# Sampling Episode Report

Duke Energy’s

Miami Fort Station

North Bend, OH

Sampling Episode 6560

Prepared for:



# U.S. Environmental Protection Agency

Engineering and Analysis Division

Office of Water

1200 Pennsylvania Avenue, NW

Washington, D.C. 20460

Prepared by:



# Eastern Research Group, Inc.

14555 Avion Parkway

Suite 200

Chantilly, VA 20151

13 April 2012

EPA Contract No. 68-C-02-095

Work Assignment 9-29

# i CONTENTS

Page

1. I NTRODUCTION 

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

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

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

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

2. F ACILITY 

# O VERVIEW 

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

2.1 FGD Scrubber Systems........................................................................................2-2

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

3. S AMPLE 

# C OLLECTION 

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

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

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

3.1.2 Effluent from FGD Wastewat er Treatment System.................................3-4

3.2 List of Analytes and Sample Preservation...........................................................3-7

3.3 Plant Operational Data.........................................................................................3-8

3.4 Deviations from the Sampling and Analysis Plan ...............................................3-8

4. L ABORATORY 

# A NALYTICAL 

# R ESULTS AND 

# D ISCUSSION 

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

4.1 Measured and Calculated Results for In fluent to FGD Wastewater Treatment

System Samples ...................................................................................................4-2

4.2 FGD Wastewater Treatment System ...................................................................4-4

5. D ATA 

# Q UALITY 

# ...............................................................................................................5-19

5.1 Analytical Quality Control.................................................................................5-19

5.2 Field Quality Control .........................................................................................5-19

5.2.1 Bottle Blanks..........................................................................................5-19

5.2.2 Equipment Blanks..................................................................................5-20

5.2.3 Field Blanks ...........................................................................................5-20

5.2.4 Field Duplicates .....................................................................................5-22

6. R EFERENCES 

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

Appendix A: A NALYTICAL 

# R ESULTS



# Appendix B: D ATA 

# R EVIEW 

# N ARRATIVES



# Appendix C: P ICTURES 

# F ROM THE 

# S AMPLING 

# E PISODE



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

# C OUPLED 

# P LASMA 

# M ASS 

# S PECTROMETRY FOR



# T RACE 

# E LEMENT 

# A NALYSIS IN 

# F LUE 

# G AS 

# D ESULFURIZATION 

# W ASTEWATERS

# ii LIST OF TABLES

Page

Table 3-1. Sample Collection Information, Miami Fort............................................................ 3-10

Table 3-2. Sample Collection at Miami Fort ............................................................................. 3-12

Table 3-3. Field Measurements, Miami Fort ............................................................................. 3-13

Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Miami Fort ................. 3-15

Table 3-5. Analytical Me thods, Miami Fort .............................................................................. 3-16

Table 3-6. Summary of Sample Container and Planned Preservation, Miami Fort .................. 3-17

Table 3-7. Sample Preservation Summary, Miami Fort ............................................................ 3-18

Table 3-8. Generating Unit Operating Characteristic s during Sample Collection,

Miami Fort ..................................................................................................................... 3-20

Table 3-9. FGD Scrubber System Operat ing Characteristics, Miami Fort................................ 3-21

Table 3-10. Coal Usage during Samp le Collection, Miami Fort ............................................... 3-22

Table 3-11. Scrubber Slurry Information du ring Sample Collection, Miami Fort .................... 3-23

Table 3-12. FGD Wastewater Tr eatment System Operation Information, Miami Fort............. 3-24

Table 4-1. Influent to FGD Wastewat er Treatment System, Miami Fort................................... 4-6

Table 4-2. Effluent from the FGD Wastewater Treatment System, Miami Fort...................... 4-12

Table 4-3. Classical Polluta nts 4-Day Average Data Summary for FGD Wastewater

Treatment System, Miami Fort...................................................................................... 4-16

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

System, Miam i Fort ....................................................................................................... 4-17

Table 5-1. Field Blank Analy tical Results, Miami Fort............................................................ 5-23

Table 5-2. Field Duplicate Re sults – Effluent fr om FGD Wastewater Treatment System,

Miami Fort ..................................................................................................................... 5-24

Table A-1. Biphasic Sample Results for Classi cals and Total Metals, Influent to FGD

Wastewater Treatment System, Day 1 Analytical Results, Miami Fort......................... A-1

Table A-2. Biphasic Sample Results for Classi cals and Total Metals, Influent to FGD

Wastewater Treatment System, Day 2 Analytical Results, Miami Fort......................... A-4

# LIST OF TABLES (Continued)

Page

iii Table A-3. Biphasic Sample Results for Classi cals and Total Metals, Influent to FGD

Wastewater Treatment System, Day 3 Analytical Results, Miami Fort......................... A-6

Table A-4. Biphasic Sample Results for Cla ssicals and Total Meta ls, Influent to FGD

Wastewater Treatment System, Day 4 Analytical Results, Miami Fort......................... A-8

Table A-5. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results,

Miami Fort .................................................................................................................... A -10

Table A-6. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results,

Miami Fort .................................................................................................................... A -18

Table A-7. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results,

Miami Fort .................................................................................................................... A -25

Table A-8. Influent to FGD Wastewater Treatment System, Day 4 Analytical Results,

Miami Fort .................................................................................................................... A -32

Table A-9. Effluent from FG D Wastewater Treatment System , Day 1 Analytical Results,

Miami Fort .................................................................................................................... A -39

Table A-10. Effluent from FG D Wastewater Treatment System , Day 2 Analytical Results,

Miami Fort .................................................................................................................... A -42

Table A-11. Effluent from FG D Wastewater Treatment System , Day 3 Analytical Results,

Miami Fort .................................................................................................................... A -46

Table A-12. Effluent from FG D Wastewater Treatment System , Day 4 Analytical Results,

Miami Fort .................................................................................................................... A -49

Table A-13. Duplicate of Effluent from FGD Wastewater Treatment System, Day 2

Analytical Results, Miami Fort..................................................................................... A-52

Table A-14. Bottle Blank and Equipment Bl ank Analytical Data, Miami Fort ....................... A-55

Table A-15. Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical

Results, Miami Fort ...................................................................................................... A-60

Table A-16. Effluent from FGD Wastewater Treatment System Field Blank, Day 1

Analytical Results, Miami Fort..................................................................................... A-62

Table A-17. Effluent from FGD Wastewater Treatment System Field Blank, Day 2

Analytical Results, Miami Fort..................................................................................... A-64

Table A-18. Effluent from FG D Wastewater Treatment System , Day 3 Analytical Results,

Miami Fort .................................................................................................................... A -65

# LIST OF TABLES (Continued)

Page

iv Table A-19. Effluent from FG D Wastewater Treatment System , Day 4 Analytical Results,

Miami Fort .................................................................................................................... A -66

# v LIST OF FIGURES

Page

Figure 2-1. Chemical Precipita tion FGD Wastewater Treatment System, Miami Fort............... 2-3

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 at the Influent to the FGD Wa stewater Treatment System........C-3

Figure C-4. Sample Collection Set Up at the Pump-Off Station .................................................C-4

Figure C-5. Composite Sample Collection Set Up at the Effluent from the FGD Wastewater

Treatment 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 July 11 - 16, 2010, at Duke Energy’s Miami Fo rt Station (Miami Fort), located in North

Bend, Ohio (Sampling Episode 6560). The focus of Episode 6560 was to characterize the purge

stream entering the flue gas desulfurization (FGD ) wastewater treatment system and the effluent

from the chemical precipitation system.

1.1 Background of Detailed Study

During EPA’s recently completed detailed study of the steam electric industry, EPA

identified metals and certain other constituents pr esent in the wastewater discharges from steam

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

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

loadings are associated with wet FGD systems pr esent at coal-fired power plants. Based on these

findings, EPA has focused the sampling progr am on characterizing the untreated FGD

wastewaters and effluent quali ty from technologies 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.

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

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

its three generating units;

 The plant operates limestone forced oxidation wet FGD systems on two of the

three generating units;

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

includes the following steps:

— Equalization and pH adjustment (lime addition),

— Organosulfide addition,

— Ferric chloride addition (discontinue d prior to the sampling episode),

— Polymer addition,

— Clarification;

 The plant operates selectiv e catalytic reaction (SCR) systems on two of the three

generating units (the same two that have associated FGD systems); and

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

# 1-2 1.3 Sampling Episode Overview

EPA and its technical contractor, Eastern Research Group, Inc. (ERG) conducted a oneday pre-sampling site visit at Miami Fort on Ma rch 1, 2010 as part of the detailed study. The

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

Energy’s Miami Fort Station (Sampling Plan) [1], which describes the sample collection

procedures used during the sampling episode.

On Sunday, July 11, 2010, EPA arrived at Miami Fort to meet with plant personnel,

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

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

Monday through Friday (July 12 - 16, 2010). The following personnel participated in EPA’s

sample collection activities:

 Ron Jordan, EPA/EAD;

 Jezebele Alicea, EPA/EAD;

 Holly Cannon, ERG;

 TJ Finseth, 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 Miami Fort’s representative and

collected samples on behalf of the plant.

# 2-1 2. F ACILITY 

# O VERVIEW



# Miami Fort operates three baseload steam el ectric generating units and each has a coalfired boiler. Unit 6, which began operation in 1960, has a generating capacity of 175 MW. Units

7 and 8, which began operation in 1975 and 1978, respectively, each has a generating capacity of

550 megawatts (MW). All three generating units burn eastern bituminous coal. The plant is

located in North Bend, Ohio, approximately 20 mile s west of Cincinnati, and discharges to the

Ohio River.

Approximately three years ago, Miami Fort retr ofitted Units 7 and 8 (but not Unit 6) with

FGD scrubber systems to control the sulfur dioxide (SO 2 

# ) releases from the plant. The removal

efficiency of both FGD systems is approximately 96 percent. In addition to the FGD scrubber

systems, Miami Fort installed an FGD wastewater treatment system to control the discharges of

the wastewater generated during the operation of the FGD scrubbe rs. Sections 2.1 and 2.2 further

discuss the FGD scrubber systems and the FGD wastewater treatment system, respectively.

Miami Fort retrofitted Units 7 and 8 with SCR systems in 2003 and 2001, respectively.

The plant operates the SCR systems, which are used to control nitrogen oxide (NO X 

# ) emissions

from the plant, year round.

The electrostatic precipitators (ESPs) at Miam i Fort are particulate control devices that

are designed to remove greater than 99 percent of the fly ash and other particulates from the flue

gas. Miami Fort utilizes ESPs to remove the fl y ash from all three units. The fly ash and other

particulates are collected in hoppe rs. The fly ash from Unit 6 is wet sluiced to the plant’s ash

pond. The fly ash from Units 7 and 8 is pneumati cally conveyed to storage silos. Miami Fort

sells most of the ash to Ready Mix. Any fly ash th at the plant cannot sell is transferred to their

landfill located approximately th ree miles away, which is owned and operated by Duke Energy.

Miami Fort injects lime into the flue gas betw een the air heater and the ESP to control the

sulfur trioxide emissions.

Miami Fort operates an ash pond with two adj acent cells operated in series. Fly ash from

Unit 6 and bottom ash from all three units are slui ced to the cell nearest the plant. Polymer is

added to the ash pond near where the sluicing pi pes deposit the ash sluice to improve total

suspended solids (TSS) removals. The plant operates the first cell using equipment to maintain

channels for the sluice water to move through th e mass of ash solids coll ected in the pond (i.e.,

the rim ditch stacking method). The plant removes the solids that settle out in the channels of the

ash pond and stacks them in piles along the perimete r of the ash channels to allow the solids to

dewater, while the water drains back into th e pond. After the solids ha ve been dewatered, the

plant hauls them to the landfill for disposal. In ad dition to fly ash and bottom ash transport water,

the ash pond also receives treated FGD wastewater and mill rejects. The ash pond discharges to

the Ohio River via Outfall 002.

Unit 6 at Miami Fort has the following configuration:

 Boiler;

 Air heater; and

 ESP.

# 2-2 Units 7 and 8 at Miami Fort ha ve the following configuration:

 Boiler;

 SCR system;

 Air heater;

 Lime injection;

 ESP; and

 FGD scrubber system.

2.1 FGD Scrubber Systems

[CBI information has been re moved from this section.]

2.2 FGD Wastewater Treatment System

[CBI information has been re moved from this section.]

# 2-3[CBI information has been removed from this section.]Figure 2-1. Chemical Precipitation FGD Wastewater Treatment System, Miami Fort

# 3-1 3. S AMPLE 

# C OLLECTION



# During the Miami Fort sampling episode, the sampling team followed the collection

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

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

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

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

activities.

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

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

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

this report presents a flow diagram of the plant’s wastewater treat ment 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 Effluent from FGD Wast ewater Treatment System;

 SP-3 Duplicate of Effluent from FGD Wastewater Treatment System (SP-2);

 SP-4 Influent to FGD Wastewater Treatme nt System (SP-1) Field Blank; and

 SP-5 Effluent from FGD Wa stewater Treatment System (SP-2) Field Blank.

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

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

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

sampling points as “true” splits (i.e., samp les for the same analyte were collected

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

therefore, for these samples, EPA and Miami Fo rt’s representative collected duplicate samples,

with one filling the bottle im mediately after the other.

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

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

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

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

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

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

“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

# 3-2 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 piping from the secondary hydrocycl one to the equalization tank. The sample was

collected prior to the wastewater entering th e equalization tank because the plant adds lime

directly to the equali zation tank and, therefore, the sampli ng point upstream of the tank provides

the best representation of the FGD scrubber purg e from the Miami Fort FGD system. Figure 2-1

identifies the sampling location for SP-1. This samp le was collected as a grab sample because the

flow into the equalization tank is not conti nuous. In addition, due to the relatively high

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

split samples using composite sampling techniques.

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-4) for total mercury, total

and dissolved metals, and dissolved hexavalent chromium (total and dissolved metals and

dissolved hexavalent chromium were collected in a 10-liter container and samples were pumped

into individual bottles later). See Section 5.2.3 for a description of the field blank sample

collection procedures at th e influent to the FGD wast ewater treatment system.

The sampling point was located on the pipe between the secondary hydrocyclone and

equalization tank, and was only accessible from th e top of the equalization tank. To collect the

wastewater samples at the influent to the F GD wastewater treatment system, the samplers

attached a 25-foot length of silicone tubing to the sample tap on top of the equalization tank and

had the tubing run to the ground level where the sa mples were collected. The end of the silicone

tubing was fitted with a “Y” spli tter, with two additional lengths of silicone tubing attached to

the “Y” splitter. Figure C-2, in Appendix C, is a picture of the tubing att ached to the sample tap

at the influent to the FGD wastewater treatment system. Figure C-3, in Appendix C, is a picture

of the sample collection set up at the influent to the FGD wastewater treatment system. The

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

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

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

Day 2 of the sampling episode, the sampling team set up a tent to cover the samplers/samples

from rain during the sample collection.

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

3.1:

# 3-3  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 w ith Miami Fort’s representatives. Figure C-4, in Appendix C, is a

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

On Day 1 only, ERG collected field blank samples (SP-4) for dissolved metals and

dissolved hexavalent chromium by pumping from a previously filled 10-liter container. See

Section 5.2.3 for a description of the field blank sa mple collection procedures at the influent to

FGD wastewater treatment system.

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

tubing into the 10-liter c ontainer filled with wastewater from the influent to the FGD wastewater

treatment system. By this time, the solids in th e wastewater had been se ttling for approximately

100 minutes. Approxima tely 0.5- 2 liters 1 

# of sample were pumped through the tubing/filter to

purge the line before collecting samples.

1 

# During Day 1, the capsule filter became clogged, so after the field blank and first sample collection, the filter was

changed and briefly purged. On Day 2, 3, and 4, the filter /tubing was purged for less than a minute, 1 liter, and 0.5

liters respectively and there was no need to change the filter.

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

Section 3.1:

 Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

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

The samples of the influent to the FGD wastew ater treatment system that were collected

represent the FGD scrubber purge from the specific unit that was pur ging at the time the samples

were collected. The following identifies which units are represented by each day of sampling:

 Day 1 – Unit 8;

 Day 2 – Unit 7;

 Day 3 – Unit 8; and

 Day 4 – Unit 7.

3.1.2 Effluent from FGD Wastew ater Treatment System

The effluent from FGD wastew ater treatment system (SP-2) was collected from a tap

located on the suction side of the pump that transfers the wastewater from the effluent tank to the

ash pond. Miami Fort installed a three-way splitter on the sample tap that had three separate taps

to collect samples from the sampling point. The sample tap was located inside the FGD

wastewater treatment building (see Figure 2-1 fo r the sampling location for SP-2). Because the

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

collection.

ERG collected the effluent from FGD wastew ater treatment system composite samples

using two automatic compositors which were prog rammed to collect individual sample volumes

into two 20-liter containers. The compositors we re programmed to collect 870 milliliters (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, prior to star ting the automatic compositors at the effluent from FGD

wastewater treatment system (SP-2), the sampling team collected field blanks (SP-5) for total

and dissolved metals and dissolved hexavalent ch romium (samples were collected in a 20-liter

container and samples were pumped into indi vidual bottles later). See Section 5.2.3 for a

description of the field blank sample collection procedures at the effluent from the FGD

wastewater treatment system.

# 3-5 Samplers set up the compositors by attaching tw o silicone tubing sets to two of the taps

on the three-way splitter. The t ubing configuration was set up such that one end was connected

to the sample tap, and one end was threaded th rough the automatic comp ositor and connected to

the large composite container. The samplers a ttached the silicone tubing to the sample tap,

opened the valve, and allowed sample to flow through both sets of tubing before calibrating

either of the automatic compositors. This en sured that the flow through the tubing during

calibration would be the exp ected flow through the tubing during sample collection. The

automatic compositors were calibrate d such that they collected 870 mL 2 

# every hour, so that the

projected complete volume would be 20 liters. After calibration, the tubi ng was attached to a

vented cap on a 20-liter composite container. The sample tap was left open during the entire

sample collection time period, and the automatic compositor pulled sample as dictated by the

sampling program. Additionally, the automatic co mpositor was capable of purging the line back

through the sample tap between each individual sample aliquot.

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

ice for the entire 24-hour compositing period. A plas tic bag was placed on top of the trash cans

to minimize contamination. Figure C-5, in Appendix C, is a picture of the composite sampling

set-up at the effluent from the bioreactor system.

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

dissolved mercury grab samples. At the first 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 FGD wastewater treatment system.

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

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

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

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

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

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

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

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

shroud was replaced for each set of mercury grab samples. After collecti ng each set of mercury

grabs, ERG filled a field test bottle and tested for pH and temperature using a calibrated pH

meter, four-colored pH paper, and a thermometer. Table 3-3 presents the field measurement data

for the effluent from FGD wastewater treatment 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

2 

# The Sampling Plan called for calibrating the compositors to collect 830 mL every hou r; however, because the

pumps that transfer the wastewater from the effluent tank to the ash pond do not operate continuously, the volume of

water that could be pulled for a specific aliquot varied depending on if the pumps were operating (less volume

collected) or idle. Therefore, the automatic compositors we re calibrated while the pumps were idle and the program

was set to collect more than 830 mL (specifically 870 mL) to account for the reduced volume that would be

collected while the pumps were operating. On Day 1, the me tals carboy collected 21 liters of sample (the volume of

the classicals carboy was not noted). On Day 2, the metals and classicals carboys collected 20 and 21 liters,

respectively. On Day 3, the metals and classicals carboys collected 20 and 21.5 liters, respectively. On Day 4, the

metals and classicals carboys collected 19.5 and 20 liters, respectively.

# 3-6 split samples with Miami Fort’s representatives; th erefore, duplicate samples were collected. The

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

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

oxidants were detected during this sampling ep isode at the effluent from FGD wastewater

treatment system. ERG samplers then preserved the total cyanide samples with sodium

hydroxide to a pH >10 S.U. and placed the samples on ice.

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

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

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

containers were moved to the pump-off area wher e 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. The samplers th en attached another short length of silicone

tubing to the capsule filter effluent, which was attached to a “Y” split ter and two lengths of

silicone tubing. This set-up allowed EPA to co llect “true” split sample s with Miami Fort’s

representatives. Figure C-4, in Appendix C, is a picture of the set-up at the pump-off station.

On Day 1 only, ERG collected field blank samp les (SP-5) for total and dissolved metals

and dissolved hexavalent chromium by pumping fro m a previously filled 20-liter container. See

Section 5.2.3 for a description of the field blank sample collection proced ures at the effluent

from FGD wastewater treatment 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

FGD wastewater treatment system . After the tubing and filter we re purged with 1-2 liters of

sample, samplers collected the following sample s 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.

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

# 3-7 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 sample s at the effluent fr om FGD wastewater

treatment system (SP-2) on Day 3 of the samp ling episode. In addition, for all analytes, ERG

collected a duplicate sample of the effluent from FGD wastewater system (SP-3) on Day 2 of the

sampling episode.

3.2 List of Analytes and Sample Preservation

Samples collected at Miami Fort were analyzed for the following pollutants:

 Classicals:

— Biochemical oxygen demand, 5-day (BOD 5 

# ),

— Chemical oxygen demand (COD),

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus,

— Total cyanide;

 Total Metals 3 

# :

— 

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

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

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

titanium, vanadium, and zinc.

 Dissolved Metals:

— 

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

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

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

3 

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

# 3-8 chemicals, and other sources. Table 3-4 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 sulfid es 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, Miami Fort plant personnel pr ovided the sampling

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

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

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

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

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

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

3.4 Deviations from the Sampling and Analysis Plan

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

described below:

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

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

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

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

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

to reach the desired pH.

 Influent to FGD wastewater treatm ent system samples (SP-1, Day 2): After

set up at the sampling location at the in fluent to FGD wast ewater treatment

system (SP-1), the sampling team had to wait approximately 15 minutes to collect

the sample because the plant staff switched the pumps that were transferring the

FGD scrubber purge to the equalization tank.

# 3-9  Field test temperature measu rement (SP-2, Grab 4, Day 4): At the effluent

from FGD wastewater treatment syst em (SP-2), the field temperature

measurement taken during Grab 4 on Day 4 was only taken with the pH meter

because the thermometer was misplaced.

 Collection of field test measu rements (SP-2, Grab 3, Day 2): The field test

samples taken in conjunction with the Day 2 Grab 3 samples at the effluent from

FGD wastewater treatment system (SP-2) were taken approximately 7 minutes

after the grab sample because the effluent wastewater transfer pump kicked on

immediately after the cyanide sample was taken. The water pressure was too low

to collect the field test sample while the pump was running, so the samplers

waited until the pump turned off in orde r to grab the field test sample.

 Collection of total mercur y (SP-2, Grab 1, Day 1): On Day 1 of sample

collection at the effluent from the FGD wastewater treatment system (SP-2), the

bottle cap for the total mercury sample was dropped, but it fell onto the bottle bag

and did not touch the ground. After the bottl e was filled, the cap was used to seal

the bottle.

 Filtering and purging the influent to FGD wastewater treatment system

sample (SP-1): When collecting the dissolved meta l samples at the influent to

FGD wastewater treatment system (SP-1) on Day 1, the capsule filter became

clogged, so after the field blank and first sample collection, the filter was changed

and briefly purged. On Day 2, 3, and 4, the filter/tubing was purged for less than a

minute, 1 liter, and 0.5 liters, respectivel y, and there was no need to change the

filter.

 Calibrating the automatic compositors at the effluent from FGD wastewater

treatment system (SP-2): The Sampling Plan called for calibrating the

compositors to collect 830 mL every hour; however, because the pumps that

transfer the wastewater from the effl uent tank to the ash pond do not operate

continuously, the volume of water that could be pulled for a specific aliquot

varied depending on if the pumps were opera ting (less volume collected) or idle.

Therefore, the automatic compositors were calibrated while the pumps were idle

and the program was set to collect more than 830 mL (specifically 870 mL) to

account for the reduced volume that would be collected while the pumps were

operating.

 Influent to FGD wastewater treatmen t system dissolved metals samples

pump-off (SP-1): The suspended solids content in the influent to the FGD

wastewater treatment system samples was high; therefore, the samplers allowed

the solids to settle for 100 minutes to two hours, before pumping off the dissolved

metals samples each day, instead of allo wing the solids to sett le for one hour as

the Sampling Plan suggested.

