# Sampling Episode Report

Duke Energy Carolinas’

Allen Steam Station

Belmont, NC

Sampling Episode 6561

Prepared for:



# U.S. Environmental Protection Agency

Engineering and Analysis Division

Office of Water

1200 Pennsylvania Avenue, NW

Washington, D.C. 20460

Prepared by:



# Eastern Research Group, Inc.

14555 Avion Parkway

Suite 200

Chantilly, VA 20151

13 April 2012

EPA Contract No. 68-C-02-095

Work Assignment 9-29

# i CONTENTS

Page

1. I NTRODUCTION 

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

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

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

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

2. F ACILITY 

# O VERVIEW 

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

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

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

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

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

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

3. S AMPLE 

# C OLLECTION 

# .......................................................................................................3-8

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

3.1.1 Influent to FGD Wastewat er Treatment System......................................3-9

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

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

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

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

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

4. 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 .......................................................................................5-3

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 Collecti on Information, Allen ..................................................................... 3-19

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

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

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

Table 3-5. Analytical Methods, Allen........................................................................................ 3-2 5

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Allen.......................................................................................................................... ...... A-4

# LIST OF TABLES (Continued)

Page

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

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

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

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

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

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

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

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

Table A-9. Effluent from Bi oreactor System, Day 1 Analyt ical Results, Allen...................... A-25

Table A-10. Effluent from Bi oreactor System, Day 2 Analyt ical Results, Allen.................... A-28

Table A-11. Effluent from Bi oreactor System, Day 3 Analyt ical Results, Allen.................... A-31

Table A-12. Effluent from Bi oreactor System, Day 4 Analyt ical Results, Allen.................... A-34

Table A-13. Duplicate of Influe nt to Bioreactor System Anal ytical Results, Allen................ A-37

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

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

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

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

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

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

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

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

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

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

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

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

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

Allen.......................................................................................................................... .... A-58

# LIST OF TABLES (Continued)

Page

iv Table A-24. Effluent from Bi oreactor System Field Blank, Day 4 Analytical Results,

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

# v LIST OF FIGURES

Page

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

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

Wastewater Treatment System, Allen.............................................................................. 2-7

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

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

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

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

Figure C-4. Sample Collection Set-Up at th e Influent to the Bioreactor System........................C-4

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

# 1-1 1. I NTRODUCTION



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

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

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

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

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

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

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

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

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

to the bioreactor system also represents the e ffluent 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.

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

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

generating units;

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

all five generating units;

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

includes the following steps:

— Equalization,

— pH adjustment (lime addition),

— Ferric chloride addition,

— Polymer addition,

— Clarification,

— Filtration, and

— Biological treatment (nitrogen and metals);

# 1-2  The plant operates a selective non-cataly tic reduction (SNCR) system on all five

generating 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 Allen on Oct ober 22, 2009. The informati on collected during the

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

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

which describes the sample collection pro cedures used during the sampling episode.

On Sunday, August 1, 2010, EPA arrived at Allen to meet with plant personnel, receive

on-site safety training, review the sampling poi nts, and determine the set-up for the sample

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

through Friday (August 2 – 6, 2010). The following personnel participated in EPA’s sample

collection activities:

 Ron Jordan, EPA/EAD;

 Bill Swietlik, EPA/EAD;

 TJ Finseth, ERG;

 Kavya Kasturi, ERG;

 Lydia Lambert, ERG;

 Jennifer Lewis, ERG; and

 Jessica Wolford, ERG.

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

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

industry. During the sampling epis ode, UWAG acted as Allen’s representative and collected

samples on behalf of the plant.

# 2-1 2. F ACILITY 

# O VERVIEW



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

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

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

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

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

Catawba River.

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

3) to control the sulfur dioxide (SO 2 

# ) releases from the plant. Units 1, 2, and 5 exhaust to FGD

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

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

remove more than 95 percent of SO 2 

# from the flue gas. With the recent addition of the FGD

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

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

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

respectively.

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

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

oxide (NO

x 

# ) emissions from the plant. Additionall y, the boilers are operated with low-NO

x 

# burners and a separated overfire air system.

The ESPs at Allen are particulate contro l devices that are de signed to remove 99.9

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

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

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

handling the fly ash wet by sluicing the fly as h in the hoppers and tr ansferring the fly ash

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

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

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

All five generating units have the following configuration:

 Boiler (SNCR system contained in boiler);

 Air preheater;

 ESP; and

 FGD scrubber system.

2.1 FGD Scrubber System

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

generating units. The plant uses limestone slurry as the sorbent for su lfur dioxide absorption.

Limestone and service water are fed to on-site ba ll mills, which pulverize the limestone to create

the slurry. From the ball mills, the slurry is tr ansferred to hydrocyclones to collect limestone

particles that are too la rge for use in the FGD system. The underflow from the hydrocyclones is

transferred to the reject tank and then sent back to the ball mill for additional processing. The

# 2-2 overflow from the hydrocyclones, which is approxima tely 30 percent solids, is transferred to the

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

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

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

levels; however, the plant typically operates onl y three levels at one time. The slurry is

pressurized and sprayed downward into the scru bber vessel through spray nozzles. As the slurry

falls downward and the flue gas flows countercurr ent to the slurry, the spray droplets of the

limestone slurry contact the flue gas and absorb the SO 2 

# , which reacts with the limestone

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

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

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

Allen intermittently blows down the gypsum slu rry from the reaction tank to control the

solids and/or chlorides concentration in the sc rubbers. The chlorides concentration in the

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

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

scrubber is 14 to 16 percent.

The gypsum slurry is pumped to the prim ary hydrocyclones where the solid gypsum is

separated from the water by centrifugal force. The solid gypsum is forced outward to the walls of

the hydrocyclones and falls downward, while the wa ter exits the top of the hydrocyclones. The

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

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

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

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

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

0.5 to 0.8 percent solids.

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

to the belts to reduce the chlorides in the gyps um to typically less th an 20 ppm. The vacuum

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

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

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

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

Carolina.

2.2 FGD Wastewater Treatment System

The FGD wastewater treatment system is de signed to receive intermittent transfers of

FGD wastewater from the FGD sy stem, which consists of seconda ry hydrocyclone overflow, at a

flow rate of approximately 400 gallons per minut e (gpm). The FGD wastew ater treatment system

consists of chemical precipitation and biologi cal treatment technologies. Allen installed the

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

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

wastewater treatment system contains the following treatment operations:

# 2-3  Physical/Chemical Separation:

— Equalization,

— pH adjustment (lime addition),

— Ferric chloride addition,

— Polymer addition,

— Clarification, and

— Filtration; and

 Biological Reactors:

— Cooling (heat extraction),

— Nutrient addition,

— First-stage biological reaction,

— Nutrient addition, and

— Second-stage biological reaction.

Figures 2-1 and 2-2, located at the end of this section, present 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 wastewat er treatment syst em. Allen also

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

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

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

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

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

and off-specification biologi cal treatment effluent.

2.2.1 Physical/Chemical Separation

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

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

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

reaction tank 3, in which fe rric chloride is added.

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

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

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

it enters the clarifiers. Hydrochl oric acid is added to the wast ewater at a point between the

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

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

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

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

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

is sent to a sump and then tran sferred to the equalization tank.

# 2-4 The sludge collected in the clarifier is tran sferred to a sludge hol ding tank. A portion of

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

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

filtrate is recycled to the equalization tank.

2.2.2 Biological Reactors

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

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

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

withstand the high levels of ch lorides in the FGD wastewater entering the biological treatment

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

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

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

In the bioreactor portion of th e treatment, Allen treats the wa stewater in two stages. Each

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

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

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

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

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

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

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

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

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

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

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

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

pH levels could affect the performance of the microbes a nd potentially allow nondesirable

microbes to propagate.

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

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

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

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

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

flow into the cell.

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

plant pumps the effluent from the first-stage bi oreactor cells backward s through each cell and it

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

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

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

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

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

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

# 2-5 cells are primarily anoxic and do not produce as much gas as the first-stage cells, requiring less

frequent degassing than the first-stage cells.

From the second stage of the bioreactor trea tment system, the wastew ater is commingled

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

basin is discharged to the Catawba River via Outfall 002.

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

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

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

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

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

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

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

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

the system and feed nutrients to the bi oreactors to sustain biological growth.

2.2.3 Sampling Points

Figure 2-2 presents the sampling points for the Allen sampling episode; they are

summarized below:

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

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

sample was collected prior to any chem ical addition or mixing with recycle

streams);

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

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

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

effluent is commingled with the heat exchanger cooling water.

# 2-6Figure 2-1. Simplified Diagram of theFGD Wastewater Treatment System, Allen

# 2-7Figure 2-2. Physical/ChemicalSeparation and Biological Reactor Portionof FGD Wastewater Treatment System, Allen

# 3-8 3. S AMPLE 

# C OLLECTION



# During the Allen sampling episode, the samp ling team followed the collection protocols

specified in the Sampling Plan. Section 3.1 desc ribes the sampling points, sample collection

methods, and field measurements. Section 3.2 desc ribes the list of analytes and the sample

preservation procedures. Secti on 3.3 discusses the plan t operational data collected during the

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

activities.

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

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

measurements. Additional details are available in Section 3 of the Sampling Plan. Figures 2-1

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

including sampling point locations.

Table 3-1 lists the sampling points, sampli ng point descriptions, type of sample

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

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

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

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

sample identification and the sample points for each day.

The sampling points for this episode were:

 SP-1 Influent to FGD Wastewater Treatment System;

 SP-2 Influent to Bioreactor System;

 SP-3 Effluent from Bioreactor System;

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

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

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

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

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

For all the sampling points, EPA collected sp lit samples with Allen’s representative by

inserting a “Y” splitter into the sample tubing configuration at each sampling point to allow for

split sample collection. EPA collected all sample s (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 Allen’s re presentative collected duplicate samples, with

one filling the bottle immediately after the other.

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

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

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

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

shallow lip and a flip-top lid 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

# 3-9 “clean hands / dirty hands” techniques, where by the inner bag is ha ndled only by the “clean

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

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

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

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

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

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

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

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

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

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

protocols.

3.1.1 Influent to FGD Wastewater Treatment System

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

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

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

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

the wastewater treatment system are fairly cons istent during the purge. In addition, due to the

relatively high concentration of suspended solids , the FGD purge was not amenable to collecting

representative split samples usi ng composite sampling techniques.

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

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

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

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

the sampling point due to truck traffic.

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

treatment system (SP-1), the sampling team collected field blanks (SP-6) for total mercury, total

and dissolved metals, and dissolved hexavalent chromium. See Section 5 .2.3 for a description of

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

system.

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

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

wastewater piping. The end of th e silicone tubing was fitted w ith a “Y” splitter, with two

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

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

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

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

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

dissolved metals samples).

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

3.1:

# 3-10  Total and dissolved mercury;

 Total metals by 200.8; and

 Total metals by 200.7.

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

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

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

untouched to allow the solids in the wastewater to settle.

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

temperature were measured immediately at the 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 Allen’s representatives. Fi gure C-3, in Appendix C, is a

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

The sampling team placed the end of the Teflon® tubing into the 10-lit er container filled

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

solids in the wastewater had b een settling for approximately 70 minutes. Approximately 0.5- 1

liters of sample were pumped through the tubi ng/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.

# 3-11 3.1.2 Influent to Bioreactor System

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

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

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

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

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

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

or rain concerns during the sample collection.

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

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

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

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

volumes into the individual sample containers.

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

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

analytes (i.e., BOD 5 

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

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

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

grab sample for cyanide during each compositing period.

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

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

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

system.

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

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

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

tap, one end was threaded through the 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-4, in Appendix C, is a picture of the composite sampling

set-up at the influent to the bioreactor system.

# 3-12 Immediately after setting up the compositors, ERG collected the first set of the total and

dissolved mercury grab samples. At the first gr ab sample every day, ERG collected field blanks

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

procedures at the influent to the bioreactor system.

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

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

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

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

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

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

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

bioreactor system.

After the collection of the 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 Allen’s representatives; theref ore, duplicate samples were collected. The total

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

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

were detected during the sampling episode at the influent to the bi oreactor system. ERG

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

placed the samples on ice.

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

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

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

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

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

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

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

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

# 3-13 the capsule filter effluent, which was attached to a “Y” splitter and two lengths of silicone

tubing. This set-up allowed EPA to collect “tru e” split samples with A llen’s representative.

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

On Day 1 only, prior to collec ting any samples of the influent to the bioreactor system,

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

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

bioreactor system.

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

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

the bioreactor system. After the tubing and filter we re purged with two liters of sample, samplers

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

 Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

Hexavalent chromium samples were immediately placed on ice after sample

collection. After the dissolved metals had b een collected, the filter was removed. Once the

tubing was purged with two liters of sample, sa mplers collected the following samples using a

“cleanbox,” as described in Section 3.1:

 Total metals by 200.8; and

 Total metals by 200.7.

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

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

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

# ),

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

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

# , Group I, and Group II samples were

immediately placed on ice af ter sample collection.

For all analytes, ERG collected QC samples at the influent to the bi oreactor system (SP2) on Day 4 of the sampling episode. In additi on, for all analytes, ERG collected a duplicate

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

3.1.3 Effluent from Bioreactor System

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

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

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

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

or rain concerns during the sample collection.

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

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

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

# 3-14 24-hour composite period. Following the composite period, ERG pumped off the specific sample

volumes into the individual sample containers.

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

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

analytes (i.e., BOD 5 

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

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

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

grab sample for cyanide during each compositing period.

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

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

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

system.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

each individual sample aliquot.

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

set-up at the effluent from the bioreactor system.

Immediately after setting up the compositors, ERG collected the first set of the total and

dissolved mercury grab samples. At the first gr ab sample every day, ERG collected field blanks

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

procedures at the effluent from the bioreactor system.

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

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

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

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

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

directly from the tap, ERG was not able to coll ect split samples with Allen’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

# 3-15 replaced for each set of mercury grab samples. After collecting each set of mercury grabs, ERG

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

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

the bioreactor system.

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

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

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

split samples with Allen’s representatives; theref ore, duplicate samples were collected. The total

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

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

were detected during this sampling episode at the effluent from the bioreactor system. ERG

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

placed the samples on ice.

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

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

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

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

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

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

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

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

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

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

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

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

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 “tru e” split samples with A llen’s representatives.

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

On Day 1 only, prior to collec ting any samples of the effluent from the bioreactor system,

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

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

the bioreactor system.

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

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

the bioreactor system. After the tubing and filter were purged with 1-2 liters of sample, samplers

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

# 3-16  Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

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

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

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

described in Section 3.1:

 Total metals by 200.8; and

 Total metals by 200.7.

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

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

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

# ),

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

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

# , Group I, and Group II samples were

immediately placed on ice af ter sample collection.

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

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

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

3.2 List of Analytes and Sample Preservation

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

 Classicals:

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

— Chemical oxygen demand (COD),

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus,

— Total cyanide;

 Total Metals 1 

# :

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

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

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

titanium, vanadium, and zinc.

1 

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

# 3-17  Dissolved Metals:

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

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

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

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

concentrations.

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

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

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

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

collection, the samplers placed the BOD 5 

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

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

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

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

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

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

hexavalent chromium samples were 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, Allen pl ant personnel provided the sampling team

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

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

operating characteristics, Table 3-9 presents th e FGD scrubber system operating characteristics,

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

presents information on the FGD scrubber slu rry generation during th e sampling episode, and

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

3.4 Deviations from the Sampling and Analysis Plan

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

described below:

 Preservation of hexavalent chromium: EPA planned to preserve the hexavalent

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

buffer solution; however, since the 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.

# 3-18  Collection of composite metals and cl assicals samples at SP-2 (Day 4): On

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

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

and metals compositors. Both compositors collected sample aliquot 13 as

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

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

collected by the metals compositor followed immediately by the classicals

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

and 0:01 for the classicals.

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

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

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

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

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

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

compositor followed immediately by the classicals compositor. Sample aliquot

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

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

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

representatives collected the total metals volumes before collecting total and

dissolved mercury samples. Allen’s re presentatives were collecting metals

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

vice versa.

# 3-19 Table 3-1. Sample Collection Information, Allen

Sampling

Point

Number Sampling Point Description Type of

Sample Sample

Collection Date Sample Collection Time

Influent to FGD Wa stewater Treatment

System – Day 1 Grab 8/2/10 1022 a 

# and 1148 b



# Influent to FGD Wa stewater Treatment

System – Day 2 Grab 8/3/10 1136 a 

# and 1312 b



# Influent to FGD Wa stewater Treatment

System – Day 3 Grab 8/4/10 1127 a 

# and 1311 b 

# SP-1

Influent to FGD Wa stewater Treatment

System – Day 4 Grab 8/5/10 1139 a 

# and 1323 b



# Composite 8/2/10

8/3/10 0900 c



# 1040 d 

# Influent to Bioreact or System – Day 1

Grab 8/2/10

8/3/10 0913 e 

# , 1519 f 

# , and 2121 g



# 0319 h



# Composite 8/3/10

8/4/10 0901 c



# 1031 d 

# Influent to Bioreact or System – Day 2

Grab 8/3/10

8/4/10 0915 e 

# , 1516 f 

# , and 2119 g



# 0319 h



# Composite 8/4/10

8/5/10 0900 c



# 1017 d 

# Influent to Bioreact or System – Day 3

Grab 8/4/10

8/5/10 0915 e 

# , 1519 f 

# , and 2121 g



# 0319 h



# Composite 8/5/10

8/6/10 0900 c



# 0827 d 

# SP-2

Influent to Bioreact or System – Day 4

Grab 8/5/10

8/6/10 0914 e 

# , 1517 f 

# , and 2118 g



# 0323 h



# Composite 8/2/10

8/3/10 0730 c



# 0952 d 

# Effluent from Bioreactor System – Day 1

Grab 8/2/10

8/3/10 0742 e 

# , 1349 f 

# , and 1948 g



# 0149 h



# Composite 8/3/10

8/4/10 0729 c



# 0945 d 

# Effluent from Bioreactor System – Day 2

Grab 8/3/10

8/4/10 0745 e 

# , 1351 f 

# , and 1951 g



# 0149 h



# Composite 8/4/10

8/5/10 0731 c



# 0941 d 

# Effluent from Bioreactor System – Day 3

Grab 8/4/10

8/5/10 0744 e 

# , 1349 f 

# , and 1953 g



# 0150 h



# Composite 8/5/10

8/6/10 0730 c



# 0655 d 

# SP-3

Effluent from Bioreactor System – Day 4

Grab 8/5/10

8/6/10 0742 e 

# , 1346 f 

# , and 1946 g



# 0146 h



# SP-4 Duplicate of Influent to Bioreactor System

– Day 3 Composite 8/4/10

8/5/10 0900 c



# 1018 d

# 3-20 Table 3-1. Sample Collection Information, Allen

Sampling

Point

Number Sampling Point Description Type of

Sample Sample

Collection Date Sample Collection Time

Grab 8/4/10

8/5/10 0916 e 

# , 1520 f 

# , and 2123 g



# 0321 h



# Composite 8/3/10

8/4/10 0729 c



# 0945 d 

# SP-5 Duplicate of Effl uent from Bioreactor

System – Day 2

Grab 8/3/10

8/4/10 0745 e 

# , 1351 f 

# , and 1951 g



# 0149 h



# SP-6 Influent to FGD Wastewater Treatment

System Field Blank Grab 8/2/10 1006 i 

# and 1141 j



# Composite 8/2/10

8/3/10 0810 k



# 1028 l 

# Influent to Bioreactor System Field Blank

– Day 1

Grab 8/2/10 0907 m



# Influent to Bioreactor System Field Blank

– Day 2 Grab 8/3/10 0909 m



# Influent to Bioreactor System Field Blank

– Day 3 Grab 8/4/10 0910 m 

# SP-7

Influent to Bioreactor System Field Blank

– Day 4 Grab 8/5/10 0908 m



# Composite 8/2/10

8/3/10 0649 k



# 0940 l 

# Effluent from Bior eactor System Field

Blank – Day 1

Grab 8/2/10 0737 m



# Effluent from Bior eactor System Field

Blank – Day 2 Grab 8/3/10 0738 m



# Effluent from Bior eactor System Field

Blank – Day 3 Grab 8/4/10 0740 m 

# SP-8

Effluent from Bior eactor System Field

Blank – Day 4 Grab 8/5/10 0737 m

a 

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

dissolved mercury, and classicals (BOD 5 

# , Group I, Group II, and total cyanide).

b 

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

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

c 

# Started metals compositor. The classical compositor wa s started approximately two minutes after the metals

compositor.

