Sampling Episode Report 

Allegheny Energy’s 

Hatfield’s Ferry Power Station 

Masontown, PA 

Sampling Episode 6564 

Prepared for:

U.S. Environmental Protection Agency

Engineering and Analysis Division 

Office of Water 

1200 Pennsylvania Avenue, NW 

Washington, D.C. 20460 

Prepared by: 

Eastern Research Group, Inc.

14555 Avion Parkway 

Suite 200 

Chantilly, VA 20151 

 13 April 2012 

EPA Contract No. 68-C-02-095 

Work Assignment 9-29
i

CONTENTS 

Page 

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

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

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

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

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

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

2.2 FGD Wastewater Treatment System ...................................................................2-3

2.2.1 Sampling Points .......................................................................................2-5

3. SAMPLE COLLECTION .......................................................................................................3-1

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

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

3.1.2 Effluent from FGD Wastewater 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. LABORATORY ANALYTICAL RESULTS AND DISCUSSION...................................................4-1

4.1 Measured and Calculated Results for Influent to FGD Wastewater Treatment 

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

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

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

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

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

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

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

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

5.2.4 Field Duplicates .......................................................................................5-3

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

Appendix A: ANALYTICAL RESULTS

Appendix B: DATA REVIEW NARRATIVES 

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

TRACE ELEMENT ANALYSIS IN FLUE GAS DESULFURIZATION WASTEWATERS
ii

LIST OF TABLES 

Page 

Table 3-1. Sample Collection Information, Hatfield’s Ferry..................................................... 3-11

Table 3-2. Sample Collection at Hatfield’s Ferry Steam Electric Plant .................................... 3-13

Table 3-3. Field Measurements, Hatfield’s Ferry...................................................................... 3-14

Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Hatfield’s Ferry.......... 3-15

Table 3-5. Analytical Methods, Hatfield’s Ferry....................................................................... 3-16

Table 3-6. Summary of Sample Container and Planned Preservation, Hatfield’s Ferry ........... 3-17

Table 3-7. Sample Preservation Summary, Hatfield’s Ferry..................................................... 3-18

Table 3-8. Generating Unit Operating Characteristics during Sample Collection, Hatfield’s 

Ferry............................................................................................................................... 3-20

Table 3-9. FGD Scrubber System Operating Characteristics, Hatfield’s Ferry ........................ 3-21

Table 3-10. Coal Usage during Sample Collection, Hatfield’s Ferry........................................ 3-22

Table 3-11. Scrubber Slurry Information during Sample Collection, Hatfield’s Ferry............. 3-23

Table 3-12. FGD Wastewater Treatment System Operation Information, Hatfield’s Ferry ..... 3-24

Table 4-1. Influent to FGD Wastewater Treatment System, Hatfield’s Ferry............................ 4-6

Table 4-2. Effluent from FGD Wastewater Treatment System, Hatfield’s Ferry .................... 4-11

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

Treatment System, Hatfield’s Ferry............................................................................... 4-15

Table 4-4. Metal Pollutant 4-Day Average Data Summary for FGD Wastewater Treatment 

System, Hatfield’s Ferry ................................................................................................ 4-16

Table 5-1. Field Blank Analytical Results, Hatfield’s Ferry ....................................................... 5-5

Table 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, 

Hatfield’s Ferry................................................................................................................ 5-6

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

Wastewater Treatment System, Day 1 Analytical Results, Hatfield’s Ferry.................. A-1

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

Wastewater Treatment System, Day 2 Analytical Results, Hatfield’s Ferry.................. A-3
LIST OF TABLES (Continued) 

Page 

iii

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

Wastewater Treatment System, Day 3 Analytical Results, Hatfield’s Ferry.................. A-5

Table A-4. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD 

Wastewater Treatment System, Day 4 Analytical Results, Hatfield’s Ferry.................. A-7

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

Hatfield’s Ferry............................................................................................................... A-9

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

Hatfield’s Ferry............................................................................................................. A-15

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

Hatfield’s Ferry............................................................................................................. A-21

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

Hatfield’s Ferry............................................................................................................. A-27

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

Hatfield’s Ferry............................................................................................................. A-34

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

Hatfield’s Ferry............................................................................................................. A-37

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

Hatfield’s Ferry............................................................................................................. A-40