# 3-10 Table 3-1. Sample Collection Information, Miami Fort

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 7/12/10 0924 a 

# and 1149 b



# Influent to FGD Wa stewater Treatment

System – Day 2 Grab 7/13/10 1034 a 

# and 1247 b



# Influent to FGD Wa stewater Treatment

System – Day 3 Grab 7/14/10 0912 a 

# and 1143 b 

# SP-1

Influent to FGD Wa stewater Treatment

System – Day 4 Grab 7/15/10 0927 a 

# and 1137 b



# Composite 7/12/10

7/13/10 0731 c



# 0841 d 

# Effluent from FGD Wastewater

Treatment System – Day 1

Grab 7/12/10

7/13/10 0752 e 

# , 1353 f 

# , and 1956 g



# 0147 h



# Composite 7/13/10

7/14/10 0730 c



# 0806 d 

# Effluent from FGD Wastewater

Treatment System – Day 2

Grab 7/13/10

7/14/10 0745 e 

# , 1346 f 

# , and 1947 g



# 0147 h



# Composite 7/14/10

7/15/10 0730 c



# 0813 d 

# Effluent from FGD Wastewater

Treatment System – Day 3

Grab 7/14/10

7/15/10 0744 e 

# , 1346 f 

# , and 1948 g



# 0150 h



# Composite 7/15/10

7/16/10 0730 c



# 0658 d 

# SP-2

Effluent from FGD Wastewater

Treatment System – Day 4

Grab 7/15/10

7/16/10 0747 e 

# , 1357 f 

# , and 1945 g



# 0145 h



# Composite 7/13/10

7/14/10 0731 c



# 0841 d 

# SP-3 Duplicate of Effluent from FGD

Wastewater Treatment System – Day 2

Grab 7/13/10

7/14/10 0746 e 

# , 1348 f 

# , and 1947 g



# 0149 h



# SP-4 Influent to FGD Wastewater Treatment

System Field Blank Grab 7/12/10 0910 i 

# and 1138 j



# Composite 7/12/10

7/13/10 0640 k



# 0829 l 

# Effluent from FGD Wastewater

Treatment System Field Blank – Day 1

Grab 7/12/10 0748 m



# Effluent from FGD Wastewater

Treatment System Field Blank – Day 2 Grab 7/13/10 0739 m



# Effluent from FGD Wastewater

Treatment System Field Blank – Day 3 Grab 7/14/10 0739 m 

# SP-5

Effluent from FGD Wastewater

Treatment System Field Blank – Day 4 Grab 7/15/10 0743 m

a 

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

and dissolved mercury) and classicals (BOD 5 

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

b 

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

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

c 

# Started compositor.

# 3-11 d 

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

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

classicals (BOD 5 

# , Group I, and Group II).

e 

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

f 

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

g 

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

h 

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

i 

# Start time for the collection of total and dissolved mercury and total metals by 200.7 and total metals by 200.8 field

blank samples.

j 

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

field blank samples.

k 

# Filled 20-L field blank carboy

l 

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

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

m



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

# 3-12Table 3-2. Sample Collection at Miami FortSamplingPointNumberSampling 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 the FGD WastewaterTreatment System4 4 4 4 4 4 4 4 4 4 4SP-2 Effluent from the FGD WastewaterTreatment System4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-3 Duplicate of Effluent from the FGDWastewater Treatment System1 1 1 1 1 1 1 1 1 11SP-4 Field Blank for Influent to the FGDWastewater Treatment System1 1 1 1 1 1SP-5 Field Blank for Effluent from theFGD Wastewater Treatment System1 1 1 1 4 1Total Number of Samples 11+1QC 11+1QC 11+1QC 11+1QC 14+1QC 9+1QC 11+1QC 9+1QC 9+1QC 9+1QC 9+1QCaGroup 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.

# 3-13Table 3-3. Field Measurements, Miami FortTemperature (°C)pH (S.U.)SamplingPointNumberSampling PointDescriptionDateTimeThermometerProbeMeteraStripsWaste StreamFlow Rate(GPM)bNotesInfluent to FGDWastewater TreatmentSystem – Day 17/12/2010 093853NAc5.55 6 148dSamplers noted that the samples had ayellow color and appeared to be high insolids. No detected sulfides or oxidants intotal cyanide grab.Influent to FGDWastewater TreatmentSystem – Day 27/13/2010 104752.550.25.56 7 148dSamplers noted that the samples had a lightyellow color. No detected sulfides oroxidants in total cyanide grab.Influent to FGDWastewater TreatmentSystem – Day 37/14/2010 09334847.55.15 6 148dSamplers noted that the samples had a lightyellow color. No detected sulfides oroxidants in total cyanide grab.SP-1Influent to FGDWastewater TreatmentSystem – Day 47/15/2010 094154515.51 7 148dNo detected sulfides or oxidants in totalcyanide grab.7/12/10 07554341.78.7 9.5246.77/12/10 135543418.63 90.07/12/10 19564239.98.44 9 243.9Effluent from FGDWastewater TreatmentSystem – Day 17/13/10 01514442.28.56 9 0.0Samples were clear with a light yellowcolor and did not have any visible solids.No detected sulfides or oxidants in totalcyanide grab.7/13/10 0750448.56 9 0.07/13/10 135044428.62 9 248.27/13/10 20054542.58.46 9 0.0Effluent from FGDWastewater TreatmentSystem – Day 27/14/10 01544239.28.62 9 244.5Samplers noted that the samples had a lightyellow color. No detected sulfides oroxidants in total cyanide grab.7/14/10 07464340.18.55 9 0.07/14/10 134744.542.58.26 9 0.07/14/10 19534442.28.66 9 0.0Effluent from FGDWastewater TreatmentSystem – Day 37/15/10 01544340.98.38 9 0.0Samples were clear with a yellow tint anddid not have any observed particulates. Nodetected sulfides or oxidants in totalcyanide grab.7/15/10 074942408.61 9 0.07/15/10 135844428.49 9 251.37/15/10 19504542.38.53 9 0.0SP-2Effluent from FGDWastewater TreatmentSystem – Day 47/16/10 01504542.48.55 9 250.0Samples were clear with a yellow tint anddid not have any observed particulates. Nodetected sulfides or oxidants in totalcyanide grab.

# 3-14aThe 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.bThe SP-2 flow rates provided in the table represent the instantaneous flow at the sampling point during the mercury grab sample collection. For the times when0.0 is shown as the flow rate, the effluent wastewater transferwere not operating and therefore, the sample was collected fromthe tap based on the head pressurefrom the wastewater volumein the effluent tank.cNot analyzed.dScrubber purge flow is a calculated value based on pump discharge pressure provided by the plant. The plant does not have a flow meter that measures the flowrate of the FGD scrubber purge entering the Equalization tank.

# 3-15 Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Miami Fort

Sample Number Sample Point Sample Description

71741 SP-1, Day 1 Influent to FGD Wastewater Treatment System - Day 1

71742 SP-1, Day 2 Influent to FGD Wastewater Treatment System - Day 2

71743 SP-1, Day 3 Influent to FGD Wastewater Treatment System - Day 3

71744 SP-1, Day 4 Influent to FGD Wastewater Treatment System - Day 4

71745 SP-2, Day 1 Effluent to FGD Wastewater Treatment System - Day 1

71746 SP-2, Day 2 Effluent to FGD Wastewater Treatment System - Day 2

71747 SP-2, Day 3 Effluent to FGD Wastewater Treatment System - Day 3

71748 SP-2, Day 4 Effluent to FGD Wastewater Treatment System - Day 4

71749 SP-3, Day 2 Duplicate of Effluent to FGD Wastewater Treatment System - Day 2

71750 SP-4, Day 1 Influent to FGD Wastewater Treatment System Field Blank - Day 1

71751 SP-5, Day 1 Effluent to FGD Wastewater Treatment System Field Blank - Day 1

71752 SP-5, Day 2 Effluent to FGD Wastewater Treatment System Field Blank - Day 2

71753 SP-5, Day 3 Effluent to FGD Wastewater Treatment System Field Blank - Day 3

71754 SP-5, Day 4 Effluent to FGD Wastewater Treatment System Field Blank - Day 4

# 3-16 Table 3-5. Analytical Methods, Miami Fort

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).

# 3-17 Table 3-6. Summary of Sample Container and Planned Preservation, Miami Fort

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, TDS, sulfate, and chloride.

b 

# Group II includes ammonia as nitrogen, COD, nitr ate/nitrite as ni trogen, TKN, and total phosphorus.

# 3-18 Table 3-7. Sample Preservation Summary, Miami Fort

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

71741 Group II Volume 1 7/12/10 H 2 

# SO 4 

# 7 <2 250

71741 Group II Volume 2 7/12/10 H 2 

# SO 4 

# 7 <2 200

(NH 4 

# ) 2 

# SO 4



# Buffer 6.5 6.8 100 71741 Hexavalent Chromium 7/12/10

NH 4 

# OH 6.8 9.5 25

(NH 4 

# ) 2 

# SO 4



# Buffer 6.5 8.5 100 71750 Hexavalent Chromium 7/12/10

NH 4 

# OH 8.5 9.5 4

71741 Total Cyanide 7/12/10 NaOH 7 10 200

71745 Total Cyanide 7/12/10 NaOH 9 10 9

71742 Group II Volume 1 7/13/10 H 2 

# SO 4 

# 7 2 150

71742 Group II Volume 2 7/13/10 H 2 

# SO 4 

# 7 2 150

71745 Group II Volume 1 7/13/10 H 2 

# SO 4 

# 9.5 <2 75

71745 Group II Volume 2 7/13/10 H 2 

# SO 4 

# 9.5 <2 75

(NH 4 

# ) 2 

# SO 4



# Buffer 6.5 7.1 100 71742 Hexavalent Chromium 7/13/10

NH 4 

# OH 7.1 9.7 67

(NH 4 

# ) 2 

# SO 4



# Buffer 8.7 8.7 100 71745 Hexavalent Chromium 7/13/10

NH 4 

# OH 8.7 9.3 10

(NH 4 

# ) 2 

# SO 4



# Buffer 6.5 8.5 50 71751 Hexavalent Chromium 7/13/10

NH 4 

# OH 8.5 9.7 20

71742 Total Cyanide 7/13/10 NaOH 6.5 10 400

71746 Total Cyanide 7/13/10 NaOH 9 10 10

71749 Total Cyanide 7/13/10 NaOH 9 10 10

71743 Group II Volume 1 7/14/10 H 2 

# SO 4 

# 6 <2 200

71743 Group II Volume 2 7/14/10 H 2 

# SO 4 

# 6 <2 200

71746 Group II Volume 1 7/14/10 H 2 

# SO 4 

# 9 2 100

71746 Group II Volume 2 7/14/10 H 2 

# SO 4 

# 9 2 100

71749 Group II Volume 2 7/14/10 H 2 

# SO 4 

# 9 2 100

71749 Group II Volume 1 7/14/10 H 2 

# SO 4 

# 9 2 100

(NH 4 

# ) 2 

# SO 4



# Buffer 6.5 7.1 100 71743 Hexavalent Chromium 7/14/10

NH 4 

# OH 7.1 9.7 60

(NH 4 

# ) 2 

# SO 4



# Buffer 8.7 8.7 100 71746 Hexavalent Chromium 7/14/10

NH 4 

# OH 8.7 9.5 15

# 3-19 Table 3-7. Sample Preservation Summary, Miami Fort

Sampling Point

Number Analysis Date Chemical

Added Initial pH Final pH Amount

Added

(drops)

(NH 4 

# ) 2 

# SO 4



# Buffer 8.7 8.7 100 71749 Hexavalent Chromium 7/14/10

NH 4 

# OH 8.7 9.7 15

71743 Total Cyanide 7/14/10 NaOH 6 10 500

71747 Total Cyanide 7/14/10 NaOH 9 10 7

71747 Total Cyanide - QC 7/14/10 NaOH 9 10 7

71744 Group II Volume 1 7/15/10 H 2 

# SO 4 

# 6 2 150

71744 Group II Volume 2 7/15/10 H 2 

# SO 4 

# 6 2 150

71747 Group II Volume 1 7/15/10 H 2 

# SO 4 

# 9 2 100

71747 Group II Volume 2 7/15/10 H 2 

# SO 4 

# 9 2 100

71747 Group II Volume 1 - QC 7/15/10 H 2 

# SO 4 

# 9 2 100

71747 Group II Volume 2 - QC 7/15/10 H 2 

# SO 4 

# 9 2 100

(NH 4 

# ) 2 

# SO 4



# Buffer 6.5 7.1 100 71744 Hexavalent Chromium 7/15/10

NH 4 

# OH 7.1 9.5 120

(NH 4 

# ) 2 

# SO 4



# Buffer 8.7 8.7 100 71747 Hexavalent Chromium - QC 7/15/10

NH 4 

# OH 8.7 9.7 30

71744 Total Cyanide 7/15/10 NaOH 6.5 10 500

71748 Total Cyanide 7/15/10 NaOH 8.5 10 12

71748 Group II Volume 2 7/16/10 H 2 

# SO 4 

# 9 2 125

71748 Group II Volume 1 7/16/10 H 2 

# SO 4 

# 6.0 2 55

(NH 4 

# ) 2 

# SO 4



# Buffer 8.7 8.7 100 71748 Hexavalent Chromium 7/16/10

NH 4 

# OH 8.7 9.5 30

# 3-20 Table 3-8. Generating Unit Operating Charact eristics during Sample Collection, Miami Fort

Unit ID Boiler Type Capacity

(MW) Electricity Production

(MW)

(or Percent Capacity %) SCR

(No, On, Off) Particulate Control System

(HS/CS ESP, or BH)

7 Opposed Firing 550 538 MW On CS ESP

8 Opposed Firing 550 545 MW On CS ESP



# CS ESP – Cold-side elect rostatic precipitator.

# 3-21Table 3-9. FGD Scrubber System Operating Characteristics, Miami FortUnit IDWet FGDSystem (Yes/No)Type ofScrubberForcedOxidation(Yes/No)SorbentAdditives (DBA,formic acid,etc.)FGD Make-upWater SourceSO2RemovalPercentageType of SolidsSeparation7 Yes Spray Yes LimestoneNone Ohio River 97.4 %SecondaryHydrocyclones8 Yes Spray Yes LimestoneNone Ohio River 96.9 %SecondaryHydrocyclones

# 3-22 Table 3-10. Coal Usage during Sa mple Collection, Miami Fort

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)

7 Bituminous 3635 Tons Northern

Appalachian/

Illinois Basin 3.36%

(Dry) 1070 ppm (Dry)

1

8 Bituminous 5331 Tons Northern

Appalachian 4.05%

(Dry) 574 ppm (dry)

7 Bituminous 4865 Tons Northern

Appalachian/

Illinois Basin 3.44%

(Dry) 635 ppm (Dry)

2

8 Bituminous 3678 Tons Northern

Appalachian 4.04%

(Dry) 582 ppm (Dry)

7 Bituminous 5417 Tons Northern

Appalachian/

Illinois Basin 3.77%

(Dry) 354 ppm (Dry)

3

8 Bituminous 5165 Tons Northern

Appalachian 4.10%

(Dry) 569 ppm (Dry)

7 Bituminous 6937 Tons Northern

Appalachian/

Illinois Basin 3.48%

(Dry) 584 ppm (Dry)

4

8 Bituminous 3382 Tons Northern

Appalachian 3.96%

(Dry) 561 ppm (Dry)

# 3-23 Table 3-11. Scrubber Slurry Information during Sample Collection, Miami Fort

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

7 7 CBI CBI CBI CBI CBI

1

8 8 CBI CBI CBI CBI CBI

7 7 CBI CBI CBI CBI CBI

2

8 8 CBI CBI CBI CBI CBI

7 7 CBI CBI CBI CBI CBI

3

8 8 CBI CBI CBI CBI CBI

7 7 CBI CBI CBI CBI CBI

4

8 8 CBI CBI CBI CBI CBI

# 3-24Table 3-12. FGD Wastewater Treatment System Operation Information, Miami FortScrubber PurgeChemical UsageDay of SamplingFlow Rate (gpm)bDurationLimeaFerric ChlorideOrganosulfide:Nalmet 1689cPolymer: Nalco7766+cAcid1 CBI CBI CBI CBI CBI CBI CBI2 CBI CBI CBI CBI CBI CBI CBI3 CBI CBI CBI CBI CBI CBI CBI4 CBI CBI CBI CBI CBI CBI CBIaLime usage is approximately [CBI information has been removed] lbs/day.bScrubber purge flow is a calculated value based on pump discharge pressure.cOrganosulfide and polymer usage are calculated values based on dosing set points.

# 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 effluent from the FGD wastewater treatment

system. Section 4.1 discusses the methods used by the laboratories for th e biphasic analysis of

SP-1. Section 4.2 presents the laborat ory analytical data for the infl uent to and effluent from the

FGD wastewater treatment system.

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

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

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

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

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

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

analysis using a method-compliant bubbler system.

For the total and dissolved mercury sample s from SP-2 and SP-3, EPA collected four

individual grab samples that were composited by Frontier and analyzed as one sample. Frontier

composited these samples by combining the entire sample bottle for each of four individual grab

samples prior to digestion and analysis; however, if one or more of the grab samples were

received with limited volume, equal volumes from each individual grab sample were combined

for the composite analysis.

The total and dissolved metals by EPA Method 200.7 were analyzed by TestAmerica

Laboratories – Denver (TestAmerica). As describe d in Section 3, the dissolved metals samples

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

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

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

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

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

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

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

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

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

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

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

Appendix A provides all analytical results for all samples collected at Miami Fort,

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

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

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

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

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

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

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

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

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

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

4.1 Measured and Calculated Results for In fluent to FGD Wastewater Treatment

System Samples

The samples of the influent to the FGD wast ewater treatment system were expected to

contain significant amounts of r eadily settleable solids, to a large degree consisting of gypsum,

unreacted limestone, and fly ash. Because of th is, EPA was concerned that there could be

analytical interferences for the metals analyses, since the acid digestion procedures used may not

be sufficiently rigorous for samples with high solid s loads. Therefore, ERG directed its contract

laboratories to separate the aque ous and solid phases of the samp le prior to conducting certain

analyses, where allowed by the analytical method and if necessary to obtain acceptable analytical

results. This biphasic approach provides EPA with measured or calculated pollutant

concentrations for the follo wing phases of the sample:

 Aqueous phase;

 Solid phase; and

 Total sample.

The metals and classicals laboratory, Test America Laboratories - Denver (TestAmerica),

and the mercury laboratory, Frontier, used two different approaches for the biphasic analysis.

This section describes the approaches used by ea ch laboratory and presen ts the results of the

analyses.

Metals and Classicals Analyses

TestAmerica used EPA Methods 200.7 and 200.8 to analyze the wastewater samples for

metals. Both EPA Methods 200.7 and 200.8 state, “Aqueous samples containing total suspended

solids ≥ 1% (w/v) should be extracted as a solid type sample.” [3, 4] Because EPA expected the

solids content to be greater than one percent, TestAmerica developed an approach for the

analysis of the FGD influent samples that consiste d of performing a pressure filtration to separate

the solids from the sample and analyzing the solid and aqueous phases separately.

Once the FGD influent samples were separa ted into solid and aqueous phases, the

aqueous portion was analyzed using EPA Method 200.7 or Method 200.8, depending on the

analyte. The solid portion of the samples asso ciated with the 200.7 analys is were prepared and

analyzed according to SW846 Method 6010B, while the solid portion of the samples associated

with the 200.8 analysis were prepared and analyzed according to SW846 Method 6020.

For solid phase analyses of n itrate/nitrite and ammonia, the analytical methods (i.e., EPA

Method 353.2 and EPA Method 350.1, respectively) do not include proce dures for analyzing

solid solids. Therefore, TestAmerica determin ed the concentration of nitrate/nitrite and

ammonia in the FGD influent solid samples by perf orming a deionized leach of the solid sample.

TestAmerica achieved this by placing a specified amount of the solid sample with an amount of

deionized water and shaking the mixture for one hour. TestAmerica than separated the leachate

from the solids using a centrifuge and then preser ved the leachate to a pH <2 S.U. and analyzed

the leachate according the specified methods.

# 4-3 TestAmerica also dried the solids prior to an alysis, so the solid c oncentration is on a dryweight basis. To calculate the total sample concentration from the solid and aqueous phase

results, the laboratory also needed to measure the original sample volum e, solid phase weight,

and filtrate volume. EPA developed the following e quation to calculate the individual metal total

concentrations for the sample.

Sample Solid Solid Filtrate Filtrate



# V ) Wt (C ) V (C ion Concentrat Sample Total   

 

# (4-1)

where:

C Filtrate 

# = concentration of the analyte in the aqueous phase of the sample;

V Filtrate 

# = volume of the filtrate;

C Solid 

# = concentration of the analyte in the solid phase of the sample;

Wt Solid 

# = weight of the solids in the sample; and

V Sample 

# = volume of the original sample.

TestAmerica used the same approach for the se ven classical pollutants that were analyzed

as biphasic samples: ammonia as nitrogen, chloride, sulfate, nitrate/nitrite, total cyanide, total

Kjeldahl nitrogen (TKN), and total phosphorus.

Mercury Analyses

Frontier used EPA Method 1631E to analyze the wastewater samples for mercury. EPA

Method 1631E does not contain a ny language stating how wastewat er samples with high solid

concentrations should be analyzed ; therefore, Frontier developed an approach for the analysis of

the FGD influent samples that minimized potenti al contamination to the samples. Frontier’s

approach consisted of using a centr ifuge to separate the solids from the sample and analyzing the

solid and aqueous phases separately.

Once the FGD influent samples were separa ted into solid and aqueous phases, the

aqueous portion was analyzed using EPA Method 1631E , just like all the other mercury samples.

The solid portion was analyzed according to the Appendix to 1631: Total Mercury in Tissue,

Sludge, Sediment, and Soil by Acid Digestion and BrCl Oxidation , which was associated with

EPA Method 1631B. Frontier digested th e samples with aqua regia (HCl/HNO 3 

# ) and then

analyzed the samples using EPA Method 1631E.

Frontier did not dry the solids prior to analysis, so the solid concentration is on a wetweight basis. To calculate the total sample concentration from the solid and aqueous phase

results, the laboratory also needed to measure the original sample volum e, solid phase weight,

and filtrate volume. EPA used Equation 4-1 to calculate the individual total mercury

concentrations for the sample.

Appendix Tables A-1 through A-4 present th e results of the biphasic analysis for

ammonia as nitrogen, nitrate/nitrit e, chloride, sulfate, nitrate/nitrite, total cyanide, TKN, total

phosphorus, total metals, and total mercury for each of the four days of sampling. Results are

rounded to three significant figures.

# 4-4 4.2 FGD Wastewater Treatment System

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 analyte for the sampling point. The total metal results

presented in Table 4-1 represent the calculated total result for all analytes for which biphasic

separation was performed. Table 4-2 presents the analytical results for all classical and metal

analytes for the four days of sampling at the e ffluent from the FGD wast ewater treatment system

(SP-2).

Tables 4-1 and 4-2 include the analytical results for all anal ytes for which EPA conducted

analyses. Results are rounded to three signifi cant digits. If an analyte was not detected in a

sample above the method detection limit, the resu lt is reported as “ND” followed by the samplespecific quantitation limit in parentheses. If an analyte was measured above the method

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

sample-specific quantitation limit in parentheses.

For Table 4-2 (effluent from the FGD wastew ater treatment system), a duplicate sample

was collected on Day 2 of the sampling episode. The Day 2 results presented in Table 4-2

represent the averag e of the original and the duplicate samp le results. Table 5-2 presents the

analytical results for the original and duplicat e results and the calculated relative percent

difference (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 4-3 presents the 4-day average results fo r all classical analytes for the influent to

the FGD wastewater treatment system (SP-1) and the efflue nt from the FGD wastewater

treatment system (SP-2). Table 4-4 presents th e 4-day average results for all metal analytes,

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

(SP-1) and the effluent from th e FGD wastewater treatment system (SP-2). The results presented

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

system was not timed to reflect the amount of time it takes the wastewater to pass through the

system.

# 4-5 Appendix Tables A-5 through A-13 present all the analytical results from the influent to

the FGD wastewater treatment system (SP-1), th e effluent from the FGD wastewater treatment

system (SP-2), and the duplicate of the effluentfrom the FGD wastewater treatment system (SP3) sample analyses, including J-values.