d 

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

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

classicals (BOD 5 

# , Group I, and Group II).

e 

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

f 

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

g 

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

h 

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

i 

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

j 

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

field blank samples.

k 

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

l 

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

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

m



# Start time for the collection of total mercury field blank samples.3-21Table 3-2. Sample Collection at Allen 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 Treatment System 4 4 4 4 4 4 4 4 4 4 4SP-2 Influent to Bioreactor System4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-3 Effluent from Bioreactor System 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-4 Duplicate of Influent to Bioreactor System 1 1 1 1 1 1 1 1 1 1 1SP-5 Duplicate of Effluent from Bioreactor System 1 1 1 1 1 1 1 1 1 11SP-6 Influent to FGD Wastewater Treatment SystemField Blank1 1 1 1 1 1SP-7 Influent to Bioreactor SystemField Blank 1 1 1 1 4 1SP-8 Effluent from Bioreactor System Field Blank 1 1 1 1 4 1Total Number of Samples 17+2QC 17+2QC 17+2QC 17+2QC 23+2QC 14+2QC17+2QC 14+2QC 14+2QC 14+2QC 14+2QCaGroup I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate, and chloride.bGroup II includes ammonia as nitrogen, nitrate/nitrite as nitrogen, total Kjeldahlnitrogen (TKN), chemical oxygen demand (COD), and total phosphorus.3-22Table 3-3. Field Measurements, AllenTemperature (°C)pHSamplingPointNumberSampling Point DescriptionDateTimeThermometerProbeMeteraStripsWasteStream FlowRate (GPM)NotesInfluent to FGD WastewaterTreatment System – Day 18/2/1010344441.56.87 383bInfluent to FGD WastewaterTreatment System – Day 28/3/10 115044.548.56.727 375cInfluent to FGD WastewaterTreatment System – Day 38/4/10 114444476.777 374dSP-1Influent to FGD WastewaterTreatment System – Day 48/5/10 115944.547.06.727 377eNo detected sulfides or oxidants intotal cyanide grab.8/2/10 091738366.887 2978/2/10 15223937.46.907 3118/2/10 21253836.66.957 304Influent to Bioreactor System– Day 18/3/10 03243836.96.797 2998/3/10 092536.9386.997 2878/3/10 152037.9396.747 3348/3/10 212237.9396.697 281Influent to Bioreactor System– Day 28/4/10 032537.6396.667 2858/4/10 092038396.607 2928/4/10 152538.639.56.587 3138/4/10 212938.739.56.90NA 245Influent to Bioreactor System– Day 38/5/10 032637.739.56.62NA 2338/5/10 091739NA6.65NA 2008/5/10 15203938.66.576 2008/5/10 21223836.76.886 221SP-2Influent to Bioreactor System– Day 48/6/10 032638.537.26.966 221No detected sulfides or oxidants intotal cyanide grab.3-23Table 3-3. Field Measurements, AllenTemperature (°C)pHSamplingPointNumberSampling Point DescriptionDateTimeThermometerProbeMeteraStripsWasteStream FlowRate (GPM)Notes8/2/10 07453331.86.887 3248/2/10 13523332.66.807 3678/2/10 19543332.66.797 283Effluent from BioreactorSystem – Day 18/3/10 01523332.36.827 3458/3/10 075232.133.56.767 2678/3/10 135533.3346.667 3448/3/10 195833.3346.687 292Effluent from BioreactorSystem – Day 28/4/10 015632.8346.727 2108/4/10 074932.8346.828 2368/4/10 135533.734.56.737 3398/4/10 195733.834.56.71NA 315Effluent from BioreactorSystem – Day 38/5/10 015333.4346.78NA 2268/5/10 074334NA6.8NA 1908/5/10 13503534.26.866 2278/5/10 19503433.26.837 241SP-3Effluent from BioreactorSystem – Day 48/6/10 015033.532.86.827 225On day 4, it was noted that the 3rdgrab sample taken on 8/5/10 at1950 contained suspended whiteparticles. The particles appeared tobe fibrous in nature and measured 1to 3 mm in length No detectedsulfides 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 of flow meter measurements collected every minute from 1022 to 1036 on 8/2/10 (time of sample collection).cBased on average of flow meter measurements collected every minute from1136 to 1149 on 8/3/10 (time of sample collection).dBased on average of flow meter measurements collected every minute from 1127 to 1143 on 8/4/10 (time of sample collection).eBased on average of flow meter measurements collected every minute from 1139 to 1159 on 8/5/10 (time of sample collection).NA – Not analyzed.

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

Sample Number Sample Point Sample Description

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

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

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

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

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

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

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

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

71799 SP-3, Day 1 Effluent fr om Bioreactor System - Day 1

71800 SP-3, Day 2 Effluent fr om Bioreactor System - Day 2

71801 SP-3, Day 3 Effluent fr om Bioreactor System - Day 3

71802 SP-3, Day 4 Effluent fr om Bioreactor System - Day 4

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

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

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

71806 SP-7, Day 1 Influent to Bior eactor System Fiel d Blank - Day 1

71807 SP-7, Day 2 Influent to Bior eactor System Fiel d Blank - Day 2

71808 SP-7, Day 3 Influent to Bior eactor System Fiel d Blank - Day 3

71809 SP-7, Day 4 Influent to Bior eactor System Fiel d Blank - Day 4

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

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

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

71813 SP-8, Day 4 Effluent from Bi oreactor System Field Blank - Day 4

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

Parameter Method Number

Classicals

Biochemical oxygen demand (BOD 5 

# ) SM 5210 B

Chemical oxygen demand (COD) EPA 410.4

Total suspended solids (TSS) SM 2540 D

Total dissolved solids (TDS) SM 2540 C

Sulfate EPA 300.0

Chloride EPA 300.0

Ammonia as nitrogen EPA 350.1

Nitrate/nitrate as nitrogen EPA 353.2

Total Kjeldahl nitrogen (TKN) EPA 351.2

Total phosphorus EPA 365.1

Total cyanide SM 4500 CN E

Total and Dissolved Metals

Mercury EPA 1631E

Hexavalent chromium (dissolved only) EPA 218.6

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

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



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

molybdenum, sodium, tin, and titanium EPA 200.7

1 

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

# 3-26 Table 3-6. Summary of Sample Contai ner and Planned Preservation, Allen

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.

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

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

71791 Group II Volume 1 8/2/10 H 2 

# SO 4 

# 7 2 28

71791 Group II Volume 2 8/2/10 H 2 

# SO 4 

# 7 2 28

(NH 4 

# ) 2 

# SO 4



# Buffer 6.0 8.3 100 71791 Hexavalent Chromium 8/2/10

NH 4 

# OH 8.3 9.5 8

(NH 4 

# ) 2 

# SO 4



# Buffer 8.7 8.7 100 71805 Hexavalent Chromium 8/2/10

NH 4 

# OH 8.7 9.5 6

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

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

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

71792 Group II Volume 1 8/3/10 H 2 

# SO 4 

# 7 2 24

71792 Group II Volume 2 8/3/10 H 2 

# SO 4 

# 7 2 24

71795 Group II Volume 1 8/3/10 H 2 

# SO 4 

# 6 2 22

71795 Group II Volume 2 8/3/10 H 2 

# SO 4 

# 6 2 22

71799 Group II Volume 1 8/3/10 H 2 

# SO 4 

# 6 2 30

71799 Group II Volume 2 8/3/10 H 2 

# SO 4 

# 6 2 30

(NH 4 

# ) 2 

# SO 4



# Buffer Not

Measured 8.5 100 71792 Hexavalent Chromium 8/3/10

NH 4 

# OH 8.5 9.5 12

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.5 100 71795 Hexavalent Chromium 8/3/10

NH 4 

# OH 8.5 9.5 10

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.7 100 71799 Hexavalent Chromium 8/3/10

NH 4 

# OH 8.7 9.5 8

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.5 100 71806 Hexavalent Chromium 8/3/10

NH 4 

# OH 8.5 9.5 8

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.7 100 71810 Hexavalent Chromium 8/3/10

NH 4 

# OH 8.7 9.5 8

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

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

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

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

71793 Group II Volume 1 8/4/10 H 2 

# SO 4 

# 7 2 28

71793 Group II Volume 2 8/4/10 H 2 

# SO 4 

# 7 2 28

# 3-28 Table 3-7. Sample Preservation Summary, Allen

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

71796 Group II Volume 1 8/4/10 H 2 

# SO 4 

# 6 2 28

71796 Group II Volume 2 8/4/10 H 2 

# SO 4 

# 6 2 28

71800 Group II Volume 1 8/4/10 H 2 

# SO 4 

# 7 2 24

71800 Group II Volume 2 8/4/10 H 2 

# SO 4 

# 7 2 24

71804 Group II Volume 1 8/4/10 H 2 

# SO 4 

# 7 2 24

71804 Group II Volume 2 8/4/10 H 2 

# SO 4 

# 7 2 24

(NH 4 

# ) 2 

# SO 4



# Buffer Not

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

NH 4 

# OH 8.1 9.5 12

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.5 100 71796 Hexavalent Chromium 8/4/10

NH 4 

# OH 8.5 9.5 10

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.5 100 71800 Hexavalent Chromium 8/4/10

NH 4 

# OH 8.5 9.5 10

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.5 100 71804 Hexavalent Chromium 8/4/10

NH 4 

# OH 8.5 9.5 10

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

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

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

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

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

71794 Group II Volume 1 8/5/10 H 2 

# SO 4 

# 6 2 28

71794 Group II Volume 2 8/5/10 H 2 

# SO 4 

# 6 2 28

71797 Group II Volume 1 8/5/10 H 2 

# SO 4 

# 5 2 20

71797 Group II Volume 2 8/5/10 H 2 

# SO 4 

# 5 2 20

71801 Group II Volume 1 8/5/10 H 2 

# SO 4 

# 5 2 26

71801 Group II Volume 2 8/5/10 H 2 

# SO 4 

# 5 2 26

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

# SO 4 

# 5 2 26

71801 Group II Volume 2-QC 8/5/10 H 2 

# SO 4 

# 5 2 26

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

# SO 4 

# 5 2 20

71803 Group II Volume 2-QC 8/5/10 H 2 

# SO 4 

# 5 2 20

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.1 100 71794 Hexavalent Chromium 8/5/10

NH 4 

# OH 8.1 9.5 14

# 3-29 Table 3-7. Sample Preservation Summary, Allen

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

(NH 4 

# ) 2 

# SO 4



# Buffer 5 8.7 100 71797 Hexavalent Chromium 8/5/10

NH 4 

# OH 8.7 9.5 8

(NH 4 

# ) 2 

# SO 4



# Buffer 5 8.7 100 71801 Hexavalent Chromium 8/5/10

NH 4 

# OH 8.7 9.5 10

(NH 4 

# ) 2 

# SO 4



# Buffer 5 8.7 100 71803 Hexavalent Chromium 8/5/10

NH 4 

# OH 8.7 9.5 8

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

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

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

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

71798 Group II Volume 1 8/6/10 H 2 

# SO 4 

# 5 2 24

71798 Group II Volume 2 8/6/10 H 2 

# SO 4 

# 5 2 24

71798 Group II Volume 1-QC 8/6/10 H 2 

# SO 4 

# 5 2 24

71798 Group II Volume 2-QC 8/6/10 H 2 

# SO 4 

# 5 2 24

71802 Group II Volume 2 8/6/10 H 2 

# SO 4 

# 6 2 28

71802 Group II Volume 1 8/6/10 H 2 

# SO 4 

# 6 2 28

(NH 4 

# ) 2 

# SO 4



# Buffer 5 8.5 100 71798 Hexavalent Chromium 8/6/10

NH 4 

# OH 8.5 9.5 8

(NH 4 

# ) 2 

# SO 4



# Buffer 6 8.5 100 71802 Hexavalent Chromium 8/6/10

NH 4 

# OH 8.5 9.5 8

# 3-30 Table 3-8. Generating Unit Operating Charac teristics during Sample Collection, Allen

Unit ID Boiler Type Capacity

(MW) Electricity Production

(MW)

(or Percent Capacity %) SNCR

(No, On, Off) Particulate Control System

(HS/CS ESP, or BH)

1 Tangential Fired 185 65.9% On CS ESP

2 Tangential Fired 185 64.3% On CS ESP

3 Tangential Fired 300 62.3% On CS ESP

4 Tangential Fired 300 75.3% On CS ESP

5 Tangential Fired 300 60.3% On CS ESP



# CS ESP – Cold-side elect rostatic precipitator.

# 3-31Table 3-9. FGD Scrubber System Operating Characteristics, AllenUnit IDWet FGDSystem (Yes/No)Type ofScrubberForcedOxidation(Yes/No)SorbentAdditives (DBA,formic acid, etc.)FGD Make-upWater SourceSO2RemovalPercentageType of SolidsSeparation1 Yes Spray Yes LimestoneNone Catawba River 96%SecondaryHydrocyclones3 Yes Spray Yes LimestoneNone Catawba River 97%SecondaryHydrocyclones

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

Day of

Sampling Unit ID Coal Type Amount of Coal

Used During Day

of Sampling

(tpd) Source of Coal

(Coal Region

and/or State) Percent

Sulfur in

Coal

(%) Chlorine Content of

Coal

(ppm)

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



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



# 3 CAPP 736 WV/VA 0.96 1,200 a



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

# 1

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



# 1 CAPP 662 KY 0.98 1,289

2 CAPP 500 KY 0.98 1,289

3 CAPP 1,799 KY 0.98 1,317

4 CAPP 2,386 KY 0.98 1,317 2

5 CAPP 1,221 KY 0.96 1,266

1 CAPP 1,645 KY 1.0 1,327

2 CAPP 1,750 KY 1.0 1,327

3 CAPP 3,081 KY 0.99 1,353

4 CAPP 2,805 KY 0.99 1,353 3

5 CAPP 3,221 KY 0.99 1,297

1 CAPP 1,228 KY 0.98 1,069

2 CAPP 1,137 KY 0.98 1,069

3 CAPP 2,260 KY 0.96 1,092

4 CAPP 2,445 KY 0.96 1,092 4

5 CAPP 2,102 KY 1.01 1,061

a 

# – Estimated value.

CAPP – Central Appalachian Coal.

WV/VA – West Virginia/Virginia region.

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

Scrubber Slurry

Blowdown Flow Rate

Day of

Sampling FGD

System ID Associated

Unit IDs Flow Rate

(gpm) Duration 

# Scrubber

Slurry

Percent

Solids Time of

Dewatering

During

Sampling Day Percent

Filtrate

Recycled

Back to

Scrubber

1 1/2/5 URE a 

# 13 hrs 13% dewatered 5 times 100%

1

3 3/4 URE a 

# 13 hrs 12% dewatered 5 times 100%

1 1/2/5 URE a 

# 12 hrs 14% dewatered 5 times 100%

2

3 3/4 URE a 

# 9 hrs 14% dewatered 4 times 100%

1 1/2/5 URE a 

# 9 hrs 15% dewatered 4 times 100%

3

3 3/4 URE a 

# 8 hrs 15% dewatered 5 times 100%

1 1/2/5 URE a 

# 7 hrs 15% dewatered 3 times 100%

4

3 3/4 URE a 

# 6 hrs 15% dewatered 3 times 100%

a 

# – Unable to reasonably estimate.

# 3-34Table 3-12. FGD Wastewater Treatment System Operation Information, AllenScrubber PurgeChemical UsageDay ofSamplingFlow Rate(gpm)Duration(hr)Lime35% FerricChlorideOrganosulfide:NAPolymer:Nalco 7130730 % HCl1 375 17pH – 8.5 S.U.1,200 lbs40 ppm19.6 gpdNA6.5 ppm3.3 gpdpH – 6.8 S.U.390 gpd2 371 16pH – 8.5 S.U.1,200 lbs40 ppm19.2 gpdNA6.5 ppm3.1 gpdpH – 6.8 S.U.400 gpd3 371 14pH – 8.5 S.U.1,200 lbs40 ppm19.3 gpdNA6.5 ppm3.1 gpdpH – 6.8 S.U.400 gpd4 366 10pH – 8.5 S.U.1,200 lbs40 ppm14.7 gpdNA6.5 ppm2.3 gpdpH – 6.8 S.U.390 gpd

# 4-1 4. L ABORATORY 

# A NALYTICAL 

# R ESULTS AND 

# D ISCUSSION



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

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

system.

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

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

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

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

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

mercury samples were subjected to a 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 Allen, including all

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

respectively.

Tables 4-1 through 4-3 include the analytical results for all analytes for which EPA

conducted analyses. Results are rounded to thre e significant digits. If an analyte was not

detected in a sample above the method detection limit, the result is reported as “ND” followed by

the sample-specific quantitation limit in parenthe ses. If an analyte was measured above the

method detection limit, but below the quantitation limit, the result is reported as “NQ” followed

by the sample-specific quantitation limit in parentheses.

For Table 4-2 (influent to the bioreactor system), a duplicate sample was collected on

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

of the original and the duplicate sample results. Table 5-1 presents the analytical results for the

original and duplicate results and the calculated re lative percent difference (RPD). For Table 4-3

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

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

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

results and the calculated RPD.

When calculating the average concentrations for the duplicate samples or for the 4-day

averages, ERG used the following methodology:

 If all results were above the quantitati on limit, then all results were averaged

together;

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

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

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

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

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

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

the average of the sample-specific quantitation limits; and

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

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

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

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

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

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

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

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

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

# 4-3 the sample collection across the treatment system was not timed to reflect the amount of time it

takes the wastewater to pass through the system.

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

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

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

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

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



# 4-4Table 4-1. Influent to FGD Wastewater Treatment System, AllenInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmoniamg/L350.11.407.3014.09.007.93Nitrate Nitrite as Nmg/L353.214.017.020.022.018.3Nitrogen, Total Kjeldahlmg/L351.216.021.026.045.027.0Biochemical Oxygen Demandmg/L5210B40.0B9.70B9.406.6016.4Chemical Oxygen Demandmg/L410.4110*NQ (200)*130140< 120Chloridemg/L300.02,8003,4004,2005,2003,900Sulfatemg/L300.01,4001,3001,3001,3001,330Cyanide, Totalmg/L4500 CN E0.2500.3400.1900.240B0.255Total Dissolved Solidsmg/L2540C7,0008,90011,00011,0009,480Total Suspended Solidsmg/L2540D1,8003,9002,0002,2002,480Phosphorus, Totalmg/L365.10.350NQ (0.0500)NQ (0.0500)NQ (0.0500)< 0.106Total MetalsAluminumug/L200.770,00076,00072,00071,00072,300Antimonyug/L200.89.3011.011.012.010.8Arsenicug/L200.8120140140140135Bariumug/L200.7750880930990888Berylliumug/L200.710.012.012.012.011.5Boronug/L200.754,000B62,000B80,000B100,000B74,000Cadmiumug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)4.00< 2.50Calciumug/L200.71,900,0002,300,0002,400,0002,700,0002,330,000Chromiumug/L200.8120^140^130^140^133Cobaltug/L200.752.059.064.067.060.5Copperug/L200.8140160160180160< - 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.



# 4-5Table 4-1. Influent to FGD Wastewater Treatment System, AllenInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageIronug/L200.764,00069,00068,00070,00067,800Leadug/L200.885.099.0100120101Magnesiumug/L200.7440,000470,000520,000590,000505,000Manganeseug/L200.73,3003,7004,1004,6003,930Mercuryng/L1631E50,30049,60044,60052,10049,200Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)41.0< 25.3Nickelug/L200.8160190190210188Seleniumug/L200.81,5001,7001,8001,8001,700Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.729,00032,00034,00038,00033,300Thalliumug/L200.82.503.203.303.103.03Tinug/L200.7NQ (200)NQ (200)NQ (200)NQ (200)NQ (200)Titaniumug/L200.71,4001,5001,6001,6001,530Vanadiumug/L200.8130150160180155Zincug/L200.8220280280330278Dissolved MetalsAluminumug/L200.7NQ (200)NQ (200)ND (200)ND (200)NQ (200)Antimonyug/L200.82.002.803.504.003.08Arsenicug/L200.88.7010.010.07.108.95Bariumug/L200.7250310410500368Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.750,000B59,000B80,000B100,000B72,300Cadmiumug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Calciumug/L200.71,500,0001,700,0002,000,0002,500,0001,930,000< - 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.



