5). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.^ - 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 seemslike an erroneous result compared to the Day 2original sample concentration and the other three sample days.For presentation purposes in this table, the duplicate result has been removed from the average of the Day 2 resultand from the calculation of the 4-day average result.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.Table 4-3. Effluent from the Bioreactor System, Belews CreekEffluent from the Bioreactor System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageMercuryng/L1631E23.121.328.236.127.2Molybdenumug/L200.7NQ (40.0)NQ (40.0)ND (40.0)NQ (40.0)NQ (40.0)Nickelug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Seleniumug/L200.88.1023.54.9022.014.6Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.748,00049,50048,00048,00048,400Thalliumug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Tinug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Titaniumug/L200.7NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Vanadiumug/L200.8ND (10.0)NQ (10.0)NQ (10.0)ND (10.0)NQ (10.0)Zincug/L200.8ND (10.0)ND (10.0)12.0FND (10.0)< 6.75

# 4-16< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analyticalresult is presented in Appendix A with a Jflag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at leastone result is a J-value.Table 4-4. Classical Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, Belews CreekAnalyteUnitsMethodInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageInfluent toBioreactorSystem (SP-2)4-Day AverageEffluent fromBioreactorSystem (SP-3)4-Day AverageClassicalsAmmoniamg/L350.1< 0.650< 1.014.46Nitrate Nitrite as Nmg/L353.216.319.8NQ (0.100)Nitrogen, Total Kjeldahlmg/L351.211.7< 2.006.04Biochemical Oxygen Demandmg/L5210BND (10.0)ND (20.0)ND (10.0)Chemical Oxygen Demandmg/L410.4215265204Chloridemg/L300.07,6007,7807,630Sulfatemg/L300.01,4301,3801,650Cyanide, Totalmg/L4500 CN ENQ (0.0775)ND (0.100)< 0.0405Total Dissolved Solidsmg/L2540C17,30020,10027,300Total Suspended Solidsmg/L2540D3,450< 5.90< 9.20Phosphorus, Totalmg/L365.1< 0.456NQ (0.0500)< 0.0963

# 4-17< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).* - The 4-day average result includes an analytical result where the accuracy is questionable. If the questionable result wasexcluded from the calculated average, the 4-dayaverage would be 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 original sample result and theresults from the other sampling days.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-5. Metal Pollutants 4-Day Average Data Summaryfor FGD Wastewater Treatment System, Belews CreekInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageInfluent toBioreactorSystem (SP-2)4-Day AverageEffluent fromBioreactorSystem (SP-3)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTotalDissolvedMetalsAluminumug/L200.788,500NQ (200)NQ (1,400)ND (200)NQ (1,400)NQ (200)Antimonyug/L200.89.282.25NQ (2.00)< 1.28ND (2.00)ND (2.00)Arsenicug/L200.8235< 3.28NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.71,230663393396380371Berylliumug/L200.78.80ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7150,000148,000150,000150,000170,000153,000Cadmiumug/L200.8< 2.53NQ (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.74,530,0003,300,0003,490,0003,490,0003,550,0003,430,000Chromiumug/L200.8253< 5.1818.818.6ND (8.00)ND (8.00)Chromium (VI)ug/L218.6NAND (10.0)NA13.2NAND (10.0)Cobaltug/L200.756.5< 23.3ND (20.0)ND (20.0)ND (20.0)ND (20.0)Copperug/L200.8155< 2.55NQ (4.00)NQ (4.00)ND (4.00)ND (4.00)Ironug/L200.7102,000ND (200)NQ (200)NQ (200)< 150< 139Leadug/L200.8125ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.7743,000695,000753,000738,000785,000739,000Manganeseug/L200.75,7304,550NQ (20.0)NQ (20.0)320304Mercuryng/L1631E255,00016,500*47,60046,200307**27.2Molybdenumug/L200.745.3NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)Nickelug/L200.82301289.739.78NQ (4.00)ND (4.00)Seleniumug/L200.86,5806651,2301,21015.714.6Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)

# 4-18< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).* - The 4-day average result includes an analytical result where the accuracy is questionable. If the questionable result wasexcluded from the calculated average, the 4-dayaverage would be 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 original sample result and theresults from the other sampling days.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-5. Metal Pollutants 4-Day Average Data Summaryfor FGD Wastewater Treatment System, Belews CreekInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageInfluent toBioreactorSystem (SP-2)4-Day AverageEffluent fromBioreactorSystem (SP-3)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTotalDissolvedSodiumug/L200.747,00046,80049,00048,90049,50048,400Thalliumug/L200.83.583.90NQ (2.00)NQ (2.00)ND (2.00)ND (2.00)Tinug/L200.7NQ (200)NQ (200)NQ (200)ND (200)ND (200)ND (200)Titaniumug/L200.71,400NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Vanadiumug/L200.8198NQ (10.0)NQ (10.0)NQ (10.0)ND (10.0)NQ (10.0)Zincug/L200.830034.0< 6.75ND (10.0)ND (10.0)< 6.75

# 5-1 5. D ATA 

# Q UALITY



# Quality assurance/quality control (QA/QC) pr ocedures 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 pr ocedures used to assess the precision

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

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

QC standard checks.

5.1 Analytical Quality Control

ERG contracted directly with analytical labor atories for the analysis of samples collected

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

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

prepared written data review narr atives describing any qualifications of the analytical data from

this episode. The data review narrat ives are included in Appendix B.

5.2 Field Quality Control

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

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

5.2.1 Bottle Blanks

ERG collects bottle blanks to evaluate possibl e contamination from the sample collection

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

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

Frontier collected the bottle blanks for the meta ls sample bottles by filling the precleaned

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

analyzed the samples using EPA Method 1638.

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

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

Frontier then analyzed the samples using EPA Method 1631E.

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

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

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

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

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

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

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

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

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

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

therefore, this contamination di d not affect the resu lts of the sampling episode. Appendix Table

# 5-2 A-15 presents all of the analytical results from the bottle blank an alyses for the bottles used to

collect the metals and mercury samples.

5.2.2 Equipment Blanks

EPA collects equipment blanks to evaluate possible contamination from the equipment

used for sample collection. The techniques used to collect field blanks (a s described in Section

5.2.3) include the sampling equipment and ther efore would identify whether the sampling

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

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

equipment supplied for the episode.

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

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

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

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

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

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

contamination from the sampling equipment. Appe ndix Table A-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, samp ling equipment decontamination procedures,

sample collection procedures, or atmospheric contamination. EPA analyzed the field blank

samples for the total and dissolved metals and total and dissolved mercury samples 3



# .

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

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

ASTM Type 1 water through a precle aned funnel attached to the si licone tubing used for sample

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

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

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

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

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

3 

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

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

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

a concentration of 0.77 ng/L in the filtration blank perf ormed 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 fr om 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 (D ay 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 repr esentative, 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 wastew ater treatment system (SP-6)

were collected by pouring ASTM Type 1 water th rough the funnel and tubi ng 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 co mposite container. Prior to fill ing 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 sa mples 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 in fluent to the bioreactor system (SP-7) and

for the effluent from the biorea ctor system (SP-8) were collect ed by shrouding one of the three

taps on the sample tap splitter with a clear pl astic 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 th e 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 cont ainer. Prior to attaching one e nd of the tubing to the sample

tap, it was placed directly into the container hol ding 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 contai ner was placed on ice in a covered plastic trash

can. The vented cap used for the field blank coll ection was the same cap that was later used for

the metals composite container.

After 24 hours, the ASTM Type 1 water in th e 20-liter field bla nk composite container

was pumped off into the individual sample bottles. The sample bottles were placed in a

“cleanbox” and the ASTM Type 1 water was pump ed through the tubing and “Y” splitter, and

into the sample bottles. EPA collected the fiel d blank samples as “true” split samples with

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

description (Section 3.1). Prior to filling the sample bot tles, the tubing was purged with

approximately one liter of ASTM Type 1 water. First the samplers collected the total metals by

200.8 and total metals by 200.7 field blank samples. Then the sampling team attached a filter to

the tubing set and purged the tubing with approximately one liter of ASTM Type 1 water. The

samplers then collected the dissolved metals by 200.8, dissolved metals by 200.7, and dissolved

hexavalent chromium field blank samples.

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

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

Tables A-16 through A-24 present al l the analytical results for the field blanks from each of the

# 5-4 sampling points, including all qua lified results and all results th at 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 dupl icate samples are separate samp les collected from the same

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

is stored and analyzed independently. The re lative 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 D S D S (%) RPD         

 

# (5-1)

where:

S = concentration of the analyte from original sample analysis;

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

RPD = relative percent difference between the original and duplicate sample

result.

During this sampling episode, EPA collected duplicate samples for the influent to the

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

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

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

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

present all the analytical results for the influent to the bioreactor syst em (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 a bove the method detection limit, but below the

quantitation limit (i.e., J-values). Appendix Tabl es A-10 and A-14 present all the analytical

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

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

that were measured above the method detectio n limit, but below the quantitation limit (i.e., Jvalues).

# 5-5< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NC – Not calculated.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Table 5-1. Field Duplicate Results – Influent to Bioreactor System, Belews CreekAnalyteMethodUnitsOriginal Influentto BioreactorSystem, Day 3Concentration (SP-2)Duplicate Influentto BioreactorSystemConcentration (SP-4)AverageResultRelativePercentDifferenceClassicalsAmmonia 350.1 mg/L 1.10 1.00 1.05 9.52Nitrate Nitrite as N 353.2 mg/L 20.0 20.0 20.0 0.00Nitrogen, Total Kjeldahl 351.2 mg/L ND (1.00) 2.80 < 1.65 NCBiochemical Oxygen Demand 5210B mg/L ND (20.0) ND (20.0) ND (20.0) NCChemical Oxygen Demand 410.4 mg/L 180 280 230 43.5Chloride 300.0 mg/L 7,400 7,400 7,400 0.00Sulfate 300.0 mg/L 2,200 1,200 1,700 58.8Cyanide, Total 4500 CN E mg/L ND (0.100) ND (0.100) ND (0.100) NCTotal Dissolved Solids 2540C mg/L 24,000 B 23,000 B 23,500 4.26Total Suspended Solids 2540D mg/L NQ (4.00) NQ (4.00) NQ (4.00) NCPhosphorus, Total 365.1 mg/L NQ (0.0500) B NQ (0.0500) B NQ (0.0500) NCTotal MetalsAluminum 200.7 ug/L NQ (200) ND (200) NQ (200) NCAntimony 200.8 ug/L NQ (2.00) NQ (2.00) NQ (2.00) NCArsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.00) NCBarium 200.7 ug/L 380 380 380 0.00Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.00) NCBoron 200.7 ug/L 150,000 B 150,000 B 150,000 0.00Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND (4.00) NCCalcium 200.7 ug/L 3,200,000 3,300,000 3,250,000 3.08Chromium 200.8 ug/L 20.0 ^ 20.0 ^ 20.0 0.00Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20.0) NCCopper 200.8 ug/L ND (4.00) ND (4.00) ND (4.00) NCIron 200.7 ug/L ND (200) ND (200) ND (200) NCLead 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCMagnesium 200.7 ug/L 720,000 720,000 720,000 0.00Manganese 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.0) NC

# 5-6< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NC – Not calculated.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Table 5-1. Field Duplicate Results – Influent to Bioreactor System, Belews CreekAnalyteMethodUnitsOriginal Influentto BioreactorSystem, Day 3Concentration (SP-2)Duplicate Influentto BioreactorSystemConcentration (SP-4)AverageResultRelativePercentDifferenceMercury 1631E ng/L 40,800 53,800 47,300 27.5Molybdenum 200.7 ug/L NQ (40.0) NQ (40.0) NQ (40.0) NCNickel 200.8 ug/L 7.20 7.20 7.20 0.00Selenium 200.8 ug/L 1,300 1,300 1,300 0.00Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCSodium 200.7 ug/L 48,000 48,000 48,000 0.00Thallium 200.8 ug/L NQ (2.00) NQ (2.00) NQ (2.00) NCTin 200.7 ug/L ND (200) ND (200) ND (200) NCTitanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.0) NCVanadium 200.8 ug/L NQ (10.0) NQ (10.0) NQ (10.0) NCZinc 200.8 ug/L ND (10.0) ND (10.0) ND (10.0) NCDissolved MetalsAluminum 200.7 ug/L ND (200) ND (200) ND (200) NCAntimony 200.8 ug/L NQ (2.00) NQ (2.00) NQ (2.00) NCArsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.00) NCBarium 200.7 ug/L 390 360 375 8.00Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.00) NCBoron 200.7 ug/L 140,000 B 140,000 B 140,000 0.00Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND (4.00) NCCalcium 200.7 ug/L 3,400,000 3,100,000 3,250,000 9.23Chromium 200.8 ug/L 20.0 ^ 19.0 ^ 19.5 5.13Chromium (VI) 218.6 ug/L 12.8 13.5 13.2 5.32Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20.0) NCCopper 200.8 ug/L ND (4.00) NQ (4.00) NQ (4.00) NCIron 200.7 ug/L NQ (200) ND (200) NQ (200) NCLead 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCMagnesium 200.7 ug/L 740,000 700,000 720,000 5.56Manganese 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.0) NC