# 4-6Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted with an‘F( )’ are qualifiers associated with the filtrate portion of thesample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - 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.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.Min – Minimum valueP – Sample was not preserved immediately following collection.V – Serial dilution is not within control limits.Table 4-1.Influent to FGD Wastewater Treatment System, Miami FortInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmonia mg/L 350.1 5.21F(H, P, Est) –S(H, P, Est) 6.12F(P, Est) –S(H, P, Est) 7.90F(P, Est) – S(P,Est) 6.06F(P, Est) –S(P, Est) 6.32Nitrate Nitrite asN mg/L 353.2 71.7F(H, P, Est) –S(H, P, Est) 86.6F(P, Est) –S(H, P, Est) 74.9F(P, Est) – S(P,Est) 82.8F(P, Est) –S(P, Est) 79.0Nitrogen, TotalKjeldahlmg/L 351.2 40.5F(H, P, Est) –S(H, P, Est)52.6F(H, P, Est) –S(H, P, Est)47.6F(P, Est) –S(P, Est)40.8F(P, Est) –S(P, Est)45.4BiochemicalOxygen Demand mg/L 5210B NQ (2.50) NQ (2.50) 3.30 ND (2.00) * < 1.70ChemicalOxygen Demandmg/L 410.4 620 670 910 720 730Chloride mg/L 300.0 9,000 9,800 9,600 9,600 9,500Sulfate mg/L 300.0 18,000 21,000 32,000 24,000 23,800Cyanide, Total mg/L4500CN E 0.255F(B, H, P, Est) –S(B, H, P) 0.644F(B, H, P, Est) –S(B, H, P) 2.05F(B, H, P, Est) –S(B, H, P) 0.198F(B, H, P, Est) –S(B, H, P) 0.787Total DissolvedSolids mg/L 2540C 56,000 68,000 59,000 50,000 58,300Total SuspendedSolidsmg/L 2540D 16,000 30,000 20,000 19,000 21,300Phosphorus,Total mg/L 365.1 0.476F(B, H, P) – S(H,P, Est) 7.68F(B, H, P) – S(H,P, Est)NQ(0.191)F(B, P) –S(P) 6.52F(B, P) – S(P,Est) < 3.69

# 4-7Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted with an‘F( )’ are qualifiers associated with the filtrate portion of thesample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - 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.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.Min – Minimum valueP – Sample was not preserved immediately following collection.V – Serial dilution is not within control limits.Table 4-1.Influent to FGD Wastewater Treatment System, Miami FortInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageTotal MetalsAluminum ug/L200.7,6010B 561,000 626,000 F(B) 687,000 F(B) – S(4) 497,000 F(B) 593,000Antimony ug/L200.8,6020 NQ (10.3) NQ (11.0) NQ (13.4) S(4, Min) NQ (9.47)NQ(11.0)Arsenic ug/L200.8,6020937 896 1,310 695 960Barium ug/L200.7,6010B 7,640F(F, Min) –S(B) 7,510 S(B) 10,400 S(B) 6,410 S(B) 7,990Beryllium ug/L200.7,6010B27.6 28.3 41.8 22.4 30.0Boron ug/L200.7,6010B 624,000 F(B, 4) – S(B) 803,000 F(B) – S(B) 844,000F(B) – S(B,4) 762,000 F(B) – S(B) 758,000Cadmium ug/L200.8,6020 342 426 522 396 422Calcium ug/L200.7,6010B1,340,000 S(B) 1,350,000F(B) –S(B)2,060,000F(B) –S(B, 4)1,140,000F(B) –S(B)1,470,000Chromium ug/L200.8,6020 4,000 S(^) 4,460 S(^) 4,430 S(4, ^) 3,640 S(^) 4,130Cobalt ug/L200.7,6010B 425 503 632 459 505

# 4-8Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted with an‘F( )’ are qualifiers associated with the filtrate portion of thesample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - 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.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.Min – Minimum valueP – Sample was not preserved immediately following collection.V – Serial dilution is not within control limits.Table 4-1.Influent to FGD Wastewater Treatment System, Miami FortInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageCopper ug/L200.8,6020 1,350 1,520 1,670 1,210 1,440Iron ug/L200.7,6010B 911,000 965,000 1,030,000 S(4) 766,000 918,000Lead ug/L200.8,6020756 842 887 651 784Magnesium ug/L200.7,6010B 7,870,000 F(4) 9,210,000 11,800,000 9,010,000 9,470,000Manganese ug/L200.7,6010B93,100 F(B, 4) 105,000 F(B) 157,000 F(B) 96,000 F(B) 113,000Mercury ng/L1631E,FGS069 166,000 148,000 231,000 44,000 147,000Molybdenum ug/L200.7,6010B506 540 641 406 523Nickel ug/L200.8,6020 2,580 F(4) 2,980 3,610 2,560 2,930Selenium ug/L200.8,6020 3,400 F(V, 4, MI) 3,650 3,330 2,920 3,330Silver ug/L200.8,6020NQ (6.06) F(F, Min) NQ (6.50)NQ (7.47) S(F, Min) NQ (5.64)NQ(6.42)

# 4-9Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted with an‘F( )’ are qualifiers associated with the filtrate portion of thesample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - 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.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.Min – Minimum valueP – Sample was not preserved immediately following collection.V – Serial dilution is not within control limits.Table 4-1.Influent to FGD Wastewater Treatment System, Miami FortInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageSodium ug/L200.7,6010B 355,000 427,000 502,000 404,000 422,000Thallium ug/L200.8,6020 52.8 S(B) 56.4 S(B) 93.5 S(B) 46.2 S(B) 62.2Tin ug/L200.7,6010BNQ (403) NQ (430) NQ (460) NQ (411) NQ (426)Titanium ug/L200.7,6010B 2,020 2,050 4,140 S(F Max) 1,820 2,510Vanadium ug/L200.8,60204,010 4,220 4,440 S(4) 3,270 3,990Zinc ug/L200.8,6020 13,900 F(B, 4) 16,300 F(B) 20,200 F(B) – S(4) 14,500 F(B) 16,200Dissolved MetalsAluminum ug/L 200.7 4,200 B 2,400 B 29,000 B 2,800 B 9,600Antimony ug/L 200.8 3.40 3.30 3.70 2.80 3.30Arsenic ug/L 200.8 4.40 4.90 6.60 5.50 5.35Barium ug/L 200.7 140 140 180 150 153Beryllium ug/L 200.7 4.70 4.10 12.0 4.60 6.35Boron ug/L 200.7 650,000 B 690,000 B 820,000 730,000 723,000Cadmium ug/L 200.8 340 390 510 420 415Calcium ug/L 200.7 690,000 670,000 620,000 640,000 655,000

# 4-10Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted with an‘F( )’ are qualifiers associated with the filtrate portion of thesample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - 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.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.Min – Minimum valueP – Sample was not preserved immediately following collection.V – Serial dilution is not within control limits.Table 4-1.Influent to FGD Wastewater Treatment System, Miami FortInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageChromium ug/L 200.8ND(8.00) ND (8.00) ND (8.00) ND (8.00) ^ND(8.00)Chromium (VI) ug/L 218.6ND(10.0) ND (10.0) ND (10.0) ND (10.0)ND(10.0)Cobalt ug/L 200.7 340 360 490 380 393Copper ug/L 200.8 54.0 50.0 110 55.0 67.3Iron ug/L 200.7 NQ (200) ND (200) NQ (200) ND (200) NQ (200)Lead ug/L 200.8ND(2.00) ND (2.00) ND (2.00) ND (2.00)ND(2.00)Magnesium ug/L 200.7 7,900,000 8,400,000 11,000,000 8,900,000 9,050,000Manganese ug/L 200.7 100,000 100,000 170,000 110,000 120,000Mercury ng/L 1631E 1,110 1,830 1,600 1,990 1,630Molybdenum ug/L 200.7 120 110 130 90.0 113Nickel ug/L 200.8 1,700 1,700 2,500 2,000 1,980Selenium ug/L 200.8 290 330 330 300 313Silver ug/L 200.8ND(2.00) ND (2.00) ND (2.00) ND (2.00)ND(2.00)Sodium ug/L 200.7 360,000 380,000 480,000 400,000 405,000Thallium ug/L 200.8 25.0 26.0 49.0 26.0 31.5Tin ug/L 200.7 NQ (200) ND (200) ND (200) ND (200) NQ (200)

# 4-11Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite, sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted with an‘F( )’ are qualifiers associated with the filtrate portion of thesample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - 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.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.Min – Minimum valueP – Sample was not preserved immediately following collection.V – Serial dilution is not within control limits.Table 4-1.Influent to FGD Wastewater Treatment System, Miami FortInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageTitanium ug/L 200.7NQ(20.0) NQ (20.0) NQ (20.0) NQ (20.0)NQ(20.0)Vanadium ug/L 200.8 12.0 13.0 20.0 16.0 ^ 15.3Zinc ug/L 200.8 6,300 6,200 11,000 7,600 7,780

# 4-12Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). 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.C – pH upon receipt was less than 10 S.U.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.S – Seed correction blank recovery low.Table 4-2. Effluent from the FGD Wastewater Treatment System, Miami FortEffluent from the FGD Wastewater System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageClassicalsAmmoniamg/L350.14.805.405.505.305.25Nitrate Nitrite as Nmg/L353.255.029558.061.0117Nitrogen, Total Kjeldahlmg/L351.221.0B22.021.0B24.0B22.0Biochemical Oxygen Demandmg/L5210B6.709.006.90*,Min4.60S,*,Min6.80Chemical Oxygen Demandmg/L410.4570480560F,Min510530Chloridemg/L300.05,3007,5007,3007,4006,880Sulfatemg/L300.08,40013,00013,00014,00012,100Cyanide, Totalmg/L4500 CN E0.210B< 1.230.600B,C1.50B< 0.884Total Dissolved Solidsmg/L2540C29,00029,50028,00033,00029,900Total Suspended Solidsmg/L2540D17.08.808.40B22.014.1Phosphorus, Totalmg/L365.10.0960B0.1230.180B,F,Min0.0750B0.118Total MetalsAluminumug/L200.7NQ (200)< 180330NQ (200)< 178Antimonyug/L200.86.806.955.705.806.31Arsenicug/L200.84.304.854.904.404.61Bariumug/L200.7150155160150154Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7300,000B320,000320,000B,F,4330,000B318,000Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)

# 4-13Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). 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.C – pH upon receipt was less than 10 S.U.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.S – Seed correction blank recovery low.Table 4-2. Effluent from the FGD Wastewater Treatment System, Miami FortEffluent from the FGD Wastewater System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageCalciumug/L200.7890,000850,000840,000800,000845,000Chromiumug/L200.817.016.514.016.015.9Cobaltug/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)260NQ (200)< 140Leadug/L200.8ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.75,600,000B5,550,0005,500,000B,F,45,700,000B5,590,000Manganeseug/L200.7170B89.0280B100B160Mercuryng/L1631E101105148165130Molybdenumug/L200.7220200180150188Nickelug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Seleniumug/L200.85605358004480594Silverug/L200.8ND (2.00)ND (2.00)ND (2.00)F,MinND (2.00)ND (2.00)Sodiumug/L200.7370,000365,000360,0004360,000364,000Thalliumug/L200.814.014.014.012.013.5Tinug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Titaniumug/L200.7ND (20.0)NQ (20.0)NQ (20.0)NQ (20.0)NQ (20.0)Vanadiumug/L200.816.017.516.018.016.9Zincug/L200.8ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)Dissolved Metals

# 4-14Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). 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.C – pH upon receipt was less than 10 S.U.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.S – Seed correction blank recovery low.Table 4-2. Effluent from the FGD Wastewater Treatment System, Miami FortEffluent from the FGD Wastewater System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageAluminumug/L200.7ND (200)NQ (200)ND (200)ND (200)NQ (200)Antimonyug/L200.87.806.806.605.806.75Arsenicug/L200.84.80< 3.004.804.70< 4.33Bariumug/L200.7140145150150146Berylliumug/L200.7ND (2.00)ND (2.00)ND (2.00)ND (2.00)ND (2.00)Boronug/L200.7300,000B325,000320,000F,4330,000319,000Cadmiumug/L200.8ND (4.00)ND (4.00)ND (4.00)ND (4.00)ND (4.00)Calciumug/L200.7880,000835,000840,0004820,000844,000Chromiumug/L200.814.014.015.0^15.0^14.5Chromium (VI)ug/L218.67.047.347.616.717.17Cobaltug/L200.7ND (20.0)ND (20.0)ND (20.0)ND (20.0)ND (20.0)Copperug/L200.8NQ (4.00)NQ (4.00)ND (4.00)ND (4.00)NQ (4.00)Ironug/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/L200.75,500,0005,750,0005,600,000F,46,000,0005,710,000Manganeseug/L200.7160B84.0250B93.0B147Mercuryng/L1631E49.761.571.384.566.8Molybdenumug/L200.7210195170150181Nickelug/L200.8NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)NQ (4.00)Seleniumug/L200.85604956404530556

# 4-15Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). 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.C – pH upon receipt was less than 10 S.U.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.S – Seed correction blank recovery low.Table 4-2. Effluent from the FGD Wastewater Treatment System, Miami FortEffluent from the FGD Wastewater System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-Day AverageSilverug/L200.8ND (2.00)ND (2.00)ND (2.00)F,MinND (2.00)ND (2.00)Sodiumug/L200.7350,000350,000350,000360,000353,000Thalliumug/L200.814.014.013.012.013.3Tinug/L200.7ND (200)ND (200)ND (200)ND (200)ND (200)Titaniumug/L200.7ND (50.0)NQ (60.0)NQ (20.0)NQ (20.0)NQ (37.5)Vanadiumug/L200.816.017.014.0^15.0^15.5Zincug/L200.8ND (10.0)ND (10.0)ND (10.0)ND (10.0)ND (10.0)

# 4-16< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).Table 4-3.Classical Pollutants 4-Day Average Data Summaryfor FGD Wastewater Treatment System, Miami FortAnalyteUnitsMethodInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent fromFGD Wastewater TreatmentSystem (SP-2)4-Day AverageClassicalsAmmoniamg/L350.16.325.25Nitrate Nitrite as Nmg/L353.279.0117Nitrogen, Total Kjeldahlmg/L351.245.422.0Biochemical Oxygen Demandmg/L5210B< 1.706.80Chemical Oxygen Demandmg/L410.4730530Chloridemg/L300.09,5006,880Sulfatemg/L300.023,80012,100Cyanide, Totalmg/L4500 CN E0.787< 0.884Total Dissolved Solidsmg/L2540C58,30029,900Total Suspended Solidsmg/L2540D21,30014.1Phosphorus, Totalmg/L365.1< 3.690.118

# 4-17< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-4.Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, Miami FortInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent fromFGD Wastewater TreatmentSystem (SP-2)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedMetalsAluminumug/L200.7593,0009,600< 178NQ (200)Antimonyug/L200.8NQ (11.0)3.306.316.75Arsenicug/L200.89605.354.61< 4.33Bariumug/L200.77,990153154146Berylliumug/L200.730.06.35ND (2.00)ND (2.00)Boronug/L200.7758,000723,000318,000319,000Cadmiumug/L200.8422415ND (4.00)ND (4.00)Calciumug/L200.71,470,000655,000845,000844,000Chromiumug/L200.84,130ND (8.00)15.914.5Chromium (VI)ug/L218.6NAND (10.0)NA7.17Cobaltug/L200.7505393ND (20.0)ND (20.0)Copperug/L200.81,44067.3ND (4.00)NQ (4.00)Ironug/L200.7918,000NQ (200)< 140ND (200)Leadug/L200.8784ND (2.00)ND (2.00)ND (2.00)Magnesiumug/L200.79,470,0009,050,0005,590,0005,710,000Manganeseug/L200.7113,000120,000160147Mercuryng/L1631E147,0001,63013066.8Molybdenumug/L200.7523113188181Nickelug/L200.82,9301,980NQ (4.00)NQ (4.00)Seleniumug/L200.83,330313594556Silverug/L200.8NQ (6.42)ND (2.00)ND (2.00)ND (2.00)Sodiumug/L200.7422,000405,000364,000353,000Thalliumug/L200.862.231.513.513.3Tinug/L200.7NQ (426)NQ (200)ND (200)ND (200)

# 4-18< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-4.Metal Pollutants 4-Day Average Data Summary for FGD Wastewater Treatment System, Miami FortInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent fromFGD Wastewater TreatmentSystem (SP-2)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTitaniumug/L200.72,510NQ (20.0)NQ (20.0)NQ (37.5)Vanadiumug/L200.83,99015.316.915.5Zincug/L200.816,2007,780ND (10.0)ND (10.0)

# 5-19 5. D ATA 

# Q UALITY



# Quality assurance/quality control (QA/QC) pr ocedures applicable to the Miami Fort

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

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

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

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

QC standard checks.

5.1 Analytical Quality Control

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

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

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

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

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

5.2 Field Quality Control

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

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

5.2.1 Bottle Blanks

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

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

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

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

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

analyzed the samples using EPA Method 1638.

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

precleaned bottle with reagent wa ter, 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 preclean ed LDPE bottle. The blank samples were then

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

No metals were detected in the bottle blanks , except for aluminum in two of the three 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 lim it used for the sample analyses (i.e., 200

ug/L); therefore, this contamination did not aff ect the results of the sampling episode. Appendix

# 5-20 Table A-14 presents all of the analytical results from the bottle blank analyses for the bottles

used to collect the metals and mercury samples.

5.2.2 Equipment Blanks

EPA collects equipment blanks to evaluate possible contamination from the equipment

used for sample collection. The techniques used to collect field blanks (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 bo ttle 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-14 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-4 and SP-5) 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, di ssolved hexavalent chromium, and total and

dissolved mercury samples 4



# .

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

for the influent to the FGD wastewater treatm ent system (SP-4) 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 Miam i Fort’s representative, using the same procedure discussed in

the sample collection de scription (Section 3.1).

4 

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

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

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

a concentration of 0.25 ng/L in the filtration blank perf ormed for the fourth day of samples, which includes the

influent to the FGD wastewater treatment system (Day 4), the third and fourth grab sample for the effluent from

FGD wastewater treatment syst em (Day 3), and the first and second grab samples for effluent from FGD wastewater

treatment system (Day 4). Mercury was not detected above the method detection limit (0.24 ng/L) in the filtration

blanks performed for the first, second, third, or fifth day of samples.

# 5-21 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-4)

were collected by pouring ASTM Type 1 water th rough the funnel and tubi ng and into a 10-liter

composite container. After approximately 100 minutes, the sampling team began pumping off

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

the tubing and filter were purged with 750 mL of bl ank water. The sample bottles were placed in

a “cleanbox” and the ASTM Type 1 water was pump ed 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 Miami Fort’s representative, using the same procedure discussed in the sample

collection descripti on (Section 3.1).

The total mercury field blank sample for th e effluent from FGD wastewater treatment

system (SP-5) was collected by shrouding one of th e three taps on the sample tap splitter with a

clear plastic bag. Before purging the sample tap, ASTM Type 1 wa ter 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

effluent from FGD wastewater treatment system (SP-5) were collected by filling a 20-liter

composite container with ASTM Ty pe 1 water. The same T-splitter tubing used to fill the metals

composite container was used with a pump to f ill the field blank composite container. Prior to

attaching one end of the tubing to the sample tap, it was placed directly into the container

holding ASTM Type 1 water. The other end of th e tubing was attached to the vented cap on top

of the 20-liter field blank composite containe r. After enough volume was pumped into the 20-

liter field blank composite contai ner, the vented cap was repla ced with a closed cap and the

container was placed on ice in a covered plasti c trash can. The vented cap used for the field

blank collection was the same cap that was late r used for the metals composite container.

After 24 hours, the ASTM Type 1 water in the field blank composite container was

pumped off into the individual sample bottles. The sample bottles were placed in a “cleanbox”

and the ASTM Type 1 water was pumped throug h the tubing and “Y” splitter, and into the

sample bottles. EPA collected the field blank samp les as “true” split samples with Miami Fort’s

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

3.1). Prior to filling the sample bottles, the tubing was purged w ith approximately one liter of

ASTM Type 1 water. First the samplers collec ted the total metals by 200.8 and total metals by

200.7 field blank samples. Then the sampling team attached a filter to the tubing set and purged

the tubing with approximately 0.75 liter of ASTM T ype 1 water. The samplers then collected the

dissolved metals by 200.8, dissolved metals by 200.7, and dissolved hexavalent chromium field

blank samples.

Table 5-1 presents the field blank analyt ical results for SP-4 and SP-5. Only those

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

included in the table. Results are rounded to three significant digits . Appendix Tables A-15

through A-19 present all the analytical results for the field blanks from each of the sampling

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

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

# 5-22 5.2.4 Field Duplicates

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

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

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

is stored and analyzed independently. The RPD be tween the two sample results is examined to

determine the precision of the data. EPA used the following equation to calculate the RPD for

the duplicate sample results.

100

2 D S D S (%) RPD 

       

 

# (5-1)

where:

S = concentration of the analyte from original sample analysis;

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

RPD = relative percent difference between the original and duplicate sample

result.