# 4-6Table 4-1. Influent to FGD Wastewater Treatment System, AllenInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageChromiumug/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)20.022.025.0< 19.3Copperug/L200.812.012.011.08.9011.0Ironug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.7400,000440,000500,000550,000473,000Manganeseug/L200.72,8003,1003,6004,0003,380Mercuryng/L1631E15.221.016.475.031.9Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)Nickelug/L200.871.077.080.093.080.3Seleniumug/L200.8230290340400315Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.728,00031,00036,00040,00033,800Thalliumug/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/L200.8ND (10.0)NQ (10.0)NQ (10.0)NQ (10.0)NQ (10.0)Zincug/L200.830.043.032.043.037.0Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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.E – MS and/or MSD exceeded the calibration range.F – MS and/or MSD not within laboratory control limits.



# 4-7Table 4-2. Influent to the Bioreactor System, AllenInfluent to the Bioreactor System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmoniamg/L350.15.806.808.8511.08.11Nitrate Nitrite as Nmg/L353.214.013.013.013.0E,F13.3Nitrogen, Total Kjeldahlmg/L351.27.708.6010.53.20F7.50Biochemical Oxygen Demandmg/L5210B7.40B5.203.653.905.04Chemical Oxygen Demandmg/L410.4NQ (200)*79.0< 72.084.0F< 83.8Chloridemg/L300.03,1003,2003,3003,6003,300Sulfatemg/L300.01,4001,4001,4001,4001,400Cyanide, Totalmg/L4500 CN ENQ (0.100)NQ (0.100)0.1300.110B< 0.0850Total Dissolved Solidsmg/L2540C7,5007,8007,1507,8007,560Total Suspended Solidsmg/L2540DNQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Phosphorus, Totalmg/L365.10.0610NQ (0.0500)NQ (0.0500)NQ (0.0500)< 0.0340Total MetalsAluminumug/L200.7ND (200)ND (200)ND (200)NQ (200)BNQ (200)Antimonyug/L200.82.202.202.302.902.40Arsenicug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7220200220250223Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.755,000B54,000B59,00064,000B,458,000Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.71,600,0001,600,0001,700,0001,800,00041,680,000Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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.E – MS and/or MSD exceeded the calibration range.F – MS and/or MSD not within laboratory control limits.



# 4-8Table 4-2. Influent to the Bioreactor System, AllenInfluent to the Bioreactor System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageChromiumug/L200.8ND (8.00)^ND (8.00)^ND (8.00)ND (8.00)^ND (8.00)Cobaltug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Copperug/L200.810.09.3011.012.010.6Ironug/L200.7NQ (200)ND (200)NQ (200)NQ (200)BNQ (200)Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)NQ (2.00)NQ (2.00)Magnesiumug/L200.7420,000400,000420,000420,0004415,000Manganeseug/L200.7400340440520B425Mercuryng/L1631E7111,3209911,1201,040Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)Nickelug/L200.88.207.908.107.908.03Seleniumug/L200.811094.088.587.094.9Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.731,00029,00030,50031,00030,400Thalliumug/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/L200.8ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Zincug/L200.8NQ (10.0)NQ (10.0)NQ (10.0)NQ (10.0)NQ (10.0)Dissolved MetalsAluminumug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Antimonyug/L200.82.402.302.252.602.39Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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.E – MS and/or MSD exceeded the calibration range.F – MS and/or MSD not within laboratory control limits.



# 4-9Table 4-2. Influent to the Bioreactor System, AllenInfluent to the Bioreactor System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageArsenicug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7220210220250225Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.757,000B56,000B58,50063,000B,458,600Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.71,700,0001,700,0001,700,0001,900,00041,750,000Chromiumug/L200.8ND (8.00)ND (8.00)ND (8.00)ND (8.00)ND (8.00)Chromium (VI)ug/L218.6ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Cobaltug/L200.7ND (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Copperug/L200.810.08.9011.012.010.5Ironug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.7410,000370,000405,000400,0004396,000Manganeseug/L200.7370320410470393Mercuryng/L1631E219483304361342Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)Nickelug/L200.89.207.408.308.208.28Seleniumug/L200.898.093.086.587.091.1Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.731,00031,00032,00031,00031,300Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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.E – MS and/or MSD exceeded the calibration range.F – MS and/or MSD not within laboratory control limits.



# 4-10Table 4-2. Influent to the Bioreactor System, AllenInfluent to the Bioreactor System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageThalliumug/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/L200.8ND (10.0)ND (10.0)NQ (10.0)ND (10.0)ND (10.0)Zincug/L200.812.0NQ (10.0)NQ (10.0)NQ (10.0)< 6.75Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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.



# 4-11Table 4-3. Effluent from the Bioreactor System, AllenEffluent from the Bioreactor System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmoniamg/L350.113.0F11.011.012.011.8Nitrate Nitrite as Nmg/L353.2NQ (0.100)0.130ND (0.100)NQ (0.100)< 0.0700Nitrogen, Total Kjeldahlmg/L351.214.0412.512.013.012.9Biochemical Oxygen Demandmg/L5210BNQ (2.50)BNQ (2.50)ND (2.00)NQ (2.50)NQ (2.38)Chemical Oxygen Demandmg/L410.4NQ (200)*67.0NQ (100)F36.0< 63.3Chloridemg/L300.03,4003,2503,2003,2003,260Sulfatemg/L300.01,5001,5001,4001,4001,450Cyanide, Totalmg/L4500 CN E0.110< 0.08000.120B0.100B< 0.103Total Dissolved Solidsmg/L2540C8,0008,4007,1007,5007,750Total Suspended Solidsmg/L2540DNQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Phosphorus, Totalmg/L365.10.1100.1600.190F0.1500.153Total MetalsAluminumug/L200.7NQ (200)NQ (200)NQ (200)NQ (200)BNQ (200)Antimonyug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Arsenicug/L200.8ND (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7210215210220214Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.765,000B,466,00063,000B,461,000B63,800Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.71,700,00041,650,0001,600,00041,600,0001,640,000Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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.



# 4-12Table 4-3. Effluent from the Bioreactor System, AllenEffluent from the Bioreactor System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageChromiumug/L200.8ND (8.00)^ND (8.00)ND (8.00)^ND (8.00)^ND (8.00)Cobaltug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Copperug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Ironug/L200.7NQ (200)NQ (200)210NQ (200)B< 128Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.7450,0004435,000410,0004420,000429,000Manganeseug/L200.7470435400440B436Mercuryng/L1631E12.630.027.717.021.8Molybdenumug/L200.7NQ (40.0)NQ (40.0)NQ (40.0)ND (40.0)NQ (40.0)Nickelug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Seleniumug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.733,00032,50031,00031,00031,900Thalliumug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Tinug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Titaniumug/L200.7NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Vanadiumug/L200.8ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Zincug/L200.8NQ (10.0)NQ (10.0)15.0NQ (10.0)< 7.50Dissolved MetalsAluminumug/L200.7NQ (200)NQ (200)NQ (200)NQ (100)NQ (175)Antimonyug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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.



# 4-13Table 4-3. Effluent from the Bioreactor System, AllenEffluent from the Bioreactor System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageArsenicug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7220220210110190Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (1.00)ND (1.75)Boronug/L200.771,000B,466,50063,000B,457,000B64,400Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.71,900,00041,700,0001,600,00041,700,0001,730,000Chromiumug/L200.8ND (8.00)ND (8.00)ND (8.00)ND (8.00)ND (8.00)Chromium (VI)ug/L218.6ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Cobaltug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (10.0)ND (17.5)Copperug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Ironug/L200.7NQ (200)BNQ (200)NQ (200)BNQ (100)BNQ (175)Leadug/L200.8ND (2.00)NQ (2.00)ND (2.00)ND (2.00)NQ (2.00)Magnesiumug/L200.7440,0004425,000400,0004190,000364,000Manganeseug/L200.7440405380190354Mercuryng/L1631E10.433.428.315.922.0Molybdenumug/L200.7NQ (40.0)ND (40.0)ND (40.0)NQ (20.0)NQ (35.0)Nickelug/L200.8NQ (4.00)NQ (4.00)ND (4.00)NQ (4.00)NQ (4.00)Seleniumug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.734,00033,50032,00016,00028,900Thalliumug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Note: 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.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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.



# 4-14Table 4-3. Effluent from the Bioreactor System, AllenEffluent from the Bioreactor System (SP-3)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageTinug/L200.7ND (200)ND (200)ND (200)ND (100)ND (175)Titaniumug/L200.7NQ (20.0)NQ (20.0)NQ (20.0)NQ (10.0)NQ (17.5)Vanadiumug/L200.8ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Zincug/L200.8NQ (10.0)NQ (10.0)NQ (10.0)NQ (10.0)NQ (10.0)< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below 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.



# 4-15Table 4-4. Classical Pollutants 4-Day Average DataSummary for FGD Wastewater Treatment System, AllenAnalyteUnitsMethodInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageInfluent toBioreactorSystem (SP-2)4-Day AverageEffluent fromBioreactorSystem (SP-3)4-Day AverageClassicalsAmmoniamg/L350.17.938.1111.8Nitrate Nitrite as Nmg/L353.218.313.3< 0.0700Nitrogen, Total Kjeldahlmg/L351.227.07.5012.9Biochemical Oxygen Demandmg/L5210B16.45.04NQ (2.38)Chemical Oxygen Demandmg/L410.4< 120< 83.8< 63.3Chloridemg/L300.03,9003,3003,260Sulfatemg/L300.01,3301,4001,450Cyanide, Totalmg/L4500 CN E0.255< 0.0850< 0.103Total Dissolved Solidsmg/L2540C9,4807,5607,750Total Suspended Solidsmg/L2540D2,480NQ (4.00)NQ (4.00)Phosphorus, Totalmg/L365.1< 0.106< 0.03400.153< - 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.



# 4-16Table 4-5. Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, AllenInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageInfluent toBioreactorSystem (SP-2)4-Day AverageEffluent fromBioreactorSystem (SP-3)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTotalDissolvedMetalsAluminumug/L200.772,300NQ (200)NQ (200)ND (200)NQ (200)NQ (175)Antimonyug/L200.810.83.082.402.39ND (2.00)ND (2.00)Arsenicug/L200.81358.95NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Bariumug/L200.7888368223225214190Berylliumug/L200.711.5ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (1.75)Boronug/L200.774,00072,30058,00058,60063,80064,400Cadmiumug/L200.8< 2.50NQ (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.72,330,0001,930,0001,680,0001,750,0001,640,0001,730,000Chromiumug/L200.8133ND (8.00)ND (8.00)ND (8.00)ND (8.00)ND (8.00)Chromium (VI)ug/L218.6NAND (10.0)NAND (10.0)NAND (2.00)Cobaltug/L200.760.5< 19.3ND (20.0)NQ (20.0)ND (20.0)ND (17.5)Copperug/L200.816011.010.610.5ND (4.00)ND (4.00)Ironug/L200.767,800ND (200)NQ (200)ND (200)< 128NQ (175)Leadug/L200.8101ND (2.00)NQ (2.00)ND (2.00)ND (2.00)NQ (2.00)Magnesiumug/L200.7505,000473,000415,000396,000429,000364,000Manganeseug/L200.73,9303,380425393436354Mercuryng/L1631E49,20031.91,04034221.822.0Molybdenumug/L200.7< 25.3NQ (40.0)NQ (40.0)NQ (40.0)NQ (40.0)NQ (35.0)Nickelug/L200.818880.38.038.28NQ (4.00)NQ (4.00)Seleniumug/L200.81,70031594.991.1NQ (4.00)NQ (4.00)Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.733,30033,80030,40031,30031,90028,900Thalliumug/L200.83.03NQ (2.00)NQ (2.00)NQ (2.00)ND (2.00)ND (2.00)Tinug/L200.7NQ (200)ND (200)ND (200)ND (200)ND (200)ND (175)Titaniumug/L200.71,530NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (17.5)< - 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.



# 4-17Table 4-5. Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, AllenInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageInfluent toBioreactorSystem (SP-2)4-Day AverageEffluent fromBioreactorSystem (SP-3)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTotalDissolvedVanadiumug/L200.8155NQ (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Zincug/L200.827837.0NQ (10.0)< 6.75< 7.50NQ (10.0)

# 5-1 5. D ATA 

# Q UALITY



# Quality assurance/quality control (QA/QC) pr ocedures applicable to the Allen sampling

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

(QAPP) [2]. This section describes the QC procedur es 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 matr ix 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

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 5.2.2 Equipment Blanks

EPA collects equipment blanks to evaluate possible contamination from the equipment

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

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

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

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

equipment supplied for the episode.

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

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

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

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

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

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

contamination from the sampling equipment. Appe ndix Table A-15 presents all of the analytical

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

collection of metals and mercury samples.

5.2.3 Field Blanks

The sampling team collected field blanks (SP-6, SP-7, and SP-8) to evaluate possible

contamination from sampling equipment, samp ling equipment decontamination procedures,

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

samples for the total and dissolved metals and total and dissolved mercury samples 2



# .

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

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

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

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

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

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

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

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

as “true” split samples with Allen’s representati ve, using the same procedure discussed in the

sample collection description (Section 3.1).

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

chromium field blank samples for the influent to the FGD 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 approximately 90 mi nutes, the sampling team began pumping off the

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

tubing was purged with approximately 0.75 liters of blank water. The sample bottles were placed

2 

# EPA did not collect a dissolved mercury field blank 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 performed fo r the first, second, third,

fourth, or fifth day of samples.

# 5-3 in a “cleanbox” and the ASTM Type 1 water wa s pumped through the tubing, capsule filter, and

“Y” splitter, and into the sample bottles. EPA co llected the field blank samples as “true” split

samples with Allen’s representative, using the sa me procedure discussed in the sample collection

description (Section 3.1).

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

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

taps on the sample tap splitter with a clear pl astic bag. Before purging the sample tap, ASTM

Type 1 water was poured directly into the sample bottles under the clear plastic bag.

The total and dissolved metals by 200.7 and metals by 200.8 field blank samples for the

influent to the bioreactor system (SP-7) and the effluent from th e bioreactor system (SP-8) were

collected by filling a 20-liter composite container with ASTM Type 1 water. The same T-splitter

tubing used to fill the metals composite container at each point was used with a pump to fill the

20-liter field blank composite cont ainer. Prior to attaching one e nd of the tubing to the sample

tap, it was placed directly into the container hol ding ASTM Type 1 water. The other end of the

tubing was attached to the vented cap on top of the 20-liter field blank composite container.

After enough volume was pumped into the 20-liter field blank composite container, the vented

cap was replaced with a closed cap and the contai ner was placed on ice in a covered plastic trash

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

the metals composite container.

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

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

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

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

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

(Section 3.1). Prior to filling the sample bottles, the tubing wa s purged with approximately one

liter of ASTM Type 1 water. First the sample rs collected the total metals by 200.8 and total

metals by 200.7 field blank samples. Then the samp ling team attached a f ilter 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, dissolv ed metals by 200.7, and dissolved hexavalent

chromium field blank samples.

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

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

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

sampling points, including all qua lified results and all results th at were measured above the

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

5.2.4 Field Duplicates

The sampling team collected field duplicate samples to assess the sampling measurement

precision for the episode. Field dupl icate samples are separate samp les collected from the same

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

is stored and analyzed independently. The 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.

# 5-4 100

2 D S D S (%) RPD         

 

# (5-1)

where:

S = concentration of the analyte from original sample analysis;

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

RPD = relative percent difference between the original and duplicate sample

result.

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

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

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

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

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

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

duplicate of the influent to the bioreactor system (SP-4) sample analyses , including all qualified

results and all results that were measured a bove the method detection limit, but below the

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

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

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

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



# 5-5 5-5Table 5-1. Field Duplicate Results – Influent to Bioreactor System, AllenAnalyteMethodUnitsOriginal Influentto BioreactorSystem, Day 3Concentration (SP-2)Duplicate Influentto BioreactorSystemConcentration (SP-4)AverageResultRelativePercentDifferenceClassicalsAmmonia350.1mg/L8.908.808.851.13Nitrate Nitrite as N353.2mg/L13.013.013.00.00Nitrogen, Total Kjeldahl351.2mg/L10.011.010.59.52Biochemical Oxygen Demand5210Bmg/L3.603.703.652.74Chemical Oxygen Demand410.4mg/LNQ (100)94.0< 72.0NCChloride300.0mg/L3,2003,4003,3006.06Sulfate300.0mg/L1,4001,4001,4000.00Cyanide, Total4500 CN Emg/L0.120B0.140B0.13015.4Total Dissolved Solids2540Cmg/L7,2007,1007,1501.40Total Suspended Solids2540Dmg/LNQ (4.00)NQ (4.00)NQ (4.00)NCPhosphorus, Total365.1mg/LNQ (0.0500)NQ (0.0500)NQ (0.0500)NCTotal MetalsAluminum200.7ug/LND (200)ND (200)ND (200)NCAntimony200.8ug/L2.302.302.300.00Arsenic200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCBarium200.7ug/L2202202200.00Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L59,000B59,000B59,0000.00Cadmium200.8ug/LND (4.00)ND (4.00)ND (4.00)NCCalcium200.7ug/L1,700,0001,700,0001,700,0000.00Chromium200.8ug/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.



# 5-6 5-6Table 5-1. Field Duplicate Results – Influent to Bioreactor System, AllenAnalyteMethodUnitsOriginal Influentto BioreactorSystem, Day 3Concentration (SP-2)Duplicate Influentto BioreactorSystemConcentration (SP-4)AverageResultRelativePercentDifferenceCobalt200.7ug/LND (20.0)ND (20.0)ND (20.0)NCCopper200.8ug/L11.011.011.00.00Iron200.7ug/LND (200)NQ (200)NQ (200)NCLead200.8ug/LND (2.00)ND (2.00)ND (2.00)NCMagnesium200.7ug/L430,000410,000420,0004.76Manganese200.7ug/L4404404400.00Mercury1631Eng/L9621,0209915.85Molybdenum200.7ug/LNQ (40.0)NQ (40.0)NQ (40.0)NCNickel200.8ug/L8.807.408.1017.3Selenium200.8ug/L91.086.088.55.65Silver200.8ug/LND (2.00)ND (2.00)ND (2.00)NCSodium200.7ug/L30,00031,00030,5003.28Thallium200.8ug/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/LND (10.0)ND (10.0)ND (10.0)NCZinc200.8ug/LNQ (10.0)NQ (10.0)NQ (10.0)NCDissolved MetalsAluminum200.7ug/LND (200)ND (200)ND (200)NCAntimony200.8ug/L2.102.402.2513.3Arsenic200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCBarium200.7ug/L2202202200.00< - 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.



# 5-7 5-7Table 5-1. Field Duplicate Results – Influent to Bioreactor System, AllenAnalyteMethodUnitsOriginal Influentto BioreactorSystem, Day 3Concentration (SP-2)Duplicate Influentto BioreactorSystemConcentration (SP-4)AverageResultRelativePercentDifferenceBeryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L59,000B58,000B58,5001.71Cadmium200.8ug/LND (4.00)ND (4.00)ND (4.00)NCCalcium200.7ug/L1,700,0001,700,0001,700,0000.00Chromium200.8ug/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/L11.011.011.00.00Iron200.7ug/LND (200)ND (200)ND (200)NCLead200.8ug/LND (2.00)ND (2.00)ND (2.00)NCMagnesium200.7ug/L420,000390,000405,0007.41Manganese200.7ug/L4204004104.88Mercury1631Eng/L3063013041.65Molybdenum200.7ug/LNQ (40.0)NQ (40.0)NQ (40.0)NCNickel200.8ug/L8.608.008.307.23Selenium200.8ug/L86.087.086.51.16Silver200.8ug/LND (2.00)ND (2.00)ND (2.00)NCSodium200.7ug/L32,00032,00032,0000.00Thallium200.8ug/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/LND (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.