# 5-7< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NC – Not calculated.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Table 5-1. Field Duplicate Results – Influent to Bioreactor System, Belews CreekAnalyteMethodUnitsOriginal Influentto BioreactorSystem, Day 3Concentration (SP-2)Duplicate Influentto BioreactorSystemConcentration (SP-4)AverageResultRelativePercentDifferenceMercury 1631E ng/L 43,500 44,400 44,000 2.05Molybdenum 200.7 ug/L NQ (40.0) NQ (40.0) NQ (40.0) NCNickel 200.8 ug/L 6.50 6.30 6.40 3.13Selenium 200.8 ug/L 1,300 1,200 1,250 8.00Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCSodium 200.7 ug/L 49,000 46,000 47,500 6.32Thallium 200.8 ug/L NQ (2.00) NQ (2.00) NQ (2.00) NCTin 200.7 ug/L ND (200) ND (200) ND (200) NCTitanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.0) NCVanadium 200.8 ug/L NQ (10.0) NQ (10.0) NQ (10.0) NCZinc 200.8 ug/L ND (10.0) NQ (10.0) NQ (10.0) NC

# 5-8< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).The total mercury duplicate resultseems erroneous based on the Day 2 original sample result and the results from the other sampling days. The duplicate sample result wasexcluded 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 the 4-day average resultpresented 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, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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 CreekAnalyteMethodUnitsOriginal Effluent fromBioreactor System, Day 2Concentration (SP-3)Duplicate Effluent fromBioreactor SystemConcentration (SP-5)AverageResultRelativePercentDifferenceClassicalsAmmonia 350.1 mg/L 4.30 4.60 4.45 6.74Nitrate Nitrite as N 353.2 mg/L NQ (0.100) ND (0.100) NQ (0.100) NCNitrogen, Total Kjeldahl 351.2 mg/L 5.80 5.70 F 5.75 1.74Biochemical OxygenDemand 5210B mg/L ND (10.0) ND (10.0) ND (10.0) NCChemical Oxygen Demand 410.4 mg/L 340 170 255 66.7Chloride 300.0 mg/L 7,600 7,800 7,700 2.60Sulfate 300.0 mg/L 1,400 1,400 1,400 0.00Cyanide, Total 4500 CN E mg/L NQ (0.100) F NQ (0.100) NQ (0.100) NCTotal Dissolved Solids 2540C mg/L 14,000 14,000 14,000 0.00Total Suspended Solids 2540D mg/L 22.0 26.0 24.0 16.7Phosphorus, Total 365.1 mg/L 0.130 B 0.130 B 0.130 0.00Total MetalsAluminum 200.7 ug/L NQ (200) NQ (200) NQ (200) NCAntimony 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCArsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.00) NCBarium 200.7 ug/L 380 380 380 0.00Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.00) NC

# 5-9< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).The total mercury duplicate resultseems erroneous based on the Day 2 original sample result and the results from the other sampling days. The duplicate sample result wasexcluded 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 the 4-day average resultpresented 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, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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 CreekAnalyteMethodUnitsOriginal Effluent fromBioreactor System, Day 2Concentration (SP-3)Duplicate Effluent fromBioreactor SystemConcentration (SP-5)AverageResultRelativePercentDifferenceBoron 200.7 ug/L 190,000 B 190,000 B 190,000 0.00Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND (4.00) NCCalcium 200.7 ug/L 3,300,000 3,300,000 3,300,000 0.00Chromium 200.8 ug/L ND (8.00) ^ ND (8.00) ^ ND (8.00) NCCobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20.0) NCCopper 200.8 ug/L ND (4.00) ND (4.00) ND (4.00) NCIron 200.7 ug/L NQ (200) NQ (200) NQ (200) NCLead 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCMagnesium 200.7 ug/L 760,000 760,000 760,000 0.00Manganese 200.7 ug/L 320 320 320 0.00Mercury 1631E ng/L 247 6,440* 3,340* 185Molybdenum 200.7 ug/L ND (40.0) ND (40.0) ND (40.0) NCNickel 200.8 ug/L ND (4.00) ND (4.00) ND (4.00) NCSelenium 200.8 ug/L 26.0 25.0 25.5 3.92Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCSodium 200.7 ug/L 50,000 50,000 50,000 0.00Thallium 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCTin 200.7 ug/L ND (200) ND (200) ND (200) NCTitanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.0) NC

# 5-10< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).The total mercury duplicate resultseems erroneous based on the Day 2 original sample result and the results from the other sampling days. The duplicate sample result wasexcluded 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 the 4-day average resultpresented 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, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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 CreekAnalyteMethodUnitsOriginal Effluent fromBioreactor System, Day 2Concentration (SP-3)Duplicate Effluent fromBioreactor SystemConcentration (SP-5)AverageResultRelativePercentDifferenceVanadium 200.8 ug/L ND (10.0) NQ (10.0) NQ (10.0) NCZinc 200.8 ug/L ND (10.0) ND (10.0) ND (10.0) NCDissolved MetalsAluminum 200.7 ug/L NQ (200) B NQ (200) B NQ (200) NCAntimony 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCArsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.00) NCBarium 200.7 ug/L 370 380 375 2.67Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.00) NCBoron 200.7 ug/L 160,000 B 160,000 B 160,000 0.00Cadmium 200.8 ug/L ND (4.00) ND (4.00) ND (4.00) NCCalcium 200.7 ug/L 3,600,000 3,600,000 3,600,000 0.00Chromium 200.8 ug/L ND (8.00) ND (8.00) ND (8.00) NCChromium (VI) 218.6 ug/L ND (10.0) T,Est ND (10.0) T,Est ND (10.0) NCCobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20.0) NCCopper 200.8 ug/L ND (4.00) ND (4.00) ND (4.00) NCIron 200.7 ug/L NQ (200) 410 < 255 NCLead 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCMagnesium 200.7 ug/L 750,000 760,000 755,000 1.32Manganese 200.7 ug/L 310 B 320 B 315 3.17

# 5-11< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).The total mercury duplicate resultseems erroneous based on the Day 2 original sample result and the results from the other sampling days. The duplicate sample result wasexcluded 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 the 4-day average resultpresented 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, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the average result indicates that all results were below the quantitation limit, but at least one result is a J-value.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.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 CreekAnalyteMethodUnitsOriginal Effluent fromBioreactor System, Day 2Concentration (SP-3)Duplicate Effluent fromBioreactor SystemConcentration (SP-5)AverageResultRelativePercentDifferenceMercury 1631E ng/L 23.4 19.2 21.3 19.7Molybdenum 200.7 ug/L ND (40.0) NQ (40.0) NQ (40.0) NCNickel 200.8 ug/L ND (4.00) ND (4.00) ND (4.00) NCSelenium 200.8 ug/L 24.0 23.0 23.5 4.26Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCSodium 200.7 ug/L 49,000 50,000 49,500 2.02Thallium 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCTin 200.7 ug/L ND (200) ND (200) ND (200) NCTitanium 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.0) NCVanadium 200.8 ug/L ND (10.0) NQ (10.0) NQ (10.0) NCZinc 200.8 ug/L ND (10.0) ND (10.0) ND (10.0) NC

# 6-1 6. R EFERENCES



# 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-1ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 TreatmentSystem, Day 1 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4711.1Nitrate Nitrite as N353.2mg/L40.0760.420Nitrogen, Total Kjeldahl351.2mg/L20.38529B,FBiochemical Oxygen Demand5210Bmg/L51.210ND (10)UChemical Oxygen Demand410.4mg/L520100220Chloride300.0mg/L5001301,5007,700Sulfate300.0mg/L100235001,600Cyanide, Total4500 CN Emg/L10.0020.01ND (0.01)U,FTotal Dissolved Solids2540Cmg/L14710017,000DTotal Suspended Solids2540Dmg/L111403,100DPhosphorus, Total365.1mg/L10.0050.050.35BTotal MetalsAluminum200.7ug/L502405,00092,0004Antimony200.8ug/L20.7228.4Arsenic200.8ug/L106.1202704Barium200.7ug/L22.5201,300Beryllium200.7ug/L20.7128.9Boron200.7ug/L501705,000150,000B,4Cadmium200.8ug/L21.244.1Calcium200.7ug/L501,70010,0004,700,0004

# A-2ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 TreatmentSystem, Day 1 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationChromium200.8ug/L1016402604,^Cobalt200.7ug/L21.12054Copper200.8ug/L104.820150Iron200.7ug/L232200100,0004Lead200.8ug/L20.732130Magnesium200.7ug/L5054010,000830,0004Manganese200.7ug/L20.51205,5004Mercury1631Eng/L20,0004,83010,100248,000Molybdenum200.7ug/L21.64045Nickel200.8ug/L20.8942304Selenium200.8ug/L103.1206,8004Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.4723.7Tin200.7ug/L24.820015JTitanium200.7ug/L21.6201,400Vanadium200.8ug/L108.4501904Zinc200.8ug/L24.1103304Dissolved MetalsAluminum200.7ug/L29.4200ND (200)U,FAntimony200.8ug/L20.7222Arsenic200.8ug/L21.242.6J

# A-3ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 TreatmentSystem, Day 1 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationBarium200.7ug/L22.520650Beryllium200.7ug/L20.712ND (2)U,FBoron200.7ug/L501705,000150,000B,4Cadmium200.8ug/L21.243.5JCalcium200.7ug/L501,70010,0003,200,0004Chromium200.8ug/L23.388.7Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.1208.6JCopper200.8ug/L20.9641.6JIron200.7ug/L232200ND (200)U,FLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400720,0004Manganese200.7ug/L20.51202,1004Mercury1631Eng/L4,0009652,02049,300Molybdenum200.7ug/L21.64019JNickel200.8ug/L20.894100Selenium200.8ug/L20.6241,3004Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00047,000Thallium200.8ug/L20.4723.9Tin200.7ug/L24.82005.5J,FTitanium200.7ug/L21.6207.6J,F

# A-4ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 TreatmentSystem, Day 1 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationVanadium200.8ug/L21.7103.2JZinc200.8ug/L24.11039

# A-5ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4710.91JNitrate Nitrite as N353.2mg/L20.0380.214Nitrogen, Total Kjeldahl351.2mg/L10.3855.7Biochemical Oxygen Demand5210Bmg/L51.210ND (10)UChemical Oxygen Demand410.4mg/L520100250Chloride300.0mg/L5001301,5007,100Sulfate300.0mg/L100235001,500Cyanide, Total4500 CN Emg/L10.020.10.031JTotal Dissolved Solids2540Cmg/L14710014,000Total Suspended Solids2540Dmg/L111404,900Phosphorus, Total365.1mg/L10.0050.050.15BTotal MetalsAluminum200.7ug/L502405,00097,0004Antimony200.8ug/L20.72210Arsenic200.8ug/L53.110230Barium200.7ug/L22.5201,200Beryllium200.7ug/L20.7129.7Boron200.7ug/L501705,000140,000B,4Cadmium200.8ug/L21.243.6JCalcium200.7ug/L501,70010,0005,300,0004Chromium200.8ug/L58.220250^Cobalt200.7ug/L21.12061Copper200.8ug/L20.964170

# A-6ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationIron200.7ug/L232200110,0004Lead200.8ug/L20.732120Magnesium200.7ug/L5054010,000760,0004Manganese200.7ug/L20.51206,0004Mercury1631Eng/L20,0004,83010,100257,000Molybdenum200.7ug/L21.64047Nickel200.8ug/L52.210240Selenium200.8ug/L51.6106,300Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00046,000Thallium200.8ug/L20.4723.2Tin200.7ug/L24.820017JTitanium200.7ug/L21.6201,500Vanadium200.8ug/L54.225210Zinc200.8ug/L51025290Dissolved MetalsAluminum200.7ug/L29.420012J,BAntimony200.8ug/L20.7222.5Arsenic200.8ug/L21.242.8JBarium200.7ug/L22.520640BBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000140,000B,4Cadmium200.8ug/L21.243.3JCalcium200.7ug/L501,70010,0003,100,000B,4

# A-7ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.12028Copper200.8ug/L20.9641.8JIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400670,0004Manganese200.7ug/L20.51205,3004Mercury1631Eng/L204.8310.1119Molybdenum200.7ug/L21.64024JNickel200.8ug/L20.894130Selenium200.8ug/L20.624400Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00045,000Thallium200.8ug/L20.4723.9Tin200.7ug/L24.82008.8JTitanium200.7ug/L21.6207.8JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.11032

# A-8ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 TreatmentSystem, Day 3 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4710.83JNitrate Nitrite as N353.2mg/L20.0380.216Nitrogen, Total Kjeldahl351.2mg/L10.3856.5Biochemical Oxygen Demand5210Bmg/L51.210ND (10)UChemical Oxygen Demand410.4mg/L520100210Chloride300.0mg/L5001301,5007,600Sulfate300.0mg/L100235001,100Cyanide, Total4500 CN Emg/L10.020.10.037JTotal Dissolved Solids2540Cmg/L14710013,000Total Suspended Solids2540Dmg/L111403,300DPhosphorus, Total365.1mg/L50.0250.251.3BTotal MetalsAluminum200.7ug/L29.420083,0004Antimony200.8ug/L20.7229.6Arsenic200.8ug/L53.110240Barium200.7ug/L22.5201,200Beryllium200.7ug/L20.7128.2Boron200.7ug/L501705,000140,000B,4Cadmium200.8ug/L21.243.7JCalcium200.7ug/L501,70010,0004,000,0004Chromium200.8ug/L58.220250^Cobalt200.7ug/L21.12056Copper200.8ug/L20.964160