During this sampling episode, EPA collected duplicate samples for the effluent from

FGD wastewater treatment system (SP-3) durin g Day 2 of the sampling episode. The duplicate

samples were analyzed for all analytes. Table 5-2 presents analytical results and the RPD for SP3. Results are rounded to three significant digits . Appendix Tables A-10 a nd A-13 present all the

analytical results for the efflue nt from FGD wastewater treatmen t system (SP-2) Day 2 and the

duplicate of the effluent from FGD wastewater treatment syst em (SP-3) sample analyses,

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

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

# 5-23Table 5-1.Field Blank AnalyticalResults, Miami FortAnalyteSample DescriptionMethodUnitsConcentrationTotal MetalsMagnesiumEffluent from FGD Wastewater Treatment System Field Blank - Day 1200.7ug/L410MercuryInfluent to FGD Wastewater Treatment System Field Blank - Day 11631Eng/L15.4

# 5-24< - 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.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.MI – Matrix interferences present.Min – Minimum value.V – Serial dilution is not within control limitsTable 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Miami FortAnalyteMethodUnitsOriginalEffluent fromFGD WastewaterTreatment System, Day2 Concentration (SP-2)DuplicateEffluent from FGDWastewaterTreatment SystemConcentration(SP-3)AverageResultRelativePercentDifferenceClassicalsAmmonia350.1mg/L5.305.505.403.70Nitrate Nitrite as N353.2mg/L2903002953.39Nitrogen, Total Kjeldahl351.2mg/L21.0B23.0B22.09.09Biochemical Oxygen Demand5210Bmg/L8.409.609.0013.3Chemical Oxygen Demand410.4mg/L40056048033.3Chloride300.0mg/L7,5007,5007,5000.00Sulfate300.0mg/L13,00013,00013,0000.00Cyanide, Total4500 CN Emg/L2.40BNQ (0.100)B< 1.23NCTotal Dissolved Solids2540Cmg/L32,00027,00029,50016.9Total Suspended Solids2540Dmg/L10.07.608.8027.3Phosphorus, Total365.1mg/L0.180B0.0650B0.12393.9Total MetalsAluminum200.7ug/L260NQ (200)< 180NCAntimony200.8ug/L6.907.006.951.44Arsenic200.8ug/L5.604.104.8530.9Barium200.7ug/L1501601556.45Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NC

# 5-25< - 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.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.MI – Matrix interferences present.Min – Minimum value.V – Serial dilution is not within control limitsTable 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Miami FortAnalyteMethodUnitsOriginalEffluent fromFGD WastewaterTreatment System, Day2 Concentration (SP-2)DuplicateEffluent from FGDWastewaterTreatment SystemConcentration(SP-3)AverageResultRelativePercentDifferenceBoron200.7ug/L320,000B,F,4320,000B320,0000.00Cadmium200.8ug/LND (4.00)ND (4.00)ND (4.00)NCCalcium200.7ug/L840,0004860,000850,0002.35Chromium200.8ug/L16.017.016.56.06Cobalt200.7ug/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/L5,500,000B,F,45,600,000B5,550,0001.80Manganese200.7ug/L88.0B90.0B89.02.25Mercury1631Eng/L99.81101059.72Molybdenum200.7ug/L2002002000.00Nickel200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCSelenium200.8ug/L540V,4,MI5305351.87Silver200.8ug/LND (2.00)F,MinND (2.00)ND (2.00)NCSodium200.7ug/L360,0004370,000365,0002.74Thallium200.8ug/L14.014.014.00.00Tin200.7ug/LND (200)ND (200)ND (200)NC

# 5-26< - 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.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.MI – Matrix interferences present.Min – Minimum value.V – Serial dilution is not within control limitsTable 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Miami FortAnalyteMethodUnitsOriginalEffluent fromFGD WastewaterTreatment System, Day2 Concentration (SP-2)DuplicateEffluent from FGDWastewaterTreatment SystemConcentration(SP-3)AverageResultRelativePercentDifferenceTitanium200.7ug/LND (20.0)NQ (20.0)NQ (20.0)NCVanadium200.8ug/L17.018.017.55.71Zinc200.8ug/LND (10.0)ND (10.0)ND (10.0)NCDissolved MetalsAluminum200.7ug/LNQ (200)BND (200)NQ (200)NCAntimony200.8ug/L6.806.806.800.00Arsenic200.8ug/LNQ (4.00)4.00< 3.00NCBarium200.7ug/L1501401456.90Beryllium200.7ug/LND (2.00)ND (2.00)ND (2.00)NCBoron200.7ug/L330,000F,4320,000325,0003.08Cadmium200.8ug/LND (4.00)ND (4.00)ND (4.00)NCCalcium200.7ug/L860,000810,000835,0005.99Chromium200.8ug/L14.014.014.00.00Chromium (VI)218.6ug/L7.327.357.340.409Cobalt200.7ug/LND (20.0)ND (20.0)ND (20.0)NCCopper200.8ug/LND (4.00)NQ (4.00)NQ (4.00)NCIron200.7ug/LND (200)ND (200)ND (200)NCLead200.8ug/LND (2.00)ND (2.00)ND (2.00)NC

# 5-27< - 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.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.MI – Matrix interferences present.Min – Minimum value.V – Serial dilution is not within control limitsTable 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Miami FortAnalyteMethodUnitsOriginalEffluent fromFGD WastewaterTreatment System, Day2 Concentration (SP-2)DuplicateEffluent from FGDWastewaterTreatment SystemConcentration(SP-3)AverageResultRelativePercentDifferenceMagnesium200.7ug/L5,900,000F,45,600,0005,750,0005.22Manganese200.7ug/L87.0B81.0B84.07.14Mercury1631Eng/L63.159.961.55.20Molybdenum200.7ug/L2001901955.13Nickel200.8ug/LNQ (4.00)NQ (4.00)NQ (4.00)NCSelenium200.8ug/L520V,4,MI47049510.1Silver200.8ug/LND (2.00)F,MinND (2.00)ND (2.00)NCSodium200.7ug/L360,000340,000350,0005.71Thallium200.8ug/L14.014.014.00.00Tin200.7ug/LND (200)ND (200)ND (200)NCTitanium200.7ug/LNQ (20.0)ND (100.0)NQ (60.0)NCVanadium200.8ug/L16.018.017.011.8Zinc200.8ug/LND (10.0)ND (10.0)ND (10.0)NC

# 6-1 6. R EFERENCES



# 1. Eastern Research Group, Inc., 2010. Sampling Plan, Duke Energy’s Miami Fort 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.

3. U.S. EPA. 2001. Method 200.7: Determination of Metals and Trace Elements in Water

and Wastes by Inductively C oupled Plasma – Atomic Emission Spectrometry. Revision

4.4.

4. U.S. EPA. 1994. Method 200.7: Determination of Trace Elements in Waters and Wastes

by Inductively Coupled Plasma - Mass Spectrometry. Revision 5.4.

# Appendix A

ANALYTICAL RESULTS

# A-1Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).V – Serial dilution is not within control limits.Table A-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatment System,Day 1 Analytical Results, Miami FortAnalyteAqueous Phase Result(mg/L for Classicals;ug/L for Metals; andng/L for Mercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/g forMercury)Calculated Total Result (mg/L for Classicals;ug/L for Metals; and ng/L for Mercury)ClassicalsAmmonia5.1H,P,Est24H,P,Est5.21F(H, P, Est) – S(H, P, Est)Nitrate Nitrite as N77H,P,Est49H,P,Est71.7F(H, P, Est) – S(H, P, Est)Nitrogen, Total Kjeldahl24H,P,Est830H,P,Est40.5F(H, P, Est) – S(H, P, Est)Cyanide, Total0.27B,H,P,Est0.35J,B,H,P0.255F(B, H, P, Est) – S(J, B, H, P)Phosphorus, Total0.01J,B,H,P21H,P,Est0.476F(J, B, H, P) – S(H, P, Est)Total MetalsAluminum6,00025,000561,000Antimony3.10.16J6.4S(J)Arsenic4.142937Barium88F,Min340B7,640F(F, Min) – S(B)Beryllium3.41.127.6Boron660,000B,4860B624,000F(B, 4) – S(B)Cadmium3202.2342Calcium610,00035,000B1,340,000S(B)

# A-2Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).V – Serial dilution is not within control limits.Table A-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatment System,Day 1 Analytical Results, Miami FortAnalyteAqueous Phase Result(mg/L for Classicals;ug/L for Metals; andng/L for Mercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/g forMercury)Calculated Total Result (mg/L for Classicals;ug/L for Metals; and ng/L for Mercury)ChromiumND (8)U180^4,000F(U) – S(^)Cobalt3205.9425Copper42591,350IronND (200)U41,000911,000F(U)LeadND (2)U34756F(U)Magnesium8,100,000420,0007,870,000F(4)Manganese95,000B,427093,100F(B, 4)Mercury2,9207,570166,000Molybdenum14017506Nickel1,5004542,580F(4)Selenium320V,4,MI1403,400F(V, 4, MI)SilverND (2)U,F,Min0.14J3.11F(U, F, Min) – S(J)Sodium360,0001,100355,000Thallium141.8B52.8S(B)Tin11J2.3J61.2F(J) - S(J)TitaniumND (20)U912,020F(U)

# A-3Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).V – Serial dilution is not within control limits.Table A-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatment System,Day 1 Analytical Results, Miami FortAnalyteAqueous Phase Result(mg/L for Classicals;ug/L for Metals; andng/L for Mercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/g forMercury)Calculated Total Result (mg/L for Classicals;ug/L for Metals; and ng/L for Mercury)Vanadium8.7J1804,010F(J)Zinc5,200B,441013,900F(B, 4)

# A-4Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-2. Biphasic Sample Results for Classicals and TotalMetals, Influent to FGD Wastewater Treatment System, Day 2Analytical Results, Miami FortAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicals andMetals and ng/g forMercury)Calculated Total Result (mg/L for Classicals;ug/L for Metals; and ng/L for Mercury)ClassicalsAmmonia5.3P,Est28H,P,Est6.12F(P, Est) – S(H, P, Est)Nitrate Nitrite as N83P,Est64H,P,Est86.6F(P, Est) – S(H, P, Est)Nitrogen, Total Kjeldahl31H,P,Est840H,P,Est52.6F(H, P, Est) – S(H, P, Est)Cyanide, Total0.62B,H,P,Est0.33J,B,H,P0.644F(B, H, P, Est) – S(J, B, H, P)Phosphorus, Total0.008J,B,H,P310H,P,Est7.68F(J, B, H, P) – S(H, P, Est)Total MetalsAluminum6,600B25,000626,000F(B)Antimony2.70.15J6.48S(J)Arsenic4.436896Barium83300B7,510S(B)Beryllium3.5128.3Boron760,000B980B803,000F(B) – S(B)Cadmium3602.3426Calcium590,000B30,000B1,350,000F(B) – S(B)ChromiumND (8)U180^4,460F(U) – S(^)Cobalt3605.4503Copper59591,520IronND (200)U39,000965,000F(U)Lead0.82J34842F(J)

# A-5Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-2. Biphasic Sample Results for Classicals and TotalMetals, Influent to FGD Wastewater Treatment System, Day 2Analytical Results, Miami FortAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicals andMetals and ng/g forMercury)Calculated Total Result (mg/L for Classicals;ug/L for Metals; and ng/L for Mercury)Magnesium8,500,00020,0009,210,000Manganese96,000B260105,000F(B)Mercury2,9907,330148,000Molybdenum14016540Nickel1,600542,980Selenium4201303,650SilverND (2)U0.14J3.47F(U) – S(J)Sodium390,0001,100427,000Thallium141.7B56.4S(B)Tin6.1J2.2J60.7F(J) – S(J)TitaniumND (20)U832,050F(U)Vanadium9.9J1704,220F(J)Zinc6,000B41016,300F(B)

# A-6Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.Max – Maximum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-3. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatment System,Day 3 Analytical Results, Miami FortAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicals andMetals and ng/g forMercury)Calculated Total Result (mg/L for Classicals;ug/L for Metals; and ng/L for Mercury)ClassicalsAmmonia7.7P,Est26P,Est7.9F(P, Est) – S(P, Est)Nitrate Nitrite as N79P,Est56P,Est74.9F(P, Est) – S(P, Est)Nitrogen, Total Kjeldahl29P,Est700P,Est47.6F(P, Est) – S(P, Est)Cyanide, Total2.2B,H,P,Est0.37J,B,H,P2.05F(B, H, P, Est) – S(J, B, H, P)Phosphorus, Total0.013J,B,P1.9J,P0.068F(J, B, P) – S(J, P)Total MetalsAluminum40,000B22,0004687,000F(B) – S(4)Antimony3.60.16J,F,Min8.06S(J, 4, Min)Arsenic7.2441,310Barium80350B10,400S(B)Beryllium101.141.8Boron880,000B950B,4844,000F(B) – S(B, 4)Cadmium5002522Calcium570,000B52,000B,42,060,000F(B) – S(B, 4)ChromiumND (8)U1504,^4,430F(U) – S(4, ^)Cobalt5005.7632Copper86541,670

# A-7Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.Max – Maximum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-3. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatment System,Day 3 Analytical Results, Miami FortAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicals andMetals and ng/g forMercury)Calculated Total Result (mg/L for Classicals;ug/L for Metals; and ng/L for Mercury)IronND (200)U35,00041,030,000F(U) – S(4)Lead0.82J30887F(J)Magnesium12,000,00023,00011,800,000Manganese160,000B300157,000F(B)Mercury3,6405,990231,000Molybdenum15017641Nickel2,400473,610Selenium4101003,330SilverND (2)U0.14J,F,Min4.14F(U) – S(J, F, Min)Sodium500,0001,300502,000Thallium342.1B93.5S(B)TinND (200)U2.4J70.9F(U) – S(J)TitaniumND (20)U140F Max4,140F(U) – S(F Max)Vanadium1415044,440S(4)Zinc11,000B340420,200F(B) – S(4)

# A-8Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-4. Biphasic Sample Results for Classicals and Total Metals,Influent to FGD Wastewater Treatment System, Day 4Analytical Results, Miami FortAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/g forMercury)Calculated Total Result (mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)ClassicalsAmmonia6.2P,Est23P,Est6.06F(P, Est) – S(P, Est)Nitrate Nitrite as N90P,Est65P,Est82.8F(P, Est) – S(P, Est)Nitrogen, Total Kjeldahl26P,Est900P,Est40.8F(P, Est) – S(P, Est)Cyanide, Total0.21B,H,P,Est0.42J,B,H,P0.198F(B, H, P, Est) – S(J, B, H, P)Phosphorus, Total0.012J,B,P340P,Est6.52F(J, B, P) – S(P, Est)Total MetalsAluminum20,000B25,000497,000F(B)Antimony2.50.14J4.95S(J)Arsenic5.936695Barium100330B6,410S(B)Beryllium3.6122.4Boron820,000B990B762,000F(B) – S(B)Cadmium3802.7396Calcium600,000B31,000B1,140,000F(B) – S(B)ChromiumND (8)U190^3,640F(U) – S(^)Cobalt3905.5459Copper72601,210IronND (200)U40,000766,000F(U)LeadND (2)U34651F(U)

# A-9Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-4. Biphasic Sample Results for Classicals and Total Metals,Influent to FGD Wastewater Treatment System, Day 4Analytical Results, Miami FortAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/g forMercury)Calculated Total Result (mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)Magnesium9,500,00021,0009,010,000Manganese100,000B28096,000F(B)Mercury4,3704,99044,000Molybdenum11016406Nickel1,700532,560Selenium4701302,920SilverND (2)U0.12J2.3F(U) – S(J)Sodium420,0001,200404,000Thallium151.7B46.2S(B)TinND (200)U2.3J44.1F(U) – S(J)TitaniumND (20)U951,820F(U)Vanadium141703,270Zinc6,700B44014,500F(B)

# A-10NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5.Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassical Pollutants - TotalAmmonia350.1mg/lNA0.1922.055.21Nitrate Nitrite as N353.2mg/lNA0.1821.1471.7Nitrogen, Total Kjeldahl351.2mg/lNA3.0215.940.5Biochemical Oxygen Demand5210Bmg/L10.32.52JChemical Oxygen Demand410.4mg/L1041200620Chloride300.0mg/L5001301,5009,000Sulfate300.0mg/L5001202,50018,000Cyanide, Total4500 CN Emg/lNA0.02050.1020.255Total Dissolved Solids2540Cmg/L14701,00056,000Total Suspended Solids2540Dmg/L15520016,000Phosphorus, Total365.1mg/lNA0.02240.1530.476Classicals Pollutants - Solid (dry weight)Ammonia350.1mg/Kg14.19.924H,P,EstNitrate Nitrite as N353.2mg/Kg10.361049H,P,EstNitrogen, Total Kjeldahl351.2mg/Kg10120510830H,P,EstCyanide, Total4500 CN Emg/Kg10.0950.460.35J,B,H,P

# A-11NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5.Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationPhosphorus, Total365.1mg/Kg10.84.821H,P,EstClassicals Pollutants -Filtered AqueousAmmonia350.1mg/L10.1125.1H,P,EstNitrate Nitrite as N353.2mg/L100.19177H,P,EstNitrogen, Total Kjeldahl351.2mg/L20.38524H,P,EstCyanide, Total4500 CN Emg/L10.020.10.27B,H,P,EstPhosphorus, Total365.1mg/L10.0050.050.01J,B,H,PMetals - Calculated TotalAluminum200.7, 6010Bug/LNA42403561,000Antimony200.8, 6020ug/LNA1.2610.36.4Arsenic200.8, 6020ug/LNA27.8315937Barium200.7, 6010Bug/LNA3.9640.37,640Beryllium200.7, 6010Bug/LNA1.3812.927.6Boron200.7, 6010Bug/LNA2655,700624,000Cadmium200.8, 6020ug/LNA1.57.89342Calcium200.7, 6010Bug/LNA3741,4801,340,000Chromium200.8, 6020ug/LNA431144,000

# A-12NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5.Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationCobalt200.7, 6010Bug/LNA3.2140.3425Copper200.8, 6020ug/LNA38.71371,350Iron200.7, 6010Bug/LNA114517911,000Lead200.8, 6020ug/LNA10.281.8756Magnesium200.7, 6010Bug/LNA5779,6207,870,000Manganese200.7, 6010Bug/LNA14.148193,100Mercury1631E, FGS-069ng/LNA1,6704,530166,000Molybdenum200.7, 6010Bug/LNA7.2581.1506Nickel200.8, 6020ug/LNA1.8810.12,580Selenium200.8, 6020ug/LNA6.1224.83,400Silver200.8, 6020ug/LNA1.416.063.11Sodium200.7, 6010Bug/LNA1,45020,300355,000Thallium200.8, 6020ug/LNA0.586.0652.8Tin200.7, 6010Bug/LNA24.440361.2Titanium200.7, 6010Bug/LNA4.5840.32,020Vanadium200.8, 6020ug/LNA222764,010Zinc200.8, 6020ug/LNA20462513,900

# A-13NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5.Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationMetals - DissolvedAluminum200.7ug/L29.42004,200BAntimony200.8ug/L20.7223.4Arsenic200.8ug/L21.244.4Barium200.7ug/L22.520140Beryllium200.7ug/L20.7124.7Boron200.7ug/L5001,70050,000650,000BCadmium200.8ug/L52.910340Calcium200.7ug/L269400690,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.120340Copper200.8ug/L20.96454Iron200.7ug/L23220047JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5005,400100,0007,900,000Manganese200.7ug/L5001305,000100,000

# A-14NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5.Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationMercury1631Eng/L5001242601,110Molybdenum200.7ug/L21.640120Nickel200.8ug/L2511501,700Selenium200.8ug/L51.610290Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000360,000Thallium200.8ug/L20.47225Tin200.7ug/L24.82008.7JTitanium200.7ug/L21.6203.2JVanadium200.8ug/L21.71012Zinc200.8ug/L1002005006,300Metals - Filtered AqueousAluminum200.7ug/L29.42006,000Antimony200.8ug/L20.7223.1Arsenic200.8ug/L21.244.1Barium200.7ug/L22.52088F,MinBeryllium200.7ug/L20.7123.4

# A-15NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5.Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationBoron200.7ug/L501705,000660,000B,4Cadmium200.8ug/L21.24320Calcium200.7ug/L269400610,000Chromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120320Copper200.8ug/L20.96442Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0008,100,0004Manganese200.7ug/L501350095,000B,4Mercury1631Eng/L5001242602,920Molybdenum200.7ug/L21.640140Nickel200.8ug/L20.8941,5004Selenium200.8ug/L20.624320V,4,MISilver200.8ug/L20.592ND (2)U,F,MinSodium200.7ug/L218010,000360,000Thallium200.8ug/L20.47214

# A-16NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5.Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationTin200.7ug/L24.820011JTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7108.7JZinc200.8ug/L20411005,200B,4Metals - Solid (dry weight)Aluminum6010Bmg/kg11.59.925,000Antimony6020mg/kg20.0270.380.16JArsenic6020mg/kg251.21442Barium6010Bmg/kg10.0750.99340BBeryllium6010Bmg/kg10.0330.51.1Boron6010Bmg/kg54.950860BCadmium6020mg/kg20.0180.192.2Calcium6010Bmg/kg1145035,000BChromium6020mg/kg251.84.8180^Cobalt6010Bmg/kg10.0990.995.9Copper6020mg/kg251.7659Iron6010Bmg/kg13.81541,000

# A-17NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.MI – Matrix interferences present.Min – Minimum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5.Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationLead6020mg/kg250.433.634Magnesium6010Bmg/kg13.72020,000Manganese6010Bmg/kg10.0990.99270MercuryFGS-069ng/g4,00071.91987,570Molybdenum6010Bmg/kg10.26217Nickel6020mg/kg20.0480.2954Selenium6020mg/kg20.250.95140Silver6020mg/kg20.0390.190.14JSodium6010Bmg/kg1585001,100Thallium6020mg/kg20.00670.191.8BTin6010Bmg/kg10.99.92.3JTitanium6010Bmg/kg10.140.9991Vanadium6020mg/kg250.9212180Zinc6020mg/kg257.524410

# A-18NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6.Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassical Pollutants - TotalAmmonia350.1mg/lNA0.2142.36.12Nitrate Nitrite as N353.2mg/lNA0.2031.2786.6Nitrogen, Total Kjeldahl351.2mg/lNA3.361852.6Biochemical Oxygen Demand5210Bmg/L10.32.51.9JChemical Oxygen Demand410.4mg/L1041200670Chloride300.0mg/L5001301,5009,800Sulfate300.0mg/L5001202,50021,000Cyanide, Total4500 CN Emg/lNA0.02320.1160.644Total Dissolved Solids2540Cmg/L14701,00068,000Total Suspended Solids2540Dmg/L15520030,000Phosphorus, Total365.1mg/lNA0.2081.297.68Classicals Pollutants - Solid (dry weight)Ammonia350.1mg/Kg14.11028H,P,EstNitrate Nitrite as N353.2mg/Kg10.359.964H,P,EstNitrogen, Total Kjeldahl351.2mg/Kg10120520840H,P,EstCyanide, Total4500 CN Emg/Kg10.110.530.33J,B,H,PPhosphorus, Total365.1mg/Kg108.250310H,P,EstClassicals Pollutants -Filtered AqueousAmmonia350.1mg/L10.1125.3P,Est

# A-19NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6.Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationNitrate Nitrite as N353.2mg/L100.19183P,EstNitrogen, Total Kjeldahl351.2mg/L20.38531H,P,EstCyanide, Total4500 CN Emg/L10.020.10.62B,H,P,EstPhosphorus, Total365.1mg/L10.0050.050.008J,B,H,PMetals - Calculated TotalAluminum200.7, 6010Bug/LNA44.3430626,000Antimony200.8, 6020ug/LNA1.36116.48Arsenic200.8, 6020ug/LNA28.5351896Barium200.7, 6010Bug/LNA4.27437,510Beryllium200.7, 6010Bug/LNA1.4713.228.3Boron200.7, 6010Bug/LNA2866,240803,000Cadmium200.8, 6020ug/LNA1.658.55426Calcium200.7, 6010Bug/LNA3921,5201,350,000Chromium200.8, 6020ug/LNA45.51204,460Cobalt200.7, 6010Bug/LNA3.3843503Copper200.8, 6020ug/LNA40.61431,520Iron200.7, 6010Bug/LNA119551965,000Lead200.8, 6020ug/LNA10.986.2842Magnesium200.7, 6010Bug/LNA63810,7009,210,000Manganese200.7, 6010Bug/LNA15.6535105,000

# A-20NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6.Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationMercury1631E, FGS-069ng/LNA1,5204,120148,000Molybdenum200.7, 6010Bug/LNA7.5885.5540Nickel200.8, 6020ug/LNA2.0510.82,980Selenium200.8, 6020ug/LNA6.5826.43,650Silver200.8, 6020ug/LNA1.526.53.47Sodium200.7, 6010Bug/LNA1,52021,400427,000Thallium200.8, 6020ug/LNA0.6386.556.4Tin200.7, 6010Bug/LNA25.543060.7Titanium200.7, 6010Bug/LNA4.86432,050Vanadium200.8, 6020ug/LNA23.32834,220Zinc200.8, 6020ug/LNA19662116,300Metals - DissolvedAluminum200.7ug/L29.42002,400BAntimony200.8ug/L20.7223.3Arsenic200.8ug/L21.244.9Barium200.7ug/L22.520140Beryllium200.7ug/L20.7124.1Boron200.7ug/L5001,70050,000690,000BCadmium200.8ug/L52.910390Calcium200.7ug/L269400670,000

# A-21NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6.Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.120360Copper200.8ug/L20.96450Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5005,400100,0008,400,000Manganese200.7ug/L5001305,000100,000Mercury1631Eng/L5001242601,830Molybdenum200.7ug/L21.640110Nickel200.8ug/L2511501,700Selenium200.8ug/L51.610330Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000380,000Thallium200.8ug/L20.47226Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6202.1JVanadium200.8ug/L21.71013Zinc200.8ug/L1002005006,200

# A-22NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6.Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationMetals - Filtered AqueousAluminum200.7ug/L29.42006,600BAntimony200.8ug/L20.7222.7Arsenic200.8ug/L21.244.4Barium200.7ug/L22.52083Beryllium200.7ug/L20.7123.5Boron200.7ug/L501705,000760,000BCadmium200.8ug/L21.24360Calcium200.7ug/L269400590,000BChromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120360Copper200.8ug/L20.96459Iron200.7ug/L232200ND (200)ULead200.8ug/L20.7320.82JMagnesium200.7ug/L5054010,0008,500,000Manganese200.7ug/L501350096,000BMercury1631Eng/L5001242602,990Molybdenum200.7ug/L21.640140Nickel200.8ug/L20.8941,600Selenium200.8ug/L20.624420

# A-23NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6.Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000390,000Thallium200.8ug/L20.47214Tin200.7ug/L24.82006.1JTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.7109.9JZinc200.8ug/L1020506,000BMetals - Solid (dry weight)Aluminum6010Bmg/kg11.49.125,000Antimony6020mg/kg20.0250.360.15JArsenic6020mg/kg251.11436Barium6010Bmg/kg10.0690.91300BBeryllium6010Bmg/kg10.030.451Boron6010Bmg/kg54.545980BCadmium6020mg/kg20.0170.182.3Calcium6010Bmg/kg1134530,000BChromium6020mg/kg251.74.5180^Cobalt6010Bmg/kg10.0910.915.4Copper6020mg/kg251.65.659Iron6010Bmg/kg13.51439,000