# 5-8 5-8Table 5-1. Field Duplicate Results – Influent to Bioreactor System, AllenAnalyteMethodUnitsOriginal Influentto BioreactorSystem, Day 3Concentration (SP-2)Duplicate Influentto BioreactorSystemConcentration (SP-4)AverageResultRelativePercentDifferenceZinc200.8ug/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.



# 5-9Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, AllenAnalyteMethodUnitsOriginal Effluentfrom BioreactorSystem, Day 2Concentration (SP-3)DuplicateEffluent fromBioreactorSystemConcentration (SP-5)AverageResultRelativePercentDifferenceClassicalsAmmonia350.1mg/L11.011.011.00.00Nitrate Nitrite as N353.2mg/L0.1300.1300.1300.00Nitrogen, Total Kjeldahl351.2mg/L12.013.012.58.00Biochemical Oxygen Demand5210Bmg/LNQ (2.50)NQ (2.50)NQ (2.50)NCChemical Oxygen Demand410.4mg/L79.055.067.035.8Chloride300.0mg/L3,2003,3003,2503.08Sulfate300.0mg/L1,5001,5001,5000.00Cyanide, Total4500 CN Emg/L0.110NQ (0.100)< 0.0800NCTotal Dissolved Solids2540Cmg/L8,1008,7008,4007.14Total Suspended Solids2540Dmg/LNQ (4.00)NQ (4.00)NQ (4.00)NCPhosphorus, Total365.1mg/L0.1600.1600.1600.00Total MetalsAluminum200.7ug/LNQ (200)NQ (200)NQ (200)NCAntimony200.8ug/LND (2.00)ND (2.00)ND (2.00)NCArsenic200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCBarium200.7ug/L2202102154.65Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L66,000B66,000B66,0000.00Cadmium200.8ug/LND (4.00)ND (4.00)ND (4.00)NCCalcium200.7ug/L1,700,0001,600,0001,650,0006.06< - 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.



# 5-10Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, AllenAnalyteMethodUnitsOriginal Effluentfrom BioreactorSystem, Day 2Concentration (SP-3)DuplicateEffluent fromBioreactorSystemConcentration (SP-5)AverageResultRelativePercentDifferenceChromium200.8ug/LND (8.00)^ND (8.00)^ND (8.00)NCCobalt200.7ug/LND (20.0)ND (20.0)ND (20.0)NCCopper200.8ug/LND (4.00)ND (4.00)ND (4.00)NCIron200.7ug/LNQ (200)NQ (200)NQ (200)NCLead200.8ug/LND (2.00)ND (2.00)ND (2.00)NCMagnesium200.7ug/L440,000430,000435,0002.30Manganese200.7ug/L4404304352.30Mercury1631Eng/L28.431.530.010.4Molybdenum200.7ug/LNQ (40.0)NQ (40.0)NQ (40.0)NCNickel200.8ug/LND (4.00)NQ (4.00)NQ (4.00)NCSelenium200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCSilver200.8ug/LND (2.00)ND (2.00)ND (2.00)NCSodium200.7ug/L33,00032,00032,5003.08Thallium200.8ug/LND (2.00)ND (2.00)ND (2.00)NCTin200.7ug/LND (200)ND (200)ND (200)NCTitanium200.7ug/LNQ (20.0)NQ (20.0)NQ (20.0)NCVanadium200.8ug/LND (10.0)ND (10.0)ND (10.0)NCZinc200.8ug/LNQ (10.0)NQ (10.0)NQ (10.0)NCDissolved MetalsAluminum200.7ug/LNQ (200)NQ (200)NQ (200)NCAntimony200.8ug/LND (2.00)ND (2.00)ND (2.00)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.



# 5-11Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, AllenAnalyteMethodUnitsOriginal Effluentfrom BioreactorSystem, Day 2Concentration (SP-3)DuplicateEffluent fromBioreactorSystemConcentration (SP-5)AverageResultRelativePercentDifferenceArsenic200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCBarium200.7ug/L2202202200.00Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L66,000B67,000B66,5001.50Cadmium200.8ug/LND (4.00)ND (4.00)ND (4.00)NCCalcium200.7ug/L1,700,0001,700,0001,700,0000.00Chromium200.8ug/LND (8.00)ND (8.00)ND (8.00)NCChromium (VI)218.6ug/LND (2.00)ND (2.00)ND (2.00)NCCobalt200.7ug/LND (20.0)ND (20.0)ND (20.0)NCCopper200.8ug/LND (4.00)ND (4.00)ND (4.00)NCIron200.7ug/LNQ (200)BNQ (200)BNQ (200)NCLead200.8ug/LNQ (2.00)ND (2.00)NQ (2.00)NCMagnesium200.7ug/L430,000420,000425,0002.35Manganese200.7ug/L4104004052.47Mercury1631Eng/L33.133.733.41.80Molybdenum200.7ug/LND (40.0)ND (40.0)ND (40.0)NCNickel200.8ug/LNQ (4.00)ND (4.00)NQ (4.00)NCSelenium200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCSilver200.8ug/LND (2.00)ND (2.00)ND (2.00)NCSodium200.7ug/L34,00033,00033,5002.99Thallium200.8ug/LND (2.00)ND (2.00)ND (2.00)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.



# 5-12Table 5-2. Field Duplicate Results – Effluent from Bioreactor System, AllenAnalyteMethodUnitsOriginal Effluentfrom BioreactorSystem, Day 2Concentration (SP-3)DuplicateEffluent fromBioreactorSystemConcentration (SP-5)AverageResultRelativePercentDifferenceTin200.7ug/LND (200)ND (200)ND (200)NCTitanium200.7ug/LNQ (20.0)NQ (20.0)NQ (20.0)NCVanadium200.8ug/LND (10.0)ND (10.0)ND (10.0)NCZinc200.8ug/LNQ (10.0)NQ (10.0)NQ (10.0)NC

# 6-1 6. R EFERENCES



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

Steam Station. July 1. DCN SE00501.

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

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

# Appendix A

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



# A-1Table A-1. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L10.1111.4Nitrate Nitrite as N353.2mg/L20.0380.214Nitrogen, Total Kjeldahl351.2mg/L10.38516Biochemical Oxygen Demand5210Bmg/L12.82440BChemical Oxygen Demand410.4mg/L520100110*Chloride300.0mg/L200516002,800Sulfate300.0mg/L50122501,400Cyanide, Total4500 CN Emg/L10.020.10.25Total Dissolved Solids2540Cmg/L1471007,000Total Suspended Solids2540Dmg/L1281001,800Phosphorus, Total365.1mg/L10.0050.050.35Total MetalsAluminum200.7ug/L29.420070,000Antimony200.8ug/L20.7229.3Arsenic200.8ug/L21.24120Barium200.7ug/L22.520750Beryllium200.7ug/L20.71210Boron200.7ug/L10331,00054,000BCadmium200.8ug/L21.241.9JCalcium200.7ug/L103402,0001,900,000Chromium200.8ug/L23.38120^Cobalt200.7ug/L21.12052Copper200.8ug/L20.964140Iron200.7ug/L23220064,000Lead200.8ug/L20.73285ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-2Table A-1. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMagnesium200.7ug/L221400440,000Manganese200.7ug/L20.51203,300Mercury1631Eng/L4,0009652,02050,300Molybdenum200.7ug/L21.64032JNickel200.8ug/L20.894160Selenium200.8ug/L20.6241,500Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00029,000Thallium200.8ug/L20.4722.5Tin200.7ug/L24.82008.9JTitanium200.7ug/L21.6201,400Vanadium200.8ug/L21.710130Zinc200.8ug/L24.110220Dissolved MetalsAluminum200.7ug/L29.420024JAntimony200.8ug/L20.7222Arsenic200.8ug/L21.248.7Barium200.7ug/L22.520250Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00050,000BCadmium200.8ug/L21.241.5JCalcium200.7ug/L501,70010,0001,500,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.12017JCopper200.8ug/L20.96412Iron200.7ug/L232200ND (200)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-3Table A-1. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400400,000Manganese200.7ug/L20.51202,800Mercury1631Eng/L102.415.0515.2Molybdenum200.7ug/L21.64013JNickel200.8ug/L20.89471Selenium200.8ug/L20.624230Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00028,000Thallium200.8ug/L20.4720.93JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6202.5JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.11030ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-4Table A-2. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L10.1117.3Nitrate Nitrite as N353.2mg/L20.0380.217Nitrogen, Total Kjeldahl351.2mg/L10.38521Biochemical Oxygen Demand5210Bmg/L10.32.59.7BChemical Oxygen Demand410.4mg/L1041200130J,*Chloride300.0mg/L200516003,400Sulfate300.0mg/L50122501,300Cyanide, Total4500 CN Emg/L10.020.10.34Total Dissolved Solids2540Cmg/L119408,900Total Suspended Solids2540Dmg/L1281003,900Phosphorus, Total365.1mg/L10.0050.050.015JTotal MetalsAluminum200.7ug/L29.420076,000Antimony200.8ug/L20.72211Arsenic200.8ug/L21.24140Barium200.7ug/L22.520880Beryllium200.7ug/L20.71212Boron200.7ug/L10331,00062,000BCadmium200.8ug/L21.242.9JCalcium200.7ug/L103402,0002,300,000Chromium200.8ug/L23.38140^Cobalt200.7ug/L21.12059Copper200.8ug/L20.964160Iron200.7ug/L23220069,000Lead200.8ug/L20.73299ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-5Table A-2. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMagnesium200.7ug/L221400470,000Manganese200.7ug/L20.51203,700Mercury1631Eng/L4,0009652,02049,600Molybdenum200.7ug/L21.64034JNickel200.8ug/L20.894190Selenium200.8ug/L20.6241,700Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00032,000Thallium200.8ug/L20.4723.2Tin200.7ug/L24.82008.9JTitanium200.7ug/L21.6201,500Vanadium200.8ug/L21.710150Zinc200.8ug/L24.110280Dissolved MetalsAluminum200.7ug/L29.420029JAntimony200.8ug/L20.7222.8Arsenic200.8ug/L21.2410Barium200.7ug/L22.520310Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00059,000BCadmium200.8ug/L21.241.6JCalcium200.7ug/L501,70010,0001,700,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.12020Copper200.8ug/L20.96412Iron200.7ug/L232200ND (200)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-6Table A-2. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400440,000Manganese200.7ug/L20.51203,100Mercury1631Eng/L204.8310.121Molybdenum200.7ug/L21.64018JNickel200.8ug/L20.89477Selenium200.8ug/L20.624290Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00031,000Thallium200.8ug/L20.4721.3JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.1JVanadium200.8ug/L21.7102JZinc200.8ug/L24.11043ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-7Table A-3. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L20.11214Nitrate Nitrite as N353.2mg/L50.0950.520Nitrogen, Total Kjeldahl351.2mg/L41.52026Biochemical Oxygen Demand5210Bmg/L10.32.59.4Chemical Oxygen Demand410.4mg/L28.140130Chloride300.0mg/L200516004,200Sulfate300.0mg/L50122501,300Cyanide, Total4500 CN Emg/L10.020.10.19Total Dissolved Solids2540Cmg/L14710011,000Total Suspended Solids2540Dmg/L1281002,000Phosphorus, Total365.1mg/L10.0050.050.024JTotal MetalsAluminum200.7ug/L29.420072,000Antimony200.8ug/L20.72211Arsenic200.8ug/L21.24140Barium200.7ug/L22.520930Beryllium200.7ug/L20.71212Boron200.7ug/L10331,00080,000BCadmium200.8ug/L21.243.2JCalcium200.7ug/L103402,0002,400,000Chromium200.8ug/L23.38130^Cobalt200.7ug/L21.12064Copper200.8ug/L20.964160Iron200.7ug/L23220068,000Lead200.8ug/L20.732100Magnesium200.7ug/L221400520,000ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-8Table A-3. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationManganese200.7ug/L20.51204,100Mercury1631Eng/L4,0009652,02044,600Molybdenum200.7ug/L21.64035JNickel200.8ug/L20.894190Selenium200.8ug/L20.6241,800Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00034,000Thallium200.8ug/L20.4723.3Tin200.7ug/L24.82009.4JTitanium200.7ug/L21.6201,600Vanadium200.8ug/L21.710160Zinc200.8ug/L24.110280Dissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7223.5Arsenic200.8ug/L21.2410Barium200.7ug/L22.520410Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00080,000BCadmium200.8ug/L21.242JCalcium200.7ug/L501,70010,0002,000,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)Cobalt200.7ug/L21.12022Copper200.8ug/L20.96411Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-9Table A-3. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMagnesium200.7ug/L221400500,000Manganese200.7ug/L20.51203,600Mercury1631Eng/L204.8310.116.4Molybdenum200.7ug/L21.64019JNickel200.8ug/L20.89480Selenium200.8ug/L20.624340Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00036,000Thallium200.8ug/L20.4721.7JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.2JVanadium200.8ug/L21.7101.7JZinc200.8ug/L24.11032ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-10Table A-4. Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, AllenAnalyteMethodsUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L10.05519Nitrate Nitrite as N353.2mg/L50.0950.522Nitrogen, Total Kjeldahl351.2mg/L41.52045Biochemical Oxygen Demand5210Bmg/L10.32.56.6Chemical Oxygen Demand410.4mg/L28.140140Chloride300.0mg/L200516005,200Sulfate300.0mg/L50122501,300Cyanide, Total4500 CN Emg/L10.020.10.24BTotal Dissolved Solids2540Cmg/L14710011,000Total Suspended Solids2540Dmg/L1281002,200Phosphorus, Total365.1mg/L10.0050.050.046JTotal MetalsAluminum200.7ug/L29.420071,000Antimony200.8ug/L20.72212Arsenic200.8ug/L21.24140Barium200.7ug/L22.520990Beryllium200.7ug/L20.71212Boron200.7ug/L10331,000100,000BCadmium200.8ug/L21.244Calcium200.7ug/L103402,0002,700,000Chromium200.8ug/L23.38140^Cobalt200.7ug/L21.12067Copper200.8ug/L20.964180Iron200.7ug/L23220070,000Lead200.8ug/L20.732120Magnesium200.7ug/L221400590,000ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-11Table A-4. Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, AllenAnalyteMethodsUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationManganese200.7ug/L20.51204,600Mercury1631Eng/L4,0009652,02052,100Molybdenum200.7ug/L21.64041Nickel200.8ug/L20.894210Selenium200.8ug/L20.6241,800Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00038,000Thallium200.8ug/L20.4723.1Tin200.7ug/L24.82009JTitanium200.7ug/L21.6201,600Vanadium200.8ug/L21.710180Zinc200.8ug/L24.110330Dissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7224Arsenic200.8ug/L21.247.1Barium200.7ug/L22.520500Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000100,000BCadmium200.8ug/L21.242.3JCalcium200.7ug/L501,70010,0002,500,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)Cobalt200.7ug/L21.12025Copper200.8ug/L20.9648.9Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-12Table A-4. Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, AllenAnalyteMethodsUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMagnesium200.7ug/L221400550,000Manganese200.7ug/L20.51204,000Mercury1631Eng/L204.8310.175Molybdenum200.7ug/L21.64023JNickel200.8ug/L20.89493Selenium200.8ug/L20.624400Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00040,000Thallium200.8ug/L20.4721.7JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.1JVanadium200.8ug/L21.7102.3JZinc200.8ug/L24.11043ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-13Table A-5. Influent to Bioreactor System, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L10.1115.8Nitrate Nitrite as N353.2mg/L20.0380.214Nitrogen, Total Kjeldahl351.2mg/L20.1527.7Biochemical Oxygen Demand5210Bmg/L10.32.57.4BChemical Oxygen Demand410.4mg/L104120096J,*Chloride300.0mg/L200516003,100Sulfate300.0mg/L50122501,400Cyanide, Total4500 CN Emg/L10.020.10.084JTotal Dissolved Solids2540Cmg/L119407,500Total Suspended Solids2540Dmg/L11.142.4JPhosphorus, Total365.1mg/L10.0050.050.061Total MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.2Arsenic200.8ug/L21.242.3JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00055,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,600,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.96410Iron200.7ug/L23220036JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400420,000ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-14Table A-5. Influent to Bioreactor System, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationManganese200.7ug/L20.5120400Mercury1631Eng/L500121252711Molybdenum200.7ug/L21.64020JNickel200.8ug/L20.8948.2Selenium200.8ug/L20.624110Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00031,000Thallium200.8ug/L20.4720.78JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6205.3JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1105.3JDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.4Arsenic200.8ug/L21.242.9JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00057,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,700,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.96410Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-15Table A-5. Influent to Bioreactor System, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMagnesium200.7ug/L221400410,000Manganese200.7ug/L20.5120370Mercury1631Eng/L204.8310.1219Molybdenum200.7ug/L21.64018JNickel200.8ug/L20.8949.2Selenium200.8ug/L20.62498Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00031,000Thallium200.8ug/L20.4720.87JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6202.9JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.11012ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-16Table A-6. Influent to Bioreactor System, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L10.05516.8Nitrate Nitrite as N353.2mg/L20.0380.213Nitrogen, Total Kjeldahl351.2mg/L20.1528.6Biochemical Oxygen Demand5210Bmg/L10.32.55.2Chemical Oxygen Demand410.4mg/L28.14079Chloride300.0mg/L200516003,200Sulfate300.0mg/L50122501,400Cyanide, Total4500 CN Emg/L10.020.10.082JTotal Dissolved Solids2540Cmg/L119407,800Total Suspended Solids2540Dmg/L11.141.2JPhosphorus, Total365.1mg/L10.0050.050.033JTotal MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.2Arsenic200.8ug/L21.242.2JBarium200.7ug/L22.520200Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00054,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,600,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.9649.3Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400400,000Manganese200.7ug/L20.5120340ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-17Table A-6. Influent to Bioreactor System, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L10024.150.51,320Molybdenum200.7ug/L21.64019JNickel200.8ug/L20.8947.9Selenium200.8ug/L20.62494Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00029,000Thallium200.8ug/L20.4720.87JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.5JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1104.9JDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.3Arsenic200.8ug/L21.242.9JBarium200.7ug/L22.520210Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00056,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,700,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1201.2JCopper200.8ug/L20.9648.9Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400370,000Manganese200.7ug/L20.5120320ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-18Table A-6. Influent to Bioreactor System, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L10024.150.5483Molybdenum200.7ug/L21.64018JNickel200.8ug/L20.8947.4Selenium200.8ug/L20.62493Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00031,000Thallium200.8ug/L20.4720.91JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.1JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1108JND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-19Table A-7. Influent to Bioreactor System, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L10.05518.9Nitrate Nitrite as N353.2mg/L20.0380.213Nitrogen, Total Kjeldahl351.2mg/L20.15210Biochemical Oxygen Demand5210Bmg/L10.32.53.6Chemical Oxygen Demand410.4mg/L52010072JChloride300.0mg/L200516003,200Sulfate300.0mg/L50122501,400Cyanide, Total4500 CN Emg/L10.020.10.12BTotal Dissolved Solids2540Cmg/L119407,200Total Suspended Solids2540Dmg/L11.141.6JPhosphorus, Total365.1mg/L10.0050.050.027JTotal MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.3Arsenic200.8ug/L21.242.2JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00059,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,700,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.96411Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400430,000Manganese200.7ug/L20.5120440ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-20Table A-7. Influent to Bioreactor System, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L10024.150.5962Molybdenum200.7ug/L21.64020JNickel200.8ug/L20.8948.8Selenium200.8ug/L20.62491Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00030,000Thallium200.8ug/L20.4720.96JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.1JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1106.8JDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.1Arsenic200.8ug/L21.242.4JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00059,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,700,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)Cobalt200.7ug/L21.1201.3JCopper200.8ug/L20.96411Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400420,000Manganese200.7ug/L20.5120420ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-21Table A-7. Influent to Bioreactor System, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L500121252306Molybdenum200.7ug/L21.64019JNickel200.8ug/L20.8948.6Selenium200.8ug/L20.62486Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00032,000Thallium200.8ug/L20.4720.94JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.3JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1106.3JND – 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.E – MS and/or MSD exceeded the calibration range.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-22Table A-8. Influent to Bioreactor System, Day 4 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L20.11211Nitrate Nitrite as N353.2mg/L20.0380.213E,FNitrogen, Total Kjeldahl351.2mg/L10.07713.2FBiochemical Oxygen Demand5210Bmg/L10.32.53.9Chemical Oxygen Demand410.4mg/L28.14084FChloride300.0mg/L200516003,600Sulfate300.0mg/L50122501,400Cyanide, Total4500 CN Emg/L10.020.10.11BTotal Dissolved Solids2540Cmg/L119407,800Total Suspended Solids2540Dmg/L11.141.6JPhosphorus, Total365.1mg/L10.0050.050.02JTotal MetalsAluminum200.7ug/L29.420013J,BAntimony200.8ug/L20.7222.9Arsenic200.8ug/L21.241.8JBarium200.7ug/L22.520250Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00064,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,800,0004Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.96412Iron200.7ug/L23220046J,BLead200.8ug/L20.7321.3JND – 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.E – MS and/or MSD exceeded the calibration range.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-23Table A-8. Influent to Bioreactor System, Day 4 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMagnesium200.7ug/L221400420,0004Manganese200.7ug/L20.5120520BMercury1631Eng/L5001212521,120Molybdenum200.7ug/L21.64021JNickel200.8ug/L20.8947.9Selenium200.8ug/L20.62487Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00031,000Thallium200.8ug/L20.4721.1JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6205.7JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1109JDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.6Arsenic200.8ug/L21.241.5JBarium200.7ug/L22.520250Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00063,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,900,0004Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1201.2JCopper200.8ug/L20.96412ND – 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.E – MS and/or MSD exceeded the calibration range.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-24Table A-8. Influent to Bioreactor System, Day 4 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400400,0004Manganese200.7ug/L20.5120470Mercury1631Eng/L500121252361Molybdenum200.7ug/L21.64018JNickel200.8ug/L20.8948.2Selenium200.8ug/L20.62487Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00031,000Thallium200.8ug/L20.4721JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.4JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1106.6JND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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).



