# Sampling Episode Report

Mirant Mid-Atlantic, LLC’s

Dickerson Generating Station

Dickerson, MD

Sampling Episode 6562

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 Systems........................................................................................2-2

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

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

2.2.2 Biological Sequencing Batch 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 the SBR ..................................................................................3-3

3.1.3 Effluent from the SBR .............................................................................3-6

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

3.3 Plant Operational Data.......................................................................................3-10

3.4 Deviations from the Sampling and Analysis Plan .............................................3-10

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 Information, Dickerson.............................................................. 3-12

Table 3-2. Sample Collection at Dickerson Steam Station........................................................ 3-14

Table 3-3. Field Measurements, Dickerson ............................................................................... 3-15

Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Dickerson................... 3-17

Table 3-5. Analytical Me thods, Dickerson................................................................................ 3-18

Table 3-6. Summary of Sample Container and Planned Preservation, Dickerson .................... 3-19

Table 3-7. Sample Preservati on Summary, Dickerson .............................................................. 3-20

Table 3-8. Generating Unit Operating Characteris tics during Sample Coll ection, Dickerson.. 3-23

Table 3-9. FGD Scrubber System Operat ing Characteristics, Dickerson.................................. 3-24

Table 3-10. Coal Usage during Samp le Collection, Dickerson................................................. 3-25

Table 3-11. Scrubber Slurry Information du ring Sample Collection, Dickerson...................... 3-25

Table 3-12. FGD Wastewater Tr eatment System Operation Information, Dickerson .............. 3-26

Table 4-1. Influent to FGD Wastewat er Treatment System, Dickerson..................................... 4-4

Table 4-2. Influent to the SBR System, Dickerson..................................................................... 4-7

Table 4-3. Effluent from th e SBR System, Dickerson.............................................................. 4-11

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

Treatment System, Dickerson........................................................................................ 4-14

Table 4-5. Metal Pollutants 4- Day Average Data Summary fo r FGD Wastewater Treatment

System, Dickerson ......................................................................................................... 4-15

Table 5-1. Field Blank Analy tical Results, Dickerson ............................................................... 5-5

Table 5-2. Field Duplicate Results – Influent to S BR System, Dickerson................................. 5-6

Table 5-3. Field Duplicate Results – Effluent from SB R System, Dickerson............................ 5-9

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

Dickerson ...................................................................................................................... .. A-1

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

Dickerson ...................................................................................................................... .. A-4

# LIST OF TABLES (Continued)

Page

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

Dickerson ...................................................................................................................... .. A-7

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

Dickerson ...................................................................................................................... A-10

Table A-5. Influent to SBR System, Da y 1 Analytical Results, Dickerson............................. A-13

Table A-6. Influent to SBR System, Da y 2 Analytical Results, Dickerson............................. A-16

Table A-7. Influent to SBR System, Da y 3 Analytical Results, Dickerson............................. A-19

Table A-8. Influent to SBR System, Da y 4 Analytical Results, Dickerson............................. A-22

Table A-9. Effluent from SBR System, Day 1 Analytical Results, Dickerson ....................... A-25

Table A-10. Effluent from SBR System, Day 2 Analytical Results, Dickerson ..................... A-28

Table A-11. Effluent from SBR System, Day 3 Analytical Results, Dickerson ..................... A-31

Table A-12. Effluent from SBR System, Day 4 Analytical Results, Dickerson ..................... A-34

Table A-13. Duplicate of Influe nt to SBR System, Day 3 Analy tical Results, Dickerson...... A-37

Table A-14. Duplicate of Effluent from SB R System, Day 2 Analytical Results,

Dickerson ...................................................................................................................... A-40

Table A-15. Bottle Blank and Equipment Bl ank Analytical Data, Dickerson ......................... A-43

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

Results, Dickerson ........................................................................................................ A-48

Table A-17. Influent to SBR Sy stem Field Blank, Day 1 Analy tical Results, Dickerson....... A-50

Table A-18. Influent to SBR Sy stem Field Blank, Day 2 Analy tical Results, Dickerson....... A-52

Table A-19. Influent to SBR Sy stem Field Blank, Day 3 Analy tical Results, Dickerson....... A-53

Table A-20. Influent to SBR Sy stem Field Blank, Day 4 Analy tical Results, Dickerson....... A-54

Table A-21. Effluent fr om SBR System Field Blank, Day 1 An alytical Results, Dickerson.. A-55

Table A-22. Effluent fr om SBR System Field Blank, Day 2 An alytical Results, Dickerson.. A-57

Table A-23. Effluent fr om SBR System Field Blank, Day 3 An alytical Results, Dickerson.. A-58

Table A-24. Effluent fr om SBR System Field Blank, Day 4 An alytical Results, Dickerson.. A-59

# iv LIST OF FIGURES

Page

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

Generating Station ........................................................................................................... 2- 7

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

Wastewater Treatment System, Di ckerson Generating Station....................................... 2-8

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

Figure C-2. Sample Set Up at the Influent to the FGD Wastewater Treatment System..............C-2

Figure C-3. Composite Sample Collection Set Up at the Influent to the SBR System ...............C-3

Figure C-4. Composite Sample Collection Set Up at the Effluent from the SBR System ..........C-4

# 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 August 22 - 27, 2010, at Mirant Mid-Atla ntic, LLC’s Dickerson Generating Station

(Dickerson), located in Dick erson, Maryland (Sampling Episode 6562). The focus of Episode

6562 was to characterize the purge stream ente ring the flue gas desulfurization (FGD)

wastewater treatment system and the influent to and effluent from the sequencing batch reactor

(SBR) system. The influent to the SBR 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.

Dickerson was selected by EPA for sampling ba sed on the following site characteristics:

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

its three generating units;

 The plant operates limestone forced oxidation wet FGD systems on all three 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 removal);

# 1-2  The plant operates select ive non-catalytic reduction (S NCR) systems on all three

units; and

 The plant produces a commerc ial-grade gypsum by-product.

1.3 Sampling Episode Overview

EPA and its technical contractor, Eastern Research Group, Inc. (ERG) conducted a oneday pre-sampling site visit at Dickerson on March 9, 2010 as part of the detailed study. The

information collected during the pre-sa mpling site visit was used to create Sampling Plan,

Mirant Mid-Atlantic, LLC’s Dickerson Generating Station (Sampling Plan) [1], which describes

the sample collection procedures used during the sampling episode.

On Sunday, August 22, 2010, EPA arrived at Dick erson 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 (August 23 – 27, 2010). The following personnel participated in EPA’s

sample collection activities:

 Ron Jordan, EPA/EAD;

 Jezebele Alicea, EPA/EAD;

 Meghan Camp, ERG;

 Holly Cannon, ERG;

 TJ Finseth, ERG;

 Kavya Kasturi, ERG; and

 Elizabeth Sabol, 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 episod e, UWAG acted as Dickerson’ s representative and collected

samples on behalf of the plant.

# 2-1 2. F ACILITY 

# O VERVIEW



# Dickerson operates three steam electric generati ng units and each has a coal-fired boiler.

Units 1, 2, and 3, which came on line in 1959, 1960, and 1962, respectively, each have a capacity

of 182 megawatts (MW). All three generating units burn eastern bituminous coal. Dickerson also

has two combustion turbines on site that ar e 167 MW each. The Dickerson plant and supporting

facilities are located on approximately 1,000 acres in Dickerson, MD, near the Potomac River.

Mirant owns 800 acres for the plant and the other 200 acres are owned by Pepco for switch

yards, right-of-ways, etc.

In December 2009, Dickerson retrofitted a ll three units with a common wet FGD

scrubber system to contro l the sulfur dioxide (SO 2 

# ) releases from the plant. The wet FGD

scrubber is designed to remove more than 95 percent of SO 2 

# from the flue gas. With the addition

of the FGD scrubber system, Dickerson also inst alled an FGD wastewater treatment system to

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

Sections 2.1 and 2.2 further discuss the FGD scr ubber system and the FGD wastewater treatment

system, respectively.

Dickerson retrofitted Units 1, 2, and 3 with SNCR systems in July 2009, to control

nitrogen oxide (NO

x 

# ) releases from the plant. Dickers on only operates the SNCR systems during

ozone season, May 1 through September 30.

The three electrostatic preci pitators (ESPs) and one comm on baghouse at Dickerson are

particulate control devices that are designed to remove 99.5 and 99.8 percent of the fly ash and

other particulates from the flue gas, respectiv ely. Dickerson utilizes E SPs and the baghouse to

remove the fly ash from all three units. Forty pe rcent of the flue gas fr om each unit goes to the

individual unit’s ESP, while the remaining 60 per cent is routed to the common baghouse. The fly

ash and other particulates are collected in hoppers and are pneumatically transferred to fly ash

silos.

Units 1, 2, and 3 have the following configuration:

 Boiler (ammonia injectio n for SNCR system);

 Air preheater;

 ESP (unit-specific) a nd baghouse (common); and

 FGD scrubber system (common).

Between 0134 and 0326 on Tuesday morning, which is prior to the end of the day 1 24-

hour sample compositing period, Dickerson shut dow n all three generating units due to lack of

electricity demand 1 

# . The station continued to operate th e FGD wastewater treatment system at

reduced flow rates and EPA continued to coll ect samples as planned through the end of the

sampling episode. Additionally, the FGD system wa s shut down, but the pl ant occasionally blew

down from the scrubber and opera ted the dewatering equipment to allow EPA to collect the

influent samples. The sampling team monitored flow rates during the remainder of the sampling

episode. The generating station and FGD scrubber did not resume operation until after the end of

the sampling episode.

1 

# Unit 3 was shut down at 0134, Unit 1 was shut down at 0312, and Unit 2 was shut down at 0326 on August 24,

2010.

# 2-2 2.1 FGD Scrubber Systems

Dickerson operates one wet FGD scrubber system that treats the flue gas from all three

coal-fired generating units. The plant uses limesto ne slurry as the sorbent for sulfur dioxide

absorption. Limestone and service water are fe d to on-site ball mills, which pulverize the

limestone to create the slurry. From the ball mills, th e slurry is transferred to classifiers to collect

limestone particles that are too large for us e in the FGD system. The underflow from the

classifiers is sent back to the ball mill for additional processing. The overflow from the

classifiers, which is approximately 28 percent soli ds (by weight), is tran sferred to the limestone

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

The fresh limestone slurry is fed to the reac tion tank of the FGD system where the slurry

is pumped to the various levels of the FGD sc rubber with the recycle pumps. The FGD system

has three levels of flooding headers. The floodi ng headers supply the slurry to the dual flow

tray. As the slurry falls downward in the scrubber vessel, the flue gas flows countercurrent to the

limestone slurry. The droplets of the slurry contact the flue gas and absorb the SO 2 

# , which reacts

with the limestone particles a nd produces calcium sulfite. Th e droplets continue to flow

downward in the scrubber until they settle on the dual flow tray, form ing a layer of slurry that the

flue gas must pass through to exit the FGD system. The spray droplet s continue to flow

downward in the scrubber until they reach the reaction tank. Dickerson bubbles air through the

reaction tank to oxidize the calcium sulf ite to calcium sulfate (i.e., gypsum).

Dickerson controls the chlorides concentra tion in the scrubber to less than 20,000 parts

per million (ppm). Typically, the chlorides concen tration in the scrubber is about 15,000 ppm.

The solids concentration in the scrubber ranges from 18 to 22 percent solids. Dickerson transfers

the blowdown from the scrubber to the gypsum dewatering operations.

The scrubber blowdown is pumped to the pr imary hydrocyclones where the solid gypsum

is separated from the water by centrifugal force. Th e solid gypsum is forced outward to the walls

of the hydrocyclones and falls downward, while the water exits the top of the hydrocyclones.

The gypsum from the primary hydrocyclones is tr ansferred to the vac uum filter belts. The

overflow from the primary hydrocyclones is pumped to the secondary hydrocyclones. The

underflow from the secondary hydrocyclones is sent to the FGD filtrate tank for recycle back to

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

pumped to the FGD wastewater treatment system.

Dickerson washes the gypsum sent to the vac uum filter belts with service water, as the

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

approximately 10 percent. Dickerson has a 20-ye ar contract to sell gypsum that is 94 to 99

percent pure, has a moisture content of less than 9 percent, and has less than 100 ppm chlorides.

Off-specification (“off-spec”) gypsum and other solids are sent to a waste management site in

Virginia. Dickerson generated 2 or 3 days of off-specification gypsum at the beginning of the

FGD start up, but has always met the specifica tions since that time. Dickerson expects to

generate approximately 150,000 tons of gypsum per year.

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

# 2-3 typical flow rate of 75 gallons per minute (gpm ) and a design maximum flow rate of 110 gpm.

The plant typically transfers FGD purge to the wast ewater treatment system four to six times per

day, depending on the unit loading. The average to tal daily flow rate is approximately 84,000

gallons per day (gpd) and the maximum daily flow rate is 158,000 gpd.

The plant operates the FGD wastewater tr eatment system 24 hours per day. Dickerson

installed the wastewater treatment system to treat the FGD scrubbe r purge wastewater to meet its

permit limits, which include limits for total susp ended solids (TSS) and nitrogen. The Dickerson

FGD wastewater treatment system cont ains the following treatment operations:

 Physical/Chemical Separation;

— Equalization,

— pH adjustment (lime addition),

— Organosulfide addition,

— Ferric chloride addition,

— Polymer addition,

— Clarification;

— Hydrochloric acid addition; and

 Biological Reactors;

— Influent equalization,

— Cooling (heat extraction),

— Carbon source addition,

— Hypochloric acid addition,

— SBR process,

— Effluent equalization, and

— Filtration.

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 for 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 wastewat er was found to contain between 0.3 and 1.1

percent solids, had a pH of 6.5 to 7.5 S.U. and a temperature between 29 and 44 °C. The

equalization tank also receives water from the filtra te sump (which includes filter press filtrate,

backwash reject from the continuous backwash gr avity filters, building trench drains, and tank

overflow).

2.2.1 Physical/Chemical Separation

From the equalization tank, the wastewater enters reaction ta nk 1 in which lime slurry is

added to increase the pH to 8.3 S. U. to precipitate the soluble me tals as insoluble hydroxides and

oxyhydroxides. The plant also a dds organosulfide (i.e., TMT-15) to reaction tank 1 to form

sulfide complexes which have very low solubilit y products. Wastewater th en cascades by gravity

# 2-4 into reaction tank 2 in which ferric chloride is added to form a dense flocculant, enhance the

settling characteristics of the precipitate, and promote iron coprecipitation.

The plant adds an anionic polymer as the wastewater flows from reaction tank 2 to the

solids contact clarifier. The polymer is introduced at the inlet of the clarifier. The solids contact

clarifier contains a sludge bed th at facilitates removal of the so lids in the wastewater. In the

afternoon of day 3 of the sampling episode, th e clarifier sludge bed overturned. The condition

was identified by turbidity measurements and wa stewater treatment operators added polymer to

counteract the situation. At 1630 on August 25, the wastewater tr eatment operator stated that

turbidity levels were still el evated, although the polymer addition had reduced the turbidity. The

operator said that SP-2 day 1 and 2 samples shoul d be unaffected, but day 3 and 4 samples would

be affected. The sampling team monitored sample color and turbidity of the samples during the

remainder of the sampling episode.

As the clarifier overflow is transferred to the sequencing batch reactor (SBR) influent

equalization tank, the plant injects hydrochloric acid into the wastew ater to adjust the pH to 7

prior to the biological treatment system. After the hydrochloric acid addition, the wastewater

flows to the SBR influent equalization tank. The hydraulic residence time for the chemical

precipitation portion of the FGD wastewater treat ment system is approximately 16 hours, based

on operating level conditions.

The majority of the sludge from the clarif ier is transferred to a sludge holding tank;

however, the plant recycles approximately 50 to 60 gpm of clarifier sludge back to reaction tank

1 to act as seed crystals for gypsum nucleation. The plant maintains a TSS concentration of 5

percent solids in the outlet from reaction tank 1. The sludge in the sludge holding tank is pumped

to a filter press for dewatering. The filter press filtrate is sent to the filtrate sump. The filter press

cake is transferred to the waste management site in Virginia, where the FGD solids and off-spec

gypsum are sent. Dickerson performs approxima tely 5 filter press operations per day.

2.2.2 Biological Sequencing Batch Reactors

Water from the clarifier as well as the SBR decant flush and backwash reject from the

tertiary continuous backwash filte rs is transferred to the SBR in fluent equalization tank where it

is then pumped through heat exchangers. After the heat exchangers have reduced the temperature

of the water to approximately 95 degrees Fahrenheit, the wastewater is recycled back to the SBR

influent equalization tank. Hypoc hloric acid (to reduce the pH of the water) and a carbon source

(i.e., glycerin, to promote cell growth in the biol ogical treatment process) are also added to the

SBR influent equalization tank. The food to mass ra tio in the SBR system ranges from 4:1 to 8:1

depending on the desired mixed liquor volatile su spended solids concentration. Water is then

batch transferred to two 178,705 gallon SBR tanks operating in parallel.

Dickerson uses an SBR to biologically tr eat the wastewater to remove nitrogen by

nitrification and denitrificati on. Currently, the SBR tanks are open to the atmosphere, but the

plant has erected tarps to cover the tanks. Di ckerson plans to construct a building that will

enclose the SBR by the winter of 2010/2011. The pur pose of the tarps/build ing is to reduce the

heat loss that occurs during cold weather.

Each batch of the SBR consists of the following five cycles:

# 2-5  Fill

o Anoxic: Food is loaded into the basi n and soluble BOD is absorbed and

stored by the facultative biomass until air is received to metabolize the

food. Good settling, facultative organisms predominate.

o Aerated: Air is pumped in and mixed to initiate metabolism. During the

initial stages of Aerated Fill, both nitrification and denitrification occur.

The ammonia is converted to nitrates within the highly aerated plume of the

jet. The nitrates are converted to n itrogen gas in the low dissolved oxygen

areas of the basin. The denitrifyi ng organisms use the BOD as a food

source and the oxygen off the nitrates converting the nitrates to nitrogen

gas. A secondary denitrification phase can be inserted at any point during

the aerated cycle (Aerated Fill & Re act cycles). During this step, the

blowers are turned off and the jet pump continues to mix, providing anoxic

mixing to drive denitrification.

 React: No additional flow or food is added forcing the organisms to scour for any

remaining BOD. Aeration continues until complete biodegradation is achieved.

The cycle continues until the biomass enters its “famine” state at which time the

residual dissolved oxygen levels begin to rise quickly.

 Settle: No influent is introduced and no effluent is decanted allowing the biomass

to settle in quiescent conditions.

 Decant: An automatic valve is opened and the upper one-third of the basin is

discharged.

 Idle: While waiting to receive fl ow settled sludge is wasted.

During the decant cycle, the water is transf erred from the SBR to the SBR effluent

equalization tank. The hydraulic residence time of the biological portion of the wastewater

treatment system, including the eq ualization tanks, is approxim ately 16 hours. The hydraulic

residence time of the SBR itself is a minimum of four hours. From the S BR effluent equalization

tank, the wastewater is then pumped to continuo us backwash gravity filters. Backwash reject

returns to the SBR influent equalization tank for reprocessing. The filtered effluent is conveyed

via gravity to the treated water storage tank.

Water in the treated water storage tank is monitored for NPDES compliance prior to

commingling with the main cooling water disc harge. The commingled water then discharges

through a canal that carries it approximately 1⁄4 mile downstream where it is discharged through

Outfall 001 to the Potomac River.

2.2.3 Sampling Points

Figure 2-2 shows the sampling points for th e Dickerson 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 ch emical addition or treatment system

recirculation flow streams);

# 2-6  An in-process sample of the influent to the SBR, at the heat exchanger tank pump

discharge sample tap (after HCl addition); and

 A sample of the effluent from the SBR, downstream of the continuous backwash

gravity filters and upstream of treated water storage tank.