# A-24NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6.Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationLead6020mg/kg250.413.434Magnesium6010Bmg/kg13.41820,000Manganese6010Bmg/kg10.0910.91260MercuryFGS-069ng/g4,00071.11967,330Molybdenum6010Bmg/kg10.241.816Nickel6020mg/kg20.0460.2754Selenium6020mg/kg20.240.9130Silver6020mg/kg20.0370.180.14JSodium6010Bmg/kg1544501,100Thallium6020mg/kg20.00630.181.7BTin6010Bmg/kg10.839.12.2JTitanium6010Bmg/kg10.130.9183Vanadium6020mg/kg250.8711170Zinc6020mg/kg257.123410

# A-25NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.Max – Maximum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7.Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassical Pollutants – TotalAmmonia350.1mg/lNA 0.2232.157.9Nitrate Nitrite as N353.2mg/lNA 0.1861.2274.9Nitrogen, Total Kjeldahl351.2mg/lNA 3.919.447.6Biochemical Oxygen Demand5210Bmg/L10.32.53.3Chemical Oxygen Demand410.4mg/L1041200910Chloride300.0mg/L5001301,5009,600Sulfate300.0mg/L1,0002305,00032,000Cyanide, Total4500 CN Emg/lNA0.02180.1092.05Total Dissolved Solids2540Cmg/L14701,00059,000Total Suspended Solids2540Dmg/L15520020,000Phosphorus, Total365.1mg/lNA0.02860.1910.068Classicals Pollutants - Solid (dry weight)Ammonia350.1mg/Kg14.11026P,EstNitrate Nitrite as N353.2mg/Kg10.359.956P,EstNitrogen, Total Kjeldahl351.2mg/Kg10120500700P,EstCyanide, Total4500 CN Emg/Kg10.110.550.37J,B,H,PPhosphorus, Total365.1mg/Kg10.814.91.9J,PClassicals Pollutants -Filtered AqueousAmmonia350.1mg/L10.1127.7P,EstNitrate Nitrite as N353.2mg/L100.19179P,EstNitrogen, Total Kjeldahl351.2mg/L20.38529P,Est

# A-26NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.Max – Maximum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7.Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCyanide, Total4500 CN Emg/L10.020.12.2B,H,P,EstPhosphorus, Total365.1mg/L10.0050.050.013J,B,PMetals - Calculated TotalAluminum200.7, 6010Bug/LNA50.1460687,000Antimony200.8, 6020ug/LNA1.4613.48.06Arsenic200.8, 6020ug/LNA30.13581,310Barium200.7, 6010Bug/LNA4.414610,400Beryllium200.7, 6010Bug/LNA1.5715.741.8Boron200.7, 6010Bug/LNA2936,020844,000Cadmium200.8, 6020ug/LNA1.649.32522Calcium200.7, 6010Bug/LNA2,0107,1702,060,000Chromium200.8, 6020ug/LNA47.41234,430Cobalt200.7, 6010Bug/LNA3.7746632Copper200.8, 6020ug/LNA42.21481,670Iron200.7, 6010Bug/LNA1365991,030,000Lead200.8, 6020ug/LNA1187.5887Magnesium200.7, 6010Bug/LNA6049,83011,800,000Manganese200.7, 6010Bug/LNA14.8491157,000Mercury1631E, FGS-069ng/LNA2,8607,810231,000Molybdenum200.7, 6010Bug/LNA8.5793.2641Nickel200.8, 6020ug/LNA2.2712.33,610

# A-27NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.Max – Maximum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7.Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationSelenium200.8, 6020ug/LNA10.647.23,330Silver200.8, 6020ug/LNA1.77.474.14Sodium200.7, 6010Bug/LNA1,79023,200502,000Thallium200.8, 6020ug/LNA0.6367.4793.5Tin200.7, 6010Bug/LNA29.646070.9Titanium200.7, 6010Bug/LNA5.32464,140Vanadium200.8, 6020ug/LNA23.72964,440Zinc200.8, 6020ug/LNA36.610220,200Metals - DissolvedAluminum200.7ug/L10471,00029,000BAntimony200.8ug/L20.7223.7Arsenic200.8ug/L21.246.6Barium200.7ug/L22.520180Beryllium200.7ug/L20.71212Boron200.7ug/L5001,70050,000820,000Cadmium200.8ug/L5029100510Calcium200.7ug/L269400620,000Chromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.120490Copper200.8ug/L20.964110

# A-28NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.Max – Maximum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7.Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationIron200.7ug/L23220042JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5005,400100,00011,000,000Manganese200.7ug/L5001305,000170,000Mercury1631Eng/L5001242601,600Molybdenum200.7ug/L21.640130Nickel200.8ug/L50221002,500Selenium200.8ug/L51.610330Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000480,000Thallium200.8ug/L20.47249Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6201.8JVanadium200.8ug/L21.71020Zinc200.8ug/L2004101,00011,000Metals - Filtered AqueousAluminum200.7ug/L29.420040,000BAntimony200.8ug/L20.7223.6Arsenic200.8ug/L21.247.2Barium200.7ug/L22.52080Beryllium200.7ug/L20.71210

# A-29NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.Max – Maximum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7.Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationBoron200.7ug/L501705,000880,000BCadmium200.8ug/L21.24500Calcium200.7ug/L269400570,000BChromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120500Copper200.8ug/L20.96486Iron200.7ug/L232200ND (200)ULead200.8ug/L20.7320.82JMagnesium200.7ug/L5054010,00012,000,000Manganese200.7ug/L5013500160,000BMercury1631Eng/L5001242603,640Molybdenum200.7ug/L21.640150Nickel200.8ug/L20.8942,400Selenium200.8ug/L103.120410Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000500,000Thallium200.8ug/L20.47234Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.71014Zinc200.8ug/L10205011,000BMetals - Solid (dry weight)

# A-30NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.Max – Maximum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7.Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationAluminum6010Bmg/kg11.49.322,0004Antimony6020mg/kg20.0270.390.16J,F,MinArsenic6020mg/kg200.981244Barium6010Bmg/kg10.0710.93350BBeryllium6010Bmg/kg10.0310.471.1Boron6010Bmg/kg54.647950B,4Cadmium6020mg/kg20.0180.192Calcium6010Bmg/kg56623052,000B,4Chromium6020mg/kg201.53.91504,^Cobalt6010Bmg/kg10.0930.935.7Copper6020mg/kg201.44.954Iron6010Bmg/kg13.61435,0004Lead6020mg/kg200.352.930Magnesium6010Bmg/kg13.51923,000Manganese6010Bmg/kg10.0930.93300MercuryFGS-069ng/g4,00072.11995,990Molybdenum6010Bmg/kg10.241.917Nickel6020mg/kg20.0490.2947Selenium6020mg/kg20.260.97100Silver6020mg/kg20.0390.190.14J,F,MinSodium6010Bmg/kg1554701,300

# A-31NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.Max – Maximum value.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7.Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationThallium6020mg/kg20.00680.192.1BTin6010Bmg/kg10.859.32.4JTitanium6010Bmg/kg10.130.93140F MaxVanadium6020mg/kg200.759.71504Zinc6020mg/kg20.611.93404

# A-32NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8.Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassical Pollutants - TotalAmmonia350.1mg/lNA 0.17826.06Nitrate Nitrite as N353.2mg/lNA0.1791.182.8Nitrogen, Total Kjeldahl351.2mg/lNA2.6414.540.8Biochemical Oxygen Demand5210Bmg/L10.242ND (2)U,*Chemical Oxygen Demand410.4mg/L1041200720Chloride300.0mg/L5001301,5009,600Sulfate300.0mg/L5001202,50024,000Cyanide, Total4500 CN Emg/lNA0.02020.1010.198Total Dissolved Solids2540Cmg/L14701,00050,000Total Suspended Solids2540Dmg/L19233019,000Phosphorus, Total365.1mg/lNA0.16316.52Classicals Pollutants - Solid (dry weight)Ammonia350.1mg/Kg14.11023P,EstNitrate Nitrite as N353.2mg/Kg10.359.965P,EstNitrogen, Total Kjeldahl351.2mg/Kg10120520900P,EstCyanide, Total4500 CN Emg/Kg10.110.540.42J,B,H,PPhosphorus, Total365.1mg/Kg108.350340P,EstClassicals Pollutants -Filtered AqueousAmmonia350.1mg/L10.1126.2P,Est

# A-33NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8.Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationNitrate Nitrite as N353.2mg/L100.19190P,EstNitrogen, Total Kjeldahl351.2mg/L20.38526P,EstCyanide, Total4500 CN Emg/L10.020.10.21B,H,P,EstPhosphorus, Total365.1mg/L10.0050.050.012J,B,PMetals - Calculated TotalAluminum200.7, 6010Bug/LNA44.9411497,000Antimony200.8, 6020ug/LNA1.199.474.95Arsenic200.8, 6020ug/LNA26291695Barium200.7, 6010Bug/LNA4.0941.16,410Beryllium200.7, 6010Bug/LNA1.4313.722.4Boron200.7, 6010Bug/LNA2715,720762,000Cadmium200.8, 6020ug/LNA1.457.46396Calcium200.7, 6010Bug/LNA4071,5501,140,000Chromium200.8, 6020ug/LNA39.41033,640Cobalt200.7, 6010Bug/LNA3.341.1459Copper200.8, 6020ug/LNA35.31221,210Iron200.7, 6010Bug/LNA121545766,000Lead200.8, 6020ug/LNA9.2872.7651Magnesium200.7, 6010Bug/LNA5789,5409,010,000Manganese200.7, 6010Bug/LNA14.147696,000

# A-34NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8.Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationMercury1631E, FGS-069ng/LNA6911,83044,000Molybdenum200.7, 6010Bug/LNA7.5884.1406Nickel200.8, 6020ug/LNA1.769.372,560Selenium200.8, 6020ug/LNA5.5422.62,920Silver200.8, 6020ug/LNA1.35.642.3Sodium200.7, 6010Bug/LNA1,58020,900404,000Thallium200.8, 6020ug/LNA0.565.6446.2Tin200.7, 6010Bug/LNA25.441144.1Titanium200.7, 6010Bug/LNA4.941.11,820Vanadium200.8, 6020ug/LNA19.72393,270Zinc200.8, 6020ug/LNA16852414,500Metals - DissolvedAluminum200.7ug/L29.42002,800BAntimony200.8ug/L20.7222.8Arsenic200.8ug/L21.245.5Barium200.7ug/L22.520150Beryllium200.7ug/L20.7124.6Boron200.7ug/L5001,70050,000730,000Cadmium200.8ug/L52.910420Calcium200.7ug/L269400640,000

# A-35NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8.Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationChromium200.8ug/L23.38ND (8)U,^Chromium (VI)218.6ug/L51.9610ND (10)UCobalt200.7ug/L21.120380Copper200.8ug/L20.96455Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5005,400100,0008,900,000Manganese200.7ug/L5001305,000110,000Mercury1631Eng/L5001242601,990Molybdenum200.7ug/L21.64090Nickel200.8ug/L2511502,000Selenium200.8ug/L51.610300Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000400,000Thallium200.8ug/L20.47226Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6202JVanadium200.8ug/L21.71016^Zinc200.8ug/L25511207,600Metals - Filtered Aqueous

# A-36NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8.Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationAluminum200.7ug/L29.420020,000BAntimony200.8ug/L20.7222.5Arsenic200.8ug/L21.245.9Barium200.7ug/L22.520100Beryllium200.7ug/L20.7123.6Boron200.7ug/L501705,000820,000BCadmium200.8ug/L21.24380Calcium200.7ug/L269400600,000BChromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120390Copper200.8ug/L20.96472Iron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0009,500,000Manganese200.7ug/L5013500100,000BMercury1631Eng/L5001242604,370Molybdenum200.7ug/L21.640110Nickel200.8ug/L20.8941,700Selenium200.8ug/L20.624470Silver200.8ug/L20.592ND (2)U

# A-37NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8.Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationSodium200.7ug/L218010,000420,000Thallium200.8ug/L20.47215Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.71014Zinc200.8ug/L1020506,700BMetals - Solid (dry weight)Aluminum6010Bmg/kg11.91225,000Antimony6020mg/kg20.0280.40.14JArsenic6020mg/kg251.31536Barium6010Bmg/kg10.0951.2330BBeryllium6010Bmg/kg10.0410.621Boron6010Bmg/kg56.162990BCadmium6020mg/kg20.0190.22.7Calcium6010Bmg/kg1186231,000BChromium6020mg/kg251.95190^Cobalt6010Bmg/kg10.121.25.5Copper6020mg/kg251.86.260Iron6010Bmg/kg14.81940,000Lead6020mg/kg250.453.734

# A-38NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.Est – Estimated value.H – Sample was prepared/analyzed beyond the specified holding time.J – Result measured above the MDL, but less than the quantitation limit.P – Sample was not preserved immediately following collection.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8.Influent to FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationMagnesium6010Bmg/kg14.62521,000Manganese6010Bmg/kg10.121.2280MercuryFGS-069ng/g4,00071.91984,990Molybdenum6010Bmg/kg10.322.516Nickel6020mg/kg20.050.353Selenium6020mg/kg20.260.99130Silver6020mg/kg20.040.20.12JSodium6010Bmg/kg1746201,200Thallium6020mg/kg20.0070.21.7BTin6010Bmg/kg11.1122.3JTitanium6010Bmg/kg10.181.295Vanadium6020mg/kg250.9512170Zinc6020mg/kg257.825440

# A-39ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-9.Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia350.1mg/L10.05514.8Nitrate Nitrite as N353.2mg/L100.19155Nitrogen, Total Kjeldahl351.2mg/L40.31421BBiochemical Oxygen Demand5210Bmg/L10.32.56.7Chemical Oxygen Demand410.4mg/L1041200570Chloride300.0mg/L5001301,5005,300Sulfate300.0mg/L5001202,5008,400Cyanide, Total4500 CN Emg/L10.020.10.21BTotal Dissolved Solids2540Cmg/L14710029,000Total Suspended Solids2540Dmg/L11.1417Phosphorus, Total365.1mg/L10.0050.050.096BTotal MetalsAluminum200.7ug/L29.4200180JAntimony200.8ug/L20.7226.8Arsenic200.8ug/L21.244.3Barium200.7ug/L22.520150Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L5001,70050,000300,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400890,000Chromium200.8ug/L23.3817Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)U

# A-40ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-9.Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationIron200.7ug/L232200110JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0005,600,000BManganese200.7ug/L20.5120170BMercury1631Eng/L204.8710.2101Molybdenum200.7ug/L21.640220Nickel200.8ug/L20.8943.4JSelenium200.8ug/L20.624560Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000370,000Thallium200.8ug/L20.47214Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.71016Zinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7227.8Arsenic200.8ug/L21.244.8Barium200.7ug/L22.520140Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000300,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400880,000

# A-41ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-9.Effluent from FGD Wastewater Treatment System, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationChromium200.8ug/L23.3814Chromium (VI)218.6ug/L10.3927.04Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.9641.4JIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0005,500,000Manganese200.7ug/L20.5120160BMercury1631Eng/L204.8710.249.7Molybdenum200.7ug/L21.640210Nickel200.8ug/L20.8942.2JSelenium200.8ug/L20.624560Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000350,000Thallium200.8ug/L20.47214Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L54.150ND (50)UVanadium200.8ug/L21.71016Zinc200.8ug/L24.110ND (10)U

# A-42ND – Not detected (number in parentheses is the quantitation limit).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.MI – Matrix interferences present.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).V – Serial dilution is not within control limits.Table A-10.Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia350.1mg/L10.05515.3Nitrate Nitrite as N353.2mg/L500.955290Nitrogen, Total Kjeldahl351.2mg/L40.31421BBiochemical Oxygen Demand5210Bmg/L10.32.58.4Chemical Oxygen Demand410.4mg/L1041200400Chloride300.0mg/L5001301,5007,500Sulfate300.0mg/L5001202,50013,000Cyanide, Total4500 CN Emg/L10.020.12.4BTotal Dissolved Solids2540Cmg/L14710032,000Total Suspended Solids2540Dmg/L11.1410Phosphorus, Total365.1mg/L10.0050.050.18BTotal MetalsAluminum200.7ug/L29.4200260Antimony200.8ug/L20.7226.9Arsenic200.8ug/L21.245.6Barium200.7ug/L22.520150Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10033010,000320,000B,F,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400840,0004

# A-43ND – Not detected (number in parentheses is the quantitation limit).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.MI – Matrix interferences present.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).V – Serial dilution is not within control limits.Table A-10.Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationChromium200.8ug/L23.3816Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200110JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L1001,10020,0005,500,000B,F,4Manganese200.7ug/L20.512088BMercury1631Eng/L204.8710.299.8Molybdenum200.7ug/L21.640200Nickel200.8ug/L20.8943.3JSelenium200.8ug/L20.624540V,4,MISilver200.8ug/L20.592ND (2)U,F,MinSodium200.7ug/L218010,000360,0004Thallium200.8ug/L20.47214Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.71017Zinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.420024J,BAntimony200.8ug/L20.7226.8

# A-44ND – Not detected (number in parentheses is the quantitation limit).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.MI – Matrix interferences present.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).V – Serial dilution is not within control limits.Table A-10.Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationArsenic200.8ug/L21.243.8JBarium200.7ug/L22.520150Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000330,000F,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400860,000Chromium200.8ug/L23.3814Chromium (VI)218.6ug/L10.3927.32Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0005,900,000F,4Manganese200.7ug/L20.512087BMercury1631Eng/L204.9710.463.1Molybdenum200.7ug/L21.640200Nickel200.8ug/L20.8942.2JSelenium200.8ug/L20.624520V,4,MISilver200.8ug/L20.592ND (2)U,F,MinSodium200.7ug/L218010,000360,000Thallium200.8ug/L20.47214

# A-45ND – Not detected (number in parentheses is the quantitation limit).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.MI – Matrix interferences present.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).V – Serial dilution is not within control limits.Table A-10.Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.5JVanadium200.8ug/L21.71016Zinc200.8ug/L24.110ND (10)U

# A-46ND – 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.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-11.Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05515.5Nitrate Nitrite as N353.2mg/L100.19158Nitrogen, Total Kjeldahl351.2mg/L40.31421BBiochemical Oxygen Demand5210Bmg/L10.32.56.9*,MinChemical Oxygen Demand410.4mg/L1041200560F,MinChloride300.0mg/L5001301,5007,300Sulfate300.0mg/L5001202,50013,000Cyanide, Total4500 CN Emg/L10.020.10.6B,CTotal Dissolved Solids2540Cmg/L14710028,000Total Suspended Solids2540Dmg/L11.148.4BPhosphorus, Total365.1mg/L10.0050.050.18B,F,MinTotal MetalsAluminum200.7ug/L29.4200330Antimony200.8ug/L20.7225.7Arsenic200.8ug/L21.244.9Barium200.7ug/L22.520160Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10033010,000320,000B,F,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400840,000Chromium200.8ug/L23.3814Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200260

# A-47ND – 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.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-11.Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L1001,10020,0005,500,000B,F,4Manganese200.7ug/L20.5120280BMercury1631Eng/L10024.451148Molybdenum200.7ug/L21.640180Nickel200.8ug/L20.8942.9JSelenium200.8ug/L103.1208004Silver200.8ug/L20.592ND (2)U,F,MinSodium200.7ug/L218010,000360,0004Thallium200.8ug/L20.47214Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6207.5JVanadium200.8ug/L21.71016Zinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7226.6Arsenic200.8ug/L21.244.8Barium200.7ug/L22.520150Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000320,000F,4Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400840,0004Chromium200.8ug/L23.3815^Chromium (VI)218.6ug/L10.3927.61

# A-48ND – 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.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-11.Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0005,600,000F,4Manganese200.7ug/L20.5120250BMercury1631Eng/L204.8710.271.3Molybdenum200.7ug/L21.640170Nickel200.8ug/L20.8942.3JSelenium200.8ug/L103.1206404Silver200.8ug/L20.592ND (2)U,F,MinSodium200.7ug/L218010,000350,000Thallium200.8ug/L20.47213Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.6JVanadium200.8ug/L21.71014^Zinc200.8ug/L24.110ND (10)U

# A-49ND – 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.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-12.Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05515.3Nitrate Nitrite as N353.2mg/L100.19161Nitrogen, Total Kjeldahl351.2mg/L40.31424BBiochemical Oxygen Demand5210Bmg/L10.32.54.6S,*,MinChemical Oxygen Demand410.4mg/L1041200510Chloride300.0mg/L5001301,5007,400Sulfate300.0mg/L5001202,50014,000Cyanide, Total4500 CN Emg/L10.020.11.5BTotal Dissolved Solids2540Cmg/L14710033,000Total Suspended Solids2540Dmg/L12.2822Phosphorus, Total365.1mg/L10.0050.050.075BTotal MetalsAluminum200.7ug/L29.420053JAntimony200.8ug/L20.7225.8Arsenic200.8ug/L21.244.4Barium200.7ug/L22.520150Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10033010,000330,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400800,000Chromium200.8ug/L23.3816Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200130JLead200.8ug/L20.732ND (2)U

# A-50ND – 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.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-12.Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMagnesium200.7ug/L1001,10020,0005,700,000BManganese200.7ug/L20.5120100BMercury1631Eng/L10024.150.5165Molybdenum200.7ug/L21.640150Nickel200.8ug/L20.8942.8JSelenium200.8ug/L20.624480Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000360,000Thallium200.8ug/L20.47212Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6206.5JVanadium200.8ug/L21.71018Zinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7225.8Arsenic200.8ug/L21.244.7Barium200.7ug/L22.520150Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000330,000Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400820,000Chromium200.8ug/L23.3815^Chromium (VI)218.6ug/L10.3926.71Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)U

# A-51ND – 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.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.S – Seed correction blank recovery low.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-12.Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0006,000,000Manganese200.7ug/L20.512093BMercury1631Eng/L204.8310.184.5Molybdenum200.7ug/L21.640150Nickel200.8ug/L20.8941.8JSelenium200.8ug/L20.624530Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000360,000Thallium200.8ug/L20.47212Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6204.5JVanadium200.8ug/L21.71015^Zinc200.8ug/L24.110ND (10)U

# A-52ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-13.Duplicate of Effluent from FGD Wastewater Treatment System, Day 2 AnalyticalResults, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia350.1mg/L10.05515.5Nitrate Nitrite as N353.2mg/L500.955300Nitrogen, Total Kjeldahl351.2mg/L40.31423BBiochemical Oxygen Demand5210Bmg/L10.5959.6Chemical Oxygen Demand410.4mg/L1041200560Chloride300.0mg/L5001301,5007,500Sulfate300.0mg/L5001202,50013,000Cyanide, Total4500 CN Emg/L10.020.10.045J,BTotal Dissolved Solids2540Cmg/L14710027,000Total Suspended Solids2540Dmg/L11.147.6Phosphorus, Total365.1mg/L10.0050.050.065BTotal MetalsAluminum200.7ug/L29.420028JAntimony200.8ug/L20.7227Arsenic200.8ug/L21.244.1Barium200.7ug/L22.520160Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L10033010,000320,000BCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400860,000Chromium200.8ug/L23.3817Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220091JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L1001,10020,0005,600,000BManganese200.7ug/L20.512090B

# A-53ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-13.Duplicate of Effluent from FGD Wastewater Treatment System, Day 2 AnalyticalResults, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L204.8710.2110Molybdenum200.7ug/L21.640200Nickel200.8ug/L20.8942.7JSelenium200.8ug/L20.624530Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000370,000Thallium200.8ug/L20.47214Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.6205.5JVanadium200.8ug/L21.71018Zinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.7226.8Arsenic200.8ug/L21.244Barium200.7ug/L22.520140Beryllium200.7ug/L20.712ND (2)UBoron200.7ug/L501705,000320,000Cadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400810,000Chromium200.8ug/L23.3814Chromium (VI)218.6ug/L10.3927.35Cobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.9641.4JIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L5054010,0005,600,000Manganese200.7ug/L20.512081B

# A-54ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-13.Duplicate of Effluent from FGD Wastewater Treatment System, Day 2 AnalyticalResults, Miami FortAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMercury1631Eng/L204.8710.259.9Molybdenum200.7ug/L21.640190Nickel200.8ug/L20.8942.5JSelenium200.8ug/L51.610470Silver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000340,000Thallium200.8ug/L20.47214Tin200.7ug/L24.8200ND (200)UTitanium200.7ug/L108.2100ND (100)UVanadium200.8ug/L21.71018Zinc200.8ug/L24.110ND (10)U