# A-25Table A-9. Effluent from Bioreactor System, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L20.22213FNitrate Nitrite as N353.2mg/L10.0190.10.026JNitrogen, Total Kjeldahl351.2mg/L40.314144Biochemical Oxygen Demand5210Bmg/L10.32.51.7J,BChemical Oxygen Demand410.4mg/L1041200120J,*Chloride300.0mg/L200516003,400Sulfate300.0mg/L50122501,500Cyanide, Total4500 CN Emg/L10.020.10.11Total Dissolved Solids2540Cmg/L119408,000Total Suspended Solids2540Dmg/L11.141.6JPhosphorus, Total365.1mg/L10.0050.050.11Total MetalsAluminum200.7ug/L29.420039JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520210Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00065,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,700,0004Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200160JLead200.8ug/L20.732ND (2)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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).



# A-26Table A-9. Effluent from Bioreactor System, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMagnesium200.7ug/L221400450,0004Manganese200.7ug/L20.5120470Mercury1631Eng/L204.8310.112.6Molybdenum200.7ug/L21.6404.6JNickel200.8ug/L20.8941.1JSelenium200.8ug/L20.6241.2JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00033,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.8JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1104.7JDissolved MetalsAluminum200.7ug/L29.420032JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.242JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00071,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,900,0004Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet 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).



# A-27Table A-9. Effluent from Bioreactor System, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationIron200.7ug/L232200140J,BLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400440,0004Manganese200.7ug/L20.5120440Mercury1631Eng/L204.8310.110.4Molybdenum200.7ug/L21.6403.2JNickel200.8ug/L20.8941.3JSelenium200.8ug/L20.6240.8JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00034,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.4JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1106JND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-28Table A-10. Effluent from Bioreactor System, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L20.11211Nitrate Nitrite as N353.2mg/L10.0190.10.13Nitrogen, Total Kjeldahl351.2mg/L40.31412Biochemical Oxygen Demand5210Bmg/L10.32.51.8JChemical Oxygen Demand410.4mg/L28.14079Chloride300.0mg/L200516003,200Sulfate300.0mg/L50122501,500Cyanide, Total4500 CN Emg/L10.020.10.11Total Dissolved Solids2540Cmg/L119408,100Total Suspended Solids2540Dmg/L11.141.2JPhosphorus, Total365.1mg/L10.0050.050.16Total MetalsAluminum200.7ug/L29.420038JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.7JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00066,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,700,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200190JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400440,000Manganese200.7ug/L20.5120440ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-29Table A-10. Effluent from Bioreactor System, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L204.8310.128.4Molybdenum200.7ug/L21.6402.1JNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6241.7JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00033,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.2JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1105.4JDissolved MetalsAluminum200.7ug/L29.420040JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.8JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00066,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,700,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200120J,BLead200.8ug/L20.7321JMagnesium200.7ug/L221400430,000Manganese200.7ug/L20.5120410ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-30Table A-10. Effluent from Bioreactor System, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L204.8310.133.1Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.8941.4JSelenium200.8ug/L20.6241.3JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00034,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6202.8JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1107.3JND – 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).



# A-31Table A-11. Effluent from Bioreactor System, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L20.11211Nitrate Nitrite as N353.2mg/L10.0190.1ND (0.1)UNitrogen, Total Kjeldahl351.2mg/L40.31412Biochemical Oxygen Demand5210Bmg/L10.242ND (2)UChemical Oxygen Demand410.4mg/L52010046J,FChloride300.0mg/L200516003,200Sulfate300.0mg/L50122501,400Cyanide, Total4500 CN Emg/L10.020.10.12BTotal Dissolved Solids2540Cmg/L119407,100Total Suspended Solids2540Dmg/L11.142.8JPhosphorus, Total365.1mg/L10.0050.050.19FTotal MetalsAluminum200.7ug/L29.420041JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.3JBarium200.7ug/L22.520210Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00063,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,600,0004Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200210Lead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400410,0004ND – 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).



# A-32Table A-11. Effluent from Bioreactor System, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationManganese200.7ug/L20.5120400Mercury1631Eng/L204.8310.127.7Molybdenum200.7ug/L21.6401.6JNickel200.8ug/L20.8940.92JSelenium200.8ug/L20.6241.3JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00031,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.11015Dissolved MetalsAluminum200.7ug/L29.420025JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.242.2JBarium200.7ug/L22.520210Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00063,000B,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,600,0004Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220039J,BLead200.8ug/L20.732ND (2)UND – 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).



# A-33Table A-11. Effluent from Bioreactor System, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMagnesium200.7ug/L221400400,0004Manganese200.7ug/L20.5120380Mercury1631Eng/L102.415.0528.3Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6241JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00032,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.2JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1109.3JND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-34Table A-12. Effluent from Bioreactor System, Day 4 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L20.11212Nitrate Nitrite as N353.2mg/L10.0190.10.097JNitrogen, Total Kjeldahl351.2mg/L20.15213Biochemical Oxygen Demand5210Bmg/L10.32.52.2JChemical Oxygen Demand410.4mg/L14.12036Chloride300.0mg/L200516003,200Sulfate300.0mg/L50122501,400Cyanide, Total4500 CN Emg/L10.020.10.1BTotal Dissolved Solids2540Cmg/L119407,500Total Suspended Solids2540Dmg/L11.141.2JPhosphorus, Total365.1mg/L10.0050.050.15Total MetalsAluminum200.7ug/L29.420035J,BAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.6JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00061,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,600,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200140J,BLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400420,000Manganese200.7ug/L20.5120440BND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-35Table A-12. Effluent from Bioreactor System, Day 4 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L204.8310.117Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.8941.2JSelenium200.8ug/L20.6241.4JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00031,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.4JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1105.7JDissolved MetalsAluminum200.7ug/L14.710011JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.5JBarium200.7ug/L11.210110Beryllium200.7ug/L10.361ND (1)UBoron200.7ug/L501705,00057,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,700,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L10.5710ND (10)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L11610046J,BLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L111200190,000Manganese200.7ug/L10.2510190ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-36Table A-12. Effluent from Bioreactor System, Day 4 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L204.8310.115.9Molybdenum200.7ug/L10.81202.8JNickel200.8ug/L20.8941.1JSelenium200.8ug/L20.6241.2JSilver200.8ug/L20.592ND (2)USodium200.7ug/L1925,00016,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L12.4100ND (100)UTitanium200.7ug/L10.82101.6JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1105.6JND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-37Table A-13. Duplicate of Influent to Bioreactor SystemAnalytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L10.05518.8Nitrate Nitrite as N353.2mg/L20.0380.213Nitrogen, Total Kjeldahl351.2mg/L20.15211Biochemical Oxygen Demand5210Bmg/L10.32.53.7Chemical Oxygen Demand410.4mg/L28.14094Chloride300.0mg/L200516003,400Sulfate300.0mg/L50122501,400Cyanide, Total4500 CN Emg/L10.020.10.14BTotal Dissolved Solids2540Cmg/L119407,100Total Suspended Solids2540Dmg/L11.141.2JPhosphorus, Total365.1mg/L10.0050.050.035JTotal MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.3Arsenic200.8ug/L21.241.4JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00059,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,700,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.96411Iron200.7ug/L23220034JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400410,000Manganese200.7ug/L20.5120440ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-38Table A-13. Duplicate of Influent to Bioreactor SystemAnalytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L10024.150.51,020Molybdenum200.7ug/L21.64022JNickel200.8ug/L20.8947.4Selenium200.8ug/L20.62486Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00031,000Thallium200.8ug/L20.4721.1JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.4JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1104.9JDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7222.4Arsenic200.8ug/L21.242.9JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00058,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,700,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.1201.1JCopper200.8ug/L20.96411Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400390,000Manganese200.7ug/L20.5120400ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-39Table A-13. Duplicate of Influent to Bioreactor SystemAnalytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L500121252301Molybdenum200.7ug/L21.64019JNickel200.8ug/L20.8948Selenium200.8ug/L20.62487Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00032,000Thallium200.8ug/L20.4721.1JTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.3JVanadium200.8ug/L21.7101.7JZinc200.8ug/L24.1105.9JND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-40Table A-14. Duplicate of Effluent from Bioreactor System Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationClassicalsAmmonia350.1mg/L20.11211Nitrate Nitrite as N353.2mg/L10.0190.10.13Nitrogen, Total Kjeldahl351.2mg/L40.31413Biochemical Oxygen Demand5210Bmg/L10.32.51.9JChemical Oxygen Demand410.4mg/L28.14055Chloride300.0mg/L200516003,300Sulfate300.0mg/L50122501,500Cyanide, Total4500 CN Emg/L10.020.10.089JTotal Dissolved Solids2540Cmg/L119408,700Total Suspended Solids2540Dmg/L11.141.6JPhosphorus, Total365.1mg/L10.0050.050.16Total MetalsAluminum200.7ug/L29.420038JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.241.7JBarium200.7ug/L22.520210Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10331,00066,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L103402,0001,600,000Chromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200190JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400430,000Manganese200.7ug/L20.5120430ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-41Table A-14. Duplicate of Effluent from Bioreactor System Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L204.8310.131.5Molybdenum200.7ug/L21.6402.4JNickel200.8ug/L20.8940.94JSelenium200.8ug/L20.6241.5JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00032,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.7JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1104.7JDissolved MetalsAluminum200.7ug/L29.420028JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.242JBarium200.7ug/L22.520220Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,00067,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L501,70010,0001,700,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200110J,BLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400420,000Manganese200.7ug/L20.5120400ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).



# A-42Table A-14. Duplicate of Effluent from Bioreactor System Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationMercury1631Eng/L204.8310.133.7Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6241JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,00033,000Thallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6203.1JVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1104.8J

# 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 Equipmen t Blank Analytical Data, Allen

Analyte Method Process Units Concentration

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

# a 

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

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



# A-44 Table A-15. Bottle Blank and Equipmen t Blank Analytical Data, Allen

Analyte Method Process Units Concentration

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Aluminum a 

# EPA 1638 Dissolved ug/L 4.71

Antimony EPA 1638 Dissolved ug/L ND (0.50)

Arsenic EPA 1638 Dissolved ug/L ND (0.50)

Barium EPA 1638 Dissolved ug/L ND (0.10)

Beryllium EPA 1638 Dissolved ug/L ND (0.10)

Cadmium EPA 1638 Dissolved ug/L ND (0.10)

Chromium EPA 1638 Dissolved ug/L ND (1.0)

Cobalt EPA 1638 Dissolved ug/L ND (0.10)

Copper EPA 1638 Dissolved ug/L ND (0.30)

Lead EPA 1638 Dissolved ug/L ND (0.050)

Manganese EPA 1638 Dissolved ug/L ND (0.50)

Molybdenum EPA 1638 Dissolved ug/L ND (0.50)

Nickel EPA 1638 Dissolved ug/L ND (0.50)

Selenium EPA 1638 Dissolved ug/L ND (2.0)

Silver EPA 1638 Dissolved ug/L ND (0.10)

Thallium EPA 1638 Dissolved ug/L ND (0.050)

Vanadium EPA 1638 Dissolved ug/L ND (1.0)

Zinc EPA 1638 Dissolved ug/L ND (0.50)

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

Aluminum EPA 1638 Dissolved ug/L ND (2.0)

Antimony EPA 1638 Dissolved ug/L ND (0.50)

# a 

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

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



# A-45 Table A-15. Bottle Blank and Equipmen t Blank Analytical Data, Allen

Analyte Method Process Units Concentration

Arsenic EPA 1638 Dissolved ug/L ND (0.50)

Barium EPA 1638 Dissolved ug/L ND (0.10)

Beryllium EPA 1638 Dissolved ug/L ND (0.10)

Cadmium EPA 1638 Dissolved ug/L ND (0.10)

Chromium EPA 1638 Dissolved ug/L ND (1.0)

Cobalt EPA 1638 Dissolved ug/L ND (0.10)

Copper EPA 1638 Dissolved ug/L ND (0.30)

Lead EPA 1638 Dissolved ug/L ND (0.050)

Manganese EPA 1638 Dissolved ug/L ND (0.50)

Molybdenum EPA 1638 Dissolved ug/L ND (0.50)

Nickel EPA 1638 Dissolved ug/L ND (0.50)

Selenium EPA 1638 Dissolved ug/L ND (2.0)

Silver EPA 1638 Dissolved ug/L ND (0.10)

Thallium EPA 1638 Dissolved ug/L ND (0.050)

Vanadium EPA 1638 Dissolved ug/L ND (1.0)

Zinc EPA 1638 Dissolved ug/L ND (0.50)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

# a 

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

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



# A-46 Table A-15. Bottle Blank and Equipmen t Blank Analytical Data, Allen

Analyte Method Process Units Concentration

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

# a 

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

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



# A-47 Table A-15. Bottle Blank and Equipmen t Blank Analytical Data, Allen

Analyte Method Process Units Concentration

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

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

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

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

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

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

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

Lead EPA 1638 Total 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 System Field Blank, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationTotal MetalsAluminum200.7ug/L29.420018JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720043J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L26940097JChromium200.8ug/L23.38ND (8)U,^Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220092JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400ND (400)UManganese200.7ug/L20.51201.2JMercury1631Eng/L10.240.5ND (0.5)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)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 System Field Blank, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationDissolved 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/L26.72009J,BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.9642.1JIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400ND (400)UManganese200.7ug/L20.5120ND (20)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1108J

# 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 Bioreactor System Field Blank, Day1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific 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/L26.720039J,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)UZinc200.8ug/L24.1106.9JDissolved MetalsAluminum200.7ug/L29.4200ND (200)U

# A-51ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-17. Influent to Bioreactor System Field Blank, Day1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.7200ND (200)UCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400ND (400)UManganese200.7ug/L20.5120ND (20)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1107J

# 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 Bioreactor System Field Blank, Day2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific 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 Bioreactor System Field Blank, Day3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific 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 Bioreactor System Field Blank, Day4 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific 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 Bioreactor System Field Blank, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific 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/L26.720032J,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)UZinc200.8ug/L24.1106.1JDissolved 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 Bioreactor System Field Blank, Day 1 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.7200ND (200)UCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400ND (400)UManganese200.7ug/L20.5120ND (20)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.1109.5J

# A-57ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-22. Effluent from Bioreactor System Field Blank, Day 2 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-58ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-23. Effluent from Bioreactor System Field Blank, Day 3 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific 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 Bioreactor System Field Blank, Day 4 Analytical Results, AllenAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSampleSpecific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# Appendix B

DATA REVIEW NARRATIVES

# 1 

# MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

Deb Bartram, ERG

TJ Finseth, ERG

From: Randy Mercurio , ERG

Donna Tedder, ERG

Date: 9 / 1 /201 1

Subject: FGS Data R eview Narra tive for Total and Dissolved Mercury

– Episode 65 61

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

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

Atomic Fluorescence Spectrometr y (CVAFS) analysis.

Table 1 summarizes the 37 s amples ( ex cluding laboratory filter blanks) FG S extracted

and analyzed for total and dissolved mercury

.

Table 1. 

# EPA Episode 6561 Total & Dissolved Mercury

– Sample Identification

EPA

Sample # Lab Sampl e

ID # Sample

Matrix Sample Description Sampling

Date

71791 1008018

- 01 Aqueous FGD Influent Day 1 8/2/2010

71791 1008018

- 02 Aqueous Dissolved FGD Influent, Day 1 8/2/2010

71792 1008031

- 13 Aqueous FGD Influent, Day 2 8/3/2010

71792 1008031

- 14 Aqueous Di ssolved FGD Influent, Day 2 8/3/2010

71793 1008045

- 01 Aqueous FGD Influent, Day 3 8/4/2010

71793 1008045

- 02 Aqueous Dissolved FGD Influent, Day 3 8/4/2010

71794 1008062

- 01 Aqueous FGD Influent, Day 4 8/5/2010

71794 1008062

- 02 Aqueous Dissolved FGD Infl uent, Day 4 8/5/2010

71795 1008031

- 15 Aqueous FGD Bioreactor Influent, Day 1 8/3/2010

71795 1008031

- 16 Aqueous Dissolved FGD Bioreactor Influent, Day 2 8/3/2010

71796 1008045

- 03 Aqueous FGD Bioreactor Influent, Day 2 8/4/2010

71796 1008045

- 04 Aqueous D issolved FGD Bioreactor Influent, Day 2 8/4/2010

71797 1008062

- 03 Aqueous FGD Bioreactor Influent, Day 3 8/5/2010

71797 1008062

- 04 Aqueous Dissolved FGD Bioreactor Influent, Day 3 8/5/2010

71798 1008072

- 03 Aqueous FGD Bioreactor Influent , Day 4 8/6/201 0

71798 1008072

- 04 Aqueous Dissolved FGD Bioreactor Influent , Day 4 8/6/2010

71799 1008031

- 17 Aqueous FGD Bioreactor Effluent, Day 1 8/3/2010

71799 1008031

- 18 Aqueous Dissolved FGD Bioreactor Effluent, Day 1 8/3/2010

71800 1008045

- 05 Aqueous FGD Biore actor Effluent, Day 2 8/4/2010

# 2 Table 1. 

# EPA Episode 6561 Total & Dissolved Mercury

– Sample Identification

EPA

Sample # Lab Sampl e

ID # Sample

Matrix Sample Description Sampling

Date

71800 1008045

- 06 Aqueous Dissolved FGD Bioreactor Effluent, Day 2 8/4/2010

71801 1008062

- 05 Aqueous FGD Bioreactor Effluent, Day 3 8/5/2010

71801 1008062

- 06 Aqueous Dissolved FGD Bioreactor Effluent, Day 3 8/5/2010

71802 1008072

- 05 Aqueous FGD Bioreactor Effluent , Day 4 8/6/2010

71802 1008072

- 06 Aqueous Dissolved FGD Bioreactor Effluent , Day 4 8/6/2010

71803 1008062

- 07 Aqueous FGD Bioreactor Influent Duplicate 8/5/2010

71803 1008062

- 08 Aqueous Dissolved FGD Bioreactor Influent Duplicate 8/5/2010

71804 1008045

- 07 Aqueous FGD Bioreactor Effluent Duplicate, Day 2 8/4/2010

71804 1008045

- 08 Aqueous Dissolved FGD Bioreactor Effluent Duplicate,

Day 2 8/4/2010

71805 1008018

- 03 Aqueous FGD Influent Field Blank, Day 1 8/2/201 0

71806 1008018

- 06 Aqueous FGD Bioreactor Influent Field Blank, Day 1 8/2/2010

71807 1008031

- 19 Aqueous FGD Biorea ctor Influent Field Blank, Day 2 8/3/2010

71808 1008045

- 15 Aqueous FGD Bioreactor Influent Field Blank , Day 3 8/4/2010

71809 1008062

- 13 Aq ueous FGD Bioreactor Influent Field Blank , Day 4 8/5/2010

71810 1008018

- 09 Aqueous FGD Bioreactor Effluent Field Blank, Day 1 8/2/2010

71811 1008031

- 12 Aqueous FGD Bioreactor Effluent Field Blank, Day 2 8/3/2010

71812 1008045

- 16 Aqueous FGD Bioreactor E ffluent Field Blank , Day 3 8/4/2010

71813 1008062

- 14 Aqueous FGD Bioreactor Effluent Field Blank, Day 4 8/5/2010



# SUMMARY

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

.