# A-9ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 TreatmentSystem, Day 3 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationIron200.7ug/L23220099,0004Lead200.8ug/L20.732130Magnesium200.7ug/L221400670,0004Manganese200.7ug/L20.51205,6004Mercury1631Eng/L20,0004,83010,100291,000Molybdenum200.7ug/L21.64045Nickel200.8ug/L52.210230Selenium200.8ug/L51.6106,600Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00046,000Thallium200.8ug/L20.4723.4Tin200.7ug/L24.820015JTitanium200.7ug/L21.6201,400Vanadium200.8ug/L21.710200Zinc200.8ug/L51025290Dissolved MetalsAluminum200.7ug/L29.42009.6J,BAntimony200.8ug/L20.7222Arsenic200.8ug/L21.244.8Barium200.7ug/L22.520660Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000B,4Cadmium200.8ug/L21.242.5JCalcium200.7ug/L501,70010,0003,600,0004

# A-10ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 TreatmentSystem, Day 3 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L11.9610ND (10)U,T,EstCobalt200.7ug/L21.12028Copper200.8ug/L20.9644.2Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400690,0004Manganese200.7ug/L20.51205,400B,4Mercury1631Eng/L10024.150.5142Molybdenum200.7ug/L21.64025JNickel200.8ug/L20.894140Selenium200.8ug/L20.624410Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00047,000Thallium200.8ug/L20.4723.8Tin200.7ug/L24.82007.8JTitanium200.7ug/L21.6207.8JVanadium200.8ug/L21.7102.3JZinc200.8ug/L24.11032

# A-11ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4710.88JNitrate Nitrite as N353.2mg/L20.0380.215Nitrogen, Total Kjeldahl351.2mg/L10.3855.5Biochemical Oxygen Demand5210Bmg/L51.210ND (10)UChemical Oxygen Demand410.4mg/L520100180Chloride300.0mg/L5001301,5008,000Sulfate300.0mg/L100235001,500Cyanide, Total4500 CN Emg/L10.020.10.024JTotal Dissolved Solids2540Cmg/L14710025,000BTotal Suspended Solids2540Dmg/L111402,500Phosphorus, Total365.1mg/L10.0050.050.014J,BTotal MetalsAluminum200.7ug/L29.420082,000Antimony200.8ug/L20.7229.1Arsenic200.8ug/L106.120200Barium200.7ug/L22.5201,200Beryllium200.7ug/L20.7128.4Boron200.7ug/L501705,000170,000BCadmium200.8ug/L21.243.5JCalcium200.7ug/L501,70010,0004,100,000Chromium200.8ug/L101640250^Cobalt200.7ug/L21.12055Copper200.8ug/L20.964140Iron200.7ug/L232200100,000Lead200.8ug/L20.732120

# A-12ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L221400710,000Manganese200.7ug/L20.51205,800Mercury1631Eng/L20,0004,83010,100224,000Molybdenum200.7ug/L21.64044Nickel200.8ug/L104.520220Selenium200.8ug/L103.1206,600Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.4724Tin200.7ug/L24.820013JTitanium200.7ug/L21.6201,300Vanadium200.8ug/L21.710190Zinc200.8ug/L102050290Dissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.5Arsenic200.8ug/L21.244.3Barium200.7ug/L22.520700Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000BCadmium200.8ug/L21.242.1JCalcium200.7ug/L501,70010,0003,300,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.12027Copper200.8ug/L20.9641.8J

# A-13ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400700,000Manganese200.7ug/L20.51205,400Molybdenum200.7ug/L21.64024JNickel200.8ug/L20.894140Selenium200.8ug/L20.624550Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.4724Tin200.7ug/L24.82005.9JTitanium200.7ug/L21.6209.1JVanadium200.8ug/L21.7103.5JZinc200.8ug/L24.11033

# A-14ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4711.2Nitrate Nitrite as N353.2mg/L20.0380.219Nitrogen, Total Kjeldahl351.2mg/L10.3853.5J,BBiochemical Oxygen Demand5210Bmg/L102.420ND (20)UChemical Oxygen Demand410.4mg/L520100370Chloride300.0mg/L200516007,800Sulfate300.0mg/L100235001,300Cyanide, Total4500 CN Emg/L10.020.1ND (0.1)UTotal Dissolved Solids2540Cmg/L14710016,000Total Suspended Solids2540Dmg/L11.147.6Phosphorus, Total365.1mg/L10.0050.050.012J,BTotal MetalsAluminum200.7ug/L502405,000ND (5,000)UAntimony200.8ug/L20.7221.5JArsenic200.8ug/L21.241.8JBarium200.7ug/L22.520390Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,700,000Chromium200.8ug/L23.3817^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.9640.97JIron200.7ug/L23220041JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,000810,000

# A-15ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.51204.3JMercury1631Eng/L4,0009652,02046,600Molybdenum200.7ug/L21.64020JNickel200.8ug/L20.89412Selenium200.8ug/L20.6241,100Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.4721.5JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.7JVanadium200.8ug/L21.7104.7JZinc200.8ug/L24.1105.4JDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.1Arsenic200.8ug/L21.242.7JBarium200.7ug/L22.520410BBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,400,000BChromium200.8ug/L23.3817Chromium (VI)218.6ug/L11.961013.4Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.9641.2JIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)U

# A-16ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L221400760,000Manganese200.7ug/L20.51203.7JMercury1631Eng/L4,0009652,02047,000Molybdenum200.7ug/L21.64020JNickel200.8ug/L20.89413Selenium200.8ug/L20.6241,100Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00049,000Thallium200.8ug/L20.4721.8JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.2JVanadium200.8ug/L21.7103JZinc200.8ug/L24.110ND (10)U

# A-17ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4711.3Nitrate Nitrite as N353.2mg/L20.0380.219Nitrogen, Total Kjeldahl351.2mg/L10.192.50.71J,BBiochemical Oxygen Demand5210Bmg/L102.420ND (20)UChemical Oxygen Demand410.4mg/L520100320Chloride300.0mg/L5001301,5008,000Sulfate300.0mg/L100235001,300Cyanide, Total4500 CN Emg/L10.020.1ND (0.1)UTotal Dissolved Solids2540Cmg/L14710015,000Total Suspended Solids2540Dmg/L11.1412Phosphorus, Total365.1mg/L10.0050.050.012J,BTotal MetalsAluminum200.7ug/L29.4200120JAntimony200.8ug/L20.7221.5JArsenic200.8ug/L21.241.8JBarium200.7ug/L22.520380Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000140,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,300,000Chromium200.8ug/L23.3818^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)U

# A-18ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400740,000Manganese200.7ug/L20.51204JMercury1631Eng/L4,0009652,02043,000Molybdenum200.7ug/L21.64021JNickel200.8ug/L20.89411Selenium200.8ug/L20.6241,200Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00050,000Thallium200.8ug/L20.4720.85JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6209JVanadium200.8ug/L21.7104.4JZinc200.8ug/L24.11012Dissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7221.6JArsenic200.8ug/L21.242.4JBarium200.7ug/L22.520380Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,600,000Chromium200.8ug/L23.3818Chromium (VI)218.6ug/L11.961011.7T,Est

# A-19ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.9643JIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400730,000Manganese200.7ug/L20.51203.2J,BMercury1631Eng/L2,0004831,01049,300Molybdenum200.7ug/L21.64020JNickel200.8ug/L20.89410Selenium200.8ug/L20.6241,200Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00049,000Thallium200.8ug/L20.4720.77JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.2JVanadium200.8ug/L21.7105.1JZinc200.8ug/L24.110ND (10)U

# A-20ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-SpecificQLConcentrationClassicalsAmmonia350.1mg/L10.4711.1Nitrate Nitrite as N353.2mg/L50.0950.520Nitrogen, Total Kjeldahl351.2mg/L10.0771ND (1)UBiochemical Oxygen Demand5210Bmg/L102.420ND (20)UChemical Oxygen Demand410.4mg/L520100180Chloride300.0mg/L5001301,5007,400Sulfate300.0mg/L100235002,200Cyanide, Total4500 CN Emg/L10.020.1ND (0.1)UTotal Dissolved Solids2540Cmg/L14710024,000BTotal Suspended Solids2540Dmg/L11.142JPhosphorus, Total365.1mg/L10.0050.050.006J,BTotal MetalsAluminum200.7ug/L29.420070JAntimony200.8ug/L20.7221.8JArsenic200.8ug/L21.242.2JBarium200.7ug/L22.520380Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,200,000Chromium200.8ug/L23.3820^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)U

# A-21ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-SpecificQLConcentrationIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400720,000Manganese200.7ug/L20.51205JMercury1631Eng/L4,0009652,02040,800Molybdenum200.7ug/L21.64018JNickel200.8ug/L20.8947.2Selenium200.8ug/L20.6241,300Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.4720.57JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6209.2JVanadium200.8ug/L21.7103.5JZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7221.9JArsenic200.8ug/L21.242.4JBarium200.7ug/L22.520390Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000140,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,400,000

# A-22ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-SpecificQLConcentrationChromium200.8ug/L23.3820^Chromium (VI)218.6ug/L11.961012.8Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220048JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400740,000Manganese200.7ug/L20.51204.5JMercury1631Eng/L4,0009652,02043,500Molybdenum200.7ug/L21.64019JNickel200.8ug/L20.8946.5Selenium200.8ug/L20.6241,300Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00049,000Thallium200.8ug/L20.4720.58JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.7JVanadium200.8ug/L21.7104.7JZinc200.8ug/L24.110ND (10)U

# A-23ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4710.96JNitrate Nitrite as N353.2mg/L50.0950.521FNitrogen, Total Kjeldahl351.2mg/L10.07712.6Biochemical Oxygen Demand5210Bmg/L102.420ND (20)UChemical Oxygen Demand410.4mg/L520100140FChloride300.0mg/L5001301,5007,900Sulfate300.0mg/L100235001,200Cyanide, Total4500 CN Emg/L10.020.1ND (0.1)U,FTotal Dissolved Solids2540Cmg/L14710026,000BTotal Suspended Solids2540Dmg/L11.142.4JPhosphorus, Total365.1mg/L10.0050.050.0074J,BTotal MetalsAluminum200.7ug/L29.420019JAntimony200.8ug/L20.7221.3JArsenic200.8ug/L21.242JBarium200.7ug/L22.520420BBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,700,0004Chromium200.8ug/L23.3820Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220045JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400740,0004

# A-24ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.51205.1JMercury1631Eng/L2,0004831,01053,300Molybdenum200.7ug/L21.64021JNickel200.8ug/L20.8948.7Selenium200.8ug/L20.6241,3004Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00050,000Thallium200.8ug/L20.4720.61JTin200.7ug/L24.82005.1JTitanium200.7ug/L21.6209.7JVanadium200.8ug/L21.7103.9JZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7221.8JArsenic200.8ug/L21.241.9JBarium200.7ug/L22.520420Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,700,0004Chromium200.8ug/L23.3820^Chromium (VI)218.6ug/L11.961014.6Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)U

# A-25ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L221400740,0004Manganese200.7ug/L20.51203.1JMercury1631Eng/L4,0009652,02044,400Molybdenum200.7ug/L21.64021JNickel200.8ug/L20.8949.7Selenium200.8ug/L20.6241,3004Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00050,000Thallium200.8ug/L20.4720.57JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6209.1JVanadium200.8ug/L21.7103.7JZinc200.8ug/L24.110ND (10)U

# A-26ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4714.5Nitrate Nitrite as N353.2mg/L10.0190.1ND (0.1)U,FNitrogen, Total Kjeldahl351.2mg/L10.07716.1FBiochemical Oxygen Demand5210Bmg/L51.210ND (10)UChemical Oxygen Demand410.4mg/L520100240Chloride300.0mg/L200516008,000Sulfate300.0mg/L100235001,400Cyanide, Total4500 CN Emg/L10.0020.010.012FTotal Dissolved Solids2540Cmg/L14710016,000Total Suspended Solids2540Dmg/L11.146.8Phosphorus, Total365.1mg/L10.0050.050.12BTotal MetalsAluminum200.7ug/L502405,000ND (5,000)UAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.242.2JBarium200.7ug/L22.520390Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000180,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0004,000,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200130JLead200.8ug/L20.732ND (2)U

# A-27ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,000890,000Manganese200.7ug/L20.5120470Mercury1631Eng/L20048.3101230Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6247.3Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00051,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6207.7JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.420016J,BAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.2JBarium200.7ug/L22.520370BBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,200,000BChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200110J

# A-28ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400730,000Manganese200.7ug/L20.5120410Mercury1631Eng/L204.8310.123.1Molybdenum200.7ug/L21.6401.9JNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6248.1Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.2JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)U

# A-29ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4714.3Nitrate Nitrite as N353.2mg/L10.0190.10.019JNitrogen, Total Kjeldahl351.2mg/L10.07715.8Biochemical Oxygen Demand5210Bmg/L51.210ND (10)UChemical Oxygen Demand410.4mg/L520100340Chloride300.0mg/L5001301,5007,600Sulfate300.0mg/L100235001,400Cyanide, Total4500 CN Emg/L10.020.10.057J,FTotal Dissolved Solids2540Cmg/L14710014,000Total Suspended Solids2540Dmg/L11.1422Phosphorus, Total365.1mg/L10.0050.050.13BTotal MetalsAluminum200.7ug/L29.420024JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.3JBarium200.7ug/L22.520380Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000190,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,300,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200130J