# 2-7Figure 2-1. Simplified Diagram ofthe FGD Wastewater Treatment System, Dickerson Generating Station

# 2-8Figure 2-2. Physical/Chemical Separation and Biological Reactor Portion of FGD Wastewater Treatment System, DickersonGenerating StationFGD Scrubber Purge(from Purge Tank)LimePolymerEqualizationTankReaction Tank 1ReactionTank 2SP-1SP-2Indicates a Sampling PointFerricChlorideSolidsContactClarifierSludgeStorageTankFilter PressSumpSolids to WasteManagement SiteWastewater FlowSludge FlowIntermittent Wastewater FlowClarifierSludgeHydrochloricAcidSP-3OrganosulfideSBR InfluentEqualizationTankCooling WaterCooling WaterReturnCarbon SourceSequencingBatch Reactors(2)SBR EffluentEqualizationTankDecant FlushTertiaryContinuousBackwashGravityFilters (2)Treated WaterStorage TankBackwash RejectTo DischargeCanal

# 3-1 3. S AMPLE 

# C OLLECTION



# During the Dickerson sampling episode, th e 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 the SBR;

 SP-3 Effluent from the SBR;

 SP-4 Duplicate of Influent to the SBR (SP-2);

 SP-5 Duplicate of Effluent from the SBR (SP-3);

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

 SP-7 Influent to the SBR ( SP-2) Field Blank; and

 SP-8 Effluent from the SBR (SP-3) Field Blank.

For all the sampling points, EPA collected spl it samples with Dickerson’s representative

by inserting a “Y” splitte r into the sample tubing configurat ion at each sampling point to allow

for split sample collection. EPA collected all samples (other than mercury and cyanide) at all

sampling points as “true” splits (i.e., samp les 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 Dickerso n’s representative collected duplicate samples,

with one filling the bottle im mediately 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 drain of the pump that transfers the FGD wastewater from the purge tank to the

equalization tank. Figure 2-2 identifies the sa mpling location for SP-1. This sample was

collected as a grab sample. Due to the relativel y high concentration of suspended solids, the FGD

purge was not amenable to collecting represen tative split samples using composite sampling

techniques. The sampling point was located insi de the FGD gypsum transfer building. Because

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

collection.

On Day 1 only, prior to collecting the 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 pump drain. The end of the silicone tubing was fitted with 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 sample set up at the influent to the FGD wastewater treatment system. The

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

flow through the tubing for two minutes before be ginning to fill sample containers. The samplers

did not close the valve until all samples were coll ected (except the dissolved metals samples).

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

3.1:

 Total and dissolved mercury;

 Total metals by 200.8; and

 Total metals by 200.7.

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

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

# 3-3 the day, the filled 10-liter container was transported to the staging area, put on ice, and then left

untouched to allow the solids in the wastewater to settle.

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

temperature were measured immediately at the sa mpling point using four-color pH paper, a pH

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

FGD wastewater treatment system.

The samplers then filled 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 Dickerson’s representatives.

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 been settling for approximately 80 to 90 minutes. Approximately 1-

1.5 liters 2 

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

samples.

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 the SBR

The influent to the SBR (SP-2) was collected at the sample tap located at the heat

exchanger tank pump discharge to the SBR infl uent equalization tank. Dickerson installed a

three-way splitter on the sample tap, which had thr ee separate taps to collect samples from the

2 

# On days 1, 2, and 3, the filter/tubing was purged for 1 lite r. On day 4, the filter/tubing was purged for 1.5 liters.

There was no need to change the filter on any of the days.

# 3-4 sampling point. The sample tap was located outsi de (see Figure 2-2 for the sampling location for

SP-2). The sampling team set up a tent to cover the samplers/samples from rain and/or wind.

ERG collected the influent from the SBR composite samples using two automatic

compositors which were programmed to collect individual sample volum es into two 20-liter

containers. The compositors were programmed to collect 830 mL every hour during the 24-hour

composite period. Following the composite pe riod, 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 sample collection procedures at the influent to the SBR.

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.

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 t op of the trash cans

to minimize contamination. Figure C-3, in Appendix C, is a picture of the composite sampling

set-up at the influent to the SBR.

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 SBR.

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

# 3-5 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 collec t split samples with Dickerson’s representatives;

therefore, duplicate samples were collected. ER G collected another set of total and dissolved

mercury samples every six hours thereafter over the 24-hour period. The plastic shroud was

replaced for each set of mercury grab samples. After collecting each set of mercury grabs, ERG

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

meter, and a thermometer. Table 3-3 presents th e field measurement data for the influent to the

SBR.

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 Dickerson’s representatives; th erefore, duplicate samples were collected. The

total cyanide sample was immediately preserved. Lead acetate test strips and potassium-iodide

starch test strips were used to measure for su lfides and oxidants, respectively. No sulfides or

oxidants were detected during th e sampling episode at the influe nt to the SBR. ERG samplers

then preserved the total cyanide samples with so dium 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.

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 with Dickerson’s representative.

On Day 1 only, prior to collec ting any samples of the influent to the SBR, the samplers

collected a field blank sample (SP-7) for disso lved and total metals. See Section 5.2.3 for a

description of the dissolved metals field blank sa mple collection at the influent to the SBR.

# 3-6 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 SBR. After the tubing and filter were purged w ith 2 liters of sample, samplers collected the

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

 Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

Hexavalent chromium samples were 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 2 liters of sample, samplers collec ted 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 2 liters of sample, sa mplers filled 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 influent to the S BR (SP-2) on Day 4 of

the sampling episode. In addition, for all analyt es, 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 the SBR

The effluent from the SBR (SP-3) was colle cted downstream of the continuous backwash

gravity filters and upstream of the treated wate r storage tank. Dickerson installed a three-way

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

The sample tap was located outside (see Figur e 2-2 for the sampling location for SP-3). The

sampling team set up a tent to cover the samplers/samples from rain and/or wind.

ERG collected the effluent from the SBR composite samples using two automatic

compositors which were programmed to collect individual sample volum es into two 20-liter

containers. The compositors were programmed to collect 830 mL every hour during the 24-hour

composite period. Following the composite pe riod, 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.

# 3-7 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 sample collection procedures at the effluent from the SBR.

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 ca p on a 20 liter composite container. The sample

tap was left open during the enti re sample collection time period and flowed directly to the

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

sampling program and was capable of purging the lin e 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 Appendi x C, is a picture of the composite sampling

set-up at the effluent from the SBR.

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 SBR.

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 collec t split samples with Dickerson’s representatives;

therefore, duplicate samples were collected. ER G collected another set of total and dissolved

mercury samples every six hours thereafter over the 24-hour period. The plastic shroud was

replaced for each set of mercury grab samples. After collecting each set of mercury grabs, ERG

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

meter, and a thermometer. Table 3-3 presents th e field measurement data for the effluent from

the SBR.

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 Dickerson’s representatives; th erefore, duplicate samples were collected. The

total cyanide sample was immediately preserved. Lead acetate test strips and potassium-iodide

starch test strips were used to measure for su lfides and oxidants, respectively. No sulfides or

# 3-8 oxidants were detected during this sampling episode at the effluent from the SBR. ERG samplers

then preserved the total cyanide samples with so dium 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

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 with Dickerson’s representatives.

On Day 1 only, prior to collec ting any samples of the effluent from the SBR, the samplers

collected a field blank sample (SP-8) for disso lved and total metals. See Section 5.2.3 for a

description of the dissolved metals field blank sa mple collection at the effluent from the SBR.

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 SBR. After the tubing and filter were purged with 1.5-2 liters of sample, samplers collected

the following samples using a “clean box,” 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 2 liters of sample, samplers collec ted the following samples using a “cleanbox,” as

described in Section 3.1:

 Total metals by 200.8; and

 Total metals by 200.7.

# 3-9 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 2 liters of sample, sa mplers filled 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 the SBR (SP-3) on Day

3 of the sampling episode. In a ddition, for all analytes, ERG collected a duplicate sample of the

effluent from the SBR (SP-5) on Day 2 of the sampling episode.

3.2 List of Analytes and Sample Preservation

Samples collected at Dickerson were an alyzed for the following pollutants:

 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 3 

# :

— 

# 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,

3 

# In this report, EPA uses the terms “total meta ls” and “total recoverable metals” interchangeably.

# 3-10 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 preserve d with ammonium sulfate buffer solution and

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

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

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

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

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

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

3.3 Plant Operational Data

During the EPA sampling episode, Dickerson plant personnel provided 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:

 Plant Shutdown . Between 0134 and 0326 on Tuesday morning, which is prior to

the end of the day 1 24-hour sample co mpositing period, Dickerson shut down all

three generating units due to lack of elec tricity demand. The station continued to

operate the FGD wastewater treatment sy stem at reduced flow rates and EPA

continued to collect samples as planne d through the end of the sampling episode.

Additionally, the FGD system was shut down, but the plant occasionally blew

down from the scrubber and operated the dewatering equipment to allow EPA to

collect the influent samples. The samp ling team monitored flow rates during the

remainder of the sampling episode. The generating station and FGD scrubber did

not resume operation until after the end of the sampling episode.

 Clarifier Bed Turnover. In the afternoon of day 3 of the sampling episode, the

clarifier sludge bed overturned. The condition was identified by turbidity

measurements and wastewater treatment operators added polymer to counteract

the situation. At 1630 on August 25, the wast ewater treatment operator stated that

turbidity levels were still elevated, a lthough the polymer addition had reduced the

turbidity. The operator said that SP-2 day 1 and 2 samples should be unaffected,

but day 3 and 4 samples would be affected.

# 3-11  Preservation of hexavalent chromium: ERG planned to preserve the hexavalent

chromium samples to a pH between 9.3 and 9.7 S.U. using an ammonium sulfate

buffer solution; however, since the amm onium sulfate buffer solution was not

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

sulfate buffer solution, followed by as mu ch ammonium hydroxide as necessary

to reach the desired pH.

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

the influent to FGD wastewater treatm ent system (SP-1), the sampling team

dropped the total mercury volume 2 grab sample bottle inside the clean box. A

portion of the contents spilled into the clean box. Since th e majority of the sample

volume remained in the sample bottl e, additional sample volume was not

collected.

 Total mercury field blank at SP-2 (Day 2): On day 2 of sample collection at the

influent to the SBR (SP-2), the total mercury field blank volume 1 bottle was

taken out from under the plastic bag shr ouding the sampling tap prior to closing

the inner bag; however, the li d to the bottle was closed prior to the bottle leaving

the plastic bag shroud.

 Classicals compositor set up at SP-3 (Day 1): On day 1 of sample collection at

the effluent to the SBR (SP-3), the valve for the classical compositor was

inadvertently adjusted while collecting to tal mercury grab 1. The sampling team

readjusted the valve to its approximate position. The sampling team noted that

the classicals compositor collected 20 liters of sample during the day.

 Total cyanide QC sample at SP-3 (Day 3): On day 3 of sample collection at the

effluent to the SBR (SP-3), the sampling t eam collected the field test jar volume

prior to collecting the total cyanide QC sample. The “clean hands” sampler

changed her gloves prior to collect ing the total cyanide QC sample.

 Analytical method for zinc analyses: ERG had planned to analyze zinc using

EPA Method 200.8 with collision cell; how ever, after discussions with the

laboratory, EPA decided to analyz ed zinc using EPA Method 200.7.

# 3-12 Table 3-1. Sample Collection Information, Dickerson

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 08/23/10 1012 a 

# and 1146 b



# Influent to FGD Wa stewater Treatment

System – Day 2 Grab 08/24/10 1126 a 

# and 1305 b



# Influent to FGD Wa stewater Treatment

System – Day 3 Grab 08/25/10 1135 a 

# and 1311 b 

# SP-1

Influent to FGD Wa stewater Treatment

System – Day 4 Grab 08/26/10 1111 a 

# and 1300 b



# Composite 08/23/10

08/24/10 0901 c



# 1039 d 

# Influent to the SBR – Day 1

Grab 08/23/10

08/24/10 0913 e 

# , 1514 f 

# , and 2113 g



# 0314 h



# Composite 08/24/10

08/25/10 0900 c



# 1031 d 

# Influent to the SBR – Day 2

Grab 08/24/10

08/25/10 0911 e 

# , 1518 f 

# , and 2113 g



# 0312 h



# Composite 08/25/10

08/26/10 0900 c



# 1014 d 

# Influent to the SBR – Day 3

Grab 08/25/10

08/26/10 0912 e 

# , 1517 f 

# , and 2114 g



# 0314 h



# Composite 08/26/10

08/27/10 0900 c



# 0825 d 

# SP-2

Influent to the SBR – Day 4

Grab 08/26/10

08/27/10 0911 e 

# , 1516 f 

# , and 2107 g



# 0310 h



# Composite 08/23/10

08/24/10 0731 c



# 0955 d 

# Effluent from the SBR – Day 1

Grab 08/23/10

08/24/10 0745 e 

# , 1345 f 

# , and 1946 g



# 0152 h



# Composite 08/24/10

08/25/10 0730 c



# 0945 d 

# Effluent from the SBR – Day 2

Grab 08/24/10

08/25/10 0743 e 

# , 1346 f 

# , and 1948 g



# 0145 h



# Composite 08/25/10

08/26/10 0730 c



# 0939 d 

# Effluent from the SBR – Day 3

Grab 08/25/10

08/26/10 0744 e 

# , 1345 f 

# , and 1944 g



# 0143 h



# Composite 08/26/10

08/27/10 0731 c



# 0657 d 

# SP-3

Effluent from the SBR – Day 4

Grab 08/26/10

08/27/10 0743 e 

# , 1345 f 

# , and 1942 g



# 0142 h

# 3-13 Table 3-1. Sample Collection Information, Dickerson

Sampling

Point

Number Sampling Point Description Type of

Sample Sample

Collection Date Sample Collection

Time

Composite 08/25/10

08/26/10 0900 c



# 1014 d 

# SP-4 Duplicate of Influent to the SBR – Day 3

Grab 08/25/10

08/26/10 0914 e 

# , 1518 f 

# , and 2116 g



# 0315 h



# Composite 08/24/10

08/25/10 0730 c



# 0945 d 

# SP-5 Duplicate of Effluent from the SBR –

Day 2

Grab 08/24/10

08/25/10 0745 e 

# , 1348 f 

# , and 1950 g



# 0146 h



# SP-6 Influent to FGD Wastewater Treatment

System Field Blank Grab 08/23/10 0958 i 

# and 1139 j



# Composite 08/23/10

08/24/10 0823 k



# 1028 l 

# Influent to the SBR Field Blank – Day 1

Grab 08/23/10 0906 m



# Influent to the SBR Field Blank – Day 2 Grab 08/24/10 0907 m



# Influent to the SBR Field Blank – Day 3 Grab 08/25/10 0907 m 

# SP-7

Influent to the SBR Field Blank – Day 4 Grab 08/26/10 0906 m



# Composite 08/23/10

08/24/10 0650 k



# 0942 l 

# Effluent from the SBR Field Blank –

Day 1

Grab 08/23/10 0741 m



# Effluent from the SBR Field Blank –

Day 2 Grab 08/24/10 0739 m



# Effluent from the SBR Field Blank –

Day 3 Grab 08/25/10 0739 m 

# SP-8

Effluent from the SBR Field Blank –

Day 4 Grab 08/26/10 0738 m

a 

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

and dissolved mercury) and classicals (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 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 and dissolved mercury and total metals by 200.7 and total metals by 200.8 field

blank samples.

j 

# Start time for the collection of dissolved metals by 200.7 and dissolved metals by 200.8, and hexavalent chromium

field blank samples.

k 

# Filled 20L field blank carboy

l 

# Start time for the collection of total metals by 200.7 and total metals by 200.8 field blank samples and collection of

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

m



# Start time for the collection of total mercury field blank samples.

# 3-14Table 3-2. Sample Collection at Dickerson Steam StationSampling PointNumberSampling 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 the SBR 4+1QC 4+1QC 4+1QC4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-3 Effluent from the SBR4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-4 Duplicate of Influent to the SBR 1 1 1 1 1 1 1 1 1 1 1SP-5 Duplicate of Effluent from the SBR 1 1 1 1 1 1 1 1 1 11SP-6 Field Blank for Influent to FGD WastewaterTreatment System1 1 1 1 1 1SP-7 Field Blank for Influent to the SBR 1 1 1 1 4 1SP-8 Field Blank for Effluent from the SBR 1 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+2QC

# 3-15Table 3-3. Field Measurements, DickersonTemperature (°C)pHSamplingPointNumberSampling PointDescriptionDateTimeThermometerProbeMeteraStripsWasteStream FlowRate (GPM)NotesInfluent to FGDWastewater TreatmentSystem – Day 18/23/10102444396.617 82.1bNo detected sulfides or oxidants in total cyanidegrab.Influent to FGDWastewater TreatmentSystem – Day 28/24/10 1138333077.5 66.5bNo detected sulfides or oxidants in total cyanidegrab.Influent to FGDWastewater TreatmentSystem – Day 38/25/10 11493129.27.187 49.6bSamples collected were black. No detectedsulfides or oxidants in total cyanide grab.SP-1Influent to FGDWastewater TreatmentSystem – Day 48/26/10 11233330.17.017 60.2bNo detected sulfides or oxidants in total cyanidegrab.8/23/10 09153836.17.037.5 112.18/23/10 15183934.97.137 111.88/23/10 21203835.67.127 109.4Influent to SBR – Day 18/24/10 03203633.97.097 99.9No detected sulfides or oxidants in total cyanidegrab.8/24/10 091436336.987 96.68/24/10 15203632.56.927 96.08/24/10 21183431.36.956.5 87.1Influent to the SBR –Day 28/25/10 03203229.36.926.5 81.6No detected sulfides or oxidants in total cyanidegrab.8/25/10 09173128.56.97 81.18/25/10 15213128.56.97 83.98/25/10 21323128.76.876.5 78.6SP-2Influent to the SBR –Day 38/26/10 03193028.76.887.0 78.5Clarifier bed overturned and condition was notedby turbidity measurements. Samples collectedwere grey and Grab 3 had cooler temperaturesfrom previous sampling days. No detectedsulfides or oxidants in total cyanide grab.

# 3-16Table 3-3. Field Measurements, DickersonTemperature (°C)pHSamplingPointNumberSampling PointDescriptionDateTimeThermometerProbeMeteraStripsWasteStream FlowRate (GPM)Notes8/26/10 091330.5296.847 77.88/26/10 15183230.36.637 83.48/26/10 21133028.76.706.5 84.4SP-2 Influent to the SBR –Day 48/27/10 03203027.66.776.5 79.2The samples collected were mediumgrey/brownish. No detected sulfides or oxidantsin total cyanide grab.8/23/10 074831297.127 97.38/23/10 13493229.47.067 95.38/23/10 19503129.57.077 95.3Effluent from the SBR –Day 18/24/10 015831297.117 88.3The samples collected were clear. No detectedsulfides or oxidants in total cyanide grab.8/24/10 074830.527.97.017 86.38/24/10 13513028.57.047.5 88.18/24/10 20053028.37.017 88.1Effluent from the SBR –Day 28/25/10 01543027.37.077.5 86.7The samples collected were clear. No detectedsulfides or oxidants in total cyanide grab.8/25/10 07463027.87.017 86.38/25/10 13473028.37.017 66.68/25/10 194930.529.36.937.5 66.6Effluent from the SBR –Day 38/26/10 01483027.96.957.5 66.6No detected sulfides or oxidants in total cyanidegrab.8/26/10 07453027.56.917.5 66.88/26/10 13483129.36.927.5 67.88/26/10 19493129.96.957 61.7SP-3Effluent from the SBR –Day 48/27/10 01493026.86.946.5 61.7Water color was light yellow/almost clear. Nodetected sulfides or oxidants in total cyanidegrab.aThe pH meter was calibrated prior to the sampling episode and once every day during the sampling episode using prepackaged buffer solutions at pH 4.0, 7.0,and 10.0.bBased on average flow rate, in gpm, for the entire day of sampling. The flow rate does not represent the flow rate at the time of sample collection.