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

Hatfield’s Ferry............................................................................................................. A-43

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

Analytical Results, Hatfield’s Ferry ............................................................................. A-46

Table A-14. Duplicate of Effluent from FGD Wastewater Treatment System, Day 3 

Analytical Results, Hatfield’s Ferry ............................................................................. A-47

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Hatfield’s Ferry ................ A-50

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

Results, Hatfield’s Ferry ............................................................................................... A-55

Table A-17. Effluent from FGD Wastewater Treatment System Field Blank, Day 1 

Analytical Results, Hatfield’s Ferry ............................................................................. A-57

Table A-18. Effluent from FGD Wastewater Treatment System Field Blank, Day 2 

Analytical Results, Hatfield’s Ferry ............................................................................. A-59
LIST OF TABLES (Continued) 

Page 

iv

Table A-19. Effluent from FGD Wastewater Treatment System Field Blank, Day 3 

Analytical Results, Hatfield’s Ferry ............................................................................. A-60

Table A-20. Effluent from FGD Wastewater Treatment System Field Blank, Day 4 

Analytical Results, Hatfield’s Ferry ............................................................................. A-61
v

LIST OF FIGURES 

Page 

Figure 2-1. Simplified Diagram of the FGD Wastewater Treatment System, Hatfield’s Ferry 

Power Station................................................................................................................... 2-6

Figure 2-2. Detailed Diagram of the FGD Wastewater Treatment System, Hatfield’s Ferry 

Power Station................................................................................................................... 2-7
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1. INTRODUCTION

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

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

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

and evaluate treatment technologies and best management practices used to reduce pollutant 

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

place December 5-10, 2010, at Allegheny Energy’s Hatfield’s Ferry Power Station (Hatfield’s 

Ferry), located in Masontown, Pennsylvania (Sampling Episode 6564). The focus of Episode 

6564 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 present in the wastewater discharges from steam 

electric power plants that substantially contribute to the toxic loadings for the industry. 

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

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

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

the untreated FGD wastewaters and effluent quality from technologies designed to treat the 

wastewater. 

1.2 Power Plant Site Selection

EPA selected seven coal-fired steam electric plants for FGD wastewater sampling based 

on the process configurations and characteristics of the plants. 

Hatfield’s Ferry was selected by EPA for sampling based on the following site 

characteristics: 

 The plant is a coal-fired power plant that burns a blend of bituminous and PRB in 

each of its three generating units; 

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

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

includes the following steps: 

— Equalization, 

— Lime addition (pH adjustment/metal hydroxide precipitation) 

— Organosulfide addition, 

— Ferric chloride addition, 

— Polymer addition, 

— Clarification, 

— Hydrochloric acid addition (pH adjustment), 

— Filtration (sand filters); and 

 The plant operates a selective non-catalytic reduction (SNCR) system on Unit 3.
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1.3 Sampling Episode Overview

EPA and its technical contractor, Eastern Research Group, Inc. (ERG) conducted a oneday pre-sampling site visit at Hatfield’s Ferry on February 1, 2010 as part of the detailed study. 

The information collected during the pre-sampling site visit and subsequent follow-up telephone 

calls to Hatfield’s Ferry representatives was used to create Sampling Plan, Allegheny Energy’s 

Hatfield’s Ferry Steam Electric Plant (Sampling Plan) [1], which describes the sample collection 

procedures used during the sampling episode. 

On Sunday, December 5, 2010, EPA arrived at Hatfield’s Ferry to meet with plant 

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

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

Monday through Friday (December 6–10, 2010). The following personnel participated in EPA’s 

sample collection activities: 

 Ron Jordan, EPA/EAD; 

 TJ Finseth, ERG; 

 Jessica Gray, ERG; 

 Danielle Lewis, ERG; 

 Jennifer Lewis, ERG; and 

 Brandon Smith, ERG. 

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

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

industry. During the sampling episode, UWAG acted as Hatfield’s Ferry’s representative and 

collected samples on behalf of the plant. 
2-1

2. FACILITY OVERVIEW

Hatfield’s Ferry operates three steam electric units and each has a coal-fired boiler. Units 

1, 2, and 3, which came on line in 1969, 1970, and 1971 respectively, each have a net capacity of 

570 megawatts (MW). In 2009, all three generating units burned a blend of 75% bituminous and 

25% PRB coal; however, during the sampling episode the blend ranged from 58% bituminous 

and 42% PRB to 84% bituminous and 16% PRB. The Hatfield’s Ferry main plant is located on 

206 acres in Masontown, Pa. The plant also has a 246 acre landfill, but only 66.5 acres were 

active at the time of the sampling episode.