# a 

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

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



# A-55 Table A-14. Bottle Blank and Equipment Blank Analytical Data, Miami Fort

Analyte Method Process Units Concentration

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

# a 

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

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



# A-56 Table A-14. Bottle Blank and Equipment Blank Analytical Data, Miami Fort

Analyte Method Process Units Concentration

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Aluminum a 

# EPA 1638 Dissolved ug/L 4.71

Antimony EPA 1638 Dissolved ug/L ND (0.50)

Arsenic EPA 1638 Dissolved ug/L ND (0.50)

Barium EPA 1638 Dissolved ug/L ND (0.10)

Beryllium EPA 1638 Dissolved ug/L ND (0.10)

Cadmium EPA 1638 Dissolved ug/L ND (0.10)

Chromium EPA 1638 Dissolved ug/L ND (1.0)

Cobalt EPA 1638 Dissolved ug/L ND (0.10)

Copper EPA 1638 Dissolved ug/L ND (0.30)

Lead EPA 1638 Dissolved ug/L ND (0.050)

Manganese EPA 1638 Dissolved ug/L ND (0.50)

Molybdenum EPA 1638 Dissolved ug/L ND (0.50)

Nickel EPA 1638 Dissolved ug/L ND (0.50)

Selenium EPA 1638 Dissolved ug/L ND (2.0)

Silver EPA 1638 Dissolved ug/L ND (0.10)

Thallium EPA 1638 Dissolved ug/L ND (0.050)

Vanadium EPA 1638 Dissolved ug/L ND (1.0)

Zinc EPA 1638 Dissolved ug/L ND (0.50)

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

Aluminum EPA 1638 Dissolved ug/L ND (2.0)

# a 

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

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



# A-57 Table A-14. Bottle Blank and Equipment Blank Analytical Data, Miami Fort

Analyte Method Process Units Concentration

Antimony EPA 1638 Dissolved ug/L ND (0.50)

Arsenic EPA 1638 Dissolved ug/L ND (0.50)

Barium EPA 1638 Dissolved ug/L ND (0.10)

Beryllium EPA 1638 Dissolved ug/L ND (0.10)

Cadmium EPA 1638 Dissolved ug/L ND (0.10)

Chromium EPA 1638 Dissolved ug/L ND (1.0)

Cobalt EPA 1638 Dissolved ug/L ND (0.10)

Copper EPA 1638 Dissolved ug/L ND (0.30)

Lead EPA 1638 Dissolved ug/L ND (0.050)

Manganese EPA 1638 Dissolved ug/L ND (0.50)

Molybdenum EPA 1638 Dissolved ug/L ND (0.50)

Nickel EPA 1638 Dissolved ug/L ND (0.50)

Selenium EPA 1638 Dissolved ug/L ND (2.0)

Silver EPA 1638 Dissolved ug/L ND (0.10)

Thallium EPA 1638 Dissolved ug/L ND (0.050)

Vanadium EPA 1638 Dissolved ug/L ND (1.0)

Zinc EPA 1638 Dissolved ug/L ND (0.50)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

# a 

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

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



# A-58 Table A-14. Bottle Blank and Equipment Blank Analytical Data, Miami Fort

Analyte Method Process Units Concentration

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

# a 

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

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



# A-59 Table A-14. Bottle Blank and Equipment Blank Analytical Data, Miami Fort

Analyte Method Process Units Concentration

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

# A-60ND – Not detected (number in parentheses is the quantitation limit).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-15.Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsAluminum200.7ug/L29.420040JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.7200130JCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L26940086JChromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L23220045JLead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400310J,BManganese200.7ug/L20.51204.1J,BMercury1631Eng/L10.240.515.4Molybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000ND (10,000)UThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)U

# A-61ND – Not detected (number in parentheses is the quantitation limit).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-15.Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, Miami FortAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.720035JCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400130JChromium200.8ug/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/L221400210J,BManganese200.7ug/L20.512011J,BMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000190JThallium200.8ug/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-62ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.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.Effluent from FGD Wastewater Treatment System Field Blank, Day 1 AnalyticalResults, Miami FortAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsAluminum200.7ug/L29.420014JAntimony200.8ug/L20.722ND (2)UArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.7200110JCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400100JChromium200.8ug/L23.38ND (8)UCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400410BManganese200.7ug/L20.51204.3J,BMercury1631Eng/L10.240.5ND (0.5)UMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.6240.76JSilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000270JThallium200.8ug/L20.472ND (2)UTin200.7ug/L24.8200ND (200)UTitanium200.7ug/L21.620ND (20)UVanadium200.8ug/L21.710ND (10)UZinc200.8ug/L24.110ND (10)UDissolved MetalsAluminum200.7ug/L29.4200ND (200)UAntimony200.8ug/L20.722ND (2)U

# A-63ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.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.Effluent from FGD Wastewater Treatment System Field Blank, Day 1 AnalyticalResults, Miami FortAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationArsenic200.8ug/L21.24ND (4)UBarium200.7ug/L22.520ND (20)UBeryllium200.7ug/L20.712ND (2)UBoron200.7ug/L26.7200150JCadmium200.8ug/L21.24ND (4)UCalcium200.7ug/L269400ND (400)UChromium200.8ug/L23.38ND (8)UChromium (VI)218.6ug/L10.392ND (2)U,EstCobalt200.7ug/L21.120ND (20)UCopper200.8ug/L20.964ND (4)UIron200.7ug/L232200ND (200)ULead200.8ug/L20.732ND (2)UMagnesium200.7ug/L221400160J,BManganese200.7ug/L20.51201.4J,BMolybdenum200.7ug/L21.640ND (40)UNickel200.8ug/L20.894ND (4)USelenium200.8ug/L20.624ND (4)USilver200.8ug/L20.592ND (2)USodium200.7ug/L218010,000230JThallium200.8ug/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-64ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-17.Effluent from FGD Wastewater Treatment System Field Blank, Day 2 Analytical Results, Miami FortAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-65ND – 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.Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Miami FortAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsMercury1631Eng/L10.240.5ND (0.5)U

# A-66ND – 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.Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Miami FortAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific 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 Narrat ive for Total and Dissolved Mercury

– Episode 65 60

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 Spectrometry (CVAFS) analysis.

Table 1 summarizes the 27 s amples ( exc luding laboratory filter blanks) FG S extracted

and analyzed for total and dissolved mercury

.

Table 1. 

# EPA Episode 6560 Total & Dissolved Mercury

– Sample Identification

EPA

Sample # Lab Sample

I D # Sample

Matrix Sample Description Sampling

Date

71741 1007078

- 01 Aqueous FGD Influent Day 1 7/12/2010

71741 1007078

- 08 Solid FGD Influent, Day 1 (Solids) 7/12/2010

71741 1007078

- 06 Aqueous Dissolved FGD Influent, Day 1 7/12/2010

71742 1007095

- 01 Aqu eous FGD Influent, Day 2 7/13/2010

71742 1007095

- 11 Solid FGD Influent, Day 2 (Solids) 7/13/2010

71742 1007095

- 02 Aqueous Dissolved FGD Influent, Day 2 7/13/2010

71743 1007105

- 04 Aqueous FGD Influent, Day 3 7/14/2010

71743 1007105

- 11 Solid FGD Influent , Day 3 (Solids) 7/14/2010

71743 1007105

- 05 Aqueous Dissolved FGD Influent, Day 3 7/14/2010

71744 1007121

- 01 Aqueous FGD Influent, Day 4 7/15/2010

71744 1007121

- 09 Solid FGD Influent, Day 4 (Solids) 7/15/2010

71744 1007121

- 02 Aqueous Dissolved FGD Infl uent, Day 4 7/15/2010

71745 1007095

- 03 Aqueous FGD Effluent, Day 1 7/13/2010

71745 1007095

- 04 Aqueous Dissolved FGD Effluent, Day 1 7/13/2010

71746 1007105

- 06 Aqueous FGD Effluent, Day 2 7/14/2010

71746 1007105

- 07 Aqueous Dissolved FGD Effluent, Day 2 7/14/2010

71747 1007121

- 03 Aqueous FGD Effluent, Day 3 7/15/2010

71747 1007121

- 04 Aqueous Dissolved FGD Effluent, Day 3 7/15/2010

71748 1007131

- 02 Aqueous FGD Effluent, Day 4 7/16/2010

# 2 Table 1. 

# EPA Episode 6560 Total & Dissolved Mercury

– Sample Identification

EPA

Sample # Lab Sample

I D # Sample

Matrix Sample Description Sampling

Date

71748 1007131

- 03 Aqueous Dissolved FGD Effluent, Day 4 7/16/2010

7 1749 1007105

- 08 Aqueous FGD Effluent Duplicate, Day 2 7/14/2010

71749 1007105

- 09 Aqueous Dissolved FGD Effluent Duplicate, Day 2 7/14/2010

71750 1007078

- 02 Aqueous FGD Influent Field Blank, Day 1 7/12/2010

71751 1007078

- 04 Aqueous FGD Effluent Field Bla nk Day 1 7/12/2010

71752 1007095

- 05 Aqueous FGD Effluent Field Blank, Day 2 7/13/2010

71753 1007105

- 03 Aqueous FGD Effluent Field Blank, Day 3 7/14/2010

71754 1007121

- 05 Aqueous FGD Effluent Field Blank, Day 4 7/15/2010



# SUMMARY

The samples were prepa red according to EPA Method 1631E to be analyzed by CVAFS

. There were no issues requiring qualifiers with the mercury data in this episode. ERG

noted the following during the data review:

• An o ngoing p recision and r ecovery (OPR) sample was not analyzed at the

beginning and end of the solid fraction sample analysis.

• A m atrix s pike (MS) and m atrix s pike d uplicate (MSD) were not performed on a

solid sample fraction f rom this episode.

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 calibration for

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

coefficient ≥0.995

. All method specified criteria were met.

INITIAL AND C ONTINUING C ALIBRATION V ERIFICATION S

All initial and c ontinuing c alib ration v erifications ( ICVs, CCVs ) met method

- specified

criteria

.

BLANK S

All preparation blanks or laboratory reagent blanks (LRBs) and the continuing calibration

blanks (CCBs) met method

- specified criteria.

# 3 DUPLICATES

Field duplicates

, s ample 71749, were collected on s ample 71746

. The 71746/71749 total

mercury relative percent difference ( RPD ) was 9.72 % and the dissolved mercury RPD

was 5.20 %. The method

- suggested RPD criterion between field duplicates is 20%.

L aboratory duplicates were performed on samples 71742

, 71747

, and 71748 . All RPDs

were less than 20% (the method

- suggested RPD criterion between field duplicates; the

method does not require the analysis of laboratory duplicates)

.

A laboratory duplicate was not performed on the solid sample fraction from this episode;

however, FGS analyzed another client’s sample as the duplicate for this batch, which

passed the method

- specif ied criteria.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

MS and MSD s were performed on samples 71742, 7174 3

, 71747, and 71748 for the total

mercury analyses

. MS and MSDs were performed on samples 71742 and 71747 for t he

dissolved mercury analys e s. All aqueous MS/MSD recoveries were within method

specifications of 71

- 125%. All RPDs met method

- specified criteria.

A n M S / MSD w as not performed on a solid sample fraction f rom this episode. FGS

performed an MS/MSD on another client’s sample that was not part of this episode,

which met method

- specified criteria.

D ETECTION LIMITS

The laboratory MDL in the synthetic matrix was 0.239 ng/L. Results below this MDL

were reported as not detected (ND).

# 1



# MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

Deb Bartram, ERG

TJ Finseth, ERG

From: Randy Mercurio, ERG

Date: 9/1/2011

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

Episode 6560

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

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

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 6560 Total and Dissolved Metals – Sample Identification



# EPA

Sample # 

# EPA Sample Description Lab Sample

ID # 

# Sample

Matrix 

# Sampling

Date 

# Receipt

Date

71741 FGD Influent, Day 1 280

- 5257

- 1 Aqueous 7/12/2010 7/13/2010

71741 FGD Influent, Day 1

- Filtrate 280

- 5257

- 3 Aqueous 7/12/2010 7/13/2010

71741 FGD Influent, Day 1

- Solids 280

- 5257

- 4 Solid 7/12/2010 7/13/2010

71742 FGD Influent, Day 2 280

- 5302

- 1 Aqueous 7/13/2010 7/14/2010

71742 FGD Influent, Day 2

- Filtrate 280

- 5302

- 4 Aqueous 7/13/2010 7/14/2010

71742 FGD Influent, Day 2

- Solids 280

- 5302

- 5 Solid 7/13/2010 7/14/2010

71743 FGD Influent, Day 3 280

- 5343

- 1 Aqueous 7/14/2010 7/15/2010

71743 FGD Influent, Day 3

- Filtrate 280

- 5343

- 4 Aqueous 7/14/2010 7/15/2010

71743 FGD Influent, Day 3

- Solids 280

- 5343

- 5 Solid 7/14/2010 7/15/2010

71744 FGD Influent, Day 4 280

- 5398

- 1 Aqueous 7/15/2010 7/16/2010

71744 FGD Influent, Day 4

- Filtrate 280

- 5398

- 3 Aqueous 7/15/2010 7/16/2010

71744 FGD Influent, Day 4

- Solids 280

- 5398

- 4 Solid 7/15/2010 7/16/2010

71745 FGD Effluent, Day 2 280

- 5302

- 2 Aqueous 7/13/2010 7/14/2010

71746 FGD Effluent, Day 2 280

- 5343

- 2 Aqueous 7/14/2010 7/15/2010

71747 FGD Effluent, Day 3 280

- 5398

- 2 Aqueous 7/15/2010 7/16/2010

71748 FGD Effluent, Day 4 280

- 5438

- 1 Aqueous 7/16/2010 7/17/2010

71749 FGD Effluent Duplicate 280

- 5343

- 3 Aqueous 7/14/2010 7/15/2010

71750 FGD Influent Field Blank,

Day 1 

# 280

- 5257

- 2 Aqueous 7/12/2010 7/13/2010

# 2

Table 1. 

# EPA Episode 6560 Total and Dissolved Metals – Sample Identification



# EPA

Sample # 

# EPA Sample Description Lab Sample

ID # 

# Sample

Matrix 

# Sampling

Date 

# Receipt

Date

71751 FGD Effluent Field Blank,

Day 1 

# 280

- 5302

- 3 Aqueous 7/13/2010 7/14/2010



# 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.

Any significant findings are summarized below. Specific results that required additional

qualifiers appear in Table 2.

• The dissolved selenium result of 530 μ g/L for sample 71748 FGD Effluent Day 4

(280-5438-1) is greater than the total Selenium value of 480 μ g/L reported for the

same sample.

• The serial dilution analysis for total selenium for sample 71741 did not meet

TestAmerica’s requirement of ±10%.

• The matrix spike (MS) and matrix spike duplicate (MSD) analyses performed for

this sampling episode had several silver and one antimony result failed the 70-

130% control limits with poor recoveries.

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

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

performed by TestAmerica all had recoveries within the method criteria.

# 3

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit (RL); however, some elements

were found above the method detection limit (MDL) and were flagged with the “J”

qualifier indicating the concentrations were an estimated value. No additional data

qualifiers were required for method blanks.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank

(CCB)) were less than the RL; however, some elements were above the MDL and were

flagged with the “J” qualifier.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s SOP control limits of 50–150%.

LABORATORY CONTROL SAMPLES (LCS)

All LCS samples passed the method control 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 batches 280-24259 and 280-27200. 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

Serial dilutions were performed for each batch of total and dissolved samples. The serial

dilution on sample 71741 (280-5257-3) passed TestAmerica’s requirement of ±10% for

all analytes except total selenium at 14%. The total selenium result is flagged with a “V”

qualifier.

FIELD DUPLICATES

The RPD of the field duplicates 71746/71749 were less than 20% for all values above the

reporting limit, with the exception of total arsenic, which had an RPD of 30.9%. Even

# 4

though the RPD was greater than 20%, the total arsenic result was not qualified because

there are no specific control limits for field duplicates specified in EPA Method 200.8.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

MS and MSDs were performed on samples 71741, 71743, 71746, and 71747. Many

spike recoveries were outside the method contrl limits of 70–130% when sample

concentrations exceeded the spike concentration by a factor of four or more, which have

been flagged “4,” indicating concentrations in the parent samples were greater than four

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

control limits. The poor recoveries for silver are probably due to high sulfates in the

samples that could form insoluble silver sulfide and/or silver sulfate. Otherwise, the

MS/MSD spike recoveries were within the control limits of 70-130%, with the exception

of the following:

• The MS/MSD performed on sample 71741 FGD Influent, Day 1 (280-5257-3)

failed the 70–130% control limits for total silver.

• The MS/MSD performed on solid sample 71743 FGD Influent, Day 3 (280-5343-

5) failed the 70–130% control limits for antimony and silver.

• The MS/MSD performed on sample 71746 FGD Effluent, Day 2 (280-5343-2)

failed the 70–130% control limits for total and dissolved silver. The RPD for the

total silver MS/MSD also failed at 58%.

• The MS/MSD performed on sample 71747 FGD Effluent, Day 3 (280-5398-2)

failed the 70–130% control limits for total and dissolved silver. Additionally, the

RPD between the total and dissolved silver MS/MSD for this sample failed the

method control limits.

The RPD for all MS/MSD passed the method-specified criteria of 20 percent.

POST DIGESITON SPIKES

The post digestion spike (PDS) performed on sample 71747 FGD Effluent, Day 3 (280-

5398-2) failed TestAmerica’s control limits of 85–115% recovery for total selenium and

total silver, with recoveries of 69% and 80%, respectively. The selenium result was

flagged by the laboratory; however, the silver result was not flagged by the laboratory

and therefore, has been included in Table 2 below.

DETECTION LIMITS

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

of reagent water.

# 5 Table 2. Data Review Summary

Sample Analyte Qualifier/Action Reason Level Detected

71741 Selenium

(filtrate,

total) Matrix

Interference SRD Failed ±10%

Difference 320 μ g/L

71741 Silver (total) Minimum value MS/MSD Failed

70–130% recovery ND

71743 Antimony

(solid) Minimum value MS/MSD Failed

70–130% recovery 160 μ g/kg

71743 Silver

(solid) Minimum value MS/MSD Failed

70–130% recovery 140 μ g/kg

71746 Silver (total) Minimum value MS/MSD Failed

70–130% recovery ND

71746 Silver

(dissolved) Minimum value MS/MSD Failed

70–130% recovery ND

71747 Silver (total) Minimum value MS/MSD Failed

70–130% recovery ND

71747 Silver

(dissolved) Minimum value MS/MSD Failed

70–130% recovery ND

71747 Silver (total) Minimum value PDS Failed 85–

115% recovery 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

Date: 9 / 1 /2011

Subject: TestAmerica Data Review Narrative for Total and Dissolved Metals by 200.7

– Episode 6560

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 and t itanium ) for S a mple Episode 6560

. 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 6560 Total and Dissolved Metals

– Sample Identification

EPA

Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71741 FGD Influent, Day 1 280

- 5257

- 1 Aqueous 7/12/2010 7/13/2010

71741 FGD Influent, Day 1

- Filtrate 280

- 5257

- 3 Aqueous 7/12/2010 7/13/2010

71741 FGD Influent, Day 1

- Solids 280

- 5257

- 4 Solid 7/12/2010 7/13/2010

71742 FGD Influent, Day 2 280

- 5302

- 1 Aqueous 7/13/2010 7/14/2010

71742 FGD Influent, Day 2

- Filtrate 280

- 5302

- 4 Aqueous 7/13/2010 7/14/2010

71742 FGD Influent, Day 2

- Solids 280

- 5302

- 5 Solid 7/13/2010 7/14/2010

71743 FGD Influent, Day 3 280

- 5343

- 1 Aqueous 7/14/2010 7/15/2010

71743 FGD Influent, Day 3

- Filtrate 280

- 5343

- 4 Aqueous 7/14/2010 7/15/2010

71743 FGD Influent, Day 3

- Solids 280

- 5343

- 5 Solid 7/14/2010 7/15/2010

71744 FGD Influent, Day 4 280

- 5398

- 1 Aqueous 7/15/2010 7/16/2010

71744 FGD Influent, Day 4

- Filtrate 280

- 5398

- 3 Aqueous 7/15/2010 7/16/2010

71744 FGD Influent, Day 4

- Solids 280

- 5398

- 4 Solid 7/15/2010 7/16/2010

71745 FGD Effluent, Day 2 280

- 5302

- 2 Aqueous 7/13/2010 7/14/2010

71746 FGD Effluent, Day 2 280

- 5343

- 2 Aqueous 7/14/2010 7/15/2010

71747 FGD Effluent, Day 3 280

- 5398

- 2 Aqueous 7/15/2010 7/16/2010

71748 FGD Effluent, Day 4 280

- 5438

- 1 Aqueous 7/16/2010 7/17/2010

71749 FGD Effluent Duplicate 280

- 5343

- 3 Aqueous 7/14/2010 7/15/2010

# 2 Table 1. 

# EPA Episode 6560 Total and Dissolved Metals

– Sample Identification

EPA

Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71750 FGD Influent Field Blank, Day 1 280

- 5257

- 2 Aqueous 7/12/2010 7/13/2010

71751 FGD Effluent Field Blank, Day 1 280

- 5302

- 3 Aqueous 7/13/2010 7/14/2010



# SUMMARY

The sample s were prepared for total and dissolved metals analysis according to

TestAmerica ’s SOP for ICP Analysis of Trace Metals by Method 200.7

. Due to the total

suspended solids being in excess of 1% in the influent samples a phase separation was

performed creati ng four solid samples

. Any significant findings are summarized below.

Specific sample or QC results that required additional data qualifiers appear in Table 2.

• The relative percent difference (RPD) for total aluminum for the field duplicate

samples 71746 and 71749 161%; however, the duplicate sample was less than the

reporting limit; therefore, the RPD could not be accurately calculated.

• The serial dilution analysis for cobalt for sample 71741 did not meet

TestAmerica’s requirement of ± 10% difference

.

• T he MS and MSD recoveries for t itanium in the solid phase of sample 71743

failed the 70

- 130% control limits

.

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 on the

ISTD recoveries in the ±30% criterion of the calibration blank as per Section 9.11 of the

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

I NITIAL CAL IBRATION

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

All i nitial c alibration v erifications ( ICV ) and c ontinuing v alibration v erifications (CCV)

had recoveries within the method criteria.

METHOD/INSTRUMENT BLANK S

# 3 All the Method B lanks were less than the r eporting l imit (RL) ; however, some elements

had levels above the method detect ion limit ( MDL ) and were flagged with the “J”

qualifier.

All i nstrument b lanks ( ICB and CCB) were less than the RL ; however, some elements

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

.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

A ll CRI samples passed TestAmerica’s SOP control limits of 50

– 150%.

LABORATORY CONTROL SAMPLES (LCS)

All LCSs passed the method control limits of 85

- 115%.

SYNTHETIC FGD 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. Sample

71741 failed the met h od require d ±10% difference for cobalt (11%), whi ch was flagged

“V” as failing the QC criteria. Otherwise, all serial dilution percent differences were less

than 10%.

FIELD DUPLICATES

T he RPD of the field duplicates 71746/71749 were less than 20% for all values equal to

or greater than the RL, except f or total aluminum, which had an RPD of 161%. The

parent sample value (260 ug/L) was greater than the RL, but the duplicate value (28 ug/L)

was less than the RL; therefore, the RPD could not be accurately calculated.

MATRIX SPIKE AND MATIX SPIKE DUPLICATE S

M S and MSD were performed on sample s 71741 (total)

, 71743 (total solid)

, 71746 (total

and dissolved) and 71747 (total and dissolved)

. Many elements with high concentrations

frequently failed the spike recovery but were flagged with a “4” qualifier indicating that

the concentration in the parent sample was greater than four times the spike and could not

be reliably calculated

. Otherwise, the MS/MSD spike recoveries were within the control

limits of 70

– 130% with the exception of the following:

• The MS and MSD recoveries for t itanium in the solid phase of sample 71743

were 131% and 137%

, respectively.