# 3-17 Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Dickerson

Sample Number Sample Point Sample Description

71841 SP-1, Day 1 Influent to FGD Wastewater Treatment System - Day 1

71842 SP-1, Day 2 Influent to FGD Wastewater Treatment System - Day 2

71843 SP-1, Day 3 Influent to FGD Wastewater Treatment System - Day 3

71844 SP-1, Day 4 Influent to FGD Wastewater Treatment System - Day 4

71845 SP-2, Day 1 Influent to SBR System - Day 1

71846 SP-2, Day 2 Influent to SBR System - Day 2

71847 SP-2, Day 3 Influent to SBR System - Day 3

71848 SP-2, Day 4 Influent to SBR System - Day 4

71849 SP-3, Day 1 Effluent from SBR System - Day 1

71850 SP-3, Day 2 Effluent from SBR System - Day 2

71851 SP-3, Day 3 Effluent from SBR System - Day 3

71852 SP-3, Day 4 Effluent from SBR System - Day 4

71853 SP-4, Day 3 Duplicate of Influent to SBR System - Day 3

71854 SP-5, Day 2 Duplicate of Effluent from SBR System - Day 2

71855 SP-6, Day 1 Influent to FGD Wastewater Treatment System Field Blank - Day 1

71856 SP-7, Day 1 Influent to SBR System Field Blank - Day 1

71857 SP-7, Day 2 Influent to SBR System Field Blank - Day 2

71858 SP-7, Day 3 Influent to SBR System Field Blank - Day 3

71859 SP-7, Day 4 Influent to SBR System Field Blank - Day 4

71860 SP-8, Day 1 Effluent from SBR System Field Blank - Day 1

71861 SP-8, Day 2 Effluent from SBR System Field Blank - Day 2

71862 SP-8, Day 3 Effluent from SBR System Field Blank - Day 3

71863 SP-8, Day 4 Effluent from SBR System Field Blank - Day 4

# 3-18 Table 3-5. Analytical Methods, Dickerson

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, nickel, selenium,

silver, thallium, and vanadium EPA 200.8 with collision cell 1



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

manganese, molybdenum, sodium, tin, titanium, and zinc EPA 200.7

1 

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

# 3-19 Table 3-6. Summary of Sample Container and Planned Preservation, Dickerson

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.

# 3-20 Table 3-7. Sample Preservation Summary, Dickerson

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

71841 Group II Volume 1 8/23/10 H 2 

# SO 4 

# 7 2 100

71841 Group II Volume 2 8/23/10 H 2 

# SO 4 

# 7 2 100

(NH 4 

# ) 2 

# SO 4



# Buffer 7 7.9 100 71841 Hexavalent Chromium 8/23/10

NH 4 

# OH 7.9 9.5 54

(NH 4 

# ) 2 

# SO 4



# Buffer 5.5 8.5 100 71855 Hexavalent Chromium –

Field Blank 8/23/10

NH 4 

# OH 8.5 9.5 29

71841 Total Cyanide 8/23/10 NaOH 7 10 30

71845 Total Cyanide 8/23/10 NaOH 7 10 15

71849 Total Cyanide 8/23/10 NaOH 7 10 20

71842 Group II Volume 1 8/24/10 H 2 

# SO 4 

# 7 2 100

71842 Group II Volume 2 8/24/10 H 2 

# SO 4 

# 7 2 100

71845 Group II Volume 1 8/24/10 H 2 

# SO 4 

# 7 1.5 100

71845 Group II Volume 2 8/24/10 H 2 

# SO 4 

# 7 1.5 100

71849 Group II Volume 1 8/24/10 H 2 

# SO 4 

# 7 1 100

71849 Group II Volume 2 8/24/10 H 2 

# SO 4 

# 7 1 100

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.1 100 71842 Hexavalent Chromium 8/24/10

NH 4 

# OH 8.1 9.5 55

(NH 4 

# ) 2 

# SO 4



# Buffer 7.5 8.3 100 71845 Hexavalent Chromium 8/24/10

NH 4 

# OH 8.3 9.5 30

(NH 4 

# ) 2 

# SO 4



# Buffer 7.5 8.3 100 71849 Hexavalent Chromium 8/24/10

NH 4 

# OH 8.3 9.5 23

(NH 4 

# ) 2 

# SO 4



# Buffer 6.5 8.5 100 71856 Hexavalent Chromium –

Field Blank 8/24/10

NH 4 

# OH 8.5 9.5 40

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.5 100 71860 Hexavalent Chromium –

Field Blank 8/24/10

NH 4 

# OH 8.5 9.5 40

71842 Total Cyanide 8/24/10 NaOH 7 >10 125

71846 Total Cyanide 8/24/10 NaOH 7 >10 20

71850 Total Cyanide 8/24/10 NaOH 7 >10 20

71854 Total Cyanide 8/24/10 NaOH 7 >10 20

71843 Group II Volume 1 8/25/10 H 2 

# SO 4 

# 7 2 100

71843 Group II Volume 2 8/25/10 H 2 

# SO 4 

# 7 2 100

71846 Group II Volume 1 8/25/10 H 2 

# SO 4 

# 7 2 100

# 3-21 Table 3-7. Sample Preservation Summary, Dickerson

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

71846 Group II Volume 2 8/25/10 H 2 

# SO 4 

# 7 2 100

71850 Group II Volume 1 8/25/10 H 2 

# SO 4 

# 7 2 100

71850 Group II Volume 2 8/25/10 H 2 

# SO 4 

# 7 2 100

71854 Group II Volume 1 8/25/10 H 2 

# SO 4 

# 7 2 100

71854 Group II Volume 2 8/25/10 H 2 

# SO 4 

# 7 2 100

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.5 100 71843 Hexavalent Chromium 8/25/10

NH 4 

# OH 8.5 9.5 35

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.1 100 71846 Hexavalent Chromium 8/25/10

NH 4 

# OH 8.1 9.5 35

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.1 100 71850 Hexavalent Chromium 8/25/10

NH 4 

# OH 8.1 9.5 40

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.1 100 71854 Hexavalent Chromium 8/25/10

NH 4 

# OH 8.1 9.5 35

71843 Total Cyanide 8/25/10 NaOH 7 10 150

71847 Total Cyanide 8/25/10 NaOH 6.5 10 20

71851 Total Cyanide 8/25/10 NaOH 7.5 10 20

71851 Total Cyanide - QC 8/25/10 NaOH 7.5 10 20

71853 Total Cyanide 8/25/10 NaOH 6.5 10 20

71844 Group II Volume 1 8/26/10 H 2 

# SO 4 

# 7 2 100

71844 Group II Volume 2 8/26/10 H 2 

# SO 4 

# 7 2 100

71847 Group II Volume 1 8/26/10 H 2 

# SO 4 

# 7 1 100

71847 Group II Volume 2 8/26/10 H 2 

# SO 4 

# 7 1 100

71851 Group II Volume 1 8/26/10 H 2 

# SO 4 

# 7 2 100

71851 Group II Volume 2 8/26/10 H 2 

# SO 4 

# 7 2 100

71851 Group II Volume 1 - QC 8/26/10 H 2 

# SO 4 

# 7 2 100

71851 Group II Volume 2 - QC 8/26/10 H 2 

# SO 4 

# 7 2 100

71853 Group II Volume 1 8/26/10 H 2 

# SO 4 

# 7 1 100

71853 Group II Volume 2 8/26/10 H 2 

# SO 4 

# 7 1 100

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.1 100 71844 Hexavalent Chromium 8/26/10

NH 4 

# OH 8.1 9.5 45

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.3 100 71847 Hexavalent Chromium 8/26/10

NH 4 

# OH 8.3 9.5 32

# 3-22 Table 3-7. Sample Preservation Summary, Dickerson

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.3 100 71851 Hexavalent Chromium 8/26/10

NH 4 

# OH 8.3 9.5 20

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.3 100 71853 Hexavalent Chromium 8/26/10

NH 4 

# OH 8.3 9.5 30

71844 Total Cyanide 8/26/10 NaOH 7 10 200

71848 Total Cyanide 8/26/10 NaOH 6.5 >10 20

71848 Total Cyanide - QC 8/26/10 NaOH 6.5 >10 20

71852 Total Cyanide 8/26/10 NaOH 7.5 >10 20

71848 Group II Volume 1 8/27/10 H 2 

# SO 4 

# 7 2 100

71848 Group II Volume 2 8/27/10 H 2 

# SO 4 

# 7 2 120

71848 Group II Volume 1 - QC 8/27/10 H 2 

# SO 4 

# 7 2 100

71848 Group II Volume 2 - QC 8/27/10 H 2 

# SO 4 

# 7 2 100

71852 Group II Volume 1 8/27/10 H 2 

# SO 4 

# 7 2 100

71852 Group II Volume 2 8/27/10 H 2 

# SO 4 

# 7 2 100

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.3 100 71848 Hexavalent Chromium 8/27/10

NH 4 

# OH 8.3 9.5 25

(NH 4 

# ) 2 

# SO 4



# Buffer 7 8.3 100 71852 Hexavalent Chromium 8/27/10

NH 4 

# OH 8.3 9.5 22

# 3-23 Table 3-8. Generating Unit Operating Charact eristics during Sample Collection, Dickerson

Unit ID Boiler Type Capacity

(MW) Electricity Production

(MW)

(or Percent Capacity %) a 

# SCR

(No, On, Off) Particulate Control System

(HS/CS ESP, or BH)

1 Coal 191 20% Off ESP/BH

2 Coal 191 20% Off ESP/BH

3 Coal 191 20% Off ESP/BH

a 

# The percent capacity was measured on a daily basi s from midnight on August 24 to midnight on August 27.

ESP/BH 

# – Electrostatic precipitator and baghouse.

# 3-24Table 3-9. FGD Scrubber System Operating Characteristics, DickersonUnit IDWet FGDSystem (Yes/No)Type ofScrubberForcedOxidation(Yes/No)SorbentAdditives (DBA,formic acid, etc.)FGD Make-upWater SourceSO2RemovalPercentageType of SolidsSeparation1, 2, 3 Yes TrayYes Limestone NoneIndustrial WWTP– River water96.21% Vacuum FilterNote: One FGD system services all three generating units.

# 3-25 Table 3-10. Coal Usage during Sample Collection, Dickerson

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

(%)

1 Fed 2 a 

# /Brooks

Run 900 b 

# PA

WV 5.1

1.7 0.07

0.12

2 Fed 2 a 

# /Brooks

Run 825 PA

WV 5.1

1.7 0.07

0.12 1

3 Fed 2 a 

# /Brooks

Run 704 PA

WV 5.1

1.7 0.07

0.12

1 Fed 2 a 

# /Storage 655 PA

WV 4.9

1.7 0.07

0.102

2 Fed 2 a 

# 833 PA 4.9 0.07 2

3 Fed 2 a 

# 715 PA 4.9 0.07

1 NA c 

# NA c 

# NA c 

# NA c 

# NA c



# 2 NA c 

# NA c 

# NA c 

# NA c 

# NA c 

# 3

3 NA c 

# NA c 

# NA c 

# NA c 

# NA c



# 1 NA c 

# NA c 

# NA c 

# NA c 

# NA c



# 2 NA c 

# NA c 

# NA c 

# NA c 

# NA c 

# 4

3 NA c 

# NA c 

# NA c 

# NA c 

# NA c



# a 

# Fed 2 coal is sourced from the Federal Mining Complex in Northern West Virginia from a single mine, Federal 2.

b 

# Estimated value.

c 

# All three generating units were shut down on days 3 and 4 due to low electricity demand.



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

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 1, 2, 3 896 10.3 hrs 19-21% Note 1 85%

2 1 1, 2, 3 696 2 hrs 19-21% Note 1 85%

3 1 1, 2, 3 880 2.3 hrs 18.9-19.2% Note 1 85%

4 1 1, 2, 3 884 2.6 hrs 18.9-19.0% Note 1 85%



# Note 1: Once the bleed stream from the absorber starts, it may take up to 30-minutes for gypsum slurry to flow to

the slurry tank. At that point it takes up to 1-minute to dewater depending on the slurry density.

# 3-26Table 3-12. FGD Wastewater Treatment System Operation Information, DickersonChemical UsageDay of SamplingScrubber PurgeFlow Rate(gpd)Lime(tons/day)Ferric Chloride(liters/day)Organosulfide(liters/day)aPolymer(liters/day)Hydrochloric Acid(liters/day)1 118,2177.3(8.70 S.U.)115(47 ppm)NA19.5(20 ppm)820(6.9 S.U.)2 95,77515.5(8.70 S.U.)110(47 ppm)NA19.3(20 ppm)670(6.9 S.U.)3 71,39415.1(8.70 S.U.)108(47 ppm)NA18(20 ppm)360(6.9 S.U.)4 86,68915.1(8.70 S.U.)107(47 ppm)NA17.5(20 ppm)220(6.9 S.U.)aDickerson was not adding organosulfide to the wastewater treatment system during the sampling episode.Note: Values in parentheses are the set points for the system.

# 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 SBR 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 heated bromine monochlorid e digestion (i.e., sealed bottles

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

system.

For the total and dissolved mercury 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 for all samples collected at Dickerson,

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 SBR (SP-2) and the effl uent from the SBR (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 SBR), a duplic ate sample was collected on Day 3 of the

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

and the duplicate sample results. Table 5-2 presen ts the analytical result s for the original and

duplicate results and the calculated relative perc ent difference (RPD). For Table 4-3 (Effluent

from the SBR), a duplicate sample was collected on Day 2 of the sampling episode. The Day 2

results presented in Table 4-3 represent the av erage of the original and the duplicate sample

results. Table 5-3 presents the analytical resu lts 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 SBR ( SP-2), and the effluent

from the SBR (SP-3). Table 4-5 presents the 4-day average results for all metal analytes,

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

(SP-1), the influent to the SBR (SP-2), and th e effluent from the SBR (SP-3). The results

presented in this report are not paired results, meaning that the sample collection across the

# 4-3 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 SBR (SP- 2), the effluent from

the SBR (SP-3), the duplicate of the influent to th e SBR (SP-4), and the duplicate of the effluent

from the SBR (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).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 total dissolved solid result seems questionable based on the results from the other sampling days. If the Day 1 total dissolved solid result wasincluded in the calculated average,the 4-day average would be 52,000 mg/L.B – Analyte was found in the blank and sample.C – pH upon receipt was less than 10 S.U.D – Laboratory duplicate RPD greater than method-specified criteria.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Table 4-1. Influent to FGD Wastewater Treatment System, DickersonInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmonia mg/L 350.1 5.90 5.40 4.00 4.90 5.05Nitrate Nitrite as N mg/L 353.2 67.0 67.0 47.0 62.0 60.8Nitrogen, Total Kjeldahl mg/L 351.2 130 L 23.0 B 12.0 B 21.0 B 46.5Biochemical Oxygen Demand mg/L 5210B NQ (2.50) 3.70 6.30 8.00 < 4.81Chemical Oxygen Demand mg/L 410.4 110 150 110 150 130Chloride mg/L 300.0 9,200 8,400 5,700 7,400 7,680Sulfate mg/L 300.0 1,800 1,800 1,700 1,800 1,780Cyanide, Total mg/L 4500 CN E 1.20 C 1.10 B 0.740 0.760 B 0.950Total Dissolved Solids mg/L 2540C 170,000** B 15,000 12,000 11,000 D 12,700**Total Suspended Solids mg/L 2540D 3,900 11,000 3,900 3,700 5,630Phosphorus, Total mg/L 365.1 3.70 NQ (0.0500) 3.20 4.30 < 2.81Total MetalsAluminum ug/L 200.7 130,000 110,000 91,000 110,000 110,000Antimony ug/L 200.8 23.0 18.0 15.0 19.0 18.8Arsenic ug/L 200.8 280 220 190 230 230Barium ug/L 200.7 700 720 590 790 700Beryllium ug/L 200.7 15.0 12.0 10.0 13.0 12.5Boron ug/L 200.7 220,000 B 200,000 B 150,000 B 200,000 B 193,000Cadmium ug/L 200.8 31.0 27.0 21.0 27.0 26.5Calcium ug/L 200.7 2,900,000 2,700,000 2,600,000 2,600,000 2,700,000Chromium ug/L 200.8 690 ^ 570 ^ 450 ^ 570 ^ 570Cobalt ug/L 200.7 130 120 99.0 120 117Copper ug/L 200.8 660 530 440 540 543Iron ug/L 200.7 180,000 160,000 130,000 160,000 158,000

# 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).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 total dissolved solid result seems questionable based on the results from the other sampling days. If the Day 1 total dissolved solid result wasincluded in the calculated average,the 4-day average would be 52,000 mg/L.B – Analyte was found in the blank and sample.C – pH upon receipt was less than 10 S.U.D – Laboratory duplicate RPD greater than method-specified criteria.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Table 4-1. Influent to FGD Wastewater Treatment System, DickersonInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageLead ug/L 200.8 220 170 140 180 178Magnesium ug/L 200.7 1,700,000 1,600,000 1,200,000 1,600,000 1,530,000Manganese ug/L 200.7 11,000 9,800 7,800 9,900 9,630Mercury ng/L 1631E 8,550 4,830 4,030 5,630 5,760Molybdenum ug/L 200.7 520 440 360 440 440Nickel ug/L 200.8 660 580 450 570 565Selenium ug/L 200.8 1,500 1,200 920 1,200 1,210Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) ND (2.00)Sodium ug/L 200.7 200,000 190,000 160,000 190,000 185,000Thallium ug/L 200.8 NQ (2.00) NQ (2.00) 2.90 NQ (2.00) < 1.48Tin ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200) NQ (200)Titanium ug/L 200.7 6,200 5,400 4,500 5,600 5,430Vanadium ug/L 200.8 580 470 390 490 483Zinc ug/L 200.7 2,500 2,000 1,500 2,000 2,000Dissolved MetalsAluminum ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200) NQ (200)Antimony ug/L 200.8 3.70 3.80 2.80 3.50 3.45Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)Barium ug/L 200.7 250 210 130 140 183Beryllium ug/L 200.7 ND (2.00) ND (2.00)ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 210,000 B 190,000 B 150,000 B 200,000 B 188,000Cadmium ug/L 200.8 28.0 24.0 17.0 22.0 22.8Calcium ug/L 200.7 2,300,000 2,100,000 1,600,000 2,100,000 2,030,000Chromium ug/L 200.8 ND (8.00) ^ ND (8.00) ^ ND (8.00) ^ ND (8.00) ^ ND (8.00)Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10.0) ND (10.0)

# 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).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 total dissolved solid result seems questionable based on the results from the other sampling days. If the Day 1 total dissolved solid result wasincluded in the calculated average,the 4-day average would be 52,000 mg/L.B – Analyte was found in the blank and sample.C – pH upon receipt was less than 10 S.U.D – Laboratory duplicate RPD greater than method-specified criteria.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.Table 4-1. Influent to FGD Wastewater Treatment System, DickersonInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageCobalt ug/L 200.7 81.0 77.0 58.0 71.0 71.8Copper ug/L 200.8 26.0 12.0 8.30 9.20 13.9Iron ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200) NQ (200)Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) ND (2.00)Magnesium ug/L 200.7 1,600,000 1,500,000 1,200,000 1,500,000 1,450,000Manganese ug/L 200.7 11,000 10,000 8,100 10,000 9,780Mercury ng/L 1631E 177 49.7 193 24.4 111Molybdenum ug/L 200.7 250 210 180 220 215Nickel ug/L 200.8 460 420 310 380 393Selenium ug/L 200.8 150 210 150 180 173Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) ND (2.00)Sodium ug/L 200.7 210,000 200,000 160,000 200,000 193,000Thallium ug/L 200.8 2.40 NQ (2.00) NQ (2.00) NQ (2.00) < 1.35Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) ND (20.0)Vanadium ug/L 200.8 NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0)Zinc ug/L 200.7 1,300 700 370 450 705