Hatfield’s Ferry recently retrofitted all three units with wet FGD scrubber systems to 

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

June 2009, and the Unit 2 and Unit 3 FGD systems were both installed in October 2009. With the 

recent addition of the FGD scrubber systems, Hatfield’s Ferry also installed an FGD wastewater 

treatment system to control the discharges of the wastewater generated during the operation of 

the FGD scrubbers. The FGD scrubber systems are discussed further in Section 2.1 and the FGD 

wastewater treatment system is discussed further in Section 2.2. 

The plant operates a selective non-catalytic reduction (SNCR) trim system only on Unit 3 

and a ROFA system on Unit 1 to control nitrogen oxide (NOx) releases from that units. The 

SNCR trim system on Unit 3 was not in operation during the sampling episode. Hatfield’s Ferry 

also uses low NOx burners on all three units to control NOx releases from the plant. 

The electrostatic precipitators (ESPs) at Hatfield’s Ferry are particulate control devices 

that remove the fly ash and other particulates from the flue gas. Hatfield’s Ferry utilizes coldside ESPs to remove the fly ash from all three units. The ESPs are designed to remove 99 percent 

of the fly ash from the flue gas. The fly ash and other particulates are collected in hoppers and 

are pneumatically transferred to fly ash silos. 

Units 1 has the following configuration: 

 Boiler (Low NOx Burners with ROFA system located in boiler); 

 Air heater; 

 ESP; and 

 FGD scrubber system. 

Unit 2 has the following configuration: 

 Boiler (Low NOx Burners located in boiler); 

 Air heater; 

 ESP; and 

 FGD scrubber system. 

Unit 3 has the following configuration: 

 Boiler (Low NOx Burners with SNCR system located in boiler); 

 Air heater; 

 ESP; and 
2-2

 FGD scrubber system. 

2.1 FGD Scrubber System

Hatfield’s Ferry operates three forced oxidation wet FGD scrubber systems (one per unit) 

to control the emission of SO2 from the units. The plant uses limestone slurry as the sorbent for 

SO2 absorption. Limestone and service water are fed to three on-site ball mills (one per unit), 

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

hydrocyclones to collect limestone particles that are too large for use in the FGD system. The 

underflow from the hydrocyclones is sent back to the ball mills for processing. The overflow 

from the hydrocyclones, which ranges from 22 to 25 percent solids (by weight), is transferred to 

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

The fresh limestone slurry is fed to the reaction tank of the FGD systems where the slurry 

is pumped to the various levels of the FGD scrubbers with the recycle pumps. All three absorbers 

have five spray levels, but the plant usually only operates four spray levels at one time. The 

slurry is pressurized and sprayed downward into the scrubber vessel through spray nozzles. As 

the slurry falls downward and the flue gas flows counter-current to the slurry, the spray droplets 

of the limestone slurry contact the flue gas and absorb the SO2, which reacts with the limestone 

particles and produces calcium sulfite. The spray droplets flow downward until they settle on the 

first of two dual flow trays, forming a layer of slurry that the flue gas must pass through to exit 

the FGD system. The tray has small holes in it that allow the flue gas to bubble through the 

limestone slurry layered on the tray, which provides additional contact between the limestone 

slurry and the flue gas. The spray droplets fall downward to the second dual flow tray and then 

continue to flow downward in the scrubber until it reaches the reaction tank. Hatfield’s Ferry 

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

gypsum). 

The source of up to 50% of the make-up water used in the FGD systems at Hatfield’s 

Ferry is recycled wastewater treatment lagoon water. The rest of the make-up water comes 

directly from the Monongahela River. Hatfield’s Ferry personnel stated they cannot use lagoon 

water for more than 50% of the makeup water, otherwise it is difficult for the plant to control the 

pH within the FGD system. All wastewater generated at the plant, except for FGD wastewater, is 

transferred to the wastewater treatment lagoon, which includes bottom ash sluice water (after 

initial settling and pH adjustment), floor drain wastes, and boiler wash water. 