# A-30ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400760,000Manganese200.7ug/L20.5120320Mercury1631Eng/L10024.150.5247Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.62426Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00050,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.420020J,BAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.4JBarium200.7ug/L22.520370Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,600,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L11.9610ND (10)U,T,Est

# A-31ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200130JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400750,000Manganese200.7ug/L20.5120310BMercury1631Eng/L204.8310.123.4Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.62424Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00049,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.1JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)U

# A-32ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4714.4Nitrate Nitrite as N353.2mg/L10.0190.1ND (0.1)U,FNitrogen, Total Kjeldahl351.2mg/L10.07716.3B,F,HBiochemical Oxygen Demand5210Bmg/L51.210ND (10)UChemical Oxygen Demand410.4mg/L520100130FChloride300.0mg/L5001301,5007,000Sulfate300.0mg/L100235001,300Cyanide, Total4500 CN Emg/L10.020.10.039J,FTotal Dissolved Solids2540Cmg/L14710024,000BTotal Suspended Solids2540Dmg/L11.144Phosphorus, Total365.1mg/L10.0050.050.11B,FTotal MetalsAluminum200.7ug/L29.420022JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.6JBarium200.7ug/L22.520370Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000170,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,300,0004Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200300

# A-33ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400750,0004Manganese200.7ug/L20.5120260Mercury1631Eng/L10024.150.5346Molybdenum200.7ug/L21.6401.9JNickel200.8ug/L20.8940.97JSelenium200.8ug/L20.6245.1Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.3JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.420019JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.5JBarium200.7ug/L22.520370Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,300,0004Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)U

# A-34ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200170JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400740,0004Manganese200.7ug/L20.5120260Mercury1631Eng/L102.415.0528.2Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6244.9Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.5JVanadium200.8ug/L21.7102.2JZinc200.8ug/L24.11012F

# A-35ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-12.Effluent from the Bioreactor System, Day 4 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4714.5Nitrate Nitrite as N353.2mg/L10.0190.1ND (0.1)UNitrogen, Total Kjeldahl351.2mg/L10.07716Biochemical Oxygen Demand5210Bmg/L51.210ND (10)UChemical Oxygen Demand410.4mg/L520100190Chloride300.0mg/L5001301,5007,800Sulfate300.0mg/L100235002,500Cyanide, Total4500 CN Emg/L10.020.10.032JTotal Dissolved Solids2540Cmg/L14710055,000BTotal Suspended Solids2540Dmg/L11.143.6JPhosphorus, Total365.1mg/L10.0050.05ND (0.05)UTotal MetalsAluminum200.7ug/L29.420021JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.4JBarium200.7ug/L22.520380BBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000140,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,600,000Chromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200150JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400740,000

# A-36ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-12.Effluent from the Bioreactor System, Day 4 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.5120230Mercury1631Eng/L10024.150.5406Molybdenum200.7ug/L21.6403.1JNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.62425Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00049,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.8JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.420020JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.5JBarium200.7ug/L22.520370Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000140,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,600,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L11.9610ND (10)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200160JLead200.8ug/L20.732ND (2)U

# A-37ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L221400730,000Manganese200.7ug/L20.5120230Mercury1631Eng/L102.415.0536.1Molybdenum200.7ug/L21.6403JNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.62422Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.5JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)U

# A-38ND – 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 Influentto the Bioreactor System Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4711Nitrate Nitrite as N353.2mg/L50.0950.520Nitrogen, Total Kjeldahl351.2mg/L10.07712.8Biochemical Oxygen Demand5210Bmg/L102.420ND (20)UChemical Oxygen Demand410.4mg/L520100280Chloride300.0mg/L5001301,5007,400Sulfate300.0mg/L100235001,200Cyanide, Total4500 CN Emg/L10.020.1ND (0.1)UTotal Dissolved Solids2540Cmg/L14710023,000BTotal Suspended Solids2540Dmg/L11.142JPhosphorus, Total365.1mg/L10.0050.050.014J,BTotal MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7221.9JArsenic200.8ug/L21.243JBarium200.7ug/L22.520380Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,300,000Chromium200.8ug/L23.3820^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400720,000

# A-39ND – 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 Influentto the Bioreactor System Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.51205JMercury1631Eng/L2,0004831,01053,800Molybdenum200.7ug/L21.64019JNickel200.8ug/L20.8947.2Selenium200.8ug/L20.6241,300Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00048,000Thallium200.8ug/L20.4720.64JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6209.4JVanadium200.8ug/L21.7104JZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7221.7JArsenic200.8ug/L21.242.7JBarium200.7ug/L22.520360Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000140,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,100,000Chromium200.8ug/L23.3819^Chromium (VI)218.6ug/L11.961013.5Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.9641.2JIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)U

# A-40ND – 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 Influentto the Bioreactor System Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L221400700,000Manganese200.7ug/L20.51203.8JMercury1631Eng/L4,0009652,02044,400Molybdenum200.7ug/L21.64019JNickel200.8ug/L20.8946.3Selenium200.8ug/L20.6241,200Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00046,000Thallium200.8ug/L20.4720.49JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208.2JVanadium200.8ug/L21.7105.9JZinc200.8ug/L24.1106.1J

# A-41ND – 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 Effluentfrom the Bioreactor System Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.4714.6Nitrate Nitrite as N353.2mg/L10.0190.1ND (0.1)UNitrogen, Total Kjeldahl351.2mg/L10.07715.7FBiochemical Oxygen Demand5210Bmg/L51.210ND (10)UChemical Oxygen Demand410.4mg/L520100170Chloride300.0mg/L5001301,5007,800Sulfate300.0mg/L100235001,400Cyanide, Total4500 CN Emg/L10.020.10.064JTotal Dissolved Solids2540Cmg/L14710014,000Total Suspended Solids2540Dmg/L11.1426Phosphorus, Total365.1mg/L10.0050.050.13BTotal MetalsAluminum200.7ug/L29.420022JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.8JBarium200.7ug/L22.520380Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000190,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,300,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200130J

# A-42ND – 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 Effluentfrom the Bioreactor System Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400760,000Manganese200.7ug/L20.5120320Mercury1631Eng/L2,0004831,0106,440Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.62425Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00050,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6207.9JVanadium200.8ug/L21.7101.9JZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.420029J,BAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.7JBarium200.7ug/L22.520380Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0003,600,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L11.9610ND (10)U,T,Est

# A-43ND – 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 Effluentfrom the Bioreactor System Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200410Lead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400760,000Manganese200.7ug/L20.5120320BMercury1631Eng/L102.415.0519.2Molybdenum200.7ug/L21.6409.4JNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.62423Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00050,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6208JVanadium200.8ug/L21.7102.2JZinc200.8ug/L24.110ND (10)U

# a 

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

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



# A-44 Table A-15. Bottle Blank and Equipment Bl ank 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 Reco verable ug/L ND (0.040)

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

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

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

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

# a 

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

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



# A-45 Table A-15. Bottle Blank and Equipment Bl ank Analytical Data, Belews Creek

Analyte Method Process Units Concentration

Lead EPA 1638 Total Reco verable ug/L ND (0.040)

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

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

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

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

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

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

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

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

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

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

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

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

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

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

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

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

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

Aluminum a 

# EPA 1638 Dissolved ug/L 4.71

Antimony EPA 1638 Dissolved ug/L ND (0.50)

Arsenic EPA 1638 Dissolved ug/L ND (0.50)

Barium EPA 1638 Dissolved ug/L ND (0.10)

Beryllium EPA 1638 Dissolved ug/L ND (0.10)

Cadmium EPA 1638 Dissolved ug/L ND (0.10)

Chromium EPA 1638 Dissolved ug/L ND (1.0)

Cobalt EPA 1638 Dissolved ug/L ND (0.10)

Copper EPA 1638 Dissolved ug/L ND (0.30)

Lead EPA 1638 Dissolved ug/L ND (0.050)

Manganese EPA 1638 Dissolved ug/L ND (0.50)

Molybdenum EPA 1638 Dissolved ug/L ND (0.50)

Nickel EPA 1638 Dissolved ug/L ND (0.50)

Selenium EPA 1638 Dissolved ug/L ND (2.0)

Silver EPA 1638 Dissolved ug/L ND (0.10)

Thallium EPA 1638 Dissolved ug/L ND (0.050)

Vanadium EPA 1638 Dissolved ug/L ND (1.0)

Zinc EPA 1638 Dissolved ug/L ND (0.50)

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

Aluminum EPA 1638 Dissolved ug/L ND (2.0)

Antimony EPA 1638 Dissolved ug/L ND (0.50)

# a 

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

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



# A-46 Table A-15. Bottle Blank and Equipment Bl ank 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-sp litter, and two pieces of 5

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

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

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

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

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

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

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

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

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

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

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

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

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

Lead EPA 1638 Total Reco verable ug/L ND (0.040)

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

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

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

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

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

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

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

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

# a 

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

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



# A-47 Table A-15. Bottle Blank and Equipment Bl ank 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 Blan k (Three feet of Teflon® tubing, 10 feet of #73 silicone tubing, Ysplitter, and two pieces of 5 feet of #24 silicone tubing for total and di ssolved sample collection for metals)

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

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

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

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

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

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

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

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

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

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

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

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

Lead EPA 1638 Total Reco verable ug/L ND (0.040)

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

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

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

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

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

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

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

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

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

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

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

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

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

T-Splitter Tubing Set – Equipment Blank (Ten feet of #7 3 silicone tubing, T-splitter, six feet of #73 silicone

tubing, and 15 feet of #73 silicone tubing for total and dissolved sample collect ion for metal composites)

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

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

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

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

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

# a 

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

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



# A-48 Table A-15. Bottle Blank and Equipment Bl ank 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 Reco verable ug/L ND (0.040)

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

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

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

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

Nickel EPA 1638 Total R ecoverable ug/L ND (0.10)

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

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

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

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

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

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

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

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

# A-49ND – 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 SystemField Blank, Day 1 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsAluminum200.7ug/L29.420018JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720034J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400ND (400)UManganese200.7ug/L20.5120ND (20)UMercury1631Eng/L10.240.5ND (0.5)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6241.2JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)U

# A-50ND – 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 SystemField Blank, Day 1 Analytical Results, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720035J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400100JChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.9641JIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L22140072JManganese200.7ug/L20.51200.84JMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000210JThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7102.2JZinc200.8ug/L24.110ND (10)U

# A-51ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.7200ND (200)UCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400110JChromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400ND (400)UManganese200.7ug/L20.5120ND (20)UMercury1631Eng/L10.240.5ND (0.5)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)U

# A-52ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720037J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L26940077J,BChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400ND (400)UManganese200.7ug/L20.5120ND (20)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)U

# A-53ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-54ND – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-55J – 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 CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.50.27J

# A-56ND – 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 AnalyticalResults, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsAluminum200.7ug/L29.420067JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.7200ND (200)UCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400ND (400)UManganese200.7ug/L20.5120ND (20)UMercury1631Eng/L10.240.5ND (0.5)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)U

# A-57ND – 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 AnalyticalResults, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720028J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400ND (400)UManganese200.7ug/L20.5120ND (20)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)U

# A-58ND – 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 AnalyticalResults, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-59ND – 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 AnalyticalResults, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-60ND – 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 AnalyticalResults, Belews CreekAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# Appendix B

DATA REVIEW NARRATIVES

# MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

Deb Bartram, ERG

TJ Finseth, ERG

From: Randy Mercurio, ERG.

Donna Tedder, ERG

Date: 2/2/2011

Subject: FGS Data Review Narrative fo r Total Mercury – Episode 6558

Frontier Global Sciences (FGS) generated an alytical data for total mercury. FGS

analyzed the samples according to EPA Me thod 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 Bior eactor 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 Bior eactor Effluent Day 2 6/9/2010

71651 1006109-11 Aqueous FGD Bioreactor Effluent Day 3 6/10/2010

71651 1006109-12 Aqueous Dissolved FGD Bior eactor Effluent Day 3 6/10/2010

71652 1006118-03 Aqueous FGD Bioreactor Effluent Day 4 6/11/2010

71652 1006118-04 Aqueous Dissolved FGD Bior eactor 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 Fi eld 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 th at required additional qualifiers in this

dataset. The following summarizes th e findings from the data review:

 One filter blank (lab sample number 1006085-20) exceeded the method detection

level (MDL). The samples associated w ith this filter bl ank 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 la boratory is above the MDL requirement for EPA

Method 1631E; however, the MDL used fo r 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, HANDLIN G, AND ST ORAGE ISSUES

As discussed in the case narrative provided by FGS, “One (1) of the 250 mL glass bottles

submitted for grab sample 71646 FGD Bior eactor 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 dropp ed and broken durin g preservation. The

two bottles that were broken contained the dissolved mercury ali quot (lab-filtered) and

total mercury aliquot. Only one total mercur y aliquot remained for the sample; therefore

no dissolved mercury results were availabl e for sample 71644 FGD Influent Day 4.”