# 4-7Note: 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.< - 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 3 influent to the SBR systemwas detected at a concentration of 42.8 ng/L, which seems like an erroneous result compared to the Day 3 duplicate sampleconcentration and the other three sample days. For presentation purposes in this table, the original sample result has been removed from the average of the Day 3 result and fromthe 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.Table 4-2. Influent tothe SBR System, DickersonInfluent to the SBR System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmoniamg/L350.14.404.103.103.203.70Nitrate Nitrite as Nmg/L353.248.043.038.037.041.5Nitrogen, Total Kjeldahlmg/L351.210.0BNQ (10.0)B10.5NQ (10.0)B< 7.63Biochemical Oxygen Demandmg/L5210B4.003.00NQ (2.50)2.80< 2.76Chemical Oxygen Demandmg/L410.416081.0135130F127Chloridemg/L300.08,6007,8006,7006,7007,450Sulfatemg/L300.01,8001,6001,7501,7001,710Cyanide, Totalmg/L4500 CN E0.220B0.130B0.05200.0500B0.113Total Dissolved Solidsmg/L2540C14,00014,00012,50012,00013,100Total Suspended Solidsmg/L2540D38.037.070.542.046.9Phosphorus, Totalmg/L365.1NQ (0.0500)NQ (0.0500)< 0.0375NQ (0.0500)< 0.0281Total MetalsAluminumug/L200.76004501,4501,5001,000Antimonyug/L200.85.504.404.603.904.60Arsenicug/L200.8NQ (4.00)NQ (4.00)4.955.50< 3.61Bariumug/L200.7300260250230260Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7170,000B170,000B160,000150,000B,4163,000Cadmiumug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)

# 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.< - 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 3 influent to the SBR systemwas detected at a concentration of 42.8 ng/L, which seems like an erroneous result compared to the Day 3 duplicate sampleconcentration and the other three sample days. For presentation purposes in this table, the original sample result has been removed from the average of the Day 3 result and fromthe 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.Table 4-2. Influent tothe SBR System, DickersonInfluent to the SBR System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageCalciumug/L200.72,600,0002,400,0002,250,0002,100,00042,340,000Chromiumug/L200.8NQ (8.00)^NQ (8.00)^NQ (8.00)NQ (8.00)^NQ (8.00)Cobaltug/L200.7NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Copperug/L200.843.046.055.598.060.6Ironug/L200.77405701,7001,8001,200Leadug/L200.82.70NQ (2.00)3.655.00< 3.09Magnesiumug/L200.71,200,0001,200,0001,200,0001,100,00041,180,000Manganeseug/L200.790.0110265300191Mercuryng/L1631E222200446416321Molybdenumug/L200.7300260245230259Nickelug/L200.860.051.050.550.052.9Seleniumug/L200.8130110105100111Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)FND (2.00)Sodiumug/L200.7200,000200,000185,000180,000191,000Thalliumug/L200.8NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)Tinug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Titaniumug/L200.746.035.099.510070.1Vanadiumug/L200.8NQ (10.0)NQ (10.0)10.511.0< 7.88Zincug/L200.7NQ (40.0)NQ (40.0)53.065.0< 39.5Dissolved Metals

# 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.< - 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 3 influent to the SBR systemwas detected at a concentration of 42.8 ng/L, which seems like an erroneous result compared to the Day 3 duplicate sampleconcentration and the other three sample days. For presentation purposes in this table, the original sample result has been removed from the average of the Day 3 result and fromthe 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.Table 4-2. Influent tothe SBR System, DickersonInfluent to the SBR System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageAluminumug/L200.7ND (200)NQ (200)NQ (200)NQ (200)NQ (200)Antimonyug/L200.84.804.803.604.104.33Arsenicug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7280250190170223Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7180,000B170,000B160,000160,000B,4168,000Cadmiumug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Calciumug/L200.72,600,0002,500,0002,300,0002,200,00042,400,000Chromiumug/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/L200.7NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Copperug/L200.840.045.045.069.049.8Ironug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Leadug/L200.8NQ (2.00)NQ (2.00)ND (2.00)ND (2.00)NQ (2.00)Magnesiumug/L200.71,200,0001,300,0001,200,0001,200,00041,230,000Manganeseug/L200.770.0100210250158Mercuryng/L1631E5.976.785.56**5.816.03**Molybdenumug/L200.7290260240230255Nickelug/L200.854.051.049.550.051.1Seleniumug/L200.812011097.095.0106

# 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.< - 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 3 influent to the SBR systemwas detected at a concentration of 42.8 ng/L, which seems like an erroneous result compared to the Day 3 duplicate sampleconcentration and the other three sample days. For presentation purposes in this table, the original sample result has been removed from the average of the Day 3 result and fromthe 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.Table 4-2. Influent tothe SBR System, DickersonInfluent to the SBR System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageSilverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)FND (2.00)Sodiumug/L200.7190,000190,000180,000180,000185,000Thalliumug/L200.8NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)Tinug/L200.7ND (200)ND (200)ND (200)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/L200.7NQ (40.0)NQ (40.0)NQ (40.0)45.0< 26.3

# 4-11Note: 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.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.Table 4-3. Effluent fromthe SBR System, DickersonEffluent from the SBR System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmonia mg/L 350.1 NQ (1.00) NQ (1.00) NQ (1.00) NQ (1.00) NQ (1.00)Nitrate Nitrite as N mg/L 353.2 NQ (0.100) 0.110 0.140 0.150 < 0.113Nitrogen, Total Kjeldahl mg/L 351.2 13.0 B 13.0 13.0 B,4 13.0 B 13.0Biochemical Oxygen Demand mg/L 5210B 3.90 4.70 5.70 4.50 4.70Chemical Oxygen Demand mg/L 410.4 150 185 140 F 84.0 140Chloride mg/L 300.0 9,700 8,000 7,800 7,600 8,280Sulfate mg/L 300.0 1,800 1,700 1,700 1,700 1,730Cyanide, Total mg/L 4500 CN E 0.100 B NQ (0.0100) NQ (0.0100) B,F NQ (0.0100) B < 0.0288Total Dissolved Solids mg/L 2540C 15,00013,500 14,000 13,000 13,900Total Suspended Solids mg/L 2540D 8.80 14.0 8.00 14.0 11.2Phosphorus, Total mg/L 365.1 NQ (0.0500) NQ (0.0500) NQ (0.0500) NQ (0.0500) NQ (0.0500)Total MetalsAluminum ug/L 200.7 660 710 870 920 790Antimony ug/L 200.8 5.00 5.50 5.10 4.60 5.05Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)Barium ug/L 200.7 310 305 280 230 281Beryllium ug/L 200.7 ND (2.00) ND (2.00)ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 180,000 B 185,000 180,000 B,4 170,000 B 179,000Cadmium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)Calcium ug/L 200.7 2,700,000 2,750,000 2,700,000 4 2,400,000 2,640,000Chromium ug/L 200.8 ND (8.00) ^ ND (8.00) ND (8.00) ^ ND (8.00) ^ ND (8.00)Cobalt ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0)Copper ug/L 200.8 21.0 22.0 21.0 32.0 24.0Iron ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200) NQ (200)Lead ug/L 200.8 NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.00) NQ (2.00)Magnesium ug/L 200.7 1,300,000 1,250,000 1,300,000 4 1,200,000 1,260,000

# 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.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.Table 4-3. Effluent fromthe SBR System, DickersonEffluent from the SBR System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageManganese ug/L 200.7 81.0 84.5 100 160 106Mercury ng/L 1631E 7.27 9.65 10.9 8.59 9.10Molybdenum ug/L 200.7 320 315 300 260 299Nickel ug/L 200.8 78.0 64.0 58.0 50.0 62.5Selenium ug/L 200.8 110 110 110 100 108Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) F ND (2.00) ND (2.00)Sodium ug/L 200.7 220,000 225,000 230,000 4 220,000 224,000Thallium ug/L 200.8 NQ (2.00) NQ (2.00)NQ (2.00) NQ (2.00) NQ (2.00)Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0)Vanadium ug/L 200.8 NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0)Zinc ug/L 200.7 43.0 42.5 NQ (40.0) NQ (40.0) < 31.4Dissolved MetalsAluminum ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200) NQ (200)Antimony ug/L 200.8 5.70 5.10 4.50 4.80 5.03Arsenic ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)Barium ug/L 200.7 320 300 270 230 280Beryllium ug/L 200.7 ND (2.00) ND (2.00)ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 190,000 B 180,000 180,000 B,4 170,000 B 180,000Cadmium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)Calcium ug/L 200.7 2,800,000 2,750,000 2,700,000 4 2,400,000 2,660,000Chromium ug/L 200.8 ND (8.00) ^ ND (8.00) ND (8.00) ^ ND (8.00) ^ ND (8.00)Chromium (VI) ug/L 218.6 ND (10.0) ND (10.0) ND (10.0) ND (10.0) ND (10.0)Cobalt ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0)Copper ug/L 200.8 16.0 17.5 13.0 20.0 16.6Iron ug/L 200.7 NQ (200) NQ (200) NQ (200) NQ (200) NQ (200)Lead ug/L 200.8 NQ (2.00) NQ (2.00) ND (2.00) ND (2.00) NQ (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.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.Table 4-3. Effluent fromthe SBR System, DickersonEffluent from the SBR System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageMagnesium ug/L 200.7 1,300,000 1,300,000 1,300,000 4 1,200,000 1,280,000Manganese ug/L 200.7 85.0 85.0 100 160 108Mercury ng/L 1631E 1.69 4.28 8.61 F 1.21 3.95Molybdenum ug/L 200.7 330 315 290 260 299Nickel ug/L 200.8 78.0 66.5 57.0 51.0 63.1Selenium ug/L 200.8 100 105 98.0 98.0 100Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) F ND (2.00) ND (2.00)Sodium ug/L 200.7 220,000 220,000 220,000 4 210,000 218,000Thallium ug/L 200.8 NQ (2.00) NQ (2.00)NQ (2.00) NQ (2.00) NQ (2.00)Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0) NQ (20.0)Vanadium ug/L 200.8 NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0) NQ (10.0)Zinc ug/L 200.7 43.0 < 31.0 NQ (40.0) NQ (40.0) < 28.5

# 4-14< - 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 wasincluded from the calculated average, the 4-day averagewould be 52,000 mg/L.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 4-4. Classical Pollutants 4-Day Average DataSummary for FGD Wastewater Treatment System, DickersonAnalyteUnitsMethodInfluent to FGDWastewaterTreatment System (SP-1)4-Day AverageInfluent toSBRSystem (SP-2)4-Day AverageEffluent fromSBRSystem (SP-3)4-Day AverageClassicalsAmmoniamg/L350.15.053.70NQ (1.00)Nitrate Nitrite as Nmg/L353.260.841.5< 0.113Nitrogen, Total Kjeldahlmg/L351.246.5< 7.6313.0Biochemical Oxygen Demandmg/L5210B< 4.81< 2.764.70Chemical Oxygen Demandmg/L410.4130127140Chloridemg/L300.07,6807,4508,280Sulfatemg/L300.01,7801,7101,730Cyanide, Totalmg/L4500 CN E0.9500.113< 0.0288Total Dissolved Solidsmg/L2540C12,700*13,10013,900Total Suspended Solidsmg/L2540D5,63046.911.2Phosphorus, Totalmg/L365.1< 2.81< 0.0281NQ (0.0500)

# 4-15< - 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 presented has been revised to exclude the Day 3 original sample result of 42.8 ng/L. EPA determined that this is erroneous based on the duplicateresult of 5.56 ng/L and 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 Summary for FGD Wastewater Treatment System, DickersonInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageInfluent toSBRSystem (SP-2)4-Day AverageEffluent fromSBRSystem (SP-3)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTotalDissolvedMetalsAluminumug/L200.7110,000NQ (200)1,000NQ (200)790NQ (200)Antimonyug/L200.818.83.454.604.335.055.03Arsenicug/L200.8230NQ (4.00)< 3.61NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7700183260223281280Berylliumug/L200.712.5ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7193,000188,000163,000168,000179,000180,000Cadmiumug/L200.826.522.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Calciumug/L200.72,700,0002,030,0002,340,0002,400,0002,640,0002,660,000Chromiumug/L200.8570ND (8.00)NQ (8.00)ND (8.00)ND (8.00)ND (8.00)Chromium (VI)ug/L218.6NAND (10.0)NAND (10.0)NAND (10.0)Cobaltug/L200.711771.8NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Copperug/L200.854313.960.649.824.016.6Ironug/L200.7158,000NQ (200)1,200ND (200)NQ (200)NQ (200)Leadug/L200.8178ND (2.00)< 3.09NQ (2.00)NQ (2.00)NQ (2.00)Magnesiumug/L200.71,530,0001,450,0001,180,0001,230,0001,260,0001,280,000Manganeseug/L200.79,6309,780191158106108Mercuryng/L1631E5,7601113216.03*9.103.95Molybdenumug/L200.7440215259255299299Nickelug/L200.856539352.951.162.563.1Seleniumug/L200.81,210173111106108100Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.7185,000193,000191,000185,000224,000218,000Thalliumug/L200.8< 1.48< 1.35NQ (2.00)NQ (2.00)NQ (2.00)NQ (2.00)

# 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).* - The 4-day average result presented has been revised to exclude the Day 3 original sample result of 42.8 ng/L. EPA determined that this is erroneous based on the duplicateresult of 5.56 ng/L and 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 Summary for FGD Wastewater Treatment System, DickersonInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageInfluent toSBRSystem (SP-2)4-Day AverageEffluent fromSBRSystem (SP-3)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTotalDissolvedTinug/L200.7NQ (200)ND (200)ND (200)ND (200)ND (200)ND (200)Titaniumug/L200.75,430ND (20.0)70.1NQ (20.0)NQ (20.0)NQ (20.0)Vanadiumug/L200.8483NQ (10.0)< 7.88NQ (10.0)NQ (10.0)NQ (10.0)Zincug/L200.72,000705< 39.5< 26.3< 31.4< 28.5

# 5-1 5. D ATA 

# Q UALITY



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

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 Sectio n 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 4



# .

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 0.5 liters of blank water. The ASTM Type 1 water flowed through the funnel,

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

samples as “true” split samples with Dickers on’s representative, usi ng the same procedure

discussed in the sample collec tion description (Section 3.1).

4 

# 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 bl ank for the dissolved mercury sample. Mercury was not

detected above the method detection limit (0.24 ng/L) in the filtration blanks perfor med for any of the sampling

days.

# 5-3 The dissolved metals by 200.8, dissolved metals by 200.7, and dissolved hexavalent

chromium field blank samples for the influent to the FGD 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 90 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 with 1 liter of blank water. The samp le 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 samp les as “true” split samples with Dickerson’s

representative, using the same procedure discusse d in the sample collect ion description (Section

3.1).

The total mercury field blank sample for th e influent to the SBR (SP-7) and for the

effluent from the SBR (SP-8) we re collected by shrouding one of th e 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 bottl es 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 SBR (SP-7) and the effluent from the SBR (SP-8) were collected by filling a 20-

liter composite container with ASTM Type 1 wate r. The same T-splitter tubing used to fill the

metals composite container at each point was us ed with a pump to fill the 20-liter field blank

composite container. Prior to attaching one end of the tubing to the sample tap, it was placed

directly into the container holding ASTM Type 1 water. The other end of the tubing was

attached to the vented cap on top of the 20-l iter field blank composite container. After enough

volume was pumped into the 20-liter field bla nk composite container, the vented cap was

replaced with a closed cap and the container wa s placed on ice in a covered plastic trash can.

The vented cap used for the field blank collectio n 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 fi eld blank samples as “true” split samples with

Dickerson’s representative, us ing the same procedure discus sed 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.

Table 5-1 presents the field blank analytical results fo r SP-6 through SP-8. Only those

analytes that were detected in the field blank samples at levels above the quantitation limit are

included in the table. Results are rounded to three significant digits . Appendix Tables A-16

through A-24 present all the analytical results for the field blanks from each of the sampling

points, including all qualified results and all results that were measured above the method

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

# 5-4 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 RPD be tween 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

SBR (SP-4) and the effluent from the SBR ( SP-5) during day 3 and day 2 of the sampling

episode, respectively. The duplicate samples were an alyzed for all analytes. Tables 5-2 and 5-3

present the analytical results and the RPD fo r SP-4 and SP-5, respectively. Results are rounded

to three significant digits. Appe ndix Tables A-7 and A-13 present a ll the analytical results for the

influent to the SBR (SP-2) Day 3 and the duplicat e of the influent to the SBR (SP-4) sample

analyses, including all qualified results and all results that were measured above the method

detection limit, but below the quantitation limit (i .e., J-values). Appendix Tables A-10 and A-14

present all the analytical results for the effluent from the SBR (SP-3) Day 2 and the duplicate of

the effluent from the SBR (SP-5) sample analyses, including all qualified results and all results

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

# 5-5Table 5-1. Field Blank Analytical Results, DickersonAnalyteSample DescriptionMethodUnitsConcentrationMercuryInfluent to FGD Wastewater Treatment System Field Blank - Day 11631Eng/L0.730< - 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 dissolved mercury original sample result seems erroneousbased on the Day 3 duplicate sample concentration and the other three sample days. The original sample resultwas excluded from the presentation of the Day 3 average result inTable 4-2. Additionally, 5.56ng/L (instead of 24.2 ng/L) was used in the calculation of the 4-day average resultpresented in Table 4-2 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 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.B – Analyte was found in the blank and sample.



# 5-6 5-6Table 5-2. Field Duplicate Results –Influent to SBR System, DickersonAnalyteMethodUnitsOriginal Influentto SBRSystem, Day 3Concentration (SP-2)Duplicate Influentto SBRSystemConcentration (SP-4)AverageResultRelativePercentDifferenceClassicalsAmmonia 350.1 mg/L 2.90 3.30 3.10 12.9Nitrate Nitrite as N 353.2 mg/L 38.0 38.0 38.0 0.00Nitrogen, Total Kjeldahl 351.2 mg/L 10.0 B 11.0 B 10.5 9.52Biochemical Oxygen Demand 5210B mg/L NQ (2.50) NQ (2.50) NQ (2.50) NCChemical Oxygen Demand 410.4 mg/L 160 110 135 37.0Chloride 300.0 mg/L 6,700 6,700 6,700 0.00Sulfate 300.0 mg/L 1,700 1,800 1,750 5.71Cyanide, Total 4500 CN E mg/L 0.0450 B 0.0590 B 0.0520 26.9Total Dissolved Solids 2540C mg/L 12,000 13,000 12,500 8.00Total Suspended Solids 2540D mg/L 42.0 99.0 70.5 80.9Phosphorus, Total 365.1 mg/L 0.0500 NQ (0.0500) < 0.0375 NCTotal MetalsAluminum 200.7 ug/L 1,400 1,500 1,450 6.90Antimony 200.8 ug/L 4.50 4.70 4.60 4.35Arsenic 200.8 ug/L 4.50 5.40 4.95 18.2Barium 200.7 ug/L 240 260 250 8.00Beryllium 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 NQ (4.00) NQ (4.00) NQ (4.00) NCCalcium 200.7 ug/L 2,200,000 2,300,000 2,250,000 4.44Chromium 200.8 ug/L NQ (8.00) ^ NQ (8.00) ^ NQ (8.00) NCCobalt 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.0) NCCopper 200.8 ug/L 54.0 57.0 55.5 5.41Iron 200.7 ug/L 1,700 1,700 1,700 0.00< - 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 dissolved mercury original sample result seems erroneousbased on the Day 3 duplicate sample concentration and the other three sample days. The original sample resultwas excluded from the presentation of the Day 3 average result inTable 4-2. Additionally, 5.56ng/L (instead of 24.2 ng/L) was used in the calculation of the 4-day average resultpresented in Table 4-2 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 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.B – Analyte was found in the blank and sample.