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

dataset

.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no s ample receipt issues in this data package

.

I NITIAL CAL IBRATION

FGS performed the initial calibrations on each analysis day. The i nitial calibr ation 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 C ONTINUING C ALIBRATION V ERIFICATION S

All initial and c ontinuing c alib ration v erifications ( ICVs, CCVs ) met method

- specified

criteria

.

# 3 BLANK S

All the preparation blanks or laboratory reagent b lanks (LRBs) and the continuing

calibration blanks (CCBs) met method

- suggested criteria. Preparation Blanks F00900 1

-

BLK2 and F009002

- BLK4 had mercury levels of 0.10 and 0.27 ng/L

, r espectively, which

are greater than the MDL

, but less than the reporting li mit . These blank results were

appropriately fagged with a “J” qualifier

.

DUPLICATES

Field duplicates , Sample 71804, were collected on S ample 71800

. The 71800/71804

total mercury relative percent difference ( RPD ) was 10.4% and the dissolved mercury

RPD w as 1.8% . The method

- suggested RPD criterion between field duplicates is 20%.

L aboratory duplicates were performed in this episode on samples 71795

, 71796 and

71801

. All RPDs were less than 20% (the method

- suggested RPD criterion between field

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

.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

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

71796 and 71801 for the total mercury analyses. MS and MS Ds were performed on

samples 71791, 71795, 71801 & 71798 for the dissolved mercury analyses. All

MS/MSD recoveries were within method specifications of 71

- 125%. All RPDs met

method

- specified criteria.

D ETECTION LIMITS

The laboratory MDL in the syntheti c matrix was 0.239 ng/L. Results below this MDL

were reported as not detected (ND).

# 1



# MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

Deb Bartram, ERG

TJ Finseth, ERG

From: Randy Mercurio, ERG

Donna Tedder, ERG

Date: 9/1/2011

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

Episode 6561

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

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

for Sample Episode 6561. The samples were analyzed according to EPA Method 200.8.

Table 1 summarizes the samples TestAmerica extracted and analyzed for total and

dissolved metals by EPA Method 200.8.

Table 1. 

# EPA Episode 6561 Total & Dissolved Metals – Sample Identification



# EPA

Sample # EPA Sample Description 

# Lab Sample

ID # 

# Sample

Matrix 

# Sampling

Date 

# Receipt

Date

7179 1 FGD Influent, Day 1 280

- 5932

- 1 Aqueous 8/2 /2010 8/3 /2010

71 792 FGD Influent, Day 2 280

- 5964

- 1 Aqueous 8/3 /2010 8/4 /2010

71 793 FGD Influent, Day 3 280

- 6008

- 1 Aqueous 8/4 /2010 8/5 /2010

71 794 FGD Influent, Day 4 280

- 6067

- 4 Aqueous 8/5 /2010 8/6 /2010

71 795 FGD Bioreactor Influent, Day 1 280

- 5964

- 2 Aqueous 8/3 /2010 8/4 /2010

71 796 FGD Bioreactor Influent, Day 2 280

- 6008

- 2 Aqueous 8/4 /2010 8/5 /2010

71797 FGD Bioreactor Influent, Day 3 280

- 6067

- 1 Aqueous 8/5 /2010 8/6 /2010

71798 FGD Bioreactor Influent, Day 4 280

- 6117

- 1 Aqueous 8/6 /2010 8/7 /2010

717 99 FGD Bioreactor Ef fluent , Day 1 280

- 5964

- 3 Aqueous 8/3 /2010 8/4 /2010

71 800 FGD Bioreactor Effluent, Day 2 280

- 6008

- 3 Aqueous 8/4 /2010 8/5 /2010

71 801 FGD Bioreactor Ef fluent, Day 3 280

- 6067

- 2 Aqueous 8/5 /2010 8/6 /2010

71 802 FGD Bioreactor Effluent, Day 4 280

- 6117

- 2 Aqueous 8/6 /2010 8/7 /2010

71 803 FGD Bioreactor In fluent

-

Duplicate, Day 3 

# 280

- 6067

- 3 Aqueous 8/5 /2010 8/6 /2010

71 804 FGD Bioreactor Effluent

-

Duplicate, Day 2 

# 280

- 6008

- 4 Aqueous 8/4 /2010 8/5 /2010

71 805 FGD Influent Field Blank, Day

1 

# 280

- 5932

- 2 Aqueous 8/2 /2010 8/3 /2010

71 806 FGD Bioreactor In fluent Field

Blank, Day 1 

# 280

- 5964

- 4 Aqueous 8/3 /2010 8/4 /2010

# 2 Table 1. 

# EPA Episode 6561 Total & Dissolved Metals – Sample Identification



# EPA

Sample # EPA Sample Description 

# Lab Sample

ID # 

# Sample

Matrix 

# Sampling

Date 

# Receipt

Date

71 810 FGD Bioreactor Effluent Field

Blank, Day 1 

# 280

- 5964

- 5 Aqueous 8/3 /2010 8/4 /2010



# SUMMARY

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

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

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

2010, based on EPA Method 200.8, by ICP/MS analysis.

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

those identified by the laboratory) in this dataset.

INTERNAL STANDARDIZATION

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

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day or before each

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

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

INITIAL AND CONTINUING CALIBRATION VERIFICATION (ICV/CCV)

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

performed by TestAmerica all had recoveries within the method criteria.

BLANKS

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

were required for method blanks.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank

(CCB)) were less than the RL; however, antimony was above the instrument detection

limit (IDL) in one ICB and was flagged with the “J” qualifier.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

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

# 3

LABORATORY CONTROL SAMPLES (LCS)

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

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION

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

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

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

ICS.

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

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

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

Chromium in analytical batch 280-27123. The lab has confirmed with the vendor that

Chromium is a trace impurity in the ICSA solution. Therefore, corrective action was

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

SERIAL DILUTION

The serial dilution performed for the total and dissolved sample 71799 FGD Bioreactor

Effluent, Day 1 (280-5964-3) met TestAmerica’s criteria of ±10% difference.

FIELD DUPLICATES

The relative percent difference (RPD) of the field duplicates 71800/71804 and

71797/71803 were less than 20% for all values greater than the reporting limit. None of

the total or dissolved analytes in parent sample 71800 and field duplicate sample 71804

were above the RL so the RPD could not be accurately determined. The RPD for all total

and dissolved analytes above the reporting limit in parent sample 71797 and field

duplicate sample 71803 were less than TestAmerica’s ±20% requirement.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

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

71799, 71801 and 71798. Many spike recoveries were outside the method control limits

of 70–130% when sample concentrations exceeded the spike concentration by a factor of

four or more, which have been flagged with a “4” qualifier indicating concentrations in

the parent samples were greater than four times the spike amounts. Otherwise, all

MS/MSD spike recoveries were within the method control limits of 70-130%. In

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

# 4

POST DIGESITON SPIKES

The post digestion spike performed on sample 71799 FGD Bioreactor Effluent, Day 1

(280-5964-3) for total and dissolved analytes passed TestAmerica’s 85–115% control

limits.

DETECTION LIMITS

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

of reagent water.

# 1 

# MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

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

Deb Bartram

, ERG

TJ Finseth

, ERG

From: Randy Mercurio, ERG

Donna Tedder, ERG

Date: 9 / 1 /201 1

Subject: TestAmerica Data R eview Narrative for Total and Dissolved Metals by 200.7

– Episode 65 61

TestAmerica generated analytical data for total and dissolved metals ( a luminum, b oron,

b arium, b eryllium, c alcium, c obalt, i ron, m agnesium, m anganese

, m olybdenum, s odium,

t in, t itanium, and z inc ) for Sample Episode 6561

. T he samples were analyzed according

to EPA Method 200. 7

.

Table 1 summarizes the s ample s TestAmerica extracted and analyzed for total and

dissolved metals by EPA Method 200.7

.

Table 1. 

# EPA Episode 6561 Total & Dissolved Metals

– Sample Identification

EPA

Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

7179 1 FGD Influent, Day 1 280

- 5932

- 1 Aqueous 8/2 /2010 8/3 /2010

71 792 FGD Influent, Day 2 280

- 5964

- 1 Aqueous 8/3 /2010 8/4 /2010

71 793 FGD Influent, Day 3 280

- 6008

- 1 Aqueous 8/4 /2010 8/5 /2010

71 794 FGD Influent, Day 4 280

- 6067

- 4 Aqueous 8/5 /2010 8/6 /2010

71 795 FGD Bioreactor Influent, Day 1 280

- 5964

- 2 Aqueous 8/3 /2010 8/4 /2010

71 796 FGD Bioreactor Influent, Day 2 280

- 6008

- 2 Aqueous 8/4 /2010 8/5 /2010

71797 FGD Bioreactor Influent, Day 3 280

- 6067

- 1 Aqueous 8/5 /2010 8/6 /2010

71798 FGD Bioreactor Influent, Day 4 280

- 6117

- 1 Aqueous 8/6 /2010 8/7 /2010

717 99 FGD Bioreactor Ef fluent , Day 1 280

- 5964

- 3 Aqueous 8/3 /2010 8/4 /2010

71 800 FGD Bioreactor Effluent, Day 2 280

- 6008

- 3 Aqueous 8/4 /2010 8/5 /2010

71 801 FGD Bioreactor Ef fluent, Day 3 280

- 6067

- 2 Aqueous 8/5 /2010 8/6 /2010

71 802 FGD Bioreactor Effluent, Day 4 280

- 6117

- 2 Aqueous 8/6 /2010 8/7 /2010

71 803 FGD Bioreactor In fluent

- Duplicate , Day 3 280

- 6067

- 3 Aqueous 8/5 /2010 8/6 /2010

71 804 FGD Bioreactor Effluent

- Duplicate , Day 2 280

- 6008

- 4 Aqueous 8/4 /2010 8/5 /2010

71 805 FGD Influent Field Blank, Day 1 280

- 5932

- 2 Aqueous 8/2 /2010 8/3 /2010

# 2 Table 1. 

# EPA Episode 6561 Total & Dissolved Metals

– Sample Identification

EPA

Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71 806 FGD Bioreactor In fluent Field

Blank , Day 1 280

- 5964

- 4 Aqueous 8/3 /2010 8/4 /2010

71 810 FGD Bioreactor Effluent Field

Blank , Day 1 280

- 5964

- 5 Aqueous 8/3 /2010 8/4 /2010



# SUMMARY

The sample s were prepared for total and dissolved metals analysis according to

TestAmerica ’s SOP for ICP Analysis for Trace Metals by Method 200.7

.

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

those identified by the laboratory) in this dataset.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no s ample receipt issues in this data package

.

INTERNAL STANDARDIZA TION

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

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

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

I NITIAL CAL IBR ATION

TestAmerica performed the initial calibrations on each analysis day. The initial

calibration for the ICP analysis consisted of a blank and one calibration standard.

I NITIAL AND CONTINUING CALIBRATION VERIFICATION S

The i nitial c alibration v erifications ( ICV ) and c ontinuing c alibration v erifications (CCV)

performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANK S

All the m ethod b lanks were less than the r eporting l imit (RL) ; however, some elements

had l evels greater than the method detection limit ( MDL ) and were flagged with the “J”

qualifier.

All i nstrument b lanks ( initial calibration blank ( ICB ) and continuing calibration blank

( CCB ) ) were less than the RL; however, some elements had levels greater than the MDL

and were flagged with the “J” qualifier

.

# 3 LABORATORY CONTROL SAMPLES (LCS)

All LCSs passed the method control limits of 85

– 115%.

INTERFERENCE CHECK SOLUTION S

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

recoveries met the method

- specified criteria.

SERIAL DILUTION

Serial dilutions were performed for each batch of total and dissolved samples. All serial

dilution percent differences were less than 10% as required by TestAmerica’s SOP

.

REPORTING LIMIT VERIFICATION STANDARD ( CRI )

A ll CRI samples passed TestAmerica ’s control limits of 50

– 150%.

FIELD DUPLICATES

The relative percent difference (RPD) of the field duplicates 71800/71804 and

71797 /71803 were less than 20% for all total and dissolved values greater than the RL.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

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

dissolved sample s of 71798 , 71799 and 71801

. Many spike recoveries were outside the

method control limits of 70

- 130% when sample concentrations exceeded the spike

concentrations by a factor of four or more, which have been flagged with a “4” qualifier

indicating concentrations in the parent samples were greater than four times the spike

amounts. Otherwise, all MS/MSD spike recoveries were within the method control limits

of 70

- 130

, except those already qualified with a “4” as mentioned above, and therefore no

additional data qualifiers were needed

. In addition, a ll RPDs of the MS/MSDs were

within TestAmerica’s ± 20% requirement

.

POST DIGESTION SPIKE

The post digestion spike performed on sample 71799 FGD Biorea ctor Effluent, Day1

passed TestAmerica’s control limits of 85

- 115% recovery for all total and dissolved

analytes except total sodium and dissolved manganese. The post digestion spike

performed on sample 71798 FGD Bioreactor Influent, Day 4 passed TestAmerica’s

control limits of 85

- 115% recovery for all total and dissolved analytes except total

sodium.

# 4 DETECTION LIMITS

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

of reagent water.

# 1 

# MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

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

Deb Bartram

, ERG

TJ Finseth

, ERG

From: Donna Tedder, ERG

Date: 9 / 1 /201 1

S ubject: FGS Data R eview Narrative for Dissolved Hex avalent Chromium

– Episode

65 6 1

Frontier Global Sciences (FGS) generated analytical data for dissolved hexavalent

chromium for Sample Episode 6561

. FGS analyzed t he samples according to a m odified

EPA Method 2 18. 6 for dissolved hexavalent chromium by Liqu id Chromatography

– Inductively Coupled Plasma Mass Spectrometry (LC

- ICP

- MS)

.

Table 1 summarizes the s amples FGS extracted and analyzed for dissolved hexavalent

chromium

.

Table 1. 

# EPA Episode 6561 Dissolved Hexavalent Chromium

– Sample Identification

EPA

Sample

# Sample

Matrix Sample Description Sampling

Date Analysis Date

71 7 9 1 Aqueous FGD Influent Day 1 8 /2 /10 8/9 /10

717 9 2 Aqueous FGD Influent Day 2 8 / 3 /10 8/9/10

717 9 3 Aqueous FGD Influent Day 3 8/4/10 8/9/10

717 9 4 Aqueous FGD Influent Day 4 8/5/ 10 8/ 30 /10

717 9 5 Aqueous FGD Bioreactor Influent Day 1 8/3/10 8/9/10

717 9 6 Aqueous FGD Bioreactor Influent Day 2 8/4/10 8/9/10

717 9 7 Aqueous FGD Bioreactor Influent Day 3 8/5/10 8/ 30 /10

717 9 8 Aqueous FGD Bioreactor In fluent Day 4 8/6/10 8/ 30 /10

717 9 9 Aqueous FGD Bioreactor Effluent Day 1 8/3/10 8/9/10

71 80 0 Aqueous FGD Bioreactor Effluent Day 2 8/4/10 8/ 30 /10

71 80 1 Aqueous FGD Bioreactor Effluent Day 3 8/5/10 8/ 30 /10

71802 Aqueous FGD Bioreactor Effluent Day 4 8/6/10 8/ 30 /10

71803 Aqueous FGD Biore actor Influent Dup Day 3 8/5/10 8/ 30 /10

71804 Aqueous FGD Bioreactor Effluent Dup Day 2 8/4/10 8/ 30 /10

71805 Aqueous FGD Influent F ield B lank Day 1 8/2 /10 8/9/10

71806 Aqueous FGD Bioreactor Influent F ield B lank Day 1 8/3/10 8/9/10

71810 Aqueous FGD Bi oreactor Effluent F ield B lank Day 1 8/3/10 8/9/10

# 2 SUMMARY

The samples were prepared for dissolved hexavalent chromium analysis according to

FGS

- 129.01 Standard Operating Procedure ( SOP ) , a modified EPA Method 218. 6

. Several s amples ( 717 9 1, 717 9 2, 717 9 3, 71794, 71795, 71796, 71797, 71798, and 71803 )

were diluted prior to analysis due to the presence of high levels of nontarget chloride

interferences

.

T here were no issues requiring additional data qualifiers for the hexavalent chromium

data in this epis ode.

SAMPLE REC E IPT, HANDLING, AND STORAGE ISSUES

There were no s ample receipt issues in this data package

.

I NITIAL P RECISION AND ACCURACY/ R ECOVERY

The initial precision and recovery ( IPR ) performed by FGS had recoveries within the

method criteria.

O N

- GOING P RECISION AND ACCURACY/ R ECOVERY

The analytical method did not require the analysis of an on

- going precision and recovery

( OPR )

.

I NITIAL CAL IBRATION

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

the LC

- ICP

- MS analysis consisted of a blank and eight calibration standards with a

correlation factor ≥ 0.995 as required by the method

.

A secondary source initial calibration verification (ICV) was analyzed and passed ± 10 %

of true value required by the method

.

C ONTINUING C ALIBRATION V ERIFICATION

All CCVs met method

- specified criteria

, ± 10% of true value with recoveries ranging

from 95 to 109%.

BLANK

All of the prep aration blanks /laboratory reagent blanks (LRBs) and the continuing

calibration blanks (CCBs) met method

- specified requirements

.

# 3 OTHER CHECKS

The l aboratory c o ntrol s ample /duplicate (LCS /LCSD ) or laboratory fortified

blank /duplicate (LFB /LFBD ) passed method criteria of ± 10% of true value with

recoveries of 102% and 102%

. A second set of LFB /LFBD, for the later analysis date,

had recoveries of 100% and 99.3%. The method suggested that a second source quality

control sample (QCS) must be analyzed by the laboratory at least once a quarter. The

second source ICV meets this recommendation

.

D ETECTION LIMITS

The laboratory method detection limit (MDL) in the synth etic matrix was 0.392 ug/L.

Results below this MDL were reported as not detected.

DUPLICATES

There were no laboratory duplicates performed in this episode other than a duplicate of

the LCSD and a duplicate of the matrix spike ( MS )

.

Two field duplicate s w ere collected and analyzed. Sample 71 803 was a duplicate of

sample 71 7 97

. These samples were nondetects ( NDs ) , indicating the analyte was not

detected at or above the method detection limit. Sample 7180 4 was a duplicate of sample

71 800

. These samples we re also NDs.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The M S and matrix spike duplicate ( MSD ) were performed using a secondary source

spike on sample s 71791 and 71 801

. All MS/MSD recoveries were within 75%

- 125%,

with RPD s of 1.47% and 4.44% , respectively

.

# 1 

# MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

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

Deb Bartram

, ERG

TJ Finseth, ERG

From: Donna Tedder

, ERG

Date: 9 / 1 /2011

Subject: TestAmerica Data Review Narrative for Classicals Analyses

– Episode 65 61

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry

analyses for Sample Episode 65 61

. All samples were tested for the following analytes:

• Ammonia by EPA m ethod 350.1,

• Biochemical Oxygen Demand

– 5 day (BOD 5 

# ) by SM 5210B,

• Chloride and S ulfate by EPA m ethod 300.0,

• Chemical Oxygen Demand (COD) by EPA m ethod 410.4,

• Cyanide by SM 4500 CN

- 

# E,

• Nitrate / Nitrite by EPA m ethod 353.2

,

• Phosphorus by EPA m ethod 365.1,

• Total D issolved S olids (TDS) by SM 2540C,

• Total K jeldah l N itrogen (TKN) by EPA m ethod 351 .2

, and

• Total S uspended S olids (TSS) by SM 2540D

.