ONGOING PRECISION AND ACCURACY/RECOVERY

The results for all ongoing precision and recove ry (OPR) samples, in the form of blank

spike/blank spike duplicates (BS/BSDs), fe ll 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 calib ration verification (ICV) wa s 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 met hod-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. Th e samples associated with this filter

blank, 71642, 71645, 71646 (Dissolved FGD Bi oreactor Influent Day 2 only), 71649,

71657, and 71661, do not require qualif ication. All of the de tected 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 cr iteria 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 ma trix 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 fo r Total and Dissolved Metals by 200.8 –

Episode 6558

TestAmerica generated analytic al data for total and dissolv ed metals (antimony, arsenic,

cadmium, chromium, copper, lead, nickel, sele nium, 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: Inductivel y 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 c onsistently 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 th an 5% for a minimum of 4

integrations of the solution.”

INTERNAL STANDARDIZATION

All internal standards used by TestAmeri ca were within the method criteria.

INITIAL CALIBRATION

TestAmerica performed the initial calibra tions 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 calibrati on verifications (CCV)

performed by TestAmerica all had recoveries within the method criteria.

BLANKS

All the method blanks were less than the re porting limit (RL); how ever, 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 conti nuing 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 Amer ica’s 50-150% recovery limits.

2

# 3 LABORATORY CONTROL SAMPLE (LCS)

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

SYNTHETIC FGD INTERFERE NCE CHECK SOLUTION

Chromium in the ICSA solution was alwa ys above the RL of 4 ug/L, indicating

interferents were not being removed effectively. Therefor e, 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 batc h of total and dissolved samples. No QC

criteria are required by EP A 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 si gnificant concentrations did have percent

differences calculated and met the typical <10% criterion, with the ex ception 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 MATI X 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 exceed ed 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 contro l limits of 70-130% with the ex ception 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 fo r Total and Dissolved Metals by 200.7 –

Episode 6558

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

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

manganese) for Sample Episode 6558. The sa mples were analyzed according to EPA

Method 200.7.

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

dissolved metals by EPA Method 200.7.

Table 1. 

# EPA Episode 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 Analys is 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 da taset. 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, HANDLIN G, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INTERNAL STANDARDIZATION

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

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

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

INITIAL CALIBRATION

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

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

INITIAL AND CONTINUING CALIBRATION VERIFICATION

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

performed by TestAmerica all had recoveries within the method criteria.

BLANKS

All the method blanks were less than the re porting limit (RL); how ever, some elements

were found above the method detection limit (MDL) and were flagged with the “J”

qualifier.

2

# All instrument blanks (ICB a nd CCB) were less than the RL; however, som e elements

were above the MDL and were fl agged with the “J” qualifier.

RL VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmeri ca’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 perfor med using the synthetic matrix as the check solution. All

recoveries met the method-specified criteria.

SERIAL DILUTION

Serial dilutions were performed for each batc h 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 ma gnesium (12%), and Sample 71643 failed for

aluminum (12%); these elements were fla gged “V” as failing the QC criteria. These

dilution tests indicate there may be a chemi cal 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 MATI X SPIKE DUPLICATES (MSD)

Matrix spike and matrix spike duplicat es were performed on samples 71641, 71642,

71643, 71648 and 71651. Many elements with high c oncentrations frequently failed the

spike recovery and were flagge d 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 requi rements and were flagged with the “F”

qualifier. Otherwise, the MS/MSD spike recoveri es 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 th an 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 an alytical data for dissolved hexavalent

chromium for Sample Episode 6558. FGS anal yzed the samples according to a modified

EPA Method 218.6 for dissolved hexavalent chromium by Liquid Chromatography –

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

Table 1 summarizes the 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 In fluent Day 1 6/8/10 6/21/10

71646 Aqueous FGD Bioreactor Infl uent Day 2 6/9/10 6/22/10

71647 Aqueous FGD Bioreactor In fluent Day 3 6/10/10 6/22/10

71648 Aqueous FGD Bioreactor In fluent Day 4 6/11/10 6/22/10

71649 Aqueous FGD Bioreactor E ffluent Day 1 6/8/10 6/22/10

71650 Aqueous FGD Bioreactor E ffluent Day 2 6/9/10 6/22/10

71651 Aqueous FGD Bioreactor E ffluent Day 3 6/10/10 6/22/10

71652 Aqueous FGD Bioreactor E ffluent Day 4 6/11/10 6/22/10

71653 Aqueous FGD Bioreactor Infl uent Duplicate 6/10/10 6/22/10

71654 Aqueous FGD Bioreactor Effl uent 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 Infl uent FB Day 1 6/8/10 6/21/10

71660 Aqueous FGD Bioreactor Effl uent FB Day 1 6/8/10 6/22/10



# 1

# SUMMARY

Sa mples 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, 716 44, 71649, 71650, 71651, 71652, 71654, and 71660)

were diluted prior to analysis due to the pr esence of high levels of nontarget chloride

interferences.

SAMPLE RECEIPT, HANDLIN G, 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 reco very (IPR) performed by FGS had recoveries within the

method criteria.

ONGOING PRECISION AND ACCURACY/RECOVERY

The analytical method did not require the an alysis 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 bl ank and eight calibration standards with a

correlation factor ≥ 0.995 as required by the analytical method.

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

of true value required by the analytical method.

CONTINUING CALIBRATION VERIFICATION (CCV)

All CCVs met method-specified criteria ex cept the following: CCV2 and CCV3 had high

recoveries in the initial analysis sequen ce on 6/21/10. All samples affected by these

failing CCVs were successfully rean alyzed with acceptable CCVs.

BLANK

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

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

2

# 3 OTHER CHECKS

The laboratory control sample/duplicate (LCS/L CSD) passed method criteria (± 10%).

DETECTION LIMITS

The laboratory method detecti on limit (MDL) in the synthe tic matrix was 0.392 ug/L.

Results below this MDL were reported as not detected.

DUPLICATES

There were no laboratory duplicat es performed in this episod e other than a duplicate of

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

Two field duplicates were collected and analyzed. Samples 71653 and 71654 were

duplicates of Samples 71647 and 71650, resp ectively. Sample 71647 and its duplicate

had an RPD of 5%. Sample 71650 and its duplic ate 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 fo r 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 (BOD 5 

# ) by SM 5210B,

 Chloride and Sulfate by EPA Method 300.0,

 Chemical Oxygen Demand (COD) by EPA Method 410.4,

 Cyanide by SM 4500 CN

- 

# E,

 Nitrate/Nitrite by EPA Method 353.2,

 Phosphorus by EPA Method 365.1,

 Total Dissolved Solids (TDS) by SM 2540C,

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

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

Table 1 summarizes the 14 samples that TestAmerica analyzed for the above analytes.

Table 1. EPA Episode 6558 Classical An alytes – 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 An alytes – Sample Id entification

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 Effl uent - Duplicate 06/09/10

SUMMARY

Unless otherwise noted below, all samples were analyzed within the holding time

specified in 40 CFR 136 Ta ble 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 standa rd used to create the curve, the sample was

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

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

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

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

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

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

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

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

laboratory fortified blanks (LFB) met the 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 sa mples 71648 (FGD bioreactor influent) and 71651

(FGD bioreactor effluent) for each analyte to check for matrix in terferences in these

matrices. For some analytes, TestAmerica sp iked more samples than required. All MS

samples analyzed met the criteria specifie d 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

# BOD 5



# Even though TestAmerica ran at least five d ilutions on every sample, no dilutions had a

dissolved oxygen (DO) depletion great er than 2.0 mg/L. Therefore, BOD 5 

# was reported

as nondetect for all samples. All glucose-gl utamic acid standards, water blanks, and

laboratory duplicates were anal yzed appropriately and met th e 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 bi oreactor influent) and sample 71651 (FGD

bioreactor effluent). Howeve r, the MS/MSD analysis for both chloride and sulfate was

only run on sample 71648. The MS/MSD result s for sample 71648 met the criteria of 80-

120% specified in EPA Method 300.0 indicating ma trix interferences we re 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 de termine whether matrix interferences were

disrupting results in FGD bior eactor 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 fiel d 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 an alyses were 86% and 87%, respectively. The

low percent recovery could indicate that re sults 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 fo r 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 efflue nt) could be biased

low. However, EPA Method 410.4 only requires th at the result for the MS analysis be

within 90-110%, so sample 71651 was not flagged.

The RPD between sample 71647 and its fi eld 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 quali fied because there are no specific control

limits for field duplicates specified in EPA Method 410.4.

3

# Cyanide

Sa mples 71642, 71643, 71644, 71645, 71646, 71647, 71648, 71650, 71651, 71652,

71653, and 71654 were diluted prior to distillat ion by a factor of 10 due to matrix

interferences. The laboratory stated that the samples foam ed during preparation and in

order to protect the instrument s, the samples were diluted.

The results of the diluted sa mple 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 an alyze 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 show n by Table 2 below, nearly all

of the MS/MSD percent recoveries were be low the laboratory cont rol 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 pe rcent recoveries. The low MS/MSD percent

recoveries for sample 71649 suggest that cy anide 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 a bove 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 fo r 71651 and 119% for both the MS and MSD

sam ples 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 fo r 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 analys is for sample 71648 wa s 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 concentr ation of 0.019 mg/L was below the lowest

standard (0.05 mg/L) used to create the calib ration 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 th e MDL (0.005 mg/L), it is less than the RL

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

based on 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 per cent 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 qualifie d 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 quali fied by the laboratory with a “J” because

the result was below the RL, so no fu rther qualificati on 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 w ith 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 re quired 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 m g/L, which is a bove 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 a ffected by the TDS contamination in the LRB.

All 14 samples analyzed for TDS did not achie ve a constant weight after three drying

cycles. In all cases, the weight increased fr om 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 con centrations 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. Thes e 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 fiel d 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 th e 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 m eet the control limits specified in the

method. Furthermore, the MS/MSD percent r ecoveries for sample 71641 did not meet the

laboratory criteria of 54-131% . Table 3 presents the percen t 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/M SD 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 sample s and the final sample result for 71651

were analyzed in different batches. Samples of the same matrix did not appear to have

correlating percent re coveries. 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 r ecoveries above the control limits. Sample

71641 was qualified as a minimum value whil e 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 mi nimum value because the percent recovery

of the MS sample was below the control lim its specified in the method. However, this

sample was also analyzed outside of the hol d time. The ammonia and TKN results did not

agree in the first analysis, so the sample ha d 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 bei ng 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 cr iteria, these two samples we re 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: I NDUCTIVELY 

# C OUPLED 

# P LASMA 

# M ASS 

# S PECTROMETRY FOR 

# T RACE



# E LEMENT 

# A NALYSIS IN 

# F LUE 

# G AS 

# D ESULFURIZATION 

# W ASTEWATERS

# D-1 

# FGD ICP/MS SOP: Inductively Co upled Plasma Mass Spectrometry for

Trace Element Analysis in Flue Gas Desulfurization Wastewaters

1.0 Scope and Application

1.1 This document describes procedures used to measure elements in Flue Gas

Desulfurization, FGD, wastewaters. Inductively coupled plasma-mass

spectrometry (ICP/MS), as described in EPA Methods 200.8 and 1638, was used

with a collision cell to mitigate the effects of interferences in the samples. These

procedures are intended for use by analysts experienced with applying ICP/MS

to complex wastewater samples.

1.2 These procedures are applicable to the analysis of acid digested FGD

wastewater, and have been evaluated for the analysis of 13 elements of interest.

These are Al, As, Cd, Cr, Cu, Pb, Mn, Ni, Se, Ag, Tl, V and Zn. Additional

elements may be included provided that the performance criteria presented in

Sections 9 and 12 are met.

1.3 Flue Gas Desulfurization wastewaters frequently have very high levels of

calcium, sodium, magnesium, manganese, chloride and sulfate (up to thousands

of ppm). The use of instrument configurations and/or accessories designed to

accommodate samples with high dissolved solids levels is highly recommended.

2.0 Summary

2.1 Aqueous samples, digestates, or leachates are nebulized into a spray chamber

where a stream of argon carries the sample aerosol through the quartz torch and

injects it into an RF plasma. There the sample is decomposed and desolvated.

2.2 The ions produced are entrained in the plasma gas and by means of a watercooled, differentially pumped interface, introduced into a high-vacuum chamber

that houses a quadrupole mass spectrometer capable of providing a resolution

better than or equal to 0.9 amu peak width at 10% of the peak height. The ions

are separated according to their mass-to-charge ratio and measured with a

detector, such as an electron multiplier.

2.3 A collision/reaction cell utilizing He and (optionally) H 2 

# gases is used to remove

molecular interferences.

2.4 Interferences not eliminated by the collision/reaction cell must be assessed and

valid corrections applied, or the data flagged to indicate problems. Interference

correction must include compensation for interferences not removed by the

collision / reaction cell. Recommended elemental equations are listed in

Attachment 1. Use of the internal standard technique is required to compensate

for suppressions and enhancements caused by sample matrices.

3.0 Definitions

3.1 Batch – A group of samples which behave similarly with respect to the sampling

or the testing procedures being employed and which are processed as a unit.

For QC purposes, if the number of samples in a group is greater than 20, then

each group of 20 samples or less will all be handled as a separate batch

# D-2 3.2 Dissolved Metals - Those elements which pass through a 0.45-  m membrane

filter (sample is acidified after filtration).

3.3 Suspended Metals - Those elements which are retained by a 0.45-  m

membrane filter.