# 5-7 5-7Table 5-2. Field Duplicate Results –Influent to SBR System, DickersonAnalyteMethodUnitsOriginal Influentto SBRSystem, Day 3Concentration (SP-2)Duplicate Influentto SBRSystemConcentration (SP-4)AverageResultRelativePercentDifferenceLead 200.8 ug/L 3.50 3.80 3.65 8.22Magnesium 200.7 ug/L 1,200,000 1,200,000 1,200,000 0.00Manganese 200.7 ug/L 260 270 265 3.77Mercury 1631E ng/L 454 437 446 3.82Molybdenum 200.7 ug/L 240 250 245 4.08Nickel 200.8 ug/L 52.0 49.0 50.5 5.94Selenium 200.8 ug/L 110 100 105 9.52Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCSodium 200.7 ug/L 180,000 190,000 185,000 5.41Thallium 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 99.0 100 99.5 1.01Vanadium 200.8 ug/L 10.0 11.0 10.5 9.52Zinc 200.7 ug/L 53.0 53.0 53.0 0.00Dissolved MetalsAluminum 200.7 ug/L NQ (200) NQ (200) NQ (200) NCAntimony 200.8 ug/L 3.60 3.60 3.60 0.00Arsenic 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.00) NCBarium 200.7 ug/L 190 190 190 0.00Beryllium 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 NQ (4.00) NQ (4.00) NQ (4.00) NCCalcium 200.7 ug/L 2,300,000 2,300,000 2,300,000 0.00Chromium 200.8 ug/L ND (8.00) ^ ND (8.00) ^ ND (8.00) NCChromium (VI) 218.6 ug/L ND (10.0) ND (10.0) ND (10.0) NC< - 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 dissolved mercury original sample result seems erroneousbased on the Day 3 duplicate sample concentration and the other three sample days. The original sample resultwas excluded from the presentation of the Day 3 average result inTable 4-2. Additionally, 5.56ng/L (instead of 24.2 ng/L) was used in the calculation of the 4-day average resultpresented in Table 4-2 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 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.B – Analyte was found in the blank and sample.



# 5-8 5-8Table 5-2. Field Duplicate Results –Influent to SBR System, DickersonAnalyteMethodUnitsOriginal Influentto SBRSystem, Day 3Concentration (SP-2)Duplicate Influentto SBRSystemConcentration (SP-4)AverageResultRelativePercentDifferenceCobalt 200.7 ug/L NQ (20.0) NQ (20.0) NQ (20.0) NCCopper 200.8 ug/L 44.0 46.0 45.0 4.44Iron 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 1,200,000 1,200,000 1,200,000 0.00Manganese 200.7 ug/L 210 210 210 0.00Mercury 1631E ng/L 42.8* 5.56 24.2* 154Molybdenum 200.7 ug/L 240 240 240 0.00Nickel 200.8 ug/L 49.0 50.0 49.5 2.02Selenium 200.8 ug/L 94.0 100 97.0 6.19Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCSodium 200.7 ug/L 180,000 180,000 180,000 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 200.7 ug/L NQ (40.0) NQ (40.0) NQ (40.0) NC< - 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 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.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.



# 5-9Table 5-3. Field Duplicate Results –Effluent from SBR System, DickersonAnalyteMethodUnitsOriginal Effluentfrom SBRSystem, Day 2Concentration (SP-3)Duplicate Effluentfrom SBRSystemConcentration (SP-5)AverageResultRelativePercentDifferenceClassicalsAmmonia350.1mg/LNQ (1.00)NQ (1.00)NQ (1.00)NCNitrate Nitrite as N353.2mg/L0.1100.1100.1100.00Nitrogen, Total Kjeldahl351.2mg/L13.0B13.0B13.00.00Biochemical Oxygen Demand5210Bmg/L4.704.704.700.00Chemical Oxygen Demand410.4mg/L1901801855.41Chloride300.0mg/L8,2007,8008,0005.00Sulfate300.0mg/L1,7001,7001,7000.00Cyanide, Total4500 CN Emg/LNQ (0.0100)BNQ (0.0100)BNQ (0.0100)NCTotal Dissolved Solids2540Cmg/L14,00013,00013,5007.41Total Suspended Solids2540Dmg/L16.012.0D14.028.6Phosphorus, Total365.1mg/LNQ (0.0500)NQ (0.0500)NQ (0.0500)NCTotal MetalsAluminum200.7ug/L7207007102.82Antimony200.8ug/L5.705.305.507.27Arsenic200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCBarium200.7ug/L3103003053.28Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L190,000B180,000B185,0005.41Cadmium200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCCalcium200.7ug/L2,800,0002,700,0002,750,0003.64Chromium200.8ug/LND (8.00)^ND (8.00)^ND (8.00)NC< - 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 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.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.



# 5-10Table 5-3. Field Duplicate Results –Effluent from SBR System, DickersonAnalyteMethodUnitsOriginal Effluentfrom SBRSystem, Day 2Concentration (SP-3)Duplicate Effluentfrom SBRSystemConcentration (SP-5)AverageResultRelativePercentDifferenceCobalt200.7ug/LNQ (20.0)NQ (20.0)NQ (20.0)NCCopper200.8ug/L22.022.022.00.00Iron200.7ug/LNQ (200)NQ (200)NQ (200)NCLead200.8ug/LNQ (2.00)NQ (2.00)NQ (2.00)NCMagnesium200.7ug/L1,300,0001,200,0001,250,0008.00Manganese200.7ug/L86.083.084.53.55Mercury1631Eng/L13.06.309.6569.4Molybdenum200.7ug/L3203103153.17Nickel200.8ug/L64.064.064.00.00Selenium200.8ug/L1101101100.00Silver200.8ug/LND (2.00)ND (2.00)ND (2.00)NCSodium200.7ug/L230,000220,000225,0004.44Thallium200.8ug/LNQ (2.00)NQ (2.00)NQ (2.00)NCTin200.7ug/LND (200)ND (200)ND (200)NCTitanium200.7ug/LNQ (20.0)NQ (20.0)NQ (20.0)NCVanadium200.8ug/LNQ (10.0)NQ (10.0)NQ (10.0)NCZinc200.7ug/L42.043.042.52.35Dissolved MetalsAluminum200.7ug/LNQ (200)NQ (200)NQ (200)NCAntimony200.8ug/L5.404.805.1011.8Arsenic200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCBarium200.7ug/L3003003000.00< - 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 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.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.



# 5-11Table 5-3. Field Duplicate Results –Effluent from SBR System, DickersonAnalyteMethodUnitsOriginal Effluentfrom SBRSystem, Day 2Concentration (SP-3)Duplicate Effluentfrom SBRSystemConcentration (SP-5)AverageResultRelativePercentDifferenceBeryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L180,000B180,000B180,0000.00Cadmium200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCCalcium200.7ug/L2,800,0002,700,0002,750,0003.64Chromium200.8ug/LND (8.00)^ND (8.00)^ND (8.00)NCChromium (VI)218.6ug/LND (10.0)ND (10.0)ND (10.0)NCCobalt200.7ug/LNQ (20.0)NQ (20.0)NQ (20.0)NCCopper200.8ug/L17.018.017.55.71Iron200.7ug/LNQ (200)NQ (200)NQ (200)NCLead200.8ug/LNQ (2.00)NQ (2.00)NQ (2.00)NCMagnesium200.7ug/L1,300,0001,300,0001,300,0000.00Manganese200.7ug/L86.084.085.02.35Mercury1631Eng/L6.522.034.28105Molybdenum200.7ug/L3203103153.17Nickel200.8ug/L67.066.066.51.50Selenium200.8ug/L1001101059.52Silver200.8ug/LND (2.00)ND (2.00)ND (2.00)NCSodium200.7ug/L220,000220,000220,0000.00Thallium200.8ug/LNQ (2.00)NQ (2.00)NQ (2.00)NCTin200.7ug/LND (200)ND (200)ND (200)NCTitanium200.7ug/LNQ (20.0)NQ (20.0)NQ (20.0)NCVanadium200.8ug/LNQ (10.0)NQ (10.0)NQ (10.0)NC< - 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 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.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.



# 5-12Table 5-3. Field Duplicate Results –Effluent from SBR System, DickersonAnalyteMethodUnitsOriginal Effluentfrom SBRSystem, Day 2Concentration (SP-3)Duplicate Effluentfrom SBRSystemConcentration (SP-5)AverageResultRelativePercentDifferenceZinc200.7ug/L42.0NQ (40.0)< 31.0NC

# 6-1 6. R EFERENCES



# 1. Eastern Research Group, Inc., 2010. Final Sampling Plan, Mirant Mid-Atlantic, LLC’s

Dickerson Generating Station. August 19. DCN SE00503.

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.B – Analyte was found in the blank and sample.C – pH upon receipt was less than 10 S.U.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.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, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.1115.9Nitrate Nitrite as N353.2mg/L100.19167Nitrogen, Total Kjeldahl351.2mg/L11.520130LBiochemical Oxygen Demand5210Bmg/L10.32.52JChemical Oxygen Demand410.4mg/L28.140110Chloride300.0mg/L5001301,5009,200Sulfate300.0mg/L100235001,800Cyanide, Total4500 CN Emg/L40.0080.041.2CTotal Dissolved Solids2540Cmg/L14701,000170,000BTotal Suspended Solids2540Dmg/L111403,900Phosphorus, Total365.1mg/L50.0250.253.7Total MetalsAluminum200.7ug/L29.4200130,000Antimony200.8ug/L20.72223Arsenic200.8ug/L106.120280Barium200.7ug/L22.520700Beryllium200.7ug/L20.71215Boron200.7ug/L501705,000220,000BCadmium200.8ug/L21.2431Calcium200.7ug/L501,70010,0002,900,000Chromium200.8ug/L101640690^Cobalt200.7ug/L21.120130Copper200.8ug/L104.820660Iron200.7ug/L508005,000180,000Lead200.8ug/L103.610220

# 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.B – Analyte was found in the blank and sample.C – pH upon receipt was less than 10 S.U.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.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, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0001,700,000Manganese200.7ug/L20.512011,000Mercury1631Eng/L5001212528,550Molybdenum200.7ug/L21.640520Nickel200.8ug/L20.894660Selenium200.8ug/L20.6241,500Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000200,000Thallium200.8ug/L20.4721.5JTin200.7ug/L24.820037JTitanium200.7ug/L21.6206,200Vanadium200.8ug/L108.450580Zinc200.7ug/L29.1402,500Dissolved MetalsAluminum200.7ug/L29.420066JAntimony200.8ug/L20.7223.7Arsenic200.8ug/L21.242.4JBarium200.7ug/L22.520250Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000210,000BCadmium200.8ug/L21.2428Calcium200.7ug/L501,70010,0002,300,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.12081Copper200.8ug/L20.96426

# 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.B – Analyte was found in the blank and sample.C – pH upon receipt was less than 10 S.U.L – LFB or LCS percent recovery not within method-specified criteria, but iswithin laboratory-specified criteria.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, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationIron200.7ug/L23220050JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0001,600,000Manganese200.7ug/L20.512011,000Mercury1631Eng/L102.415.05177Molybdenum200.7ug/L21.640250Nickel200.8ug/L20.894460Selenium200.8ug/L20.624150Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000210,000Thallium200.8ug/L20.4722.4Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7108.6JZinc200.7ug/L29.1401,300

# 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.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-2. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.1115.4Nitrate Nitrite as N353.2mg/L100.19167Nitrogen, Total Kjeldahl351.2mg/L10.771023BBiochemical Oxygen Demand5210Bmg/L10.32.53.7Chemical Oxygen Demand410.4mg/L28.140150Chloride300.0mg/L5001301,5008,400Sulfate300.0mg/L100235001,800Cyanide, Total4500 CN Emg/L40.0080.041.1BTotal Dissolved Solids2540Cmg/L14710015,000Total Suspended Solids2540Dmg/L15520011,000Phosphorus, Total365.1mg/L10.0050.050.019JTotal MetalsAluminum200.7ug/L29.4200110,000Antimony200.8ug/L20.72218Arsenic200.8ug/L106.120220Barium200.7ug/L22.520720Beryllium200.7ug/L20.71212Boron200.7ug/L501705,000200,000BCadmium200.8ug/L21.2427Calcium200.7ug/L501,70010,0002,700,000Chromium200.8ug/L101640570^Cobalt200.7ug/L21.120120Copper200.8ug/L104.820530Iron200.7ug/L508005,000160,000Lead200.8ug/L20.732170Magnesium200.7ug/L5054010,0001,600,000

# 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.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-2. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.51209,800Mercury1631Eng/L5001212524,830Molybdenum200.7ug/L21.640440Nickel200.8ug/L20.894580Selenium200.8ug/L20.6241,200Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000190,000Thallium200.8ug/L20.4721.1JTin200.7ug/L24.820032JTitanium200.7ug/L21.6205,400Vanadium200.8ug/L108.450470Zinc200.7ug/L29.1402,000Dissolved MetalsAluminum200.7ug/L29.420037JAntimony200.8ug/L20.7223.8Arsenic200.8ug/L21.243.1JBarium200.7ug/L22.520210Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000190,000BCadmium200.8ug/L21.2424Calcium200.7ug/L501,70010,0002,100,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.12077Copper200.8ug/L20.96412Iron200.7ug/L23220038JLead200.8ug/L20.732ND (2)U

# 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.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-2. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0001,500,000Manganese200.7ug/L20.512010,000Mercury1631Eng/L102.415.0549.7Molybdenum200.7ug/L21.640210Nickel200.8ug/L20.894420Selenium200.8ug/L20.624210Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000200,000Thallium200.8ug/L20.4721.2JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7108.3JZinc200.7ug/L29.140700

# 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.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-3. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05514Nitrate Nitrite as N353.2mg/L100.19147Nitrogen, Total Kjeldahl351.2mg/L10.771012BBiochemical Oxygen Demand5210Bmg/L10.32.56.3Chemical Oxygen Demand410.4mg/L28.140110Chloride300.0mg/L200516005,700Sulfate300.0mg/L50122501,700Cyanide, Total4500 CN Emg/L40.0080.040.74Total Dissolved Solids2540Cmg/L14710012,000Total Suspended Solids2540Dmg/L1281003,900Phosphorus, Total365.1mg/L50.0250.253.2Total MetalsAluminum200.7ug/L29.420091,000Antimony200.8ug/L20.72215Arsenic200.8ug/L21.24190Barium200.7ug/L22.520590Beryllium200.7ug/L20.71210Boron200.7ug/L501705,000150,000BCadmium200.8ug/L21.2421Calcium200.7ug/L501,70010,0002,600,000Chromium200.8ug/L101640450^Cobalt200.7ug/L21.12099Copper200.8ug/L104.820440Iron200.7ug/L508005,000130,000Lead200.8ug/L20.732140Magnesium200.7ug/L5054010,0001,200,000

# 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.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-3. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.51207,800Mercury1631Eng/L5001212524,030Molybdenum200.7ug/L21.640360Nickel200.8ug/L20.894450Selenium200.8ug/L20.624920Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000160,000Thallium200.8ug/L20.4722.9Tin200.7ug/L24.820026JTitanium200.7ug/L21.6204,500Vanadium200.8ug/L108.450390Zinc200.7ug/L29.1401,500Dissolved MetalsAluminum200.7ug/L29.420070JAntimony200.8ug/L20.7222.8Arsenic200.8ug/L21.241.9JBarium200.7ug/L22.520130Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000BCadmium200.8ug/L21.2417Calcium200.7ug/L2694001,600,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.12058Copper200.8ug/L20.9648.3Iron200.7ug/L23220059JLead200.8ug/L20.732ND (2)U

# 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.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-3. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0001,200,000Manganese200.7ug/L20.51208,100Mercury1631Eng/L204.8310.1193Molybdenum200.7ug/L21.640180Nickel200.8ug/L20.894310Selenium200.8ug/L20.624150Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000160,000Thallium200.8ug/L20.4720.93JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7107.8JZinc200.7ug/L29.140370

# 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.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.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 TreatmentSystem, Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05514.9Nitrate Nitrite as N353.2mg/L100.19162Nitrogen, Total Kjeldahl351.2mg/L10.771021BBiochemical Oxygen Demand5210Bmg/L10.5958Chemical Oxygen Demand410.4mg/L28.140150Chloride300.0mg/L200516007,400Sulfate300.0mg/L50122501,800Cyanide, Total4500 CN Emg/L40.0080.040.76BTotal Dissolved Solids2540Cmg/L14710011,000DTotal Suspended Solids2540Dmg/L118673,700Phosphorus, Total365.1mg/L50.0250.254.3Total MetalsAluminum200.7ug/L29.4200110,000Antimony200.8ug/L20.72219Arsenic200.8ug/L106.120230Barium200.7ug/L22.520790Beryllium200.7ug/L20.71213Boron200.7ug/L501705,000200,000BCadmium200.8ug/L21.2427Calcium200.7ug/L501,70010,0002,600,000Chromium200.8ug/L101640570^Cobalt200.7ug/L21.120120Copper200.8ug/L104.820540Iron200.7ug/L508005,000160,000Lead200.8ug/L20.732180

# 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.D – Laboratory duplicate RPD greater than method-specified criteria.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 TreatmentSystem, Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0001,600,000Manganese200.7ug/L20.51209,900Mercury1631Eng/L5001212525,630Molybdenum200.7ug/L21.640440Nickel200.8ug/L20.894570Selenium200.8ug/L20.6241,200Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000190,000Thallium200.8ug/L20.4721.8JTin200.7ug/L24.820033JTitanium200.7ug/L21.6205,600Vanadium200.8ug/L108.450490Zinc200.7ug/L29.1402,000Dissolved MetalsAluminum200.7ug/L29.420061JAntimony200.8ug/L20.7223.5Arsenic200.8ug/L21.242.2JBarium200.7ug/L22.520140Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000200,000BCadmium200.8ug/L21.2422Calcium200.7ug/L501,70010,0002,100,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.12071Copper200.8ug/L20.9649.2Iron200.7ug/L23220046J

# 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.D – Laboratory duplicate RPD greater than method-specified criteria.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 TreatmentSystem, Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0001,500,000Manganese200.7ug/L20.512010,000Mercury1631Eng/L204.8310.124.4Molybdenum200.7ug/L21.640220Nickel200.8ug/L20.894380Selenium200.8ug/L20.624180Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000200,000Thallium200.8ug/L20.4721.3JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7109JZinc200.7ug/L29.140450

# 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-5. Influent to SBR System,Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.1114.4Nitrate Nitrite as N353.2mg/L100.19148Nitrogen, Total Kjeldahl351.2mg/L10.771010BBiochemical Oxygen Demand5210Bmg/L10.32.54Chemical Oxygen Demand410.4mg/L28.140160Chloride300.0mg/L5001301,5008,600Sulfate300.0mg/L100235001,800Cyanide, Total4500 CN Emg/L10.0020.010.22BTotal Dissolved Solids2540Cmg/L14710014,000Total Suspended Solids2540Dmg/L11.1438Phosphorus, Total365.1mg/L10.0050.050.023JTotal MetalsAluminum200.7ug/L29.4200600Antimony200.8ug/L20.7225.5Arsenic200.8ug/L21.243.6JBarium200.7ug/L22.520300Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000170,000BCadmium200.8ug/L21.243.2JCalcium200.7ug/L501,70010,0002,600,000Chromium200.8ug/L23.383.6J,^Cobalt200.7ug/L21.1203.7JCopper200.8ug/L20.96443Iron200.7ug/L232200740Lead200.8ug/L20.7322.7Magnesium200.7ug/L5054010,0001,200,000

# 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 SBR System,Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.512090Mercury1631Eng/L102.415.05222Molybdenum200.7ug/L21.640300Nickel200.8ug/L20.89460Selenium200.8ug/L20.624130Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000200,000Thallium200.8ug/L20.4721.2JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.62046Vanadium200.8ug/L21.7107.4JZinc200.7ug/L29.14033JDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7224.8Arsenic200.8ug/L21.242.2JBarium200.7ug/L22.520280Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000180,000BCadmium200.8ug/L21.242.7JCalcium200.7ug/L501,70010,0002,600,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1203.1JCopper200.8ug/L20.96440Iron200.7ug/L232200ND (200)ULead200.8ug/L20.7321.1JMagnesium200.7ug/L5054010,0001,200,000

# 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 SBR System,Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.512070Mercury1631Eng/L10.240.55.97Molybdenum200.7ug/L21.640290Nickel200.8ug/L20.89454Selenium200.8ug/L20.624120Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000190,000Thallium200.8ug/L20.4721.3JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.5JVanadium200.8ug/L21.7104.9JZinc200.7ug/L29.14029J