Table 1 summarizes the 1 4 samples that TestAmerica analyzed for the above analytes

.

Table 1. EPA Episode 6561 Classical Analytes

– Sample Identification

EPA

Sample # Sample

Matrix Sample Description Sampling

Date

71791 Water FGD Influent, Day 1 8/2/10

71792 Water FGD Influent, Day 2 8/3/10

71793 Water FGD Influent, Day 3 8/4/10

71794 Water FGD Influent, Day 4 8/5/10

71795 Water FGD Bioreactor Influent, Day 1 8/3/10

71796 Water FGD Bioreactor Influent, Day 2 8/4/10

71797 Water FGD Bioreactor Influent, Day 3 8/5/10

71798 Water FGD Bioreactor Influent, Day 4 8/6/10

71799 Water FGD Bioreactor Effluent, Day 1 8/3/10

71800 Water FGD Bioreactor Effluent, Day 2 8/4/10

71801 Water FGD Bioreactor Effluent, Day 3 8/5/10

# 2 Table 1. EPA Episode 6561 Classical Analytes

– Sample Identification

EPA

Sample # Sample

Matrix Sample Description Sampling

Date

71802 Water FGD Bioreactor Effluent, Day 4 8/6/10

71803 Water FGD Bioreactor Influent

- Duplicate 8/5/10

71804 Water FGD Bioreactor Effluent

- Duplicate 8/4/10

SUMMARY

All samples were analyzed within the holding time specified in 40 CFR 136 Table II . A ll

samples were preserved appropriately

.

Two field duplicate samples were collected and analyzed for each analyte. The r elative

p ercent d ifference (RPD ) between the sample and its duplicate was less than 20% unless

otherwise noted below.

If applicab le, the appropriate number of standards was used to create a calibration curve.

If sample results were above the highest standard used to create the curve, the sample was

diluted and reanalyzed. All sample results were between t he lowest and highest standards

unless noted below. Additionally, u nless otherwise noted, all calibration blanks and

calibration verification samples met the criteria specified in the method.

If required by the method, the quality control sample (QCS), a secondary source standard

used to verify calibration, was always within the control limits specified by the method.

As described below, the analyte of interest was detected above the method detection limit

(MDL) in some laboratory reagent blanks (LRB). However, the analyte of interest was

never detected above the reporting limit (RL) in the LRBs . If required by the method, all

laboratory fortified blanks (LFB) met the criteria specified in the method unless specified

below

.

If required by the method, a matrix spike (M S) sample was analyzed. Two MS samples

were run on sample s 71 79 8 (FGD bioreactor influent) and 71 80 1 (FGD bioreactor

effluent) for ea ch analyte to check for matrix interferences in th ese matrices

. For some

analytes, TestAmerica spiked more samples than required. All MS samples analyzed met

the criteria specified in the method unless described below.

DATA NOTES /ISSUES

Ammonia

The percent recoveries for the MS and MSD analysis for sample 71799 (FGD bioreactor

ef

fluent) were 112% and 116%, respectively, which are above the laboratory and method

control limits of 90

- 110%

. Sample 71 799 was qualified as a maximum value

. The LFB

associat ed with this sample met the method criteria.

# 3 BOD 5



# Even though TestAmerica ran five dilutions on sample 7 1801 , no dilutions had a

dissolved oxygen (DO) depletion greater than 2.0 mg/L. Therefore, BOD 5 

# was rep orted

as not detect ed for this sample

.

All glucose

- glutamic acid standards and laboratory duplicates we re analyzed

appropriately and met the criteria specified in SM 5210B

. BOD was not detected above

the RL in any method blank; h owever, for batch 25403, the results for the three

water/ unseeded blan k s w ere 0.24 mg/L, 0.21 mg/L, and 0.21 mg/L. All of these results

were greater than the method control criteria of 0.20 mg/L. Because of th ese detections in

the water/unseeded blanks

, sample s 71791, 71792, 71795, and 71799 were qualified with

a “B” meaning the analyte was found in the sample and the blank

.

Chloride and Sulfate

The MS/MSD results of sample s 71798 and 71801 for sulfate were above the calibration

curve. TestAmerica did not reanalyze the samples with a higher dilution factor because

the pe rcent recoveries were within EPA Method 300.0 control limits. If reported, these

MS/MSD results will be qualified as estimated values.

COD

The percent recovery of the LFB associated with batch 25742 was 88.9%, which was less

than the method control criteria of 90

- 110% , but did meet the historical laboratory criteria

of 80

- 115%

. The LFBD percent recovery ( 96.7% ) did meet the method criteria. Because

the laboratory originally had analyzed the percent recovery against the historical criteria,

this L FB f ailure was not noted until after the hold time had expired, so the samples were

not reanalyzed. The laboratory qualified these samples with a “*” indicating that the

LFB or LFBD was not within the control limits. Samples 71792, 71795, and 71799 were

alrea dy qualified by the laboratory with a “J” meaning the sample result was an estimated

value because it was less than the RL, so no further action was taken.

Sample s 71795 and 71801 w ere diluted by 10 fold because of matrix interferences

determined by the c hloride prescreening. The diluted resu lt s w ere below the lowest

calibration standard ; h owever, these samples were already qualified by the laboratory

with a “J” meaning the sample result was an estimated value because it was less than the

RL, so no further action was taken.

The RPD between sample 71797 and its field duplicate 71803 was 26.5 % and the RPD

between sample 71800 and its field duplicate 71804 was 35.8 %. Even though these RPDs

were greater than 20%, the samples were not qualified because there ar e no specific

control limits for field duplicates specified in EPA m ethod 410.4.

# 4 The percent recoveries for the MS/MSD analysis for sample 71798 (FGD bioreactor

influent) and for the MS analysis for sample 71 801 ( F GD bioreactor ef fl uent) w ere below

the control limits of 90

- 110% required by EPA M ethod 410.4. The percent recoveries for

the MS and MSD analyses for sample 71798 were 75% and 77%, respectively

, and t he

percent recoveries for the MS and MSD analys e s for sample 71801 were 89 % and 96 %

, respectively. The LFB associated with these samples met the method criteria. Sample

71798 was qualified as a minimum value. Results for samples with a similar matrix ( i.e.,

FGD bioreactor influent) could also be biased low. S ample 71 801 was already qualified

by the laboratory with a “J” meaning the sample result was an estimated value because it

was less than the RL ; therefore, this sample was not additionally qualified as a minimum

value.

Cyanide

Cyanide was detected at 0.00240 mg/L in the method blank associated with sample s

71794, 71797, 71798, 71801, 71802, and 71803

. Although this concentration is greater

than the MDL (0.0020 mg/L), it is lower than the RL (0.010 mg/L). Because the blank

result was less than the RL, no samples were qualified b ased on the L R B result

.

The RPD between sample 71800 and its field duplicate 71804 was 21.1% . Even though

t his RPD was greater than 20%, the samples were not qualified because there are no

specific control limits for field duplicates specified in SM 4500 CN

- 

# E

.

All samples were diluted prior to distillation by a factor of 10 due to matrix interferences

. The laboratory stated that the samples foamed during preparation and in order to protect

the instruments, the samples needed to be diluted. T he results of the diluted sample for

71795, 71796, and 71804 were below the lowest calibration standard used by the

laboratory (0.01 mg/L). However, these samples were already qualified by the laboratory

with a “J” meaning the sample result was an estimate d value because it was less than the

RL, so no further action was taken.

Nitrate / Nitrite

The result for sample 71799 was below the lowest c alibration standard . However, this

sample was already qualified by the laboratory with a “J” meaning the sample res ult was

an estimated value because it was less than the RL, so no further action was taken.

The percent recovery for the MS analysis for sample 71798 (FGD bioreactor influent)

was below the control limits of 90

- 110% required by the method and below the

laboratory control limits of 72

- 113%. T he percent recoveries of the MS and MSD

samples were 70 % and 102%, respectively. TestAmerica qualified both the MS and MSD

results for sample 71798 with an “ E ” meaning that the results exceeded the calibration

ra nge

. T he MSD sample result was above the highest calibration standard and even

though the MS sample result was within the cal ibration range

, it was expected to be

above the highest calibration standard

. If the MSD result is reported, it will be qualified

a s an estimated value because the result was above the highest calibration standard.

# 5 The MS percent recovery for sample 71799 (FGD bioreactor effluent) was not within the

method control limits, but was within the laboratory control limits. The percent

reco veries of the MS and MSD samples were 112 % and 107 %, respectively. Sample

71 799 was already qualified by the laboratory with a “J” meaning the sample result was

an estimated value because it was less than the RL, so there was no need to further

qualify the result as a maximum value.

Phosphorus

The results for S amples 71792, 71793, and 71798 were less than the lowest cali bration

standard (0.025 mg/L). However, these samples were already qualified by the laboratory

with a “J” meaning the sample result was an estimated value because it was less than the

RL, so no further action was taken.

The percent recoveries for the MS and MSD anal ys e s for sample s 71 79 8 and 71 80 1 were

not within the control limits of 90

- 110% specified in EPA Method 365.1 , but were within

the laboratory control limits of 71

- 128%

. The percent recoveries for MS and MSD

analys e s on sample 71 79 8 were both 73% and t he percent recoveries for MS and MSD

analys e s on sample 71 80 1 were both 74%

. The r esults may be biased low for samples

with similar matrix es (i.e., FGD bioreactor influent and FGD bioreactor effluent) because

of matrix interferences

. Sample 71801 w as qualified as a minimum value because the MS

percent recovery was below the method specified criteria. Sample 71798 was already

qualified by the laboratory with a “J” meaning the sample result was an estimated value

because it was less than the RL, so there was no need to further qualify the result as a

minimum value

.

The RPD between sample 7179 7 and its field duplicate 71 80 3 for phosphorus was 25.8 %.

The results for these samples were greater than the MDL, but less than the RL. These low

concentrations might be the reason for the high RPD. Even though the RPD was greater

than 20%, the sample was not qualified because there are no specific control limits for

field duplicates specified in EPA Method 365.1.

TDS

Constant weight was not achieved after 3 drying cycles for sample s 71791, 71795, 71796,

71797, 71798, 71799, 71800, 71801, 7180 2, 71803, and 71804. For sample s 71791,

71795, 71796, 71797, 71798, 71799, 71800, 71801, and 71803 the weight increased from

the first weighing to the second weighing. Method 2540C warns that samples which

contain high levels of calcium, magnesium, chlorid e, and sulfate may be hygroscopic

meaning they absorb moisture from the air. FGD wastewater contains high concentrations

of all of these species. This was likely the cause for the inconsistent weight calculations.

The samples were not qualified , but result s may be biased high

.

At least one l aboratory duplicate was analyzed per batch

. The RPDs for all l aboratory

duplicates analyzed were less than 10 % as required by SM 2540C

.

# 6 TKN

The percent recoveries for the MS and MSD analys e s for sample 71 798 ( Bioreactor

influent) did not meet the method control limits of 90 %

- 110 % or the laboratory criteria of

54 %

- 131%. The MS and MSD percent recoveries were 20 2 % and 20 6 %, respectively.

The LFB associated with this sample met the method criteria. These percent r ecoveries

suggest that results could be biased high for samples with a similar matrix (i.e., bioreactor

influent) . Sample 71798 was qualified as a maximum value.

TSS

At least one l aboratory duplicat e w as analyzed per batch . The RPDs for laboratory

duplicates for sample s 71791, 71792, 71794, and 71798 were less than 10% as required

by Method SM2540D . However, the RPD for sample 71801 was 15%

. The results for

sample 71801 and its laboratory duplicate were both qualified by th e laboratory with a

“J” meaning the sample result was an estimated value because it was less than the RL, so

sample 71801 was not additionally qualified

.

The RPD between sample 71797 and its field duplicate 71803 was 28.6%

. The RPD

between sample 71800 a nd its field duplicate 71804 was also 28.6%

. The results for these

four samples were less than the reporting limit. These low concentrations could have

caused the high RPD s

. Even though t h ese RPD s w ere greater than 20%, the samples were

not qualified becau se there are no specific control limits for field duplicates specified in

SM 2540D.

Table 2 . Data Review Summary Table

Sample Analyte Qualifier /Action Reason Level Detected

71799 Ammonia Maximum Value MS % recovery

above method

specified criteria 13 mg/L

71791 BOD B Unseeded water

blank > method

specified criteria 40 mg/L

71792 BOD B Unseeded water

blank > method

specified criteria 9.7 mg/L

71795 BOD B Unseeded water

blank > method

specified criteria 7.4 mg/L

71799 BOD B Unseeded water

blank > method

specified criteria 1.7 mg/L

# 7 Table 2 . Data Review Summary Table

Sample Analyte Qualifier /Action Reason Level Detected

71798 COD Minimum Value MS % recovery

below method

specified criteria 84 mg/L

71798 Nitrate/Nitrite Minimum Value MS % recovery

below method

specified criteria 13 mg/L

71801 Total

Phosphorus Minimum Value MS % recovery

below method

specified criteria 0.19 mg/L

71798 TKN Maximum Value MS % recovery

above method

specified criteria 3.2 mg/L

# Appendix C

PICTURES FROM THE SAMPLING EPISODE

# C

- 1 Figure C

- 1. Sampler Working Inside a “Cleanbox”

# C

- 2 Figure C

- 2

. Sample Tap and Tubing at the Influent to the FGD Wastewater Treatment

System

# C

- 3 Figure C

- 3

. Sample Collection Set Up at the Pump

- Off Station

# C

- 4 Figure C

- 4

. Composite Sample Collection Set Up at the Influent to the Bioreactor System

# C

- 5 Figure C

- 5

. Composite Sample Collection Set Up at the Effluent from the Bioreactor

System

# Appendix D

FGD ICP/MS SOP: 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.

4.0 Interferences

4.1 Isobaric Interferences

Isobaric interferences in the ICP/MS are caused by isotopes of different elements

forming ions with the same nominal mass-to-charge ratio (m/z). The

# D-3 recommended ions used for the elements in this procedure do not have

elemental isobaric interferences, except for a very small interference from

krypton on 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

analyte. Consideration should also be given to matching internal

standards to analytes with similar ionization potentials.

 Matrix effects are monitored by comparing the internal standard intensity

in the sample to the internal standard intensity of the calibration blank.

The internal standards must be between 60% and 125% of the calibration

# D-4 blank. If they are outside this window the sample is diluted by a factor of

2 (1:1) and is reanalyzed.

 Memory effects are dependent on the relative concentration differences

between samples and/or standards which are analyzed sequentially. The

rinse period between samples must be long enough to eliminate

significant memory interference (see section 10.3.6).

5.0 Safety

This procedure may involve hazardous material, operations and equipment. This

procedure does not purport to address all of the safety problems associated with its use.

It is the responsibility of the user of the method to follow appropriate safety, waste

disposal and health practices under the assumption that all samples and reagents are

potentially hazardous. Safety glasses, gloves, lab coats and closed-toe, nonabsorbent

shoes are required.

5.1 Specific Safety Concerns or Requirements

5.1.1 Eye protection that satisfies ANSI Z87.1, laboratory coat, and

nonpowdered nitrile or latex gloves must be worn while handling

samples, standards, solvents, and reagents. Disposable gloves that

have been contaminated must be removed and discarded; nondisposable gloves must be cleaned immediately.

5.1.2 The ICP plasma emits strong UV light and is harmful to vision. All

analysts must avoid looking directly at the plasma. The RF Generator

produces strong radio frequency waves, most of which are unshielded.

People with pacemakers should not go near the instrument while in

operation.

5.2 Primary Materials Used

The following is a list of the materials used in this method, which have a serious

or significant hazard rating. Note: This list does not include all materials

used in the method. The table contains a summary of the primary hazards

listed in the MSDS for each of the materials listed in the table.

# D-5 Material (1) Hazards Exposure

Limit (2) Signs and Symptoms of Exposure

Nitric Acid Corrosive

Oxidizer

Poison 2 ppmTWA

4 ppmSTEL Nitric acid is extremely hazardou s; it is corrosive, reactive,

an oxidizer, and a poison. I nhalation of vapors can cause

breathing difficulties and lead to pneumonia and pulmonary

edema, which may be fatal. Other symptoms may include

coughing, choking, and irritation of the nose, throat, and

respiratory tract. Can cause redness, pain, and severe skin

burns. Concentrated solutions cause deep ulcers and stain

skin a yellow or yellow-brown color. Vapors are irritating and

may cause damage to the eyes. Contact may cause severe

burns and permanent eye damage.

Material (1) Hazards Exposure

Limit (2) Signs and Symptoms of Exposure

Hydrochloric

Acid Corrosive

Poison 5 ppmCeiling Inhalation of vapors can cause coughing, choking,

inflammation of the nose, thr oat, and upper respiratory tract,

and in severe cases, pulmonary edema, circulatory failure,

and death. Can cause redness, pain, and severe skin burns.

Vapors are irritating and may cause damage to the eyes.

Contact may cause severe burns and permanent eye

damage.

1 – Always add acid to water to prevent violent reactions.

2 – Exposure limit refers to the OSHA regulatory exposure limit.



# 6.0 Equipment and Supplies

6.1 Instrumentation

 

# Inductively Coupled Plasma Mass Spectrometer (ICP/MS) capable of providing

resolution, less than or equal to 0.9 amu at 10% peak height from 6-253 amu

and 1.0 amu at 5% peak height from 6-253 amu with a data system that allows

corrections for isobaric interferences and the application of the internal standard

technique. The ICP/MS must be equipped with a collisio n cell for the removal of

molecular interferences. This procedure was developed using an Agilent 7500

or 7700 instrument equipped with a high matrix interface. The interface extends

the amounts of total dissolved solids that may be measured into the percent

concentration range. Any collision cell instrumentation that meets the

specifications in this procedure may be used.

 

# A discrete sample introduction system enables the use of only the exact amount

of sample volume required for data acquisition.

 

# Accessories and configuration that are designed to accommodate samples with

high levels of dissolved solids should be used.

 

# This sampling system results in less matrix being deposited in the system

during analysis and minimizes the rinse times normally needed for difficult

matrices.

 

# Autosampler with autosampler tubes.

 

# Appropriate water cooling device.

 

# Block digester with tubes.

6.2 Supplies

 

# Argon gas: High purity grade (99.99%).

# D-6  

# Helium gas: High purity grade (99.99%).

 

# Hydrogen gas: High purity grade (99.99%).

 

# Calibrated automatic pipettes or Class A glass volumetric pipettes.

7.0 Reagents and Standards

7.1 Storage and Shelf-Life

7.1.1 All standards must be stored in glass, FEP fluorocarbon or previously

unused polyethylene or polypropylene bottles. Standards stored at

concentrations as received from the vendor and mid-level dilutions must

be replaced prior to the expiration date assigned by the vendor. If no

expiration date is provided, the stocks and mid-level standards may be

stored for up to one year. They must be replaced sooner if verification

from an independent source indicates a problem (See section 10.3.5 for

initial calibration verification acceptance criteria).

7.1.2 Working standards, i.e., all standards at concentrations ready to

analyze on the ICP/MS (all except tuning mixes, ICSA and ICSAB

mixes, which are received at ready-to-use concentrations), are prepared

fresh daily.

7.2 Standards

7.2.1 Tuning Solution, 10 ppb

The tuning solution stock is purchased as a custom multi-element mix.

The concentrations of the constituents are shown in Attachment 5.

Prepare the Tuning Solution as detailed below.

 Obtain a clean 100 mL volumetric flask.

 Place 50 mL of reagent water and 2 mL of conc. HNO 3 

# and 0.5

mL of conc. HCl in the flask.

 Swirl to mix.

 Pipet 0.1mL of the Tuning Solution Stock into the flask.

 Dilute to volume with reagent water. Stopper and mix.

7.2.2 PA Tuning Solution

The dual detector solution may be commercially purchased as a custom

multi-element mix.

Prepare the PA Tuning Solution as detailed below.

 Add approximately 50 mL of the 2% HNO 3 

# / 0.5% HCl to a 100

mL volumetric flask.

 Prepare at a concentration recommended by the instrument

manufacturer.