3.4 Total Recoverable Metals - The concentration determined on an unfiltered

sample following treatment with hot, diluted mineral acids, as described in this

procedure

3.5 Instrument Detection Limit (IDL) - See Section 12.2

3.6 Sensitivity - The slope of the analytical curve (i.e., the functional relationship

between raw instrument signal and the concentration).

3.7 Tuning Solution - This is a multi-element solution containing analytes which are

representative of the entire mass range capable of being scanned by the

instrument. It is used to optimize the sensitivity of the instrument and to verify

the mass resolution meets method criteria.

3.8 Initial Calibration Verification / Quality Control Standard (ICV/QCS) - A multielement standard of known concentrations prepared to verify instrument

calibration. This solution must be an independent standard prepared near the

mid-point of the calibration curve, and at a concentration other than that used for

instrument calibration.

3.9 Continuing Calibration Verification (CCV) - A multi-element standard of known

concentrations prepared to monitor and verify the instrument daily continuing

performance.

3.10 Laboratory Control Sample / Laboratory Fortified Blank (LCS/LFB) - A multielement standard of known concentrations that is carried through the entire

sample preparation and analysis procedure. This solution is used to verify

method performance in an ideal sample matrix.

3.11 Reagent Blank - High purity (> 18 megohm-cm) water containing the same acid

matrix as the calibration standards that is carried through the entire digestion

process. The reagent blank is used to determine the concentrations of trace

metals in the reagents used to prepare and analyze the samples.

3.12 Calibration Blank - High purity (> 18 megohm- cm) water acidified with the

same acid concentrations present in the standards and samples. Also referred to

as the Initial Calibration Blank (ICB) and Continuing Calibration Blank (CCB).

3.13 Method Detection Limit (MDL) – Refers to the instructions in Appendix B to 40

CFR Part 136. Also see Section 12.1 of this document. The MDL is determined

from analysis of a sample in a given matrix containing the analyte.

3.14 Individual FGD Interference Check solutions – Single element solutions at

concentrations similar to those found in flue gas desulfurization wastewaters.

3.15 Synthetic FGD wastewater – A mixed solution of elements at typical

concentrations found in flue gas desulfurization wastewaters.

# D-3 4.0 Interferences

4.1 Isobaric Interferences

Isobaric interferences in the ICP/MS are caused by isotopes of different elements

forming ions with the same nominal mass-to-charge ratio (m/z). The

recommended ions used for the elements in this procedure do not have

elemental isobaric interferences, except for a very small interference from

krypton on 78 

# Se, which can be avoided by using argon free of krypton.

4.2 Isobaric Molecular

Isobaric molecular interferences are caused by ions consisting of more than one

atom. These molecular interferences are minimized by use of the collision cell

utilizing He and/or H 2 

# gases. Common examples are potential interferences from

40 

# Ar 35 

# Cl or 40 

# Ca 35 

# Cl on 75 

# As, or 35 

# Cl 16 

# O on 51 

# V, or 40 

# Ar 12 

# C on 52 

# Cr. Collision cell

interference removal works both by causing the interfering molecular ion to

dissociate and by reducing the kinetic energy of the ion. The latter is termed

Kinetic Energy Discrimination (KED), and is the primary mechanism for

interference removal. Polyatomic ions are larger than elemental ions and so

collide with the helium atoms in the collision cell more frequently than the smaller

elemental ions. Each collision reduces the energy of the ion, so the molecular

ions lose energy more quickly. At the end of the collision cell a positive voltage

plate prevents passage of the now low energy molecular ions. Thus, the

interference is eliminated because the molecular ions do not reach the detector.

4.3 Doubly Charged Ion Interferences

Doubly charged elemental ions are possible in cases where the second

ionization potential of the element is significantly below the fist ionization

potential for argon (15.7eV). If a doubly charged ion is formed, it will cause a

response at half of its elemental mass, potentially causing an interference.

Fortunately, most elements have high enough second ionization potentials that

formation of doubly charged ions is not an issue. For the target analytes in this

procedure, a significant potential for interference is from 150 

# Nd and 150 

# Dy

(potential interference on 75 

# As and from 156 

# Gd (potential interference on 78 

# Se). To

check for these potential interferences, monitor the response for mass 150 and

156. If the cps for these masses is > 5 times the cps for the quantitation limit for

arsenic (in the case of mass 150) or selenium (in the case of mass 156) an

interference is possible. In this case analyze a 100ppb standard of Nd and Dy (if

mass 150 is observed) or Gd (if mass 156 is observed) and measure the

response at 150 and 75 (or 156 and 78). This ratio can then be used to create an

interference correction equation. For example, if the response for a 100ppb Gd

standard at mass 156 is 10,000 cps, and the observed response for the same

standard at mass 78 is 1,000 counts, then the equation for 78 

# Se would be:

78 

# Se = 78 

# Se – ( 156 

# Gd/10)

4.4 Physical Interferences

 Physical interferences are associated with the transport and nebulization

process. Internal standards are used to compensate for these types of

interferences.

 Internal standards should be added at a level to give approximately

50,000 - 800,000 counts of raw signal intensity. The mass of the internal

standard should ideally be within 50 amu of the mass of the measured

# D-4 analyte. Consideration should also be given to matching internal

standards to analytes with similar ionization potentials.

 Matrix effects are monitored by comparing the internal standard intensity

in the sample to the internal standard intensity of the calibration blank.

The internal standards must be between 60% and 125% of the calibration

blank. If they are outside this window the sample is diluted by a factor of

2 (1:1) and is reanalyzed.

 Memory effects are dependent on the relative concentration differences

between samples and/or standards which are analyzed sequentially. The

rinse period between samples must be long enough to eliminate

significant memory interference (see section 10.3.6).

5.0 Safety

This procedure may involve hazardous material, operations and equipment. This

procedure does not purport to address all of the safety problems associated with its use.

It is the responsibility of the user of the method to follow appropriate safety, waste

disposal and health practices under the assumption that all samples and reagents are

potentially hazardous. Safety glasses, gloves, lab coats and closed-toe, nonabsorbent

shoes are required.

5.1 Specific Safety Concerns or Requirements

5.1.1 Eye protection that satisfies ANSI Z87.1, laboratory coat, and

nonpowdered nitrile or latex gloves must be worn while handling

samples, standards, solvents, and reagents. Disposable gloves that

have been contaminated must be removed and discarded; nondisposable gloves must be cleaned immediately.

5.1.2 The ICP plasma emits strong UV light and is harmful to vision. All

analysts must avoid looking directly at the plasma. The RF Generator

produces strong radio frequency waves, most of which are unshielded.

People with pacemakers should not go near the instrument while in

operation.

5.2 Primary Materials Used

The following is a list of the materials used in this method, which have a serious

or significant hazard rating. Note: This list does not include all materials

used in the method. The table contains a summary of the primary hazards

listed in the MSDS for each of the materials listed in the table.

# D-5 Material (1) Hazards Exposure

Limit (2) Signs and Symptoms of Exposure

Nitric Acid Corrosive

Oxidizer

Poison 2 ppmTWA

4 ppmSTEL Nitric acid is extremely hazardou s; it is corrosive, reactive,

an oxidizer, and a poison. I nhalation of vapors can cause

breathing difficulties and lead to pneumonia and pulmonary

edema, which may be fatal. Other symptoms may include

coughing, choking, and irritation of the nose, throat, and

respiratory tract. Can cause redness, pain, and severe skin

burns. Concentrated solutions cause deep ulcers and stain

skin a yellow or yellow-brown color. Vapors are irritating and

may cause damage to the eyes. Contact may cause severe

burns and permanent eye damage.

Material (1) Hazards Exposure

Limit (2) Signs and Symptoms of Exposure

Hydrochloric

Acid Corrosive

Poison 5 ppmCeiling Inhalation of vapors can cause coughing, choking,

inflammation of the nose, thr oat, and upper respiratory tract,

and in severe cases, pulmonary edema, circulatory failure,

and death. Can cause redness, pain, and severe skin burns.

Vapors are irritating and may cause damage to the eyes.

Contact may cause severe burns and permanent eye

damage.

1 – Always add acid to water to prevent violent reactions.

2 – Exposure limit refers to the OSHA regulatory exposure limit.



# 6.0 Equipment and Supplies

6.1 Instrumentation

 

# Inductively Coupled Plasma Mass Spectrometer (ICP/MS) capable of providing

resolution, less than or equal to 0.9 amu at 10% peak height from 6-253 amu

and 1.0 amu at 5% peak height from 6-253 amu with a data system that allows

corrections for isobaric interferences and the application of the internal standard

technique. The ICP/MS must be equipped with a collisio n cell for the removal of

molecular interferences. This procedure was developed using an Agilent 7500

or 7700 instrument equipped with a high matrix interface. The interface extends

the amounts of total dissolved solids that may be measured into the percent

concentration range. Any collision cell instrumentation that meets the

specifications in this procedure may be used.

 

# A discrete sample introduction system enables the use of only the exact amount

of sample volume required for data acquisition.

 

# Accessories and configuration that are designed to accommodate samples with

high levels of dissolved solids should be used.

 

# This sampling system results in less matrix being deposited in the system

during analysis and minimizes the rinse times normally needed for difficult

matrices.

 

# Autosampler with autosampler tubes.

 

# Appropriate water cooling device.

 

# Block digester with tubes.

6.2 Supplies

 

# Argon gas: High purity grade (99.99%).

# D-6  

# Helium gas: High purity grade (99.99%).

 

# Hydrogen gas: High purity grade (99.99%).

 

# Calibrated automatic pipettes or Class A glass volumetric pipettes.

7.0 Reagents and Standards

7.1 Storage and Shelf-Life

7.1.1 All standards must be stored in glass, FEP fluorocarbon or previously

unused polyethylene or polypropylene bottles. Standards stored at

concentrations as received from the vendor and mid-level dilutions must

be replaced prior to the expiration date assigned by the vendor. If no

expiration date is provided, the stocks and mid-level standards may be

stored for up to one year. They must be replaced sooner if verification

from an independent source indicates a problem (See section 10.3.5 for

initial calibration verification acceptance criteria).

7.1.2 Working standards, i.e., all standards at concentrations ready to

analyze on the ICP/MS (all except tuning mixes, ICSA and ICSAB

mixes, which are received at ready-to-use concentrations), are prepared

fresh daily.

7.2 Standards

7.2.1 Tuning Solution, 10 ppb

The tuning solution stock is purchased as a custom multi-element mix.

The concentrations of the constituents are shown in Attachment 5.

Prepare the Tuning Solution as detailed below.

 Obtain a clean 100 mL volumetric flask.

 Place 50 mL of reagent water and 2 mL of conc. HNO 3 

# and 0.5

mL of conc. HCl in the flask.

 Swirl to mix.

 Pipet 0.1mL of the Tuning Solution Stock into the flask.

 Dilute to volume with reagent water. Stopper and mix.

7.2.2 PA Tuning Solution

The dual detector solution may be commercially purchased as a custom

multi-element mix.

Prepare the PA Tuning Solution as detailed below.

 Add approximately 50 mL of the 2% HNO 3 

# / 0.5% HCl to a 100

mL volumetric flask.

 Prepare at a concentration recommended by the instrument

manufacturer.

7.2.3 Calibration Standards

Stock calibration standards are purchased as custom multi-element

mixes or as single element solutions. Each day of analysis, the

standards are diluted to working levels using 2% nitric acid and 0.5%

HCl acid matrix. Suggested concentrations are given in Attachment 8,

but the laboratory may adjust calibration standard concentrations as

# D-7 appropriate for the instrument and samples. At a minimum, a 3 point

curve must be used.

7.2.4 Individual FGD Interference check solutions.

7.2.4.1 All individual FGD interference check solutions should be

made up in the same acid matrix as the calibration standards.

7.2.4.2 Chloride, 10,000 mg/L

7.2.4.3 Calcium, 5,000 mg/L

7.2.4.4 Sulfate, 4,000 mg/L

7.2.4.5 Magnesium, 3,000 mg/L

7.2.4.6 Sodium, 2,000 mg/L

7.2.4.7 Boron, 500 mg/L

7.2.4.8 Iron, 500 mg/L

7.2.4.9 Nitrate, 250 mg/L

7.2.4.10 Manganese, 200 mg/L

7.2.4.11 Bromide, 100 mg/L

7.2.4.12 Fluoride, 100 mg/L

7.2.4.13 Selenium, 20 mg/L

7.2.4.14 Vanadium, 10 mg/L

7.2.4.15 Zinc, 2 mg/L

7.2.4.16 Chromium, 1 mg/L

7.2.4.17 Copper, 1 mg/L

7.2.5 Mixed Interference Check Solution (Synthetic FGD Wastewater)

7.2.5.1 Chloride, 5,000 mg/L

7.2.5.2 Calcium, 2,000 mg/L

7.2.5.3 Magnesium, 1,000 mg/L

7.2.5.4 Sulfate, 2,000 mg/L

7.2.5.5 Sodium, 1,000 mg/L

7.2.5.6 Butanol, 2000ppm

7.2.6 Initial Calibration Verification (ICV) Standard

The ICV stock is from a source different than the source for the

calibration standards. Each day of analysis, the ICV standard is

prepared in 2% HNO 3 

# and 0.5 % HCl acid to the concentrations shown

in Attachment 8.