# 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-6. Influent to SBR System,Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilution ValueSample-SpecificMDLSample-SpecificQLConcentrationClassicalsAmmonia350.1mg/L10.05514.1Nitrate Nitrite as N353.2mg/L100.19143Nitrogen, Kjeldahl351.2mg/L10.77107.5J,BBiochemical Oxygen Demand5210Bmg/L10.32.53Chemical Oxygen Demand410.4mg/L28.14081Chloride300.0mg/L200516007,800Sulfate300.0mg/L50122501,600Cyanide, Total4500 CN Emg/L10.0020.010.13BTotal Dissolved Solids2540Cmg/L14710014,000Total Suspended Solids2540Dmg/L11.1437Phosphorus, Total365.1mg/L10.0050.050.023JTotal MetalsAluminum200.7ug/L29.4200450Antimony200.8ug/L20.7224.4Arsenic200.8ug/L21.243.3JBarium200.7ug/L22.520260Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000170,000BCadmium200.8ug/L21.242JCalcium200.7ug/L501,70010,0002,400,000Chromium200.8ug/L23.383.6J,^Cobalt200.7ug/L21.1203.2JCopper200.8ug/L20.96446

# 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.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-6. Influent to SBR System,Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilution ValueSample-SpecificMDLSample-SpecificQLConcentrationIron200.7ug/L232200570Lead200.8ug/L20.7321.8JMagnesium200.7ug/L5054010,0001,200,000Manganese200.7ug/L20.5120110Mercury1631Eng/L10024.150.5200Molybdenum200.7ug/L21.640260Nickel200.8ug/L20.89451Selenium200.8ug/L20.624110Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000200,000Thallium200.8ug/L20.4721JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.62035Vanadium200.8ug/L21.7107.1JZinc200.7ug/L29.14032JDissolved MetalsAluminum200.7ug/L29.420013JAntimony200.8ug/L20.7224.8Arsenic200.8ug/L21.242.6JBarium200.7ug/L22.520250Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000170,000BCadmium200.8ug/L21.242.9JCalcium200.7ug/L501,70010,0002,500,000

# 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.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-6. Influent to SBR System,Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilution ValueSample-SpecificMDLSample-SpecificQLConcentrationChromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1203.6JCopper200.8ug/L20.96445Iron200.7ug/L232200ND (200)ULead200.8ug/L20.7320.8JMagnesium200.7ug/L5054010,0001,300,000Manganese200.7ug/L20.5120100Mercury1631Eng/L40.972.026.78Molybdenum200.7ug/L21.640260Nickel200.8ug/L20.89451Selenium200.8ug/L20.624110Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000190,000Thallium200.8ug/L20.4720.9JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.3JVanadium200.8ug/L21.7105.3JZinc200.7ug/L29.14026J

# 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.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 SBR System,Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05512.9Nitrate Nitrite as N353.2mg/L100.19138Nitrogen, Total Kjeldahl351.2mg/L10.771010BBiochemical Oxygen Demand5210Bmg/L10.32.52JChemical Oxygen Demand410.4mg/L28.140160Chloride300.0mg/L200516006,700Sulfate300.0mg/L50122501,700Cyanide, Total4500 CN Emg/L10.0020.010.045BTotal Dissolved Solids2540Cmg/L1194012,000Total Suspended Solids2540Dmg/L11.1442Phosphorus, Total365.1mg/L10.0050.050.05Total MetalsAluminum200.7ug/L29.42001,400Antimony200.8ug/L20.7224.5Arsenic200.8ug/L21.244.5Barium200.7ug/L22.520240Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000BCadmium200.8ug/L21.242.1JCalcium200.7ug/L501,70010,0002,200,000Chromium200.8ug/L23.386.2J,^Cobalt200.7ug/L21.1204.6JCopper200.8ug/L20.96454Iron200.7ug/L2322001,700Lead200.8ug/L20.7323.5Magnesium200.7ug/L5054010,0001,200,000

# 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 SBR System,Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.5120260Mercury1631Eng/L204.8310.1454Molybdenum200.7ug/L21.640240Nickel200.8ug/L20.89452Selenium200.8ug/L20.624110Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000180,000Thallium200.8ug/L20.4720.73JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.62099Vanadium200.8ug/L21.71010Zinc200.7ug/L29.14053Dissolved MetalsAluminum200.7ug/L29.420037JAntimony200.8ug/L20.7223.6Arsenic200.8ug/L21.242.2JBarium200.7ug/L22.520190Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000BCadmium200.8ug/L21.242JCalcium200.7ug/L501,70010,0002,300,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1203.9JCopper200.8ug/L20.96444Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0001,200,000

# 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 SBR System,Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.5120210Mercury1631Eng/L102.415.0542.8Molybdenum200.7ug/L21.640240Nickel200.8ug/L20.89449Selenium200.8ug/L20.62494Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000180,000Thallium200.8ug/L20.4720.93JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203JVanadium200.8ug/L21.7104.6JZinc200.7ug/L29.14035J

# 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.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.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 SBR System,Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05513.2Nitrate Nitrite as N353.2mg/L100.19137Nitrogen, Total Kjeldahl351.2mg/L10.77109.6J,BBiochemical Oxygen Demand5210Bmg/L10.32.52.8Chemical Oxygen Demand410.4mg/L28.140130FChloride300.0mg/L200516006,700Sulfate300.0mg/L50122501,700Cyanide, Total4500 CN Emg/L10.0020.010.05BTotal Dissolved Solids2540Cmg/L1194012,000Total Suspended Solids2540Dmg/L11.1442Phosphorus, Total365.1mg/L10.0050.050.042JTotal MetalsAluminum200.7ug/L29.42001,500Antimony200.8ug/L20.7223.9Arsenic200.8ug/L21.245.5Barium200.7ug/L22.520230Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000150,000B,4Cadmium200.8ug/L21.242.5JCalcium200.7ug/L501,70010,0002,100,0004Chromium200.8ug/L23.386.3J,^Cobalt200.7ug/L21.1204.9JCopper200.8ug/L20.96498Iron200.7ug/L2322001,800Lead200.8ug/L20.7325

# 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.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-8. Influent to SBR System,Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0001,100,0004Manganese200.7ug/L20.5120300Mercury1631Eng/L500121252416Molybdenum200.7ug/L21.640230Nickel200.8ug/L20.89450Selenium200.8ug/L20.624100Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L218010,000180,000Thallium200.8ug/L20.4720.73JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620100Vanadium200.8ug/L21.71011Zinc200.7ug/L29.14065Dissolved MetalsAluminum200.7ug/L29.420057JAntimony200.8ug/L20.7224.1Arsenic200.8ug/L21.242.2JBarium200.7ug/L22.520170Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000B,4Cadmium200.8ug/L21.241.9JCalcium200.7ug/L501,70010,0002,200,0004Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1203.8JCopper200.8ug/L20.96469Iron200.7ug/L232200ND (200)U

# 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.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-8. Influent to SBR System,Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0001,200,0004Manganese200.7ug/L20.5120250Mercury1631Eng/L20.481.015.81Molybdenum200.7ug/L21.640230Nickel200.8ug/L20.89450Selenium200.8ug/L20.62495Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L218010,000180,000Thallium200.8ug/L20.4720.86JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.3JVanadium200.8ug/L21.7104.9JZinc200.7ug/L29.14045

# 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.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-9. Effluent from SBR System,Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.1110.2JNitrate Nitrite as N353.2mg/L10.0190.10.07JNitrogen, Total Kjeldahl351.2mg/L50.38513BBiochemical Oxygen Demand5210Bmg/L10.32.53.9Chemical Oxygen Demand410.4mg/L28.140150Chloride300.0mg/L5001301,5009,700Sulfate300.0mg/L100235001,800Cyanide, Total4500 CN Emg/L10.0020.010.1BTotal Dissolved Solids2540Cmg/L14710015,000Total Suspended Solids2540Dmg/L11.148.8Phosphorus, Total365.1mg/L10.0050.050.016JTotal MetalsAluminum200.7ug/L29.4200660Antimony200.8ug/L20.7225Arsenic200.8ug/L21.243.4JBarium200.7ug/L22.520310Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000180,000BCadmium200.8ug/L21.242.7JCalcium200.7ug/L501,70010,0002,700,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.1206JCopper200.8ug/L20.96421Iron200.7ug/L232200130JLead200.8ug/L20.7321.4JMagnesium200.7ug/L5054010,0001,300,000Manganese200.7ug/L20.512081

# 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.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 SBR System,Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L102.415.057.27Molybdenum200.7ug/L21.640320Nickel200.8ug/L20.89478Selenium200.8ug/L20.624110Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000220,000Thallium200.8ug/L20.4721.2JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6205.2JVanadium200.8ug/L21.7104.1JZinc200.7ug/L29.14043Dissolved MetalsAluminum200.7ug/L29.420059JAntimony200.8ug/L20.7225.7Arsenic200.8ug/L21.243JBarium200.7ug/L22.520320Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000190,000BCadmium200.8ug/L21.242JCalcium200.7ug/L501,70010,0002,800,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1206.5JCopper200.8ug/L20.96416Iron200.7ug/L23220094JLead200.8ug/L20.7321.4JMagnesium200.7ug/L5054010,0001,300,000Manganese200.7ug/L20.512085

# 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.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 SBR System,Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L10.240.51.69Molybdenum200.7ug/L21.640330Nickel200.8ug/L20.89478Selenium200.8ug/L20.624100Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000220,000Thallium200.8ug/L20.4721.2JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.8JVanadium200.8ug/L21.7105.6JZinc200.7ug/L29.14043

# 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.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-10. Effluent from SBR System,Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05510.23JNitrate Nitrite as N353.2mg/L10.0190.10.11Nitrogen, Total Kjeldahl351.2mg/L50.38513BBiochemical Oxygen Demand5210Bmg/L10.32.54.7Chemical Oxygen Demand410.4mg/L28.140190Chloride300.0mg/L200516008,200Sulfate300.0mg/L50122501,700Cyanide, Total4500 CN Emg/L10.0020.010.004J,BTotal Dissolved Solids2540Cmg/L14710014,000Total Suspended Solids2540Dmg/L11.1416Phosphorus, Total365.1mg/L10.0050.050.02JTotal MetalsAluminum200.7ug/L29.4200720Antimony200.8ug/L20.7225.7Arsenic200.8ug/L21.243.1JBarium200.7ug/L22.520310Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000190,000BCadmium200.8ug/L21.243.9JCalcium200.7ug/L501,70010,0002,800,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.1204JCopper200.8ug/L20.96422Iron200.7ug/L232200130JLead200.8ug/L20.7320.91JMagnesium200.7ug/L5054010,0001,300,000Manganese200.7ug/L20.512086

# 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.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-10. Effluent from SBR System,Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L20.481.0113Molybdenum200.7ug/L21.640320Nickel200.8ug/L20.89464Selenium200.8ug/L20.624110Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000230,000Thallium200.8ug/L20.4721.1JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6205.6JVanadium200.8ug/L21.7104.7JZinc200.7ug/L29.14042Dissolved MetalsAluminum200.7ug/L29.420046JAntimony200.8ug/L20.7225.4Arsenic200.8ug/L21.243.3JBarium200.7ug/L22.520300Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000180,000BCadmium200.8ug/L21.243.3JCalcium200.7ug/L501,70010,0002,800,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1205.1JCopper200.8ug/L20.96417Iron200.7ug/L23220064JLead200.8ug/L20.7320.94JMagnesium200.7ug/L5054010,0001,300,000Manganese200.7ug/L20.512086

# 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.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-10. Effluent from SBR System,Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L20.481.016.52Molybdenum200.7ug/L21.640320Nickel200.8ug/L20.89467Selenium200.8ug/L20.624100Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000220,000Thallium200.8ug/L20.4721.2JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.3JVanadium200.8ug/L21.7105.2JZinc200.7ug/L29.14042

# 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.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.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 SBR System,Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05510.14JNitrate Nitrite as N353.2mg/L10.0190.10.14Nitrogen, Total Kjeldahl351.2mg/L50.38513B,4Biochemical Oxygen Demand5210Bmg/L10.32.55.7Chemical Oxygen Demand410.4mg/L28.140140FChloride300.0mg/L200516007,800Sulfate300.0mg/L50122501,700Cyanide, Total4500 CN Emg/L10.0020.010.0089J,B,FTotal Dissolved Solids2540Cmg/L1194014,000Total Suspended Solids2540Dmg/L11.148Phosphorus, Total365.1mg/L10.0050.050.015JTotal MetalsAluminum200.7ug/L29.4200870Antimony200.8ug/L20.7225.1Arsenic200.8ug/L21.243JBarium200.7ug/L22.520280Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000180,000B,4Cadmium200.8ug/L21.243JCalcium200.7ug/L501,70010,0002,700,0004Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.1203.3JCopper200.8ug/L20.96421Iron200.7ug/L232200140JLead200.8ug/L20.7321J

# 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.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 SBR System,Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0001,300,0004Manganese200.7ug/L20.5120100Mercury1631Eng/L10.240.510.9Molybdenum200.7ug/L21.640300Nickel200.8ug/L20.89458Selenium200.8ug/L20.624110Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L218010,000230,0004Thallium200.8ug/L20.4721.1JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6205.1JVanadium200.8ug/L21.7104.8JZinc200.7ug/L29.14031JDissolved MetalsAluminum200.7ug/L29.420042JAntimony200.8ug/L20.7224.5Arsenic200.8ug/L21.243.4JBarium200.7ug/L22.520270Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000180,000B,4Cadmium200.8ug/L21.242.5JCalcium200.7ug/L501,70010,0002,700,0004Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1204JCopper200.8ug/L20.96413Iron200.7ug/L23220054J

# 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.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 SBR System,Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0001,300,0004Manganese200.7ug/L20.5120100Mercury1631Eng/L10.240.58.61FMolybdenum200.7ug/L21.640290Nickel200.8ug/L20.89457Selenium200.8ug/L20.62498Silver200.8ug/L20.592ND (2)U,FSodium200.7ug/L218010,000220,0004Thallium200.8ug/L20.4721JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.5JVanadium200.8ug/L21.7105.9JZinc200.7ug/L29.14028J

# 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.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 SBR System,Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05510.19JNitrate Nitrite as N353.2mg/L10.0190.10.15Nitrogen, Total Kjeldahl351.2mg/L50.38513BBiochemical Oxygen Demand5210Bmg/L10.32.54.5Chemical Oxygen Demand410.4mg/L14.12084Chloride300.0mg/L200516007,600Sulfate300.0mg/L50122501,700Cyanide, Total4500 CN Emg/L10.0020.010.0094J,BTotal Dissolved Solids2540Cmg/L1194013,000Total Suspended Solids2540Dmg/L11.1414Phosphorus, Total365.1mg/L10.0050.050.027JTotal MetalsAluminum200.7ug/L29.4200920Antimony200.8ug/L20.7224.6Arsenic200.8ug/L21.243.4JBarium200.7ug/L22.520230Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000170,000BCadmium200.8ug/L21.242.7JCalcium200.7ug/L501,70010,0002,400,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.1203JCopper200.8ug/L20.96432Iron200.7ug/L232200130JLead200.8ug/L20.7321.1JMagnesium200.7ug/L5054010,0001,200,000Manganese200.7ug/L20.5120160

# 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 SBR System,Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L102.415.058.59Molybdenum200.7ug/L21.640260Nickel200.8ug/L20.89450Selenium200.8ug/L20.624100Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000220,000Thallium200.8ug/L20.4720.88JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.8JVanadium200.8ug/L21.7105.5JZinc200.7ug/L29.14032JDissolved MetalsAluminum200.7ug/L29.420051JAntimony200.8ug/L20.7224.8Arsenic200.8ug/L21.242.6JBarium200.7ug/L22.520230Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000170,000BCadmium200.8ug/L21.241.9JCalcium200.7ug/L501,70010,0002,400,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1203.7JCopper200.8ug/L20.96420Iron200.7ug/L23220045JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0001,200,000Manganese200.7ug/L20.5120160

# 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 SBR System,Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L10.240.51.21Molybdenum200.7ug/L21.640260Nickel200.8ug/L20.89451Selenium200.8ug/L20.62498Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000210,000Thallium200.8ug/L20.4720.79JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.8JVanadium200.8ug/L21.7105.7JZinc200.7ug/L29.14032J

# 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-13. Duplicate of Influent to SBR System, Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05513.3Nitrate Nitrite as N353.2mg/L100.19138Nitrogen, Total Kjeldahl351.2mg/L10.771011BBiochemical Oxygen Demand5210Bmg/L10.32.52.3JChemical Oxygen Demand410.4mg/L28.140110Chloride300.0mg/L200516006,700Sulfate300.0mg/L50122501,800Cyanide, Total4500 CN Emg/L10.0020.010.059BTotal Dissolved Solids2540Cmg/L1194013,000Total Suspended Solids2540Dmg/L11.1499Phosphorus, Total365.1mg/L10.0050.050.04JTotal MetalsAluminum200.7ug/L29.42001,500Antimony200.8ug/L20.7224.7Arsenic200.8ug/L21.245.4Barium200.7ug/L22.520260Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000BCadmium200.8ug/L21.242.8JCalcium200.7ug/L501,70010,0002,300,000Chromium200.8ug/L23.386.5J,^Cobalt200.7ug/L21.1204.6JCopper200.8ug/L20.96457Iron200.7ug/L2322001,700Lead200.8ug/L20.7323.8Magnesium200.7ug/L5054010,0001,200,000

# 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 Influent to SBR System, Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.5120270Mercury1631Eng/L204.8310.1437Molybdenum200.7ug/L21.640250Nickel200.8ug/L20.89449Selenium200.8ug/L20.624100Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000190,000Thallium200.8ug/L20.4720.84JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620100Vanadium200.8ug/L21.71011Zinc200.7ug/L29.14053Dissolved MetalsAluminum200.7ug/L29.420036JAntimony200.8ug/L20.7223.6Arsenic200.8ug/L21.243.6JBarium200.7ug/L22.520190Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000160,000BCadmium200.8ug/L21.242.3JCalcium200.7ug/L501,70010,0002,300,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1203.8JCopper200.8ug/L20.96446Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0001,200,000

# 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 Influent to SBR System, Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.5120210Mercury1631Eng/L20.481.015.56Molybdenum200.7ug/L21.640240Nickel200.8ug/L20.89450Selenium200.8ug/L20.624100Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000180,000Thallium200.8ug/L20.4720.82JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.1JVanadium200.8ug/L21.7104.7JZinc200.7ug/L29.14034J

# 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.D – Laboratory duplicate RPD greater than method-specified criteria.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-14. Duplicate of Effluent from SBR System, Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05510.2JNitrate Nitrite as N353.2mg/L10.0190.10.11Nitrogen, Total Kjeldahl351.2mg/L50.38513BBiochemical Oxygen Demand5210Bmg/L10.32.54.7Chemical Oxygen Demand410.4mg/L28.140180Chloride300.0mg/L200516007,800Sulfate300.0mg/L50122501,700Cyanide, Total4500 CN Emg/L10.0020.010.0042J,BTotal Dissolved Solids2540Cmg/L14710013,000Total Suspended Solids2540Dmg/L11.1412DPhosphorus, Total365.1mg/L10.0050.050.02JTotal MetalsAluminum200.7ug/L29.4200700Antimony200.8ug/L20.7225.3Arsenic200.8ug/L21.243JBarium200.7ug/L22.520300Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000180,000BCadmium200.8ug/L21.242.9JCalcium200.7ug/L501,70010,0002,700,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.1204.2JCopper200.8ug/L20.96422Iron200.7ug/L232200120JLead200.8ug/L20.7320.94JMagnesium200.7ug/L5054010,0001,200,000