# 4 The RPDs between the MS and MSD samples were always within ± 20% except for t he

following:

• The RPD between the MS and MSD for boron for sample 71746 was 165% for

both total and dissolved analyses.

• The RPD between the MS and MSD for magnesium for sample 71746 was 165%

for both total and dissolved analyses.

• The RPD between the MS and MSD for total boron and total magnesium for

sample 71747 was 162%.

• The RPD between the MS and MSD for dissolved boron and dissolved

magnesium for sample 71747 was 16 3 %.

POST DIGESTION SPIKE

The post digestion spike (PDS) performed on sample 71741 FGD Influent, Day 1 passed

TestAmerica’s control limits of 85

- 115% recovery for all total and dissolved analytes

except for t otal a luminum and total t itanium . The post digestion spike performed on

sample 71746 FGD Effluent, Day 2 passed TestAmerica’s control limits of 85

- 115%

recovery for all total and dissolved analytes except for total aluminum, total titanium, and

dissolved titanium.

DETECTION LIMITS

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

of reagent water.

Table 2. Data Review Summary

Sample Analyte Qualifier/Action Reason Level Detected

71743 Titanium

(solid) Maximum value MS/MSD

recovery > 130% 140 mg/kg

# 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

Su bject: FGS Data R eview Narrative for Dissolved Hex avalent Chromium

– Episode

65 60

Frontier Global Sciences (FGS) generated analytical data for dissolved hexavalent

chromium for Sample Episode 6560

. FGS analyzed t he samples according to a m odified

EPA Method 2 18. 6 for dissolved hexavalent chromium by Liq uid 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 6560 Dissolved Hexavalent Chromium

– Sample Identification

EPA

Sample

# Sample

Matrix Sample Description Sampling

Date Analysis Date

71 74 1 Aqueous FGD Influent Day 1 7/12 /10 8/9 /10

71742 Aqueous FGD Influent Day 2 7/14/10 8/9/10

71743 Aqueous FGD Influent Day 3 7/14/10 8/9/10

71744 Aqueous FGD Influent Day 4 7 /15/10 8/9/10

71745 Aqueous FGD Effluent Day 1 7/14/10 8/9/10

71746 Aqueous FGD Effluent Day 2 7/14/10 8/9/10

71747 Aqueous FGD Effluent Day 3 7/15/10 8/9/10

71748 Aqueous FGD Effluent Day 4 7/16/10 8/9/10

71749 Aqueous FGD Effluent Day 2 Duplicate 7/ 14/10 8/9/10

71750 Aqueous FGD Influent F ield B lank Day 1 7/12/10 8/9/10

71751 Aqueous FGD Effluent F ield B lank Day 1 7/14/10 8/9/10



# SUMMARY

The samples were prepared for dissolved hexavalent chromium analysis according to

FGS

- 129.01 Standard Operatin g Procedure ( SOP ) , a modified EPA Method 218. 6

.

# 2 Several s amples ( 71741, 71742, 71743, and 71744 ) were diluted prior to analysis due to

the presence of high levels of non

- target chloride interferences

.

SAMPLE REC E IPT, HANDLING, AND STORAGE ISSUES

The pH for sample 71751 (FGD Effluent Field Blank) was 9.98 S.U. upon receipt at the

laboratory, which is outside the appropriate range of 9 .0

- 9.5 S.U.; therefore, the

laboratory adjusted the pH. The final sample pH was 9.68 S.U. Because this sample was

not at the method

- specified pH, this sample was qualified as an estimated value.

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 EC OVERY

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 bl ank 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 ERIFICAT ION

All CCVs met method

- specified criteria

, ± 10% of true value with recoveries ranging

from 98.5 to 109%.

BLANK

All of the prep aration blanks /laboratory reagent blanks (LRBs) and the continuing

calibration blanks (CCBs) met method

- specified requirement s

.

OTHER CHECKS

The l aboratory c ontrol 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%

. The laboratory SOP indicated that a second source

quali ty control sample (QCS) must be analyzed by the laboratory at least once a quarter.

# 3 The data for the QCS was not included in the data package for review . However, the

ICV was a second source standard.

D ETECTION LIMITS

The laboratory method detection li mit (MDL) in the synthetic matrix was 0.392 ug/L.

Results below this MDL were reported as not detected.

DUPLICATES

There were no laboratory duplicates performed in this episode other than a duplicate of

the LCSD and a duplicate of the matrix spike ( MS )

.

One field duplicate w as collected and analyzed. Sample 71 749, with a result of 7.35

μg/L, was a duplicate of sample 71 74 6 , which had 7.32 μg/L hexavalent chromium

. These duplicate s ample s had an RPD of 0.41%, which meets the method

- suggested

criteria

.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The M S and matrix spike duplicate ( MSD ) w as performed using a secondary source

spike on sample 71 74 7

. The MS and MSD r ecoveries were 101% and 99.5%,

respectively, with an RPD of 1.07 %

. A second set of MS and MSD s were prepared on

the diluted sample and had recoveries of 95.3% and 96.0%, respectively, with an RPD of

0.64%.

Table 2. Data Review Summary Table



# Sample Analyte Qualifier Reason Level Detected

71 751 Chromium (VI) Estimated value pH outside of

method

- specified

range. ND

ND

- Not d etected

.

# 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 / 20 11

Subject: TestAmerica Data Review Narrative for Clas sicals Analyses

– Episode 65 60

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry

analyses for Sample Episode 65 60

. All samples were tested for the following analytes:

• Ammonia by EPA method 350.1,

• Biochemical Oxygen Dem and

– 5 day (BOD 5 

# ) by SM 5210B,

• Chloride and S ulfate by EPA method 300.0,

• Chemical Oxygen Demand (COD) by EPA method 410.4,

• Cyanide (total) by SM 4500 CN

- 

# E,

• Nitrate/ Nitrite by EPA method 353.2

• Phosphorus (total) by EPA method 365.1,

• Total D issolved S olids (TDS) by SM 2540C,

• Total K jeldakl N itrogen (TKN) by EPA method 351 .2

, and

• Total S uspended S olids (TSS) by SM 2540D

.

The TSS concentration of the influent samples was greater than one percent, so as

requested

, the laboratory separated the solid and liquid portions of the samples and

a nalyzed both portion s separately for the following analytes :

• Ammonia,

• Cyanide,

• Nitrate/Nitrite,

• Phosphorus, and

• TKN.

TestAmerica was also required to analyze chloride and sulfate using this phase separation

techni que

, but they mistakenly only analyze d the solids fraction and not the filtrate

fraction. Th erefore

, TestAmerica instead analyzed and reported the results for the raw

sample without phase separation for chloride and sulfate.

Table 1 summarizes the nine fi eld sampl es analyzed by TestAmerica , including how the

laboratory split and analyzed the influent samples

.

# 2 Table 1. EPA Episode 6560 Classical Analytes

– Sample Identification

EPA

Sample # Sample

Description Sampling

Date Sample

Matrix Portion of

Sample Analytes

71741 FGD Influent,

Day 1 7/12/10 Water Entire

Fraction BOD 5 

# , COD, Chloride,

Sulfate, TDS, and TSS

Water Filtrate Ammonia, Cyanide

, Nitrate/Nitrite,

Phosphorus, and TKN

Solids Solids Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Phosphor us, Sulfate, and

TKN

71742 FGD Influent,

Day 2 7/13/10 Water Entire

Fraction BOD 5 

# , COD, Chloride,

Sulfate, TDS, and TSS

Water Filtrate Ammonia, Cyanide,

Nitrate/Nitrite,

Phosphorus, and TKN

Solids Solids Ammonia, Chloride,

Cyanide, Nitrate/Nit rite,

Phosphorus, Sulfate, and

TKN

71743 FGD Influent,

Day 3 7/14/10 Water Entire

Fraction BOD 5 

# , COD, Chloride,

Sulfate, TDS, and TSS

Water Filtrate Ammonia, Cyanide,

Nitrate/Nitrite,

Phosphorus, and TKN

Solids Solids Ammonia, Chloride,

Cyanide, N itrate/Nitrite,

Phosphorus, Sulfate, and

TKN

71744 FGD Influent,

Day 4 7/15/10 Water Entire

Fraction BOD 5 

# , COD, Chloride,

Sulfate, TDS, and TSS

Water Filtrate Ammonia, Cyanide,

Nitrate/Nitrite,

Phosphorus, and TKN

Solids Solids Ammonia, Chloride,

Cyanide, Nitrate/Nitrite,

Phosphorus, Sulfate, and

TKN

71745 FGD Effluent,

Day 1 7/13/10 Water Entire

Fraction All analytes

71746 FGD Effluent,

Day 2 7/14/10 Water Entire

Fraction All analytes

71747 FGD Effluent,

Day 3 7/15/10 Water Entire

Fraction All analytes

# 3 Table 1. EPA Episode 6560 Classical Analytes

– Sample Identification

EPA

Sample # Sample

Description Sampling

Date Sample

Matrix Portion of

Sample Analytes

71748 FGD Effluent,

Day 4 7/16/10 Water Entire

Fraction All analytes

71749 FGD Effluent

- Duplicate 7/14/10 Water Entire

Fraction All analytes

SUMMARY

All samples were analyzed within the holding time specified in 40 CFR 136 Table II

unless o therwise noted below

.

TestAmerica could not perform the phase separation of the preserved Group II influent

samples; t herefore, t he laboratory use d some of the extra volume from the unpreserved

metals sample volume for the analyses . After phase separation , TestAmerica preserved

the samples accordingly. Because of this process, the ammonia, nitrate/nitrite, TKN,

phosphorus, and cyanide influent samples used for the analyses were not preserved

immediately following sample collection as required by the method

.

One field duplicate sample was collected and analyzed for each analyte. Th e 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, all c alibration 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 spec ified by the method.

As described below, the analyte of interest was detected above the method detection limit

(MDL) in some laboratory reagent blanks (LRB). However, the analyte of interest was

never detected above the reporting limit (RL) in the LRBs

. If required by the method, all

laboratory fortified blanks (LFB) met the criteria specified in the method

.

If required by the method, a matrix spike (M S) analysis was run on sample 71 747 (FGD

effluent ) for each analyte to check for matrix interferences

. F or some analytes,

TestAmerica s piked more sample s than required

. All MS samples analyzed met the

criteria specified in the method unless described below.

# 4 DATA NOTES /ISSUES

Ammonia

As stated above, filtrate and solid aliquots of sample s 71741

- 71744 w ere not preserved

immediately after sample collection. Instead

, TestAmerica preserved the sample after

phase separation. Because these samples were not preserved immediately as required by

the method, these samples were qualified as estimated value s

.

The filtrate of sample 71741 and the solids portion of 71742 were analyzed one day after

the 28

- day hold time. The solids portion of sample 71741 was analyzed two day s after the

28

- day hold time. These samples were already qualified as estimated values because they

were not preserved immediately following sample collection, so no further action was

necessary.

T he results for the MS/MSD samples for 71 74 7 were above the highest calibration

standard. The laboratory did not dilute and re analyze these samples becau se the MS/MSD

percent recoveries were within the control limits specified by EPA method 350.1.

Therefore, if the MS/MSD results for sample 71 74 7 are reported

, they will be qualified as

estimated value s

. The result for sample 71 74 7 was within the calibratio n range, so this

sample does not need to be qualified. The LFB associated with sample 71747 met the

method criteria.

BOD 5



# TestAmerica analyzed five dilutions, but no dilutions had a dissolved oxygen (DO)

depletion greater than 2.0 mg/L for sample 71744. Therefore, BOD 5 

# was reported as not

detect ed for th is sample

. The rest of the samples had at least one dilution with a DO

depletion greater than 2.0 mg/L. As required in the method, the final result was calculated

by taking the average of the results for all dilutions with a DO depletion greater than 2.0

mg/L and a final DO greater than 1.0 mg/L

.

The glucose

- glutamic acid (GGA) standards associated with sample s 71744 and 71747

h ad percent recover ies of 80% and 78% . The GGA standards associated with sampl e

71748 had percent recoveries of 79% and 81%. These percent recoveries were below the

meth od and laboratory criteria of 85

- 115%. TestAmerica flagged these samples with a

“*” meaning the laboratory control sample was not within laboratory control limits. B OD

was not detected in sample 71744, so no further qualification was necessary for this

sample. Sample s 71747 and 71748 were additionally qualified as minimum value s

.

The see d correction factor associated with sample 71748 was 0.5328 mg/L , which is less

t han the method and laboratory control limits of 0.6

- 1.0 mg/L. The result for this sample

could be biased low. This sample was qualified by TestAmerica with an “s” meaning the

seed control blank (SCB) recovery was low. Since t his sample was already qualifie d as a

minimum value because th e GGA percent recovery was low, no further action was taken.

# 5 All laboratory duplicates and water blanks were analyzed appropriately and met method

criteria.

Chloride and Sulfate

The laboratory diluted the MSD sample for 71 747 by 500 fold, but the diluted result for

sulfate w as still above the highest calibration standard. The laboratory did not reanalyze

this sample with a higher dilution factor, because the MSD percent recover y w as within

the control limits specified by EPA method 300.0. Therefore, if the MSD result for

sample 71 74 7 for sulfate is reported, it will be qualified as an estimated value

.

COD

The RPD between sample 71746 and its field duplicate 71749 for COD was 33.3%. Even

though the RPD was greater than 2 0%, the sample was not qualified because there are no

control limits for field duplicates specified in EPA Method 410.4

.

T he percent recoveries for the MS and MSD samples associated with 71 74 7 were 87%

and 93 % respectively. The MS percent recovery did n ot meet the method control limits

of 90

- 110%

. Because t he percent recovery for the MS sample w as below the method

control limits

, sample 71747 was flagged as a minimum value.

Cyanide

As stated above, filtrate and solid aliquots of sample s 71741

- 71744 were not preserved

immediately after sample collection. Instead

, TestAmerica preserved the sample after

phase separation. Solid aliquots of sample s 71741

- 71744 were all qualified by the

laboratory with a “J” meaning the sample result was an estimated val ue because it was

less than the RL, so there was no need to further qualify these samples. Because the

filtrate aliquots of sample s 71741

- 71744 were not preserved immediately as required by

the method, these samples were qualified as estimated values.

S ample 71747 w as preserved to pH 10 with NaOH immediately after sample collection,

but the pH was neutral when the sample w as received by the laboratory. The laboratory

added more NaOH to correct the pH upon receipt. Th is sample w as flagged as an

estimated value.

Both the filtrate and solids fraction of sample s 71741, 71742, 71743, and 71744 were

analyzed 16, 15, 14, and 13 days respectively past the 14

- day hold time. Since all of these

samples were already qualified as estimated value s because the sample w as not preserved

appropriately or because the sample result was greater than the MDL but less than the RL

(i.e., a J

- value) , no further action was necessary.

Cyanide was detected at 0.00240 mg/L in the LRB associated with the filtrate fraction of

sample s 71741

- 71744. Additionally, cyanide was detected at 0.141 mg/kg in the LRB

associated with the solids fraction of sample s 71741

- 71744

. Cyanide was also detected

# 6 at 0.00499 mg/L in the LRB associated with the sample s 71745

- 71749. Because all of

these blank results were less than the RL, no samples were qualified based on these L R B

results.

All samples w ere diluted prior to distillation by a factor of 10 due to matrix interferences

. T he diluted result for sample 71749 was less than the lowe st calibrat ion standard. The

solid fraction results for sample s 71741

- 71744 were also all below the lowest calibration

standard. T hese sample results 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

there was no need to further qualify these samples.

The RPD between sample 71746 and its field duplicate 71749 for cyanide was 193 %.

Even though the RPD was greater than 20%, the sample was not qualified because there

are no control limits for field duplicates specified in SM 4500 CN

- 

# E.

Nitrate/ Nitrite

As stated above, filtrate and solid aliquots of sample s 71741

- 71744 were not preserved

immediately after sample collection. Instead

, TestAmerica preserved the sample after

phase separation. Because these samples were not preserved immediately as required by

the method, these samples were qualified as estimated values.

The 28

- day hold time was exceeded by one day for the filtrate fraction of sample 71741

and for the solids fracti on of sample 71742. The solids fraction of sample 71741 was

analyzed two days past the holding time. These samples were already qualified as

estimated values because they were not preserved immediately following sample

collection, so no further action was necessary.

Phosphorus

As stated above, filtrate and solid aliquots of sample s 71741

- 71744 were not preserved

immediately after sample collection. Instead

, TestAmerica preserved the sample after

phase separation. Filtrate sample s 71741

- 71744 and soli d sample 71743 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 there was no need to further qualify these samples.

Solid sample s 71741, 71742, and 71744 were qualified as estimated values because they

were not preserved immediately following sample collection, as required by the method

.

The filtrate and solids fraction s from sample 71741 were analyzed two days after the 28

- day hold time and the filtrate and solids frac tion s from sample 71742 w ere analyzed one

day outside of the hold time. TestAmerica did not flag these results ; therefore, ERG

qualified these samples with an “H”. These samples were already qualified as estimated

values because they were not preserved imm ediately following sample collection.

Phosphorus was detected at 0.00837 mg/L in the laboratory reagent blank associated with

sample s 71745

- 71749. Phosphorus was also detected at 0.00977 mg/L in the laboratory

# 7 reagent blank associated with the filtrate of sample s 71741

- 71744. Because all of these

blank results were less than the RL, no samples were qualified based on these LRB

results.

The filt rate results for sample s 71741

- 71744 were all below the lowest calibration

standard. These samples were alr eady 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 these samples.

The RPD between sample 71746 and its field duplicate 71749 for phosphorus was 93.9 %.

Even though the RPD was greater than 20%, the sample was not qualified because there

are no control limits for field duplicates specified in the method

.

The percent recoveries for the MS and MSD anal ys e s for sample 71 74 7 , 55% and 57%,

respecti vely, were not within the method control limits of 90

- 110% or within the

laboratory control limits of 71

- 128%

. R esults for samples with a similar matrix (i.e., FGD

effluent) could be biased low because of matrix interferences

. Sample 71747 was

qualified as a minimum value because the MS percent recovery was less than the control

limits specified in the method.

TDS

Two l aboratory duplicates were analyzed

. The RPDs for these l aboratory duplicates were

less than 10 % , which is required by the method.

Sample s 71743, 71746, 71748, and 71749 did not achieve a constant weight after three

drying cycles. SM 2540C warns that samples that contain high levels of calcium,

magnesium, chloride, and sulfate may be hygroscopic, meaning they absorb moisture

from the air. F GD wastewater contains high concentrations of all of these species, so this

may be the cause for the inconsistent weight calculations. These samples were not

qualified , but results may be biased high

.

TKN

As stated above, filtrate and solid aliquots of s ample s 71741

- 71744 were not preserved

immediately after sample collection. Instead

, TestAmerica preserved the sample after

phase separation. Because these samples were not preserved immediately as required by

the method, these samples were qualified as e stimated values.

The solids and filtrate fraction of sample s 71741 and 71742 were analyzed two days and

one day after the 28

- day hold time , respectively

. These samples were already qualified as

estimated values because they were not preserved immediately following sample

collection, so no further action was necessary.

# 8 TKN was detected at 0.234 mg/L in the laboratory reagent blank associated with sample s

71745

- 71749. Because this blank result was less than the RL, no samples were qualified

based on the LRB result.

TestAmerica p er formed MS and MSD analys e s on sample 71747. T he percent recoveries

for the MS and MSD samples were 88% and 116% and the results were 23.2 and 24.0

mg/L. The samples d id not meet the method control limits of 90

- 110% , but did meet the

laboratory control limits of 54

- 131%. The sample concentration was greater than 4 times

the spike amount in the MS and MSD samples , so TestAmerica stated that the percent

recoveries and RPDs could not be reliably calculated. Considering that the MS pe rcent

recovery was below the control limits and the MSD percent recovery was above the

limits, this was likely the case. Sample 71747 was not qualified because it is not possible

to determine if the MS/MSD failure was a result of matrix interferences or ca used by the

low spiking level

.

TSS

Four laboratory duplicates were analyzed. The RPDs for these laboratory duplicates were

less than or equal to 10% as required by the method.

TSS was detected at 1.60 mg/L in the method blank ( MB ) associated with samp le 71747.

Because this blank result was less than the RL, no samples were qualified based on the

MB result

The RPD between sample 71 74 6 and its field duplicate 71 749 for TSS was 27.3 %. Even

th ough the RPD was greater than 20% , the sample was not qualified because there are no

specific control limits for field duplicates specified in the SM 2540D.

Table 2 . Data Review Summary Table

Sample Analyte Qualifier /Action Reason Level

Detected

71741

( f

iltrate) Ammonia Estimated v alue Sample not preserved

immedia tely following

collection. Analyzed one

day past holding time 5.1 mg/L

71741

( s olid) Ammonia Estimated value Sample not preserved

immediately following

collection. Analyzed two

days past holding time 24 mg/kg

71742

(filtrate) Ammonia Estimated value Samp le not preserved

immediately following

collection 5.3 mg/L

# 9 Table 2 . Data Review Summary Table

Sample Analyte Qualifier /Action Reason Level

Detected

71742

(solid) Ammonia Estimated value Sample not preserved

immediately following

collection. Analyzed one

day past holding time 28 mg/kg

71743

(filtrate) Ammonia Estimated value Sample not preser ved

immediately following

collection 7.7 mg/L

71743

(solid) Ammonia Estimated value Sample not preserved

immediately following

collection 26 mg/kg

71744

(filtrate) Ammonia Estimated value Sample not preserved

immediately following

collection 6.2 mg/L

71 744

(solid) Ammonia Estimated value Sample not preserved

immediately following

collection 23 mg/kg

71747 BOD 5 

# Minimum value GGA % recovery below

method

- specified criteria 6.9 mg/L

71748 BOD 5 

# Minimum value GGA % recovery and

SCB recovery below

method

- spec ified criteria 4.6 mg/L

71747 COD Minimum value MS % recovery below

method

- specified criteria 560 mg/L

71741

(filtrate) Total Cyanide H, Estimated

value Sample not preserved

immediately following

collection. Analyzed 16

days past holding time 0.27 mg/L

71742

(filtrate) Total Cyanide H, Estimated

value Sample not preserved

immediately following

collection. Analyzed 15

days past holding time 0.62 mg/L

71743

(filtrate) Total Cyanide H, Estimated

value Sample not preserved

immediately following

collection. Analyzed 14

days past holding time 2.2 mg/L

71744

(filtrate) Total Cyanide H, Estimated

value Sample not preserved

immediately following

collection. Analyzed 13

days past holding time 0.21 mg/L

71747 Total Cyanide Estimated value pH upon receipt < 10 0.6 0 mg/L

# 10 Table 2 . Data Review Summary Table

Sample Analyte Qualifier /Action Reason Level

Detected

71741

(filtrate) Nitrate/nitrite H, Estimated

value Sample not preserved

immediately following

collection. Analyzed 1

day past holding time 77 mg/L

71741

(solids) Nitrate/nitrite H, Estimated

value Sample not preserved

immediately following

collec tion. Analyzed two

day s past holding time 49 mg/kg

71742

(filtrate) Nitrate/nitrite Estimated value Sample not preserved

immediately following

collection. 83 mg/L

71742

(solids) Nitrate/nitrite H, Estimated

value Sample not preserved

immediately followin g

collection. Analyzed one

day past holding time 64 mg/kg

71743

(filtrate) Nitrate/nitrite Estimated value Sample not preserved

immediately following

collection. 79 mg/L

71743

(solids) Nitrate/nitrite Estimated value Sample not preserved

immediately foll owing

collection. 56 mg/kg

71744

(filtrate) Nitrate/nitrite Estimated value Sample not preserved

immediately following

collection. 90 mg/L

71744

(solids) Nitrate/nitrite Estimated value Sample not preserved

immediately following

collection. 65 mg/kg

717 41

(filtrate) Total

Phosphorus H Analyzed two days past

holding time 0.0096

mg/L

71741

(solids) Total

Phosphorus H, Estimated

value Sample not preserved

immediately following

collection. Analyzed two

days past holding time 21 mg/kg

71742

(filtrate) Total

Phosphorus H Analyzed one day past

holding time 0.0081

mg/L

71742

(solids) Total

Phosphorus H, Estimated

value Sample not preserved

immediately following

collection. Analyzed one

day past holding time 310 mg/kg

71744

(solids) Total

Phosphorus Estimated value Sample not preserved

immediately following

collection. 340 mg/kg

# 11 Table 2 . Data Review Summary Table

Sample Analyte Qualifier /Action Reason Level

Detected

71747 Total

Phosphorus Minimum value MS % recovery below

method

- specified criteria 0.18 mg/L

71741

(filtrate) TKN H, Estimated

value Sample not preserved

immediately following

collec tion. Analyzed two

days past holding time 24 mg/L

71741

(solids) TKN H, Estimated

value Sample not preserved

immediately following

collection. Analyzed two

days past holding time 830 mg/kg

71742

(filtrate) TKN H, Estimated

value Sample not preserved

imme diately following

collection. Analyzed one

day past holding time 31 mg/L

71742

(solids) TKN H, Estimated

value Sample not preserved

immediately following

collection. Analyzed one

day past holding time 840 mg/kg

71743

(filtrate) TKN Estimated value Sample not preserved

immediately following

collection. 29 mg/L

71743

(solids) TKN Estimated value Sample not preserved

immediately following

collection. 700 mg/kg

71744

(filtrate) TKN Estimated value Sample not preserved

immediately following

collection. 26 mg /L

71744

(solids) TKN Estimated value Sample not preserved

immediately following

collection. 900 mg/kg

# 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 at the Influent to the FGD Wastewater Treatment System

# C

- 4 Figure C

- 4

. Sample Collection Set Up at the Pump

- Off Station

# C

- 5 Figure C

- 5

. Composite Sample Collection Set Up at the Effluent from the FGD Wastewater

Treatment 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

# D-6  

# Argon gas: High purity grade (99.99%).

 

# Helium gas: High purity grade (99.99%).

 

# Hydrogen gas: High purity grade (99.99%).

 

# Calibrated automatic pipettes or Class A glass volumetric pipettes.

7.0 Reagents and Standards

7.1 Storage and Shelf-Life

7.1.1 All standards must be stored in glass, FEP fluorocarbon or previously

unused polyethylene or polypropylene bottles. Standards stored at

concentrations as received from the vendor and mid-level dilutions must

be replaced prior to the expiration date assigned by the vendor. If no

expiration date is provided, the stocks and mid-level standards may be

stored for up to one year. They must be replaced sooner if verification

from an independent source indicates a problem (See section 10.3.5 for

initial calibration verification acceptance criteria).