# D-8 7.2.7 Continuing Calibration Verification (CCV) Standard

The CCV is prepared from the same source as the calibration

standards. The CCV standards are prepared fresh each day of analysis

in 2% HNO 3 

# /0.5% HCl. The concentrations are shown in Attachment 8.

Prepare the Working CCV as detailed below.

 Dilute by 2X a known volume of the Working Calibration

Standard in the 2% HNO 3 

# / 0.5% HCl acid matrix.

7.2.8 Spiking Stock Solution

The spike stock solution is prepared from the same stocks as the

calibration standards using the 2% HNO 3 

# / 0.5% HCl acid matrix. Spike

concentrations are listed in Attachment 8.

7.3 Reagents

7.3.1 Reagent Water - ASTM Type I or equivalent for the elements of

interest, generated using an ion-exchange water polishing system

capable of achieving 18.0 megohm-cm.

7.3.2 Blank Matrix 2% HNO 3 

# and 0.5% HCl.

8.0 Sample Collection, Preservation, Shipment and Storage

Sample container, preservation techniques and holding times may vary and are

dependent on sample matrix, method of choice, regulatory compliance, and/or specific

contract or client requests. Listed below are the holding times and the references that

include preservation requirements.

Matrix Sample

Container Min. Sample

Size Preservation Holding Time Reference

Waters HDPE 50 mLs HNO 3 

# , pH < 2 180 Days 40 CFR Part 136.3

Soils Glass or

HDPE 4 oz Cool 4 + 2 o 

# C 180 Days N/A

9.0 Quality Control

9.1 Quality control requirements are also summarized in Attachment 7.

9.2 Ongoing data quality checks are compared with established performance criteria

to determine if the results of analyses meet the performance characteristics of

the method. Any QC result that fails to meet control criteria must be

documented.

9.3 Individual interference check solutions

The individual interference check solutions listed in section 7.2.6 are analyzed

prior to initiating sample analysis, and at least once per quarter while FGD

wastewaters are being analyzed, and after any major changes to instrument

operating conditions. Concentrations of target elements observed should be less

than their reporting limits. In some cases it may not be possible to obtain

interference check solutions that are completely free of contamination. In this

# D-9 case, results up to 5X the reporting limit are acceptable if it is possible to

demonstrate that the isotopic ratios correspond to natural abundances. For

example, the natural abundances of zinc isotopes are Zn 64 

# 48.6%; Zn 66 

# 27.9%;

Zn 67 

# 4.1%; Zn 68 

# 18.8%; Zn 70 

# 0.6%. The measured ratios are not expected to be

exact, especially for low abundance isotopes, and some isotope may be masked

by other elements in the solution, (for example Zn 70 

# in the above example will be

masked by Ge 70 

# ) but it must be possible to explain the observed ratios.

Because Arsenic, Manganese and Aluminum are monoisotopic, this

demonstration is not possible and the level of interference observed must be less

than the reporting limit

.

9.4 Synthetic FGD interference check solution

The synthetic FGD matrix solution listed in section 7.2.7 is analyzed prior to

initiating sample analysis, and at least once per day (immediately after

calibration) while FGD wastewaters are being analyzed, and after any major

changes to instrument operating conditions. Internal standard recovery must

meet method criteria (Section 9.9) and concentrations of target elements

observed should be less than their reporting limits. In some cases it may not be

possible to obtain interference check solutions that are completely free of

contamination. In this case, results up to 5X the reporting limit are acceptable if it

is possible to demonstrate that the isotopic ratios correspond to natural

abundances. For example, the natural abundances of zinc isotopes are Zn 64



# 48.6%; Zn 66 

# 27.9%; Zn 67 

# 4.1%; Zn 68 

# 18.8%; Zn 70 

# 0.6%. The measured ratios are

not expected to be exact, and some isotopes may be masked by other elements

in the solution, (for example Zn 70 

# in the above example will be masked by Ge 70 

# )

but it must be possible to explain the observed ratios. Because Arsenic,

Manganese and Aluminum are monoisotopic, this demonstration is not possible,

and the level of interference observed must be less than the reporting limit.

If the Synthetic FGD solution has to be diluted in order to analyze it

effectively on the ICP/MS, then all samples and QC (including the MDL

replicates) must be diluted by at least the same factor.

9.4.1 Laboratory fortified Synthetic FGD solution

The synthetic FGD solution is spiked with 40ppb of each of the target

elements (400ppb for zinc and 4000ppb for aluminum) and analyzed

once per day, immediately after the synthetic FGD check in section 9.4.

All target elements must be recovered within 70-130% of the true value.

If the Laboratory Fortified Synthetic FGD solution has to be diluted

in order to analyze it effectively on the ICP/MS, then all samples

and QC (including the MDL replicates) must be diluted by at least

the same factor.

9.5 Linear range determination

The linear range for each element is determined prior to initiating sample

analysis and at least once per year thereafter. The linear range must also be

determined subsequent to changes that will have a major effect on instrument

sensitivity, such as changing the detector. The linear range is established using a

single element standard at the desired linear range. The result of the analysis

must be within 10% of the true value.

# D-10 9.6 Method Blank / Laboratory Reagent Blank (MB/LRB)

The method blank consists of reagent water that has been processed in

the same manner as the samples. One method blank must be processed with

each preparation batch.

Acceptance Criteria: Method blank results are acceptable if the concentration

for each analyte of interest is less than the reporting limit.

Corrective Action: If the method blank does not meet the acceptance

criteria, the source of contamination should be

investigated to determine if the problem can be

minimized or eliminated. Samples associated with the

contaminated blank shall be reprocessed for analysis, or

under the following circumstances, may be reported as

qualified (qualifier flags or narrative comments must be

included on report):

 The same analyte was not detected in the

associated samples;

 The method blank concentration is less than 1/10 of

the measured concentration of any sample in the

batch;

 The method blank concentration is less than 1/10

the specified regulatory limit; or

 The analyte is a common laboratory contaminant

(copper, iron, lead, calcium, magnesium,

potassium, sodium, or zinc) less than 2 times the

RL. Note that some programs do not recognize

common lab contaminants.

If the above criteria are not met and reanalysis is not

possible, then the sample data must be qualified. This

anomaly must be addressed in the project narrative

and the client must be notified.

9.7 Laboratory Control Sample / Laboratory Fortified Blank (LCS/LFB)

The LCS consists of reagent water that is spiked with the analytes of

interest as summarized in Attachment 8. One LCS must be processed (digestion

and analysis) for each preparation batch.

Acceptance Criteria: LCS control limits are based on three standard

deviations of past laboratory results. These limits are not

to exceed 85-115% recovery. The control limits are

maintained in a LIMS or other appropriate system.

Corrective Action: If the LCS % recovery falls outside of the control limits for

any analyte, that analyte is judged to be out of control.

All associated samples must be reprocessed for

analysis. One possible exception is a recovery for a

given element above the upper control limit with no

detection for the same element in the samples.

9.8 Matrix Spike / Matrix Spike Duplicate / Laboratory Fortified Sample Matrix /

Laboratory Fortified Matrix Duplicate (MS/MSD/LFSM/LFMD)

# D-11 MS is prepared by taking a second aliquot of a selected sample and spiking it

with the analytes of interest as summarized in Attachment 8. An MSD is

prepared by taking a third aliquot of a selected sample and spiking it with the

analytes of interest as summarized in Attachment 8. The MS and MSD are

processed in the same manner as the samples. One MS/MSD pair must be

processed every 10 samples.

Acceptance Criteria: Control limits are based on three standard deviations of

past laboratory results. These limits are not to exceed

70-130% recovery, and 20% relative percent difference

(RPD). The control limits are maintained in the LIMS

system. If the sample concentration for a specific analyte

in the sample selected for spiking is greater than the

concentration added by the spike, then recovery

accuracy will be reduced. In this case a dilution test may

be performed. A 1:5 dilution should agree within 20% of

the original determination. If not, a physical or chemical

interference is suspected, and must be discussed in the

sample narrative.

Corrective Action: If MS/MSD results and any applicable dilution tests do

not meet the acceptance criteria and all other quality

control criteria have been met, then a matrix interference

is suspected. Failed matrix spikes are flagged, and are

discussed in the final report case narrative.

9.9 Internal Standards Evaluation for Samples

The internal standards in samples must be between 60 and 125% of the intensity

in the calibration blank. If the sample intensities fall outside this range, the

calibration blank is reanalyzed to confirm the instrument has not drifted out of

control. If the criteria is met, the sample is diluted by a factor of 2 (1:1) and

reanalyzed. IS limits and corrective actions for standards and blanks are

described in Section 10.

10.0 Procedure

10.1 One-time procedural variations are allowed only if deemed necessary in the

professional judgment of the supervisor to accommodate variation in sample

matrix, radioactivity, chemistry, sample size, or other parameters. Any variation

in procedure shall be completely documented. Any unauthorized deviations from

this procedure must also be documented as a nonconformance, with a cause

and corrective action described.

10.2 Sample Preparation

10.2.1 EPA Method 1638 was used as the reference for the digestion of the

samples in which Section 12.2.8 describes Closed Vessel digestion.

10.2.2 Transfer a 50mL (+/- 0.5mL) aliquot from a well mixed acid preserved

sample to a 50mL digestion tube.

10.2.3 Add 0.5mL of concentrated nitric acid and 0.25 mL hydrochloric acid.

10.2.4 Spike the LCS and MS/MSD samples per spiking protocols.

# D-12 10.2.5 The total volume of the solution in the tube is now greater than 50 mLs.

The final volume will be 50 ml following the procedure to eliminate the

discrepancy in the initial and final volumes.

10.2.6 Tightly cap each digestion vessel.

10.2.7 Place the digestion tube into a block digester adjusted to achieve a

temperature of approximately 85 o 

# C.

10.2.8 Heat for 2 hours after 85 o 

# C is obtained.

10.2.9 Remove from the block and allow to cool.

10.3 Calibration

10.3.1 Instrument Start Up

Set up the instrument according to manufacturer’s operating instructions.

Allow the instrument to become thermally stable for at least 30 minutes

before tuning.

10.3.2 Instrument Tuning / Mass Calibration

Tune the instrument with a solution containing elements representing all

of the mass regions of interest. The relative standard deviations must be

less than 5% for a minimum of 4 integrations of the solution. Mass

calibration and resolution checks using the tuning solution must be

completed at the beginning of every day.

Mass Calibration Check – The mass calibration results must be within

0.1 amu from the true value. If this criterion

is not met, the mass calibration must be

adjusted before running samples.

Mass Resolution Check - The resolution must be verified to be less

than 0.9 amu full width at 10% peak height.

10.3.3 Mass 75 interference check

The concentration determined for arsenic (mass 75) must be less than

0.25 x the reporting limit when the blank matrix (2% nitric acid / 0.5%

hydrochloric acid) is infused (using the collision gas mode used for

arsenic).

10.3.4 Initial Calibration

The ICP/MS is calibrated each day of operation using a blank and at

least 3 standards (see Section 7.2.3). Report the average of at least

three integrations.

The validity of the calibration is determined by the subsequent

calibration verifications, which are performed at concentrations as

described in the next sections.

10.3.5 Second-Source Initial Calibration Verification (ICV)

A 40  g/L / 4,000 ug/L ICV standard (see Section 7.2.8) is analyzed

immediately after the initial calibration. This is a standard obtained from

a different vendor than the standard used for calibration. This analysis

also satisfies the Method 200.8 requirement for a Quality Check

Standard (QCS).

# D-13 Acceptance Criteria: The ICV recovery must be within 90-110%.

Additionally, the internal standard recoveries for

200.8 must fall between 60 and 125% of true

values. The ICV can be reanalyzed, but must

be successful twice in succession or corrective

action must be taken.

Corrective Action: If the ICV results are outside of the acceptance

limits, investigate the accuracy of the

standards, correct as necessary, and

recalibrate.

10.3.6 Calibration Blank

Checks for the memory effects described at Section 4.4 may be

accomplished by analysis of an initial calibration blank (ICB) after the

ICV. Continuing calibration blanks (CCBs) are analyzed after each

continuing calibration verification.

Acceptance Criteria: Results for the calibration blanks must be less

than the RL.

Corrective Action: If the calibration blank exceeds acceptance

limits, then the possibility of instrument

contamination should be examined, particularly

the possibility of carry-over from high level

samples. The blank can be reanalyzed, and if

successful, analysis can continue. However,

samples tested after high-level samples should

be retested. If the reanalysis is not successful,

then the analysis should be terminated. After

the problem is corrected, recalibrate and

reanalyze all samples tested since the last

acceptable CCB.

10.3.7 Reporting Limit (RL) Verification Standard

An independent standard is analyzed after the ICV to monitor the lab’s

ability to produce reliable results at RL-level concentrations. The RL

verification standard is analyzed after the daily ICB.

Acceptance Criteria: For project reporting limits at or above two

times the MDL, the results should be within

50% of the expected value. Some programs

may require tighter control, in which case the

RLs will need to be three or more times the

MDL concentration.

Corrective Action: If the RL verification fails to meet acceptance

limits, data for the associated samples must be

assessed. For example, if the results are high,

consider blank contamination, and if the results

are low, consider MDL verifications. At a

minimum, sample results must be qualified in

the final report.