# 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.D – Laboratory duplicate RPD greater than method-specified criteria.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-14. Duplicate of Effluent from SBR System, Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationManganese200.7ug/L20.512083Mercury1631Eng/L40.972.026.3Molybdenum200.7ug/L21.640310Nickel200.8ug/L20.89464Selenium200.8ug/L20.624110Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000220,000Thallium200.8ug/L20.4721JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6205.1JVanadium200.8ug/L21.7104.3JZinc200.7ug/L29.14043Dissolved MetalsAluminum200.7ug/L29.420047JAntimony200.8ug/L20.7224.8Arsenic200.8ug/L21.243.3JBarium200.7ug/L22.520300Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000180,000BCadmium200.8ug/L21.242.5JCalcium200.7ug/L501,70010,0002,700,000Chromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1205JCopper200.8ug/L20.96418Iron200.7ug/L23220065JLead200.8ug/L20.7320.96J

# 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.D – Laboratory duplicate RPD greater than method-specified criteria.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-14. Duplicate of Effluent from SBR System, Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L5054010,0001,300,000Manganese200.7ug/L20.512084Mercury1631Eng/L10.240.52.03Molybdenum200.7ug/L21.640310Nickel200.8ug/L20.89466Selenium200.8ug/L20.624110Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000220,000Thallium200.8ug/L20.4721.2JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6205.1JVanadium200.8ug/L21.7105.4JZinc200.7ug/L29.14039J

# a 

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

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



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

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)

# a 

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

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



# A-44 Table A-15. Bottle Blank and Equipment Blank Analytical Data, Dickerson

Analyte Method Process Units Concentration

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)

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)

# a 

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

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



# A-45 Table A-15. Bottle Blank and Equipment Blank Analytical Data, Dickerson

Analyte Method Process Units Concentration

Aluminum EPA 1638 Dissolved ug/L ND (2.0)

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)

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)

# a 

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

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



# A-46 Table A-15. Bottle Blank and Equipment Blank Analytical Data, Dickerson

Analyte Method Process Units Concentration

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)

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)

# a 

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

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



# A-47 Table A-15. Bottle Blank and Equipment Blank Analytical Data, Dickerson

Analyte Method Process Units Concentration

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)

# A-48ND – 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, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 28 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) U,^Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 0.56 JMercury 1631E ng/L 1 0.24 0.5 0.73Molybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 ND (10,000) UThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) U

# 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, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 31 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 140 JChromium 200.8 ug/L 2 3.3 8 ND (8) U,^Chromium (VI) 218.6 ug/L 1 0.39 2 ND (2) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 69 JManganese 200.7 ug/L 2 0.51 20 0.58 JMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 ND (10,000) UThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 1.7 JVanadium 200.8 ug/L 2 1.7 10 3.4 JZinc 200.7 ug/L 2 9.1 40 13 J

# 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-17. Influent to SBR System Field Blank, Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific 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/L26.720038J,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/L20.624ND (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)UZinc200.7ug/L29.140ND (40)UDissolved MetalsAluminum200.7ug/L29.420041J

# 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 SBR System Field Blank, Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720033J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)U,^Chromium (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/L21.7102.9JZinc200.7ug/L29.140ND (40)U

# A-52ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-18. Influent to SBR System Field Blank, Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-53ND – 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 SBR System Field Blank, Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific 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-20. Influent to SBR System Field Blank, Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-55ND – 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 SBRSystem Field Blank, Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific 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/L26.720022J,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/L20.624ND (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)UZinc200.7ug/L29.140ND (40)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)U

# 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 SBRSystem Field Blank, Day 1 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720017J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220070JLead200.8ug/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/L21.7102.8JZinc200.7ug/L29.140ND (40)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-22. Effluent from SBRSystem Field Blank, Day 2 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-58ND – 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-23. Effluent from SBRSystem Field Blank, Day 3 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific 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-24. Effluent from SBRSystem Field Blank, Day 4 Analytical Results, DickersonAnalyteMethodUnitsDilutionValueSampleSpecific 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

Date: 9/1/2011

Subject: FGS Data Review Narrative for Tota l and Dissolved Mercury – Episode 6562

Frontier Global Sciences (FGS) generated analytical data for total and dissolved mercury.

FGS analyzed the samples according to EPA Method 1631E for mercury by Cold Vapor

Atomic Fluorescence Spectrometry (CVA-FS) analysis.

Table 1 summarizes the 37 samples (excluding laboratory filter blanks) FGS extracted

and analyzed for total and dissolved mercury.

Table 1. 

# EPA Episode 6562 Total & Dissolved Mercury – Sample Identification

EPA

Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

71841 1008203-01 Aqueous FGD Influent Day 1 8/23/2010

71841 1008203-02 Aqueous Dissolved FGD Influent, Day 1 8/23/2010

71842 1008207-06 Aqueous FGD Influent, Day 2 8/24/2010

71842 1008207-07 Aqueous Dissolved FGD Influent, Day 2 8/24/2010

71843 1008223-13 Aqueous FGD Influent, Day 3 8/25/2010

71843 1008223-14 Aqueous Dissolved FGD Influent, Day 3 8/25/2010

71844 1008240-09 Aqueous FGD Influent, Day 4 8/26/2010

71844 1008240-10 Aqueous Dissolved FGD Influent, Day 4 8/26/2010

71845 1008207-08 Aqueous FGD SBR Influent, Day 1 8/24/2010

71845 1008207-09 Aqueous Dissolved FGD SBR Influent, Day 1 8/24/2010

71846 1008223-15 Aqueous FGD SBR Influent, Day 2 8/25/2010

71846 1008223-16 Aqueous Dissolved FGD SBR Influent, Day 2 8/25/2010

71847 1008240-11 Aqueous FGD SBR Influent, Day 3 8/26/2010

71847 1008240-12 Aqueous Dissolved FGD SBR Influent, Day 3 8/26/2010

71848 1008250-03 Aqueous FGD SBR Influent , Day 4 8/27/2010

71848 1008250-04 Aqueous Dissolved FGD SBR Influent , Day 4 8/27/2010

71849 1008207-10 Aqueous FGD SBR Effluent, Day 1 8/24/2010

71849 1008207-11 Aqueous Dissolved FGD SBR Effluent, Day 1 8/24/2010

71850 1008223-17 Aqueous FGD SBR Effluent, Day 2 8/25/2010

71850 1008223-18 Aqueous Dissolved FGD SBR Effluent, Day 2 8/25/2010



# 1

# Table 1. 

# EPA Episode 6562 Total & Dissolved Mercury – Sample Identification

EPA Lab Sample Sample Sampling

Sample # ID # Matrix Sample Description Date

71851 1008240-13 Aqueous FGD SBR Effluent, Day 3 8/26/2010

71851 1008240-14 Aqueous Dissolved FGD SBR Effluent, Day 3 8/26/2010

71852 1008250-05 Aqueous FGD SBR Effluent , Day 4 8/27/2010

71852 1008250-06 Aqueous Dissolved FGD SBR Effluent , Day 4 8/27/2010

71853 1008240-15 Aqueous FGD SBR Infl uent - Duplicate 8/26/2010

71853 1008240-16 Aqueous Dissolved FGD SBR Influent - Duplicate 8/26/2010

71854 1008223-19 Aqueous FGD SBR Efflue nt Duplicate, Day 2 8/25/2010

71854 1008223-20 Aqueous Dissolved FGD SBR E ffluent Duplicate, Day 2 8/25/2010

71855 1008203-03 Aqueous FGD Influent Field Blank, Day 1 8/23/2010

71856 1008203-06 Aqueous FGD SBR Influent Field Blank, Day 1 8/23/2010

71857 1008207-12 Aqueous FGD SBR Influent Field Blank, Day 2 8/24/2010

71858 1008223-11 Aqueous FGD SBR Influent Field Blank, Day 3 8/25/2010

71859 1008240-07 Aqueous FGD SBR Influent Field Blank, Day 4 8/26/2010

71860 1008203-09 Aqueous FGD SBR Effluent Field Blank, Day 1 8/23/2010

71861 1008207-19 Aqueous FGD SBR Effluent Field Blank, Day 2 8/24/2010

71862 1008223-12 Aqueous FGD SBR Effluent Field Blank, Day 3 8/25/2010

71863 1008240-08 Aqueous FGD SBR Effluent Field Blank, Day 4 8/26/2010



# 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.

SAMPLE RECEIPT, HANDLIN G, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysis day. The initial calibration for

the CVAFS analysis consisted of a blank and five calibration standards with a correlation

coefficient ≥ 0.995. All method specified criteria were met.

INITIAL AND CONTINUING CAL IBRATION VERIFICATIONS

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

criteria.

2

# 3 BLANKS

All instrument and preparation blanks met meth od-specified criteria. Preparation Blanks

F009230-BLK1, F009230-BLK2, F009252-BLK5, F009277-BLK1, F009277-BLK3,

F009277-BLK4 and F009277-BLK5 had mercury le vels greater than or equal to the

MDL but less than the reporting limit and thes e were appropriately flagged with the “J”

qualifier. No additional qualifiers were required.

DUPLICATES

Field duplicates, samples 71854 and 71853, were collected on samples 71850 and 71847,

respectively. The 71850/71854 relative percen t difference (RPD) was 17.4% for total

mercury and 26.3% for dissolved merc ury. The 71847/71853 RPD was 3.8% for total

mercury and 154% for dissolved mercury. The method-suggested RPD criteria between

field duplicates is 20%.

Laboratory duplicates were performed in this episode on samples 71848, 71846, and

71847. All RPDs were less than 20% (the me thod-suggested RPD criterion between field

duplicates; the method does not require the analysis of laboratory duplicates).

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

Matrix spikes (MS) and ma trix spike duplicates (MSD) were performed on samples

71846, 71844, 71847, 71851 and 71848 for the total mercury analyses. MS and MSDs

were performed on samples 71851 and 71848 for the dissolved mercury analyses. All

aqueous MS/MSD recoveries were within the method specifications of 71-125%, except

for the dissolved mercury MSD for sample 71851, which had a recovery of 60.1%.

Therefore, the dissolved mercury result for sample 71851 was flagged with the

laboratory’s QM-07 qualifier. All RP Ds met method-specified criteria.

# 1



# MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

Deb Bartram, ERG

TJ Finseth, ERG

From: Randy Mercurio, ERG

Date: 9/1/2011

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

Episode 6562

Test America generated analytical data for total and dissolved metals (antimony, arsenic,

cadmium, chromium, copper, lead, nickel, selenium, silver, thallium, and vanadium).The

samples were analyzed according to EPA Method 200.8.

Table 1 summarizes the samples Test America extracted and analyzed for total and

dissolved metals by EPA Method 200.8.

Table 1. 

# EPA Episode 6562 Total & Dissolved Metals – Sample Identification



# EPA

Sample

# 

# EPA Sample

Description 

# Lab

Sample ID

# 

# Sample

Matrix 

# Sampling

Date 

# Receipt

Date

71841 

# FGD Influent, Day 1 280-6658-1 Aqueous 8/23/2010 8/24/2010

71842 

# FGD Influent, Day 2 280-6685-1 Aqueous 8/24/2010 8/25/2010

71843 

# FGD Influent, Day 3 280-6742-1 Aqueous 8/25/2010 8/26/2010

71844 

# FGD Influent, Day 4 280-6791-1 Aqueous 8/26/2010 8/27/2010

71845 

# FGD SBR Influent, Day 1 280-6685-2 Aqueous 8/24/2010 8/25/2010

71846 

# FGD SBR Influent, Day 2 280-6742-2 Aqueous 8/25/2010 8/26/2010

71847 

# FGD SBR Influent, Day 3 280-6791-2 Aqueous 8/26/2010 8/27/2010

71848 

# FGD SBR Influent, Day 4 280-6827-1 Aqueous 8/27/2010 8/28/2010

71849 

# FGD SBR Effluent, Day 1 280-6685-3 Aqueous 8/24/2010 8/25/2010

71850 

# FGD SBR Effluent, Day 2 280-6742-3 Aqueous 8/25/2010 8/26/2010

71851 

# FGD SBR Effluent, Day 3 280-6791-3 Aqueous 8/26/2010 8/27/2010

71852 

# FGD SBR Effluent, Day 4 280-6827-2 Aqueous 8/27/2010 8/28/2010

71853 

# FGD SBR Influent

-

Duplicate, Day 3 280-6791-4 Aqueous 8/26/2010 8/27/2010

71854 

# FGD SBR Effluent

-

Duplicate, Day 2 280-6742-4 Aqueous 8/25/2010 8/26/2010

71855 

# FGD Influent Field Blank,

Day 1 280-6658-2 Aqueous 8/23/2010 8/24/2010

71856 

# FGD SBR Influent Field

Blank, Day 1 280-6685-4 Aqueous 8/24/2010 8/25/2010

# 2 Table 1. 

# EPA Episode 6562 Total & Dissolved Metals – Sample Identification



# EPA

Sample

# 

# EPA Sample

Description 

# Lab

Sample ID

# 

# Sample

Matrix 

# Sampling

Date 

# Receipt

Date

71860 

# FGD SBR Effluent Field

Blank, Day 1 280-6685-5 Aqueous 8/24/2010 8/25/2010



# SUMMARY

The samples were prepared for total and dissolved metals analysis according to Test

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

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

2010, based on EPA Method 200.8, by ICP/MS analysis. Any significant findings are

summarized below. No additional data qualifiers were required.

• All matrix spike (MS) and matrix spike duplicates (MSD) for total and dissolved

silver failed the 70-130% control limits with poor recoveries. The poor recoveries

are probably due to high sulfates in this episode’s samples that could form

insoluble silver sulfide and/or silver sulfate.

INTERNAL STANDARDIZATION

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

INITIAL CALIBRATION

Test America performed the initial calibrations on each analysis day or before each

analysis if more than one analysis was performed in one day. The initial calibration for

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

INITIAL AND CONTINUING CALIBRATION VERIFICATION (ICV/CCV)

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

performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit. No additional qualifiers were

required for method blanks.

All instrument blanks (ICB and CCB) were less than the reporting limit.

# 3

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed Test America’s 50–150% recovery limits.

LABORATORY CONTROL SAMPLES (LCS)

All LCS samples passed the method limits of 85–115%.

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION (ICSA)

Based on TestAmerica’s SOP, all interference check sample A (ICSA) results had

analytes of interest with concentrations less than the RL or less than five times the RL

when known inherent contaminants are present in the stock solution used to make the

ICS.

All interference check sample B (ICSAB) synthetic spikes recovered within

TestAmerica’s SOP criteria of 70–130% of the true value.

The ICSA solution for the method 200.8 analysis exceeded the acceptance limits for

Chromium in analytical batches 280-29239 and 280-29244. The lab has confirmed with

the vendor that Chromium is a trace impurity in the ICSA solution. Therefore, corrective

action was deemed unnecessary; the associated data have been flagged “^”.

SERIAL DILUTION (SRD)

The serial dilution performed for the total and dissolved sample 71851 FGD SBR

Effluent, Day 3 (280-6791-3) met Test America’s requirement of ±10% difference.

FIELD DUPLICATES

The relative percent difference (RPD) of the field duplicates (71850/71854 &

71847/71853) were less than ±20% for all values equal to or greater than the reporting

limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

MS and MSDs were performed on the total and dissolved samples of 71848 and 71851.

Many spikes that failed outside of the 70–130% method control limits were flagged with

a “4” qualifier indicating concentrations in the parent samples were greater than 4 times

the spike amounts. All MS/MSDs for total and dissolved silver failed the 70–130%

control limits. The poor recoveries of Silver are probably due to high sulfates (1600–1800

mg/L) in this episode’s samples that could form insoluble silver sulfide and/or silver

sulfate. Otherwise, all MS/MSDs were within the 70–130% method control limits. The

RPD for all MS/MSD passed the method-specified criteria of 20 percent, except for total

silver for sample 71748 MS/MSD analyses, which had an RPD of 96%.

# 4

POST DIGESITON SPIKES

The post digestion spike performed on sample 71851 FGD SBR Effluent, Day 3 (280-

6791-3) for total and dissolved analytes passed TestAmerica’s 85–115% control limits

with the exception of silver. The poor recoveries of silver are probably due to high

sulfates (1600–1800 mg/L) in this episode’s samples that could form insoluble silver

sulfide and/or silver sulfate.

DETECTION LIMITS

The laboratory performed an MDL study in the synthetic FGD wastewater matrix, instead

of reagent water.

# MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

Deb Bartram, ERG

TJ Finseth, ERG

From: Randy Mercurio, ERG

Date: 9/1/2011

Subject: TestAmerica Data Review Narrative fo r Total and Dissolved Metals by 200.7 –

Episode 6562

Test America generated analytical data for total and dissolved me tals (aluminum, boron,

barium, beryllium, calcium, cobalt, iron, ma gnesium, manganese, molybdenum, sodium,

tin, titanium, and zinc). The samples we re analyzed according to EPA Method 200.7.

Table 1 summarizes the samples Test Ameri ca extracted and analyzed for total and

dissolved metals by EPA Method 200.7.

Table 1. 

# EPA Episode 6562 Total & Dissolved Metals – Sample Identification

EPA

Sample

# EPA Sample

Description Lab

Sample ID

# Sample

Matrix Sampling

Date Receipt

Date

71841 FGD Influent, Day 1 280-6658-1 Aqueous 8/23/2010 8/24/2010

71842 FGD Influent, Day 2 280-6685-1 Aqueous 8/24/2010 8/25/2010

71843 FGD Influent, Day 3 280-6742-1 Aqueous 8/25/2010 8/26/2010

71844 FGD Influent, Day 4 280-6791-1 Aqueous 8/26/2010 8/27/2010

71845 FGD SBR Influent, Day 1 280-6685-2 Aqueous 8/24/2010 8/25/2010

71846 FGD SBR Influent, Day 2 280-6742-2 Aqueous 8/25/2010 8/26/2010

71847 FGD SBR Influent, Day 3 280-6791-2 Aqueous 8/26/2010 8/27/2010

71848 FGD SBR Influent, Day 4 280-6827-1 Aqueous 8/27/2010 8/28/2010

71849 FGD SBR Effluent, Day 1 280-6685-3 Aqueous 8/24/2010 8/25/2010

71850 FGD SBR Effluent, Day 2 280-6742-3 Aqueous 8/25/2010 8/26/2010

71851 FGD SBR Effluent, Day 3 280-6791-3 Aqueous 8/26/2010 8/27/2010

71852 FGD SBR Effluent, Day 4 280-6827-2 Aqueous 8/27/2010 8/28/2010

71853 FGD SBR Influent -

Duplicate, Day 3 280-6791-4 Aqueous 8/26/2010 8/27/2010

71854 FGD SBR Effluent -

Duplicate, Day 2 280-6742-4 Aqueous 8/25/2010 8/26/2010

71855 FGD Influent Field Blank,

Day 1 280-6658-2 Aqueous 8/23/2010 8/24/2010



# 1

# Table 1. 

# EPA Episode 6562 Total & Dissolved Metals – Sample Identification

EPA

Sample

# EPA Sample

Description Lab

Sample ID

# Sample

Matrix Sampling Receipt

Date Date

71856 FGD SBR Influent Field

Blank, Day 1 280-6685-4 Aqueous 8/24/2010 8/25/2010

71860 FGD SBR Effluent Field

Blank, Day 1 280-6685-5 Aqueous 8/24/2010 8/25/2010



# SUMMARY

The samples were prepared for total and dissolved metals analysis according to Test

America’s SOP for ICP Analysis for Trace Metals by Method 200.7.

There were no findings from the data review that required additional qualifiers (excluding

those identified by the laboratory) in this dataset.

SAMPLE RECEIPT, HANDLIN G, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INTERNAL STANDARDIZATION

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

the ISTD recoveries within the ±30% criter ion of the calibration blank as per Section

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

INITIAL CALIBRATION

Test America 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 CAL IBRATION VERIFICATIONS

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

performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the re porting limit; however, some had levels above

the MDL and were flagged with the “J” qualifier.

All instrument blanks (ICB and CCB) were less than the reporting limit; however, some

elements were above the MDL and we re flagged with the “J” qualifier.

2

# 3 LABORATORY CONTROL SAMPLES (LCS)

All LCSs passed the method control limits of 85–115%.