7.2.3 Calibration Standards

Stock calibration standards are purchased as custom multi-element

mixes or as single element solutions. Each day of analysis, the

standards are diluted to working levels using 2% nitric acid and 0.5%

HCl acid matrix. Suggested concentrations are given in Attachment 8,

but the laboratory may adjust calibration standard concentrations as

# D-7 appropriate for the instrument and samples. At a minimum, a 3 point

curve must be used.

7.2.4 Individual FGD Interference check solutions.

7.2.4.1 All individual FGD interference check solutions should be

made up in the same acid matrix as the calibration standards.

7.2.4.2 Chloride, 10,000 mg/L

7.2.4.3 Calcium, 5,000 mg/L

7.2.4.4 Sulfate, 4,000 mg/L

7.2.4.5 Magnesium, 3,000 mg/L

7.2.4.6 Sodium, 2,000 mg/L

7.2.4.7 Boron, 500 mg/L

7.2.4.8 Iron, 500 mg/L

7.2.4.9 Nitrate, 250 mg/L

7.2.4.10 Manganese, 200 mg/L

7.2.4.11 Bromide, 100 mg/L

7.2.4.12 Fluoride, 100 mg/L

7.2.4.13 Selenium, 20 mg/L

7.2.4.14 Vanadium, 10 mg/L

7.2.4.15 Zinc, 2 mg/L

7.2.4.16 Chromium, 1 mg/L

7.2.4.17 Copper, 1 mg/L

7.2.5 Mixed Interference Check Solution (Synthetic FGD Wastewater)

7.2.5.1 Chloride, 5,000 mg/L

7.2.5.2 Calcium, 2,000 mg/L

7.2.5.3 Magnesium, 1,000 mg/L

7.2.5.4 Sulfate, 2,000 mg/L

7.2.5.5 Sodium, 1,000 mg/L

7.2.5.6 Butanol, 2000ppm

7.2.6 Initial Calibration Verification (ICV) Standard

The ICV stock is from a source different than the source for the

calibration standards. Each day of analysis, the ICV standard is

prepared in 2% HNO 3 

# and 0.5 % HCl acid to the concentrations shown

in Attachment 8.

7.2.7 Continuing Calibration Verification (CCV) Standard

# D-8 The CCV is prepared from the same source as the calibration

standards. The CCV standards are prepared fresh each day of analysis

in 2% HNO 3 

# /0.5% HCl. The concentrations are shown in Attachment 8.

Prepare the Working CCV as detailed below.

 Dilute by 2X a known volume of the Working Calibration

Standard in the 2% HNO 3 

# / 0.5% HCl acid matrix.

7.2.8 Spiking Stock Solution

The spike stock solution is prepared from the same stocks as the

calibration standards using the 2% HNO 3 

# / 0.5% HCl acid matrix. Spike

concentrations are listed in Attachment 8.

7.3 Reagents

7.3.1 Reagent Water - ASTM Type I or equivalent for the elements of

interest, generated using an ion-exchange water polishing system

capable of achieving 18.0 megohm-cm.

7.3.2 Blank Matrix 2% HNO 3 

# and 0.5% HCl.

8.0 Sample Collection, Preservation, Shipment and Storage

Sample container, preservation techniques and holding times may vary and are

dependent on sample matrix, method of choice, regulatory compliance, and/or specific

contract or client requests. Listed below are the holding times and the references that

include preservation requirements.

Matrix Sample

Container Min. Sample

Size Preservation Holding Time Reference

Waters HDPE 50 mLs HNO 3 

# , pH < 2 180 Days 40 CFR Part 136.3

Soils Glass or

HDPE 4 oz Cool 4 + 2 o 

# C 180 Days N/A

9.0 Quality Control

9.1 Quality control requirements are also summarized in Attachment 7.

9.2 Ongoing data quality checks are compared with established performance criteria

to determine if the results of analyses meet the performance characteristics of

the method. Any QC result that fails to meet control criteria must be

documented.

9.3 Individual interference check solutions

The individual interference check solutions listed in section 7.2.6 are analyzed

prior to initiating sample analysis, and at least once per quarter while FGD

wastewaters are being analyzed, and after any major changes to instrument

operating conditions. Concentrations of target elements observed should be less

than their reporting limits. In some cases it may not be possible to obtain

interference check solutions that are completely free of contamination. In this

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

# D-9 example, the natural abundances of zinc isotopes are Zn 64 

# 48.6%; Zn 66 

# 27.9%;

Zn 67 

# 4.1%; Zn 68 

# 18.8%; Zn 70 

# 0.6%. The measured ratios are not expected to be

exact, especially for low abundance isotopes, and some isotope may be masked

by other elements in the solution, (for example Zn 70 

# in the above example will be

masked by Ge 70 

# ) but it must be possible to explain the observed ratios.

Because Arsenic, Manganese and Aluminum are monoisotopic, this

demonstration is not possible and the level of interference observed must be less

than the reporting limit

.

9.4 Synthetic FGD interference check solution

The synthetic FGD matrix solution listed in section 7.2.7 is analyzed prior to

initiating sample analysis, and at least once per day (immediately after

calibration) while FGD wastewaters are being analyzed, and after any major

changes to instrument operating conditions. Internal standard recovery must

meet method criteria (Section 9.9) and concentrations of target elements

observed should be less than their reporting limits. In some cases it may not be

possible to obtain interference check solutions that are completely free of

contamination. In this case, results up to 5X the reporting limit are acceptable if it

is possible to demonstrate that the isotopic ratios correspond to natural

abundances. For example, the natural abundances of zinc isotopes are Zn 64



# 48.6%; Zn 66 

# 27.9%; Zn 67 

# 4.1%; Zn 68 

# 18.8%; Zn 70 

# 0.6%. The measured ratios are

not expected to be exact, and some isotopes may be masked by other elements

in the solution, (for example Zn 70 

# in the above example will be masked by Ge 70 

# )

but it must be possible to explain the observed ratios. Because Arsenic,

Manganese and Aluminum are monoisotopic, this demonstration is not possible,

and the level of interference observed must be less than the reporting limit.

If the Synthetic FGD solution has to be diluted in order to analyze it

effectively on the ICP/MS, then all samples and QC (including the MDL

replicates) must be diluted by at least the same factor.

9.4.1 Laboratory fortified Synthetic FGD solution

The synthetic FGD solution is spiked with 40ppb of each of the target

elements (400ppb for zinc and 4000ppb for aluminum) and analyzed

once per day, immediately after the synthetic FGD check in section 9.4.

All target elements must be recovered within 70-130% of the true value.

If the Laboratory Fortified Synthetic FGD solution has to be diluted

in order to analyze it effectively on the ICP/MS, then all samples

and QC (including the MDL replicates) must be diluted by at least

the same factor.

9.5 Linear range determination

The linear range for each element is determined prior to initiating sample

analysis and at least once per year thereafter. The linear range must also be

determined subsequent to changes that will have a major effect on instrument

sensitivity, such as changing the detector. The linear range is established using a

single element standard at the desired linear range. The result of the analysis

must be within 10% of the true value.

# D-10 9.6 Method Blank / Laboratory Reagent Blank (MB/LRB)

The method blank consists of reagent water that has been processed in

the same manner as the samples. One method blank must be processed with

each preparation batch.

Acceptance Criteria: Method blank results are acceptable if the concentration

for each analyte of interest is less than the reporting limit.

Corrective Action: If the method blank does not meet the acceptance

criteria, the source of contamination should be

investigated to determine if the problem can be

minimized or eliminated. Samples associated with the

contaminated blank shall be reprocessed for analysis, or

under the following circumstances, may be reported as

qualified (qualifier flags or narrative comments must be

included on report):

 The same analyte was not detected in the

associated samples;

 The method blank concentration is less than 1/10 of

the measured concentration of any sample in the

batch;

 The method blank concentration is less than 1/10

the specified regulatory limit; or

 The analyte is a common laboratory contaminant

(copper, iron, lead, calcium, magnesium,

potassium, sodium, or zinc) less than 2 times the

RL. Note that some programs do not recognize

common lab contaminants.

If the above criteria are not met and reanalysis is not

possible, then the sample data must be qualified. This

anomaly must be addressed in the project narrative

and the client must be notified.

9.7 Laboratory Control Sample / Laboratory Fortified Blank (LCS/LFB)

The LCS consists of reagent water that is spiked with the analytes of

interest as summarized in Attachment 8. One LCS must be processed (digestion

and analysis) for each preparation batch.

Acceptance Criteria: LCS control limits are based on three standard

deviations of past laboratory results. These limits are not

to exceed 85-115% recovery. The control limits are

maintained in a LIMS or other appropriate system.

Corrective Action: If the LCS % recovery falls outside of the control limits for

any analyte, that analyte is judged to be out of control.

All associated samples must be reprocessed for

analysis. One possible exception is a recovery for a

given element above the upper control limit with no

detection for the same element in the samples.

9.8 Matrix Spike / Matrix Spike Duplicate / Laboratory Fortified Sample Matrix /

Laboratory Fortified Matrix Duplicate (MS/MSD/LFSM/LFMD)

MS is prepared by taking a second aliquot of a selected sample and spiking it

with the analytes of interest as summarized in Attachment 8. An MSD is

# D-11 prepared by taking a third aliquot of a selected sample and spiking it with the

analytes of interest as summarized in Attachment 8. The MS and MSD are

processed in the same manner as the samples. One MS/MSD pair must be

processed every 10 samples.

Acceptance Criteria: Control limits are based on three standard deviations of

past laboratory results. These limits are not to exceed

70-130% recovery, and 20% relative percent difference

(RPD). The control limits are maintained in the LIMS

system. If the sample concentration for a specific analyte

in the sample selected for spiking is greater than the

concentration added by the spike, then recovery

accuracy will be reduced. In this case a dilution test may

be performed. A 1:5 dilution should agree within 20% of

the original determination. If not, a physical or chemical

interference is suspected, and must be discussed in the

sample narrative.

Corrective Action: If MS/MSD results and any applicable dilution tests do

not meet the acceptance criteria and all other quality

control criteria have been met, then a matrix interference

is suspected. Failed matrix spikes are flagged, and are

discussed in the final report case narrative.

9.9 Internal Standards Evaluation for Samples

The internal standards in samples must be between 60 and 125% of the intensity

in the calibration blank. If the sample intensities fall outside this range, the

calibration blank is reanalyzed to confirm the instrument has not drifted out of

control. If the criteria is met, the sample is diluted by a factor of 2 (1:1) and

reanalyzed. IS limits and corrective actions for standards and blanks are

described in Section 10.

10.0 Procedure

10.1 One-time procedural variations are allowed only if deemed necessary in the

professional judgment of the supervisor to accommodate variation in sample

matrix, radioactivity, chemistry, sample size, or other parameters. Any variation

in procedure shall be completely documented. Any unauthorized deviations from

this procedure must also be documented as a nonconformance, with a cause

and corrective action described.

10.2 Sample Preparation

10.2.1 EPA Method 1638 was used as the reference for the digestion of the

samples in which Section 12.2.8 describes Closed Vessel digestion.

10.2.2 Transfer a 50mL (+/- 0.5mL) aliquot from a well mixed acid preserved

sample to a 50mL digestion tube.

10.2.3 Add 0.5mL of concentrated nitric acid and 0.25 mL hydrochloric acid.

10.2.4 Spike the LCS and MS/MSD samples per spiking protocols.

# D-12 10.2.5 The total volume of the solution in the tube is now greater than 50 mLs.

The final volume will be 50 ml following the procedure to eliminate the

discrepancy in the initial and final volumes.

10.2.6 Tightly cap each digestion vessel.

10.2.7 Place the digestion tube into a block digester adjusted to achieve a

temperature of approximately 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).

Acceptance Criteria: The ICV recovery must be within 90-110%.

Additionally, the internal standard recoveries for

# D-13 200.8 must fall between 60 and 125% of true

values. The ICV can be reanalyzed, but must

be successful twice in succession or corrective

action must be taken.

Corrective Action: If the ICV results are outside of the acceptance

limits, investigate the accuracy of the

standards, correct as necessary, and

recalibrate.

10.3.6 Calibration Blank

Checks for the memory effects described at Section 4.4 may be

accomplished by analysis of an initial calibration blank (ICB) after the

ICV. Continuing calibration blanks (CCBs) are analyzed after each

continuing calibration verification.

Acceptance Criteria: Results for the calibration blanks must be less

than the RL.

Corrective Action: If the calibration blank exceeds acceptance

limits, then the possibility of instrument

contamination should be examined, particularly

the possibility of carry-over from high level

samples. The blank can be reanalyzed, and if

successful, analysis can continue. However,

samples tested after high-level samples should

be retested. If the reanalysis is not successful,

then the analysis should be terminated. After

the problem is corrected, recalibrate and

reanalyze all samples tested since the last

acceptable CCB.

10.3.7 Reporting Limit (RL) Verification Standard

An independent standard is analyzed after the ICV to monitor the lab’s

ability to produce reliable results at RL-level concentrations. The RL

verification standard is analyzed after the daily ICB.

Acceptance Criteria: For project reporting limits at or above two

times the MDL, the results should be within

50% of the expected value. Some programs

may require tighter control, in which case the

RLs will need to be three or more times the

MDL concentration.

Corrective Action: If the RL verification fails to meet acceptance

limits, data for the associated samples must be

assessed. For example, if the results are high,

consider blank contamination, and if the results

are low, consider MDL verifications. At a

minimum, sample results must be qualified in

the final report.

10.3.8 Continuing Calibration Verification (CCV) Standard

A 50  g/L CCV standard is analyzed after every set of ten samples and

at the end of the analytical sequence.

# D-14 Acceptance Criteria: The CCV recovery must be within 85-115%. In

addition, the IS recovery must be within 60-

125%. If CCV results are not within these

limits, the CCV can be reanalyzed, but it must

be successful twice in succession or further

corrective action must be taken.

Corrective Action: If the CCV fails acceptance criteria, then the

analysis should be terminated. Recalibrate and

reanalyze all samples tested since the last

acceptable CCB.

10.4 Sample Analysis

10.4.1 Report the average of at least three integrations for all field and QC

samples analyzed.

10.4.2 Flush the system with the rinse blank for at least 30 seconds between

samples and standards during the analytical run. Evaluate the

effectiveness of this time and increase the flush time, if needed.

10.4.3 It may be valuable to monitor additional isotopes for elements that are

potentially susceptible to interferences. In particular, monitoring

additional isotopes for selenium may help data analysis.

10.4.4 Dilute and reanalyze samples that are more concentrated than the

highest calibration standard for an analyte or specific isotope of interest.

No analyte may be reported from an analysis of a diluted sample in

which the analyte concentration is less than 5 times the RL.

The analytical run sequence should be performed as follows to meet all

quality control criteria:

Instrument initialization

Warm-up

Tune instrument

Perform mass calibration

Perform resolution check

Validate tuning criteria

Calibration blank

Calibration standard 1

Calibration standard 2

Calibration standard 3

ICV

ICB

RL verification standard

Synthetic FGD matrix

Spiked synthetic FGD matrix

Carryover check

CCV

CCB

10 Samples (which can include all sample types)

CCV

CCB

11.0 Calculations / Data Reduction

# D-15 11.1 LCS percent recoveries are calculated according to the equation:

11.2 ICV percent recoveries are calculated according to the equation:

11.3 CCV percent recoveries are calculated according to the equation:

11.4 Matrix Spike Recoveries are calculated according to the following equation:



# Where:

SSR = Spike Sample Result

SR = Sample Result

SA = Spike Added

NOTE: When the sample concentration is less than the detection limit, use SR = 0

for the purpose of calculating %R



# .

11.5 The relative percent difference (RPD) between sample duplicates is

calculated according to the following equation:



# Where:

DU1 = Sample result

DU2 = Sample duplicate result

11.6 The final concentration for an aqueous sample is calculated as follows: 

# % 100

Value True LCS Value Found LRB

- Value Found LCS %       

 R

% 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

# D-16 2 1 g/L) ( Result

V D V C  

 



# Where:

C = Concentration from instrument readout, ppb

D = Instrument dilution factor

V1 = Final volume in liters after sample preparation

V2 = Initial volume of sample digested in liters

12.0 Method Performance

12.1 Method Detection Limit Study (MDL)

An initial method detection limit study must be performed on each instrument

before samples can be analyzed. MDL studies are conducted annually as

follows:

 

# Prepare seven samples at three to five times the estimated MDL

concentration. The MDL samples are prepared in the Synthetic FGD

wastewater matrix and in reagent water.

 

# Prepare and analyze the MDL standards as described in Section 10.

 

# Calculate the average concentration found in μg/L, and the standard

deviation of the concentration(s) in μg/L, for each analyte.

 

# The MDL is calculated as Students t for the 99 th 

# percentile times the standard

deviation of the MDL replicate results, following the procedure at 40CFR Part

136, Appendix B.

NOTE1: Perform the MDL study in the synthetic FGD

wastewater matrix. Spiking this matrix provides detection

limits that are better matched to the complex matrix

typical of FGD wastewater. These limits can be

significantly higher than those obtained in a reagent water

matrix. In some cases (zinc in particular), the level of

contamination in the synthetic FGD solution may be high

enough to result in somewhat elevated MDLs.

NOTE2: An FGD-MDL may be less than the MDL observed in

method blanks. If this occurs frequently, the FGD-MDL

should be elevated to the mean of the method blanks plus

the Student t factor times the standard deviation of the

method blanks.

12.2 Instrument Detection Limit Study

Instrument detection limit (IDL) studies are conducted quarterly for each

instrument and each mass used for analysis.

 

# Prepare ten blanks.

 

# Analyze the IDL blanks on three non-consecutive days.

 

# The IDL is equal to three times the standard deviation of the blank results.

12.3 Demonstration of Capabilities

All personnel are required to perform an initial demonstration of proficiency

(IDOC) on the instrument they will be using for analysis prior to testing samples.

# D-17 On-going proficiency must be demonstrated annually. IDOCs and on-going

proficiency demonstrations are conducted as follows.

Four aliquots of the ICV are analyzed using the same instrumental conditions

and procedures used to analyze samples. The analyst must employ ICV’s from

four distinct analytical sequences. Using these four ICV’s demonstrates the

analyst’s ability to optimize and calibrate the instrument and to prepare analytical

solutions. Calculate the average recovery and standard deviation of the recovery

for each analyte of interest.

 

# If any analyte does not meet the acceptance criteria, (85-115% recovery,

unless other criteria are established) the test must be repeated. Only those

analytes that did not meet criteria in the first test need to be evaluated.

Repeated failure for any analyte indicates the need for the laboratory to

evaluate the analytical procedure and take corrective action.

12.4 Training Requirements

12.4.1 Each analyst performing the method must complete a demonstration of

capability (DOC) by successfully preparing and/or analyzing four

consecutive LCSs, or a blind performance evaluation (PE) sample, or

other acceptable QC samples. Analysts who continue to perform the

method must successfully complete a demonstration of capability

annually.

13.0 Pollution Control

13.1.1 For information about pollution prevention that may be applicable to

laboratory operations, consult “Less is Better: Laboratory Chemical

Management for Waste Reduction” available from the American

Chemical Society’s Department of Government Relations and Science

Policy, 1155 16th Street N.W., Washington, D.C., 20036, or online at

http://www.ups.edu/x7432.xml.

14.0 Waste Management

All waste must be disposed of in accordance with Federal, State, and local

regulations.

15.0 References / Cross-References

15.1 EPA Method 200.8, “Determination of Trace Elements in Waters and Wastes

by Inductively Coupled Plasma - Mass Spectrometry”, Revision 5.4, EMMC

Version.

15.2 EPA Method 1638, “Determination of Trace Elements in Ambient Waters by

Inductively Coupled Plasma – Mass Spectrometry, January 1996

16.0 Attachments

Attachment 1: Recommended Elemental Equations

Attachment 2: Internal Standards and Corresponding Metals

Attachment 3: Sample Preservation and Holding Times

# D-18 Attachment 4: Suggested Mass Choices

Attachment 5: Tuning Solution

Attachment 6: Suggested Tuning and Response Factor Criteria

Attachment 7: Summary of Quality Control Requirements

Attachment 8: Calibration, 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.

####