10.3.8 Continuing Calibration Verification (CCV) Standard

# D-14 A 50  g/L CCV standard is analyzed after every set of ten samples and

at the end of the analytical sequence.

Acceptance Criteria: The CCV recovery must be within 85-115%. In

addition, the IS recovery must be within 60-

125%. If CCV results are not within these

limits, the CCV can be reanalyzed, but it must

be successful twice in succession or further

corrective action must be taken.

Corrective Action: If the CCV fails acceptance criteria, then the

analysis should be terminated. Recalibrate and

reanalyze all samples tested since the last

acceptable CCB.

10.4 Sample Analysis

10.4.1 Report the average of at least three integrations for all field and QC

samples analyzed.

10.4.2 Flush the system with the rinse blank for at least 30 seconds between

samples and standards during the analytical run. Evaluate the

effectiveness of this time and increase the flush time, if needed.

10.4.3 It may be valuable to monitor additional isotopes for elements that are

potentially susceptible to interferences. In particular, monitoring

additional isotopes for selenium may help data analysis.

10.4.4 Dilute and reanalyze samples that are more concentrated than the

highest calibration standard for an analyte or specific isotope of interest.

No analyte may be reported from an analysis of a diluted sample in

which the analyte concentration is less than 5 times the RL.

The analytical run sequence should be performed as follows to meet all

quality control criteria:

Instrument initialization

Warm-up

Tune instrument

Perform mass calibration

Perform resolution check

Validate tuning criteria

Calibration blank

Calibration standard 1

Calibration standard 2

Calibration standard 3

ICV

ICB

RL verification standard

Synthetic FGD matrix

Spiked synthetic FGD matrix

Carryover check

CCV

CCB

10 Samples (which can include all sample types)

CCV

CCB

# D-15 11.0 Calculations / Data Reduction

11.1 LCS percent recoveries are calculated according to the equation:

11.2 ICV percent recoveries are calculated according to the equation:

11.3 CCV percent recoveries are calculated according to the equation:

11.4 Matrix Spike Recoveries are calculated according to the following equation:



# Where:

SSR = Spike Sample Result

SR = Sample Result

SA = Spike Added

NOTE: When the sample concentration is less than the detection limit, use SR = 0

for the purpose of calculating %R



# .

11.5 The relative percent difference (RPD) between sample duplicates is

calculated according to the following equation:



# Where:

DU1 = Sample result

DU2 = Sample duplicate result % 100

Value True ICV Value Found ICV %       

 R

% 100

Value True CCV Value Found CCV %       

 R

% 100

SA SR

- SSR %       

 R



#   100

2 1 2 1 / 2 1 /

  

 

 

 

 

 DU DU DU DU RPD % 100

Value True LCS Value Found LRB

- Value Found LCS %       

 R

# D-16 11.6 The final concentration for an aqueous sample is calculated as follows:



# 2 1 g/L) ( Result

V D V C  

 



# Where:

C = Concentration from instrument readout, ppb

D = Instrument dilution factor

V1 = Final volume in liters after sample preparation

V2 = Initial volume of sample digested in liters

12.0 Method Performance

12.1 Method Detection Limit Study (MDL)

An initial method detection limit study must be performed on each instrument

before samples can be analyzed. MDL studies are conducted annually as

follows:

 

# Prepare seven samples at three to five times the estimated MDL

concentration. The MDL samples are prepared in the Synthetic FGD

wastewater matrix and in reagent water.

 

# Prepare and analyze the MDL standards as described in Section 10.

 

# Calculate the average concentration found in μg/L, and the standard

deviation of the concentration(s) in μg/L, for each analyte.

 

# The MDL is calculated as Students t for the 99 th 

# percentile times the standard

deviation of the MDL replicate results, following the procedure at 40CFR Part

136, Appendix B.

NOTE1: Perform the MDL study in the synthetic FGD

wastewater matrix. Spiking this matrix provides detection

limits that are better matched to the complex matrix

typical of FGD wastewater. These limits can be

significantly higher than those obtained in a reagent water

matrix. In some cases (zinc in particular), the level of

contamination in the synthetic FGD solution may be high

enough to result in somewhat elevated MDLs.

NOTE2: An FGD-MDL may be less than the MDL observed in

method blanks. If this occurs frequently, the FGD-MDL

should be elevated to the mean of the method blanks plus

the Student t factor times the standard deviation of the

method blanks.

12.2 Instrument Detection Limit Study

Instrument detection limit (IDL) studies are conducted quarterly for each

instrument and each mass used for analysis.

 

# Prepare ten blanks.

 

# Analyze the IDL blanks on three non-consecutive days.

 

# The IDL is equal to three times the standard deviation of the blank results.

# D-17 12.3 Demonstration of Capabilities

All personnel are required to perform an initial demonstration of proficiency

(IDOC) on the instrument they will be using for analysis prior to testing samples.

On-going proficiency must be demonstrated annually. IDOCs and on-going

proficiency demonstrations are conducted as follows.

Four aliquots of the ICV are analyzed using the same instrumental conditions

and procedures used to analyze samples. The analyst must employ ICV’s from

four distinct analytical sequences. Using these four ICV’s demonstrates the

analyst’s ability to optimize and calibrate the instrument and to prepare analytical

solutions. Calculate the average recovery and standard deviation of the recovery

for each analyte of interest.

 

# If any analyte does not meet the acceptance criteria, (85-115% recovery,

unless other criteria are established) the test must be repeated. Only those

analytes that did not meet criteria in the first test need to be evaluated.

Repeated failure for any analyte indicates the need for the laboratory to

evaluate the analytical procedure and take corrective action.

12.4 Training Requirements

12.4.1 Each analyst performing the method must complete a demonstration of

capability (DOC) by successfully preparing and/or analyzing four

consecutive LCSs, or a blind performance evaluation (PE) sample, or

other acceptable QC samples. Analysts who continue to perform the

method must successfully complete a demonstration of capability

annually.

13.0 Pollution Control

13.1.1 For information about pollution prevention that may be applicable to

laboratory operations, consult “Less is Better: Laboratory Chemical

Management for Waste Reduction” available from the American

Chemical Society’s Department of Government Relations and Science

Policy, 1155 16th Street N.W., Washington, D.C., 20036, or online at

http://www.ups.edu/x7432.xml.

14.0 Waste Management

All waste must be disposed of in accordance with Federal, State, and local

regulations.

15.0 References / Cross-References

15.1 EPA Method 200.8, “Determination of Trace Elements in Waters and Wastes

by Inductively Coupled Plasma - Mass Spectrometry”, Revision 5.4, EMMC

Version.

15.2 EPA Method 1638, “Determination of Trace Elements in Ambient Waters by

Inductively Coupled Plasma – Mass Spectrometry, January 1996

# D-18 16.0 Attachments

Attachment 1: Recommended Elemental Equations

Attachment 2: Internal Standards and Corresponding Metals

Attachment 3: Sample Preservation and Holding Times

Attachment 4: Suggested Mass Choices

Attachment 5: Tuning Solution

Attachment 6: Suggested Tuning and Response Factor Criteria

Attachment 7: Summary of Quality Control Requirements

Attachment 8: Calibration, Calibrati on Verification, and Spike Concentrations

# D-19 Attachment 1

Recommended Elemental Equations

Element Isobaric

Correction Mathematical Equation

Pb None (1.0000)(208M) + (1.0000)(207M) + (1.0000)(206M)

6Li Li (natural) (1.0000)(6M) - (0.0813)(7M)

In Sn (1.0000)(115M) - (0.0149)(118M)

The 6 

# Li correction equation is only needed if 6Li is us ed as an internal standard for low mass elements.

Attachment 2: Internal Standards and Corresponding Metals

Internal Std. Associated elements 1,2



# Sc Na, Mg, Al, K, Ca, V, Cr, Mn

Ge Fe, Ni, Cu, Zn, As, Se

In Ag, Cd

Ho Tl, Pb

Footnote: (1) Na, Mg, K, Ca and Fe are included in the synthetic FGD wastewater but their

analytical determination is optional – the in terferences caused by these elements are more

important than the determination of their exact concentration.

(2) Other internal standards may be used. For example, 6 

# Li, Ga, Rh, Bi, Ho and Tb may be

considered for use as internal standards.

# D-20 Attachment 3: Sample Preservation and Holding Times

Measurement

Parameter Container (1) Preservative (2) Maximum Holding

Time (3)

Waters:

Metals (4) P,G HNO 3 

# to pH < 2 6 months

Soils/Sediments/Wastes:

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

digestion.

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

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

collection or shipped to the laboratory unpreserved for preservation at the

laboratory.

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

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

considered valid. Holding times are calcu lated from the date when the sample

was collected.

(4) Samples are filtered immediately on-site by the sampler before adding

preservative for dissolved elements.

# D-21 Attachment 4: Suggested Mass Choices

Masses listed indicate the masses which have the most impact on data quality and the elemental

equations used to collect the data.

Mass Element of Interest Analysis mode

27 Aluminum No gas

75 Arsenic He

111 Cadmium He

52 Chromium He

63 Copper He

208, 207, 206 Lead No gas or He

24 Magnesium No gas

55 Manganese He

60 Nickel He

39 Potassium No gas or He

78 Selenium He (H 2 

# )

107 Silver He

23 Sodium No gas or He

205 Thallium No gas or He

51 Vanadium He

66 Zinc He

NOTE : It is strongly recommended that elements other than those of interest be

monitored to indicate other potential molecular interferences which could

affect the data quality.

# D-22 Attachment 5: Tuning Solution

A tuning solution containing elements representing all of the mass regions of interest must be analyzed.

Below are two groups of suggested solutions which cover a typical mass calibration range.

Method 200.8

Element Concentration (  g/L)

Mg 10

Rh 10

Ba 10

Be 10

U 10

Ce 10

Y 10

Pb 10

Li 10

Co 10

In 10

Tl 10

# D-23 Attachment 6: Suggested Tuning and Response Factor Criteria

No Gas Mode

Li7 >2000cps

Tl205 >3000cps

CeO/Ce 156/140 1%

Ce++/Ce+ 70/140 <3%

He Mode:

ArAr 78 2-3 counts/sec

ArCl 75 2-3 counts/sec

# D-24 Attachment 7: Summary of Quality Control Requirements

QC Parameter Frequency Acceptance Criteria Corrective Action

ICV/QCS Beginning of every

analytical run. 90 - 110% recovery.

200.8 IS, 60-125% rec. Terminate analysis;

correct the problem;

recalibrate.

ICB/CCB Immediately after each

ICV. The result is < RL

200.8 IS, 60-125% rec. Terminate analysis;

correct the problem;

recalibrate.

Synthetic FGD

interference check Prior to initiating

analysis and at least

quarterly. Result for target elements

is < RL, unless actual

presence of target

element can be

demonstrated, in which

case result is < 5X RL. Correct the problem prior

to sample analysis.

Individual element

interference checks Prior to initiating

analysis and at least

quarterly. Result for target elements

is < RL, unless actual

presence of target

element can be

demonstrated, in which

case result is < 5X RL. Correct the problem prior

to sample analysis.

CCV Beginning and end of run

and every 10 samples OR

every 2 hours, whichever

is more frequent.

Beginning and end of

each lot. 90 - 110% recovery.

IS, 60-125% rec. If unacceptable,

terminate analysis;

correct the problem;

recalibrate the

instrument, reverify

calibration and rerun all

samples since the last

acceptable CCV.

CCB Immediately following

each CCV. The result must be < RL

200.8 IS, 60-125% rec. If unacceptable,

terminate analysis;

correct the problem,

recalibrate the

instrument, reverify

calibration and rerun

all samples since the

last acceptable CCB.

# D-25 Attachment 7: Summary of Quality Control Requirements (continued)

QC Parameter Frequency Acceptance Criteria Corrective Action

Method

Blank/Laboratory

Reagent Blank One per lot of 20 field

samples or fewer. The result must be less

than the RL.

Sample results greater

than 10x the blank

concentration or samples

for which the

contaminant is < RL, do

not require redigestion or

reanalysis. Re-run once. If > than

the RL, Redigest and

reanalyze samples.

Note exceptions under

criteria section.

See Section 9.4 for

additional requirements.

Matrix Spike/Laboratory

Fortified Matrix One every ten samples or

fewer. Must be within

laboratory control limits. See section 9.6 for

additional requirements.

# D-26 Attachment 8: Calibration, Calibration Verification, and Spike Concentrations

Element Initial Calibration

(  g/L) ICV

(  g/L) CCV

(  g/L) LCS

(  g/L) MS/MSD

(  g/L)

Aluminum 100, 1,000, 10,000 4000 5000 4000 4000

Arsenic 1, 10, 100 40 50 40 40

Cadmium 1, 10, 100 40 50 40 40

Chromium 1, 10, 100 40 50 40 40

Copper 1, 10, 100 40 50 40 40

Lead 1, 10, 100 40 50 40 40

Manganese 1, 10, 100 40 50 40 40

Nickel 1, 10, 100 40 50 40 40

Selenium 1, 10, 100 40 50 40 40

Silver 1, 10, 100 40 50 40 40

Thallium 1, 10, 100 40 50 40 40

Vanadium 1, 10, 100 40 50 40 40

Zinc 1, 10, 100 40 50 40 40

Additional elements may be included in the calib ration solution at the above levels. Levels

may be adjusted to meet specific requirements.

####