INTERFERENCE CHECK SOLUTIONS

Interference checks were perfor med using the synthetic matrix as the check solution. All

data quality objectives met TestAmerica’s SOP criteria.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed Test Amer ica’s SOP control limits of 50–150%.

FIELD DUPLICATES

The total and dissolved relative percent differences (RPDs) of the field duplicates (71854

and 71853) to parent samples (71850 and 71847, respectively) were less than 20% for

values greater than the reporting limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matr ix spike duplicates (MSD) were performed on the total and

dissolved samples of 71848 and 71851. Some el ements with high concentrations

frequently failed the EPA 200.7 Method spik e recovery control limits of 70–130% but

were flagged with a “4” qualifier indicating th at the concentration in the parent sample

was greater than 4 times the spike and coul d not be reliably calculated. No MS/MSD

spike recoveries failed the EPA 200.7 Me thod control limits of 70–130%, except those

already qualified with a “4” as mentione d above, and therefor e no additional data

qualifiers were needed. In addition, al l RPDs of the MS/MSDs were within

TestAmerica’s ± 20% requirements.

SERIAL DILUTION (SRD)

Serial dilutions were performe d for each batch of total and di ssolved samples. All serial

dilution percent differences were less than 10% as required by Test America’s SOP.

POST DIGESTION SPIKE

Both total and dissolved post digestion sp ike samples performed passed the method

criteria of 85–115%.

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: Donna Tedder, ERG

Date: 9/1/2011

Subject: FGS Data Review Narrative for Dissolved Hexavalent Chromium – Episode

6562

Frontier Global Sciences (FGS) generated an alytical data for dissolved hexavalent

chromium for Sample Episode 6562. 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 samples FGS extracted and analyzed for dissolved hexavalent

chromium.

Table 1. 

# EPA Episode 6562 Dissolved Hexavalent Chromium – Sample Identification

EPA

Sample

# Sample

Matrix Sample Description Sampling

Date Analysis Date

71841 Aqueous FGD Influent Day 1 8/2/10 8/9/10

71842 Aqueous FGD Influent Day 2 8/3/10 8/9/10

71843 Aqueous FGD Influent Day 3 8/4/10 8/9/10

71844 Aqueous FGD Influent Day 4 8/5/10 8/30/10

71845 Aqueous FGD Bior eactor Influent Day 1 8/3/10 8/9/10

71846 Aqueous FGD Bior eactor Influent Day 2 8/4/10 8/9/10

71847 Aqueous FGD Bior eactor Influent Day 3 8/5/10 8/30/10

71848 Aqueous FGD Bior eactor Influent Day 4 8/6/10 8/30/10

71849 Aqueous FGD Bioreactor E ffluent Day 1 8/3/10 8/9/10

71850 Aqueous FGD Bioreactor E ffluent Day 2 8/4/10 8/30/10

71851 Aqueous FGD Bioreactor E ffluent Day 3 8/5/10 8/30/10

71852 Aqueous FGD Bioreactor E ffluent Day 4 8/6/10 8/30/10

71853 Aqueous FGD Bioreactor Infl uent Dup Day 3 8/5/10 8/30/10

71854 Aqueous FGD Bioreactor Effl uent Dup Day 2 8/4/10 8/30/10

71855 Aqueous FGD Influent Field Blank Day 1 8/2/10 8/9/10

71856 Aqueous FGD Bioreact or Influent Field Blank Day 1 8/3/10 8/9/10

71860 Aqueous FGD Bioreact or Effluent Field Blan k Day 1 8/3/10 8/9/10



# 1

# SUMMARY

The sam ples were prepared for dissolved hexavalent chromium analysis according to

FGS-129.01 Standard Operating Procedure (SOP), a modified EPA Method 218.6.

Several samples (71841, 71842, 71843, 71844, 71845, 71846, 71847, 71848, 71849,

71850, 71851, 71852, 71853, and 71854) were diluted prior to analysis due to the

presence of high levels of nontarget chloride interferences.

There were no issues requiring additional data qualifiers fo r the hexavalent chromium

data in this episode.

SAMPLE RECEIPT, HANDLIN G, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INITIAL PRECISION AND ACCURACY/RECOVERY

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

method criteria.

ON-GOING PRECISION AND ACCURACY/RECOVERY

The analytical method did not require the analysis of an on-going precision and recovery

(OPR).

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysis day. The initial calibration for

the LC-ICP-MS analysis consisted of a bl ank and eight calibration standards with a

correlation factor ≥ 0.995 as required by the method.

A secondary source initial calib ration verification (ICV) wa s analyzed and passed ± 10%

of true value required by the method.

CONTINUING CALIBRATION VERIFICATION

All CCVs met method-specified criteria, ± 10% of true value with recoveries ranging

from 95 to 107%.

BLANK

All of the preparation blanks/laboratory reagent blanks (LRBs) and the continuing

calibration blanks (CCBs) met met hod-specified requirements.

2

# 3 OTHER CHECKS

The laboratory control sample/duplicate (LCS/LCSD) or laboratory fortified

blank/duplicate (LFB/LFBD) pa ssed method criteria of ± 10% of true value with

recoveries of 97.9% and 102%. A second set of LFB/LFBD, for the later analysis date,

had recoveries of 100% and 95.5%. The method suggested that a s econd source quality

control sample (QCS) must be analyzed by the laboratory at least once a quarter. The

second source ICV meets this recommendation.

DETECTION LIMITS

The laboratory method detection limit (MDL ) in the synthetic matrix was 0.392 ug/L.

Results below this MDL were reported as not detected.

DUPLICATES

There were no laboratory 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. Sample 71854 was a duplicate of

effluent sample 71850. These samples were non detects (NDs), indicating the analyte was

not detected at or above the method detect ion limit. Sample 71853 was a duplicate of

influent sample 71847. These samples were also NDs.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The MS and matrix spike duplicate (MSD) we re performed using a secondary source

spike on samples 71844, 71848, and 71851. All MS/M SD recoveries were within 75%-

125%, with RPDs of 0.461%, 0.274% , and 4.03%, 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: Donna Tedder, ERG

Date: 9/1/2011

Subject: TestAmerica Data Review Narrative fo r Classicals Analyses – Episode 6562

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry

analyses for Sample Episode 6562. 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 6562 Classical An alytes – Sample Identification

EPA

Sample # Sample

Matrix Sample Description Sampling

Date

71841 Water FGD Influent, Day 1 8/23/10

71842 Water FGD Influent, Day 2 8/24/10

71843 Water FGD Influent, Day 3 8/25/10

71844 Water FGD Influent, Day 4 8/26/10

71845 Water FGD SBR Influent, Day 1 8/24/10

71846 Water FGD SBR Influent, Day 2 8/25/10

71847 Water FGD SBR Influent, Day 3 8/26/10

71848 Water FGD SBR Influent, Day 4 8/27/10

71849 Water FGD SBR Effl uent, Day 1 8/24/10

71850 Water FGD SBR Effl uent, Day 2 8/25/10

71851 Water FGD SBR Effl uent, Day 3 8/26/10

1

# Table 1. EPA Episode 6562 Classical An alytes – Sample Id entification

EPA

Sample # Sample

Matrix Sampling

Sample Description Date

71852 Water FGD SBR Effl uent, Day 4 8/27/10

71853 Water FGD SBR Influent - Duplicate 8/26/10

71854 Water FGD SBR Efflue nt - Duplicate 8/25/10

SUMMARY

All samples were analyzed within the holdi ng time specified in 40 CFR 136 Table II. All

samples were preserved appropriately.

Two field duplicate samples were collected a nd 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 otherwise noted below. Additionally, un less otherwise noted, all calibration blanks

and calibration verification samples met the criteria specified in the method.

If required by the method, the quality control sample (QCS), a 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 crit eria specified in the method unless specified

below.

If required by the method, a matrix spike (MS) sample was analyzed on samples 71848

(FGD bioreactor influent) a nd 71851 (FGD bioreactor effluent ) for each analyte to check

for matrix interferences. For some analytes , TestAmerica spiked more samples than

required. All MS samples analyzed met the criteria specified in the method unless

described below.

DATA NOTES/ISSUES

Ammonia

The MS and MSD results for sample 71841 were above the calibration range. Because

the percent recoveries were within the control limits specified by EPA method 350.1, the

laboratory did not reanalyze the samples usi ng a higher dilution fact or. If reported, the

MS and MSD results will be qualified as estimated values. The result for sample 71841

2

# was within the calibra tion range, so this sa mple was not qualified. The LFB associated

with this sample met the method criteria.

BOD 5



# The data reviewer identified no issues. All gl ucose-glutamic acid standards, water blanks,

and laboratory duplicates were analyzed approp riately and met the criteria specified in

SM 5210B.

Chloride and Sulfate

The MS and MSD results for samples 71848 and 71851 for sulfate and chloride were

above the calibration curve. TestAmerica di d not reanalyze the samples with a higher

dilution factor because the percent recove ries were within EPA method 300.0 control

limits. If reported, these MS and MSD results will be qualified as estimated values. The

LFB associated with this sa mple met the method criteria.

COD

The RPD between sample 71847 and its field duplicate 71853 was 37.0%. Even though

the RPD was greater than 20%, the sample wa s not qualified because there are no specific

control limits for field duplicat es specified in EPA method 410.4.

The percent recoveries for the MS a nd MSD analyses for sample 71848 (FGD SBR

influent) and 71851 (FGD SBR effluent) were below the control limits of 90-110%

required by EPA method 410.4. The percent recove ries for the MS and MSD analyses for

sample 71848 were 71% and 72%, respectively, and the percent recoveries for the MS

and MSD analyses for sample 71851 were 75% and 76%, respectively. These low percent

recoveries suggest that results for samples with a sim ilar matrix (FGD SBR influent and

FGD SBR effluent) could be biased lo w. Samples 71848 and 71851 were qualified as

minimum values. The LFB percent recoveries a ssociated with all samples met the method

criteria.

Cyanide

Sample 71841 was preserved to a pH greater than 10 S.U. after sample collection, but

when the laboratory received the sample, the pH was neutral. The laboratory added more

NaOH to increase the pH to greater than 10 S.U. upon receipt. This sample was qualified

as an estimated value.

Cyanide was detected at 0.00273 mg/L in the laboratory reagent blank (LRB) associated

with samples 71841, 71842, 71845, and 71849 and also detected at 0.00274 mg/L in the

LRB associated with samples 71843, 71846, 71850, and 71854. Additionally, cyanide

was detected at 0.00586 mg/L in the LR B associated with samples 71844, 71847, 71848,

71851, 71852, and 71853. These blank results were greater than the MDL (0.0020 mg/L),

3

# but less than the RL (0.010 mg/L). Because all of the blank results were less than the RL,

no samples were qualified based on these LRB results.

Results for the following samples were less than the lowest calib ration standard (0.01

mg/L): 71850, 71851, 71852, and 71854. Because all of these samples were already

flagged by TestAmerica with a “J”, meaning the sample result was an estimated value

because it was less than the RL, no fu rther qualification was necessary.

The percent recoveries for the MS and MSD analyses of sample 71851 were both 22%.

The laboratory spiked the sample with 0.100 mg /L. The percent recove ries of both the

MS and MSD samples were outside of th e laboratory control criteria of 90-110%.

However, because there are no criteria fo r MS/MSD analyses specified in SM 4500 CN



# E and sample 71851 was already qualified with a “J” meaning the result was less than the

RL, further qualification was unnecessary.

The RPD between sample 71847 and its field duplicate 71853 was 26.9%. Even though

this RPD was greater than 20%, the samples were not qualified because there are no

specific control limits for field duplicates specified in SM 4500 CN

- 

# E.

Nitrate/Nitrite

The MS and MSD results for 71841 were above the calibration curve. Because the

percent recoveries were w ithin the control lim its specified by EPA method 353.2, the

laboratory did not reanalyze the samples usi ng a higher dilution fact or. If reported, the

MS and MSD results will be qualified as estimated values. The result for sample 71841

was within the calibration range, so this sa mple was not qualified. The LFB associated

with this sample met the method criteria.

Phosphorus

The percent recoveries for the MS/MSD anal ysis of sample 71851 were not within the

control limits of 90-110% specified in EPA Method 365.1, but were within the laboratory

control limits of 71-128%. Th e percent recoveries of th e MS and MSD samples were

83% and 86%, respectively. Sample 71851 was qualified by the laboratory with a “J”

meaning the result was less than the RL, so no further qualification was necessary. The

LRB percent recovery met the method criteria.

Samples 71842, 71845, 71846, 71849, 71850, 71851, and 71854 were less than the

lowest calibration standard (0.025 mg/L). Test America flagged these samples with a “J”,

so further qualification was not necessary.

The RPD between sample 71847 and its field duplicate 71853 for phosphorus was 22.2%.

The result for sample 71853 was greater than the MDL, but less than the RL and the

result for sample 71847 was the RL itself. The low concentrations of these samples might

be the reason for the high RPD. Even though the RPD was greater than 20%, the sample

4

# was not qualified because there are n o specific control limits for field duplicates specified

in EPA Method 365.1.

TDS

Constant weight was not achieved after 3 drying cycles for samples 71843, 71844, 71845,

71846, 71847, 71848, 71849, 71850, 71851, 71852, 71853, and 71854 in analytical batch

29115. It should be noted that the weight increa sed from the first weighing to the second

weighing for all samples. Method 2540C warns that samples which contain high levels of

calcium, magnesium, chloride, and sulfate may be hygroscopic meaning they absorb

moisture from the air. FGD wastewater contai ns high concentratio ns of all of these

species. This was likely the cause for the inconsistent weight calculations. The samples

were not qualified, but results may be biased high.

The RPDs for laboratory duplicates from samples 71842 and 71848 were less than 10%

as required by SM 2540C; however, the RPD for sample 71844 was 14%. Because the

RPD was greater than the method contro l limits, sample 71844 was qualified as an

estimated value.

TDS was detected above the MDL (4.7 mg/L), but below th e RL (10 mg/L) at 7.0 mg/L

in the method blank (MB) associated with sample 71841. Because the blank result was

less than the RL, no samples were qualified.

TKN

The percent recovery for the LFB associat ed with sample 71841 was not within the

method control limits of 90-110%, but was wi thin the laboratory control limits of 77-

115%. The percent recove ries for the LFB and LFBD were 89% and 90%, respectively.

Because the percent recovery of the LFB was below the method criteria, sample 71841

was qualified as a minimum value.

TestAmerica performed MS and MSD analys es on sample 71851. The percent recoveries

for the MS and MSD samples were 114% a nd 113%, respectively. The samples did not

meet the method control limits of 90-110%, but did meet the laboratory control limits of

54-131%. The LFB associated with this batch was within the labora tory control limits.

The sample concentration was greater than 4 times the spike amount in the MS and MSD

samples, so TestAmerica stated that the percent recoveries and RPDs could not be

reliably calculated. Sample 71851 was not qualified because it is not possible to

determine if the MS/MSD failure was a result of matrix interferences or caused by low

spiking level.

TKN was detected at 0.237 mg/L in the laborat ory reagent blank associated with samples

71842 - 71854. The blank result was greater than the MDL (0.077 mg/L), but less than

the RL (1.0 mg/L). Because the blank result was less than the RL, it was not necessary to

qualify any samples.

5

# 6 TSS

One laboratory duplicate was analyzed per ba tch. The RPDs for the laboratory duplicates

of samples 71841, 71842, 71848, 71851, and 71852 were less than 10% as required by

the method. However, the RPD for the labo ratory duplicate of sample 71854 was 18%.

Because the laboratory duplicate RPD was gr eater than the method control criteria,

sample 71854 was qualified as an estimated value.

The RPD between sample 71847 and its field duplicate 71853 was 80.9%. The RPD

between sample 71850 and its field duplicat e 71854 was 28.6%. Even though these RPDs

were greater than 20%, the samples were not qualified because there are no specific

control limits for field duplicates specified in SM 2540D.

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level Detected

71848 COD Minimum Value MS % recovery

below methodspecified criteria 130 mg/L

71851 COD Minimum Value MS % recovery

below methodspecified criteria 140 mg/L

71841 Cyanide Estimated Value pH upon receipt <

10 S.U. 1.2 mg/L

71844 TDS Estimated Value Lab duplicate

RPD > methodspecified criteria 11,000 mg/L

71841 TKN Minimum Value LFB % recovery

below methodspecified criteria 130 mg/L

71854 TSS Estimated Value Lab duplicate

RPD > methodspecified criteria 12 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 Set Up at the Influent to the FGD Wastewater Treatment System

# C

- 3 Figure C

- 3

. Composite Sample Collection Set Up at the Influent to the SBR System

# C

- 4 Figure C

- 4

. Composite Sample Collection Set Up at the Effluent from the SBR 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.

# D-6 6.2 Supplies

 

# Argon gas: High purity grade (99.99%).

 

# Helium gas: High purity grade (99.99%).

 

# Hydrogen gas: High purity grade (99.99%).

 

# Calibrated automatic pipettes or Class A glass volumetric pipettes.

7.0 Reagents and Standards

7.1 Storage and Shelf-Life

7.1.1 All standards must be stored in glass, FEP fluorocarbon or previously

unused polyethylene or polypropylene bottles. Standards stored at

concentrations as received from the vendor and mid-level dilutions must

be replaced prior to the expiration date assigned by the vendor. If no

expiration date is provided, the stocks and mid-level standards may be

stored for up to one year. They must be replaced sooner if verification

from an independent source indicates a problem (See section 10.3.5 for

initial calibration verification acceptance criteria).

7.1.2 Working standards, i.e., all standards at concentrations ready to

analyze on the ICP/MS (all except tuning mixes, ICSA and ICSAB

mixes, which are received at ready-to-use concentrations), are prepared

fresh daily.

7.2 Standards

7.2.1 Tuning Solution, 10 ppb

The tuning solution stock is purchased as a custom multi-element mix.

The concentrations of the constituents are shown in Attachment 5.

Prepare the Tuning Solution as detailed below.

 Obtain a clean 100 mL volumetric flask.

 Place 50 mL of reagent water and 2 mL of conc. 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

# D-7 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

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

# D-8 prepared in 2% HNO 3 

# and 0.5 % HCl acid to the concentrations shown

in Attachment 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

# D-9 wastewaters are being analyzed, and after any major changes to instrument

operating conditions. Concentrations of target elements observed should be less

than their reporting limits. In some cases it may not be possible to obtain

interference check solutions that are completely free of contamination. In this

case, results up to 5X the reporting limit are acceptable if it is possible to

demonstrate that the isotopic ratios correspond to natural abundances. For

example, the natural abundances of zinc isotopes are 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

# D-10 single element standard at the desired linear range. The result of the analysis

must be within 10% of the true value.

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.

# D-11 9.8 Matrix Spike / Matrix Spike Duplicate / Laboratory Fortified Sample Matrix /

Laboratory Fortified Matrix Duplicate (MS/MSD/LFSM/LFMD)

MS is prepared by taking a second aliquot of a selected sample and spiking it

with the analytes of interest as summarized in Attachment 8. An MSD is

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.

# D-12 10.2.4 Spike the LCS and MS/MSD samples per spiking protocols.

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.

# D-14 10.3.8 Continuing Calibration Verification (CCV) Standard

A 50  g/L CCV standard is analyzed after every set of ten samples and

at the end of the analytical sequence.

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)

# D-15 CCV

CCB

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: % 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 DU1 = Sample result

DU2 = Sample duplicate result

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.

# D-17  

# Analyze the IDL blanks on three non-consecutive days.

 

# The IDL is equal to three times the standard deviation of the blank results.

12.3 Demonstration of Capabilities

All personnel are required to perform an initial demonstration of proficiency

(IDOC) on the instrument they will be using for analysis prior to testing samples.

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.

# D-18 15.2 EPA Method 1638, “Determination of Trace Elements in Ambient Waters by

Inductively Coupled Plasma – Mass Spectrometry, January 1996

16.0 Attachments

Attachment 1: Recommended Elemental Equations

Attachment 2: Internal Standards and Corresponding Metals

Attachment 3: Sample Preservation and Holding Times

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.

####