7.1.2 Working standards, i.e., all standards at concentrations ready to

analyze on the ICP/MS (all except tuning mixes, ICSA and ICSAB

mixes, which are received at ready-to-use concentrations), are prepared

fresh daily.

7.2 Standards

7.2.1 Tuning Solution, 10 ppb

The tuning solution stock is purchased as a custom multi-element mix.

The concentrations of the constituents are shown in Attachment 5.

Prepare the Tuning Solution as detailed below.

 Obtain a clean 100 mL volumetric flask.

 Place 50 mL of reagent water and 2 mL of conc. HNO 3 

# and 0.5

mL of conc. HCl in the flask.

 Swirl to mix.

 Pipet 0.1mL of the Tuning Solution Stock into the flask.

 Dilute to volume with reagent water. Stopper and mix.

7.2.2 PA Tuning Solution

The dual detector solution may be commercially purchased as a custom

multi-element mix.

Prepare the PA Tuning Solution as detailed below.

 Add approximately 50 mL of the 2% HNO 3 

# / 0.5% HCl to a 100

mL volumetric flask.

 Prepare at a concentration recommended by the instrument

manufacturer.

7.2.3 Calibration Standards

Stock calibration standards are purchased as custom multi-element

mixes or as single element solutions. Each day of analysis, the

standards are diluted to working levels using 2% nitric acid and 0.5%

HCl acid matrix. Suggested concentrations are given in Attachment 8,

# D-7 but the laboratory may adjust calibration standard concentrations as

appropriate for the instrument and samples. At a minimum, a 3 point

curve must be used.

7.2.4 Individual FGD Interference check solutions.

7.2.4.1 All individual FGD interference check solutions should be

made up in the same acid matrix as the calibration standards.

7.2.4.2 Chloride, 10,000 mg/L

7.2.4.3 Calcium, 5,000 mg/L

7.2.4.4 Sulfate, 4,000 mg/L

7.2.4.5 Magnesium, 3,000 mg/L

7.2.4.6 Sodium, 2,000 mg/L

7.2.4.7 Boron, 500 mg/L

7.2.4.8 Iron, 500 mg/L

7.2.4.9 Nitrate, 250 mg/L

7.2.4.10 Manganese, 200 mg/L

7.2.4.11 Bromide, 100 mg/L

7.2.4.12 Fluoride, 100 mg/L

7.2.4.13 Selenium, 20 mg/L

7.2.4.14 Vanadium, 10 mg/L

7.2.4.15 Zinc, 2 mg/L

7.2.4.16 Chromium, 1 mg/L

7.2.4.17 Copper, 1 mg/L

7.2.5 Mixed Interference Check Solution (Synthetic FGD Wastewater)

7.2.5.1 Chloride, 5,000 mg/L

7.2.5.2 Calcium, 2,000 mg/L

7.2.5.3 Magnesium, 1,000 mg/L

7.2.5.4 Sulfate, 2,000 mg/L

7.2.5.5 Sodium, 1,000 mg/L

7.2.5.6 Butanol, 2000ppm

7.2.6 Initial Calibration Verification (ICV) Standard

The ICV stock is from a source different than the source for the

calibration standards. Each day of analysis, the ICV standard is

prepared in 2% HNO 3 

# and 0.5 % HCl acid to the concentrations shown

in Attachment 8.

# D-8 7.2.7 Continuing Calibration Verification (CCV) Standard

The CCV is prepared from the same source as the calibration

standards. The CCV standards are prepared fresh each day of analysis

in 2% HNO 3 

# /0.5% HCl. The concentrations are shown in Attachment 8.

Prepare the Working CCV as detailed below.

 Dilute by 2X a known volume of the Working Calibration

Standard in the 2% HNO 3 

# / 0.5% HCl acid matrix.

7.2.8 Spiking Stock Solution

The spike stock solution is prepared from the same stocks as the

calibration standards using the 2% HNO 3 

# / 0.5% HCl acid matrix. Spike

concentrations are listed in Attachment 8.

7.3 Reagents

7.3.1 Reagent Water - ASTM Type I or equivalent for the elements of

interest, generated using an ion-exchange water polishing system

capable of achieving 18.0 megohm-cm.

7.3.2 Blank Matrix 2% HNO 3 

# and 0.5% HCl.

8.0 Sample Collection, Preservation, Shipment and Storage

Sample container, preservation techniques and holding times may vary and are

dependent on sample matrix, method of choice, regulatory compliance, and/or specific

contract or client requests. Listed below are the holding times and the references that

include preservation requirements.

Matrix Sample

Container Min. Sample

Size Preservation Holding Time Reference

Waters HDPE 50 mLs HNO 3 

# , pH < 2 180 Days 40 CFR Part 136.3

Soils Glass or

HDPE 4 oz Cool 4 + 2 o 

# C 180 Days N/A

9.0 Quality Control

9.1 Quality control requirements are also summarized in Attachment 7.

9.2 Ongoing data quality checks are compared with established performance criteria

to determine if the results of analyses meet the performance characteristics of

the method. Any QC result that fails to meet control criteria must be

documented.

9.3 Individual interference check solutions

The individual interference check solutions listed in section 7.2.6 are analyzed

prior to initiating sample analysis, and at least once per quarter while FGD

wastewaters are being analyzed, and after any major changes to instrument

operating conditions. Concentrations of target elements observed should be less

than their reporting limits. In some cases it may not be possible to obtain

interference check solutions that are completely free of contamination. In this

# D-9 case, results up to 5X the reporting limit are acceptable if it is possible to

demonstrate that the isotopic ratios correspond to natural abundances. For

example, the natural abundances of zinc isotopes are Zn 64 

# 48.6%; Zn 66 

# 27.9%;

Zn 67 

# 4.1%; Zn 68 

# 18.8%; Zn 70 

# 0.6%. The measured ratios are not expected to be

exact, especially for low abundance isotopes, and some isotope may be masked

by other elements in the solution, (for example Zn 70 

# in the above example will be

masked by Ge 70 

# ) but it must be possible to explain the observed ratios.

Because Arsenic, Manganese and Aluminum are monoisotopic, this

demonstration is not possible and the level of interference observed must be less

than the reporting limit

.

9.4 Synthetic FGD interference check solution

The synthetic FGD matrix solution listed in section 7.2.7 is analyzed prior to

initiating sample analysis, and at least once per day (immediately after

calibration) while FGD wastewaters are being analyzed, and after any major

changes to instrument operating conditions. Internal standard recovery must

meet method criteria (Section 9.9) and concentrations of target elements

observed should be less than their reporting limits. In some cases it may not be

possible to obtain interference check solutions that are completely free of

contamination. In this case, results up to 5X the reporting limit are acceptable if it

is possible to demonstrate that the isotopic ratios correspond to natural

abundances. For example, the natural abundances of zinc isotopes are Zn 64



# 48.6%; Zn 66 

# 27.9%; Zn 67 

# 4.1%; Zn 68 

# 18.8%; Zn 70 

# 0.6%. The measured ratios are

not expected to be exact, and some isotopes may be masked by other elements

in the solution, (for example Zn 70 

# in the above example will be masked by Ge 70 

# )

but it must be possible to explain the observed ratios. Because Arsenic,

Manganese and Aluminum are monoisotopic, this demonstration is not possible,

and the level of interference observed must be less than the reporting limit.

If the Synthetic FGD solution has to be diluted in order to analyze it

effectively on the ICP/MS, then all samples and QC (including the MDL

replicates) must be diluted by at least the same factor.

9.4.1 Laboratory fortified Synthetic FGD solution

The synthetic FGD solution is spiked with 40ppb of each of the target

elements (400ppb for zinc and 4000ppb for aluminum) and analyzed

once per day, immediately after the synthetic FGD check in section 9.4.

All target elements must be recovered within 70-130% of the true value.

If the Laboratory Fortified Synthetic FGD solution has to be diluted

in order to analyze it effectively on the ICP/MS, then all samples

and QC (including the MDL replicates) must be diluted by at least

the same factor.

9.5 Linear range determination

The linear range for each element is determined prior to initiating sample

analysis and at least once per year thereafter. The linear range must also be

determined subsequent to changes that will have a major effect on instrument

sensitivity, such as changing the detector. The linear range is established using a

single element standard at the desired linear range. The result of the analysis

must be within 10% of the true value.

# D-10 9.6 Method Blank / Laboratory Reagent Blank (MB/LRB)

The method blank consists of reagent water that has been processed in

the same manner as the samples. One method blank must be processed with

each preparation batch.

Acceptance Criteria: Method blank results are acceptable if the concentration

for each analyte of interest is less than the reporting limit.

Corrective Action: If the method blank does not meet the acceptance

criteria, the source of contamination should be

investigated to determine if the problem can be

minimized or eliminated. Samples associated with the

contaminated blank shall be reprocessed for analysis, or

under the following circumstances, may be reported as

qualified (qualifier flags or narrative comments must be

included on report):

 The same analyte was not detected in the

associated samples;

 The method blank concentration is less than 1/10 of

the measured concentration of any sample in the

batch;

 The method blank concentration is less than 1/10

the specified regulatory limit; or

 The analyte is a common laboratory contaminant

(copper, iron, lead, calcium, magnesium,

potassium, sodium, or zinc) less than 2 times the

RL. Note that some programs do not recognize

common lab contaminants.

If the above criteria are not met and reanalysis is not

possible, then the sample data must be qualified. This

anomaly must be addressed in the project narrative

and the client must be notified.

9.7 Laboratory Control Sample / Laboratory Fortified Blank (LCS/LFB)

The LCS consists of reagent water that is spiked with the analytes of

interest as summarized in Attachment 8. One LCS must be processed (digestion

and analysis) for each preparation batch.

Acceptance Criteria: LCS control limits are based on three standard

deviations of past laboratory results. These limits are not

to exceed 85-115% recovery. The control limits are

maintained in a LIMS or other appropriate system.

Corrective Action: If the LCS % recovery falls outside of the control limits for

any analyte, that analyte is judged to be out of control.

All associated samples must be reprocessed for

analysis. One possible exception is a recovery for a

given element above the upper control limit with no

detection for the same element in the samples.

9.8 Matrix Spike / Matrix Spike Duplicate / Laboratory Fortified Sample Matrix /

Laboratory Fortified Matrix Duplicate (MS/MSD/LFSM/LFMD)

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

# D-15 11.0 Calculations / Data Reduction

11.1 LCS percent recoveries are calculated according to the equation:

11.2 ICV percent recoveries are calculated according to the equation:

11.3 CCV percent recoveries are calculated according to the equation:

11.4 Matrix Spike Recoveries are calculated according to the following equation:



# Where:

SSR = Spike Sample Result

SR = Sample Result

SA = Spike Added

NOTE: When the sample concentration is less than the detection limit, use SR = 0

for the purpose of calculating %R



# .

11.5 The relative percent difference (RPD) between sample duplicates is

calculated according to the following equation:



# Where:

DU1 = Sample result

DU2 = Sample duplicate result % 100

Value True ICV Value Found ICV %       

 R

% 100

Value True CCV Value Found CCV %       

 R

% 100

SA SR

- SSR %       

 R



#   100

2 1 2 1 / 2 1 /

  

 

 

 

 

 DU DU DU DU RPD % 100

Value True LCS Value Found LRB

- Value Found LCS %       

 R

# D-16 11.6 The final concentration for an aqueous sample is calculated as follows:



# 2 1 g/L) ( Result

V D V C  

 



# Where:

C = Concentration from instrument readout, ppb

D = Instrument dilution factor

V1 = Final volume in liters after sample preparation

V2 = Initial volume of sample digested in liters

12.0 Method Performance

12.1 Method Detection Limit Study (MDL)

An initial method detection limit study must be performed on each instrument

before samples can be analyzed. MDL studies are conducted annually as

follows:

 

# Prepare seven samples at three to five times the estimated MDL

concentration. The MDL samples are prepared in the Synthetic FGD

wastewater matrix and in reagent water.

 

# Prepare and analyze the MDL standards as described in Section 10.

 

# Calculate the average concentration found in μg/L, and the standard

deviation of the concentration(s) in μg/L, for each analyte.

 

# The MDL is calculated as Students t for the 99 th 

# percentile times the standard

deviation of the MDL replicate results, following the procedure at 40CFR Part

136, Appendix B.

NOTE1: Perform the MDL study in the synthetic FGD

wastewater matrix. Spiking this matrix provides detection

limits that are better matched to the complex matrix

typical of FGD wastewater. These limits can be

significantly higher than those obtained in a reagent water

matrix. In some cases (zinc in particular), the level of

contamination in the synthetic FGD solution may be high

enough to result in somewhat elevated MDLs.

NOTE2: An FGD-MDL may be less than the MDL observed in

method blanks. If this occurs frequently, the FGD-MDL

should be elevated to the mean of the method blanks plus

the Student t factor times the standard deviation of the

method blanks.

12.2 Instrument Detection Limit Study

Instrument detection limit (IDL) studies are conducted quarterly for each

instrument and each mass used for analysis.

 

# Prepare ten blanks.

 

# Analyze the IDL blanks on three non-consecutive days.

 

# The IDL is equal to three times the standard deviation of the blank results.

# D-17 12.3 Demonstration of Capabilities

All personnel are required to perform an initial demonstration of proficiency

(IDOC) on the instrument they will be using for analysis prior to testing samples.

On-going proficiency must be demonstrated annually. IDOCs and on-going

proficiency demonstrations are conducted as follows.

Four aliquots of the ICV are analyzed using the same instrumental conditions

and procedures used to analyze samples. The analyst must employ ICV’s from

four distinct analytical sequences. Using these four ICV’s demonstrates the

analyst’s ability to optimize and calibrate the instrument and to prepare analytical

solutions. Calculate the average recovery and standard deviation of the recovery

for each analyte of interest.

 

# If any analyte does not meet the acceptance criteria, (85-115% recovery,

unless other criteria are established) the test must be repeated. Only those

analytes that did not meet criteria in the first test need to be evaluated.

Repeated failure for any analyte indicates the need for the laboratory to

evaluate the analytical procedure and take corrective action.

12.4 Training Requirements

12.4.1 Each analyst performing the method must complete a demonstration of

capability (DOC) by successfully preparing and/or analyzing four

consecutive LCSs, or a blind performance evaluation (PE) sample, or

other acceptable QC samples. Analysts who continue to perform the

method must successfully complete a demonstration of capability

annually.

13.0 Pollution Control

13.1.1 For information about pollution prevention that may be applicable to

laboratory operations, consult “Less is Better: Laboratory Chemical

Management for Waste Reduction” available from the American

Chemical Society’s Department of Government Relations and Science

Policy, 1155 16th Street N.W., Washington, D.C., 20036, or online at

http://www.ups.edu/x7432.xml.

14.0 Waste Management

All waste must be disposed of in accordance with Federal, State, and local

regulations.

15.0 References / Cross-References

15.1 EPA Method 200.8, “Determination of Trace Elements in Waters and Wastes

by Inductively Coupled Plasma - Mass Spectrometry”, Revision 5.4, EMMC

Version.

15.2 EPA Method 1638, “Determination of Trace Elements in Ambient Waters by

Inductively Coupled Plasma – Mass Spectrometry, January 1996

# D-18 16.0 Attachments

Attachment 1: Recommended Elemental Equations

Attachment 2: Internal Standards and Corresponding Metals

Attachment 3: Sample Preservation and Holding Times

Attachment 4: Suggested Mass Choices

Attachment 5: Tuning Solution

Attachment 6: Suggested Tuning and Response Factor Criteria

Attachment 7: Summary of Quality Control Requirements

Attachment 8: Calibration, Calibrati on Verification, and Spike Concentrations

# D-19 Attachment 1

Recommended Elemental Equations

Element Isobaric

Correction Mathematical Equation

Pb None (1.0000)(208M) + (1.0000)(207M) + (1.0000)(206M)

6Li Li (natural) (1.0000)(6M) - (0.0813)(7M)

In Sn (1.0000)(115M) - (0.0149)(118M)

The 6 

# Li correction equation is only needed if 6Li is us ed as an internal standard for low mass elements.

Attachment 2: Internal Standards and Corresponding Metals

Internal Std. Associated elements 1,2



# Sc Na, Mg, Al, K, Ca, V, Cr, Mn

Ge Fe, Ni, Cu, Zn, As, Se

In Ag, Cd

Ho Tl, Pb

Footnote: (1) Na, Mg, K, Ca and Fe are included in the synthetic FGD wastewater but their

analytical determination is optional – the in terferences caused by these elements are more

important than the determination of their exact concentration.

(2) Other internal standards may be used. For example, 6 

# Li, Ga, Rh, Bi, Ho and Tb may be

considered for use as internal standards.

# D-20 Attachment 3: Sample Preservation and Holding Times

Measurement

Parameter Container (1) Preservative (2) Maximum Holding

Time (3)

Waters:

Metals (4) P,G HNO 3 

# to pH < 2 6 months

Soils/Sediments/Wastes:

The preservation required for soil/sediment/waste sa mples is maintenance at 4°C ( ± 2°C) until

digestion.

Footnotes : (1) Polyethylene (P) or glass (G).

(2) Sample preservation is performed by the sampler immediately upon sample

collection or shipped to the laboratory unpreserved for preservation at the

laboratory.

(3) Samples must be analyzed as soon as possible after collection. The times listed

are the maximum times that sample may be held before analysis and still

considered valid. Holding times are calcu lated from the date when the sample

was collected.

(4) Samples are filtered immediately on-site by the sampler before adding

preservative for dissolved elements.

# D-21 Attachment 4: Suggested Mass Choices

Masses listed indicate the masses which have the most impact on data quality and the elemental

equations used to collect the data.

Mass Element of Interest Analysis mode

27 Aluminum No gas

75 Arsenic He

111 Cadmium He

52 Chromium He

63 Copper He

208, 207, 206 Lead No gas or He

24 Magnesium No gas

55 Manganese He

60 Nickel He

39 Potassium No gas or He

78 Selenium He (H 2 

# )

107 Silver He

23 Sodium No gas or He

205 Thallium No gas or He

51 Vanadium He

66 Zinc He

NOTE : It is strongly recommended that elements other than those of interest be

monitored to indicate other potential molecular interferences which could

affect the data quality.

# D-22 Attachment 5: Tuning Solution

A tuning solution containing elements representing all of the mass regions of interest must be analyzed.

Below are two groups of suggested solutions which cover a typical mass calibration range.

Method 200.8

Element Concentration (  g/L)

Mg 10

Rh 10

Ba 10

Be 10

U 10

Ce 10

Y 10

Pb 10

Li 10

Co 10

In 10

Tl 10

# D-23 Attachment 6: Suggested Tuning and Response Factor Criteria

No Gas Mode

Li7 >2000cps

Tl205 >3000cps

CeO/Ce 156/140 1%

Ce++/Ce+ 70/140 <3%

He Mode:

ArAr 78 2-3 counts/sec

ArCl 75 2-3 counts/sec

# D-24 Attachment 7: Summary of Quality Control Requirements

QC Parameter Frequency Acceptance Criteria Corrective Action

ICV/QCS Beginning of every

analytical run. 90 - 110% recovery.

200.8 IS, 60-125% rec. Terminate analysis;

correct the problem;

recalibrate.

ICB/CCB Immediately after each

ICV. The result is < RL

200.8 IS, 60-125% rec. Terminate analysis;

correct the problem;

recalibrate.

Synthetic FGD

interference check Prior to initiating

analysis and at least

quarterly. Result for target elements

is < RL, unless actual

presence of target

element can be

demonstrated, in which

case result is < 5X RL. Correct the problem prior

to sample analysis.

Individual element

interference checks Prior to initiating

analysis and at least

quarterly. Result for target elements

is < RL, unless actual

presence of target

element can be

demonstrated, in which

case result is < 5X RL. Correct the problem prior

to sample analysis.

CCV Beginning and end of run

and every 10 samples OR

every 2 hours, whichever

is more frequent.

Beginning and end of

each lot. 90 - 110% recovery.

IS, 60-125% rec. If unacceptable,

terminate analysis;

correct the problem;

recalibrate the

instrument, reverify

calibration and rerun all

samples since the last

acceptable CCV.

CCB Immediately following

each CCV. The result must be < RL

200.8 IS, 60-125% rec. If unacceptable,

terminate analysis;

correct the problem,

recalibrate the

instrument, reverify

calibration and rerun

all samples since the

last acceptable CCB.

# D-25 Attachment 7: Summary of Quality Control Requirements (continued)

QC Parameter Frequency Acceptance Criteria Corrective Action

Method

Blank/Laboratory

Reagent Blank One per lot of 20 field

samples or fewer. The result must be less

than the RL.

Sample results greater

than 10x the blank

concentration or samples

for which the

contaminant is < RL, do

not require redigestion or

reanalysis. Re-run once. If > than

the RL, Redigest and

reanalyze samples.

Note exceptions under

criteria section.

See Section 9.4 for

additional requirements.

Matrix Spike/Laboratory

Fortified Matrix One every ten samples or

fewer. Must be within

laboratory control limits. See section 9.6 for

additional requirements.

# D-26 Attachment 8: Calibration, Calibration Verification, and Spike Concentrations

Element Initial Calibration

(  g/L) ICV

(  g/L) CCV

(  g/L) LCS

(  g/L) MS/MSD

(  g/L)

Aluminum 100, 1,000, 10,000 4000 5000 4000 4000

Arsenic 1, 10, 100 40 50 40 40

Cadmium 1, 10, 100 40 50 40 40

Chromium 1, 10, 100 40 50 40 40

Copper 1, 10, 100 40 50 40 40

Lead 1, 10, 100 40 50 40 40

Manganese 1, 10, 100 40 50 40 40

Nickel 1, 10, 100 40 50 40 40

Selenium 1, 10, 100 40 50 40 40

Silver 1, 10, 100 40 50 40 40

Thallium 1, 10, 100 40 50 40 40

Vanadium 1, 10, 100 40 50 40 40

Zinc 1, 10, 100 40 50 40 40

Additional elements may be included in the calib ration solution at the above levels. Levels

may be adjusted to meet specific requirements.

####