Hatfield’s Ferry intermittently blows down the gypsum slurry from the absorber vessel to 

control the solids and chlorides concentration in each of the scrubbers. The plant initiates a 

blowdown once solids reach 21% within the absorber. The plant continues to blowdown until the 

solids reduce to 18-19% within the absorber. The plant also monitors the chloride level in the 

absorber; however, by maintaining the correct level of solids, the plant maintains an adequate 

chloride level in the absorber between 8,000 and 10,000 ppm without the need for additional 

blowdown. The maximum allowable chloride concentration for the absorber is 12,500 ppm. For 

all three units, blowdown from the absorbers occurs in ten hour increments with four to five 

hours between each blowdown. Hatfield’s Ferry transfers the blowdown from the scrubber 

absorber to the gypsum dewatering operations. 

The scrubber blowdown is pumped to the primary hydrocyclones (one per unit with 

spares) where the solid gypsum is separated from the water by centrifugal force. The solid 
2-3

gypsum is forced outward to the walls of the hydrocyclones and falls downward, while the water 

exits the top of the hydrocyclones. The underflow from the primary hydrocyclones is transferred 

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

reclaim tanks, with a tap in the line to transfer a percentage of the flow to the secondary 

hydrocyclone, and ultimately back to the absorber. The underflow from the secondary 

hydrocyclones is transferred to the reclaim tank and recycled back to the absorber. The overflow 

from the secondary hydrocyclones is pumped to the FGD wastewater treatment system. 

Overflow from the secondary hydrocyclone is not designed to be recycled back to the absorber, 

however, any leakage would be directed to the reclaim tank and recycled back to the absorber. 

Hatfield’s Ferry does not wash the gypsum sent to the vacuum filter belts as the gypsum 

is poured onto the belts. The plant stated that although the system is designed to wash the 

gypsum to remove chlorides, the plant does not conduct this wash because Hatfield’s Ferry does 

not have any contracts in place to sell the gypsum. Additionally, washing the gypsum would 

cause their average monthly discharge flow rate to rise above their current NPDES permit limit 

(160 gpm). The gypsum contains a moisture content of 10% after the vacuum belt filters. 

Hatfield’s Ferry transfers the gypsum to an on-site landfill for disposal. The landfill is lined and 

has a leachate collection system. The filtrate from the vacuum belt filters is transferred to the 

reclaim tanks and ultimately recycled back to the absorber. 

2.2 FGD Wastewater Treatment System

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

secondary hydrocyclone overflow. The design flow rate for the treatment system is 500 gpm. 

Hatfield’s Ferry operates the FGD wastewater treatment system 24 hours per day, 7 days 

per week. The wastewater treatment system was installed to treat the FGD scrubber purge 

wastewater to meet the plant’s permit limits. The plant’s FGD wastewater treatment system 

contains the following treatment operations: 

 Equalization; 

 Lime addition (pH adjustment/metal hydroxide precipitation); 

 Organosulfide addition; 

 Ferric chloride addition; 

 Polymer addition; 

 Clarification; 

 Hydrochloric acid addition (pH adjustment); and 

 Filtration (sand filters). 

Figures 2-1 and 2-2 located at the end of this section, present process flow diagrams of 

the FGD wastewater treatment system, as well as the sampling locations from EPA’s sampling 

episode. Figure 2-1 presents a simplified diagram of the FGD wastewater treatment system. 

Figure 2-2 presents a more complex diagram providing more detail on the chemical precipitation 

treatment operations. 

The secondary hydrocyclone overflow from the scrubbers is transferred to the purge tank 

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

sampling episode, the FGD influent wastewater was found to contain between 4 and 7 percent 
2-4

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

equalization tank also receives water from the wastewater treatment sump and off-specification 

effluent from the FGD wastewater treatment system. The wastewater treatment sump includes 

wastewater such as filter backwash and filtrate from the filter press that dewater the sludge from 

the clarifiers. Sumps from the dewatering area are also transferred to the equalization tank; 

however, the sumps in the limestone preparation are not transferred to the equalization tank. 

From the equalization tank, the wastewater flows into the bottom of reaction tank 1. 

Hatfield’s Ferry adds lime to reaction tank 1 to encourage metal hydroxide precipitation and to 

increase the pH from 5.5 S.U. (pH in the absorber) to between 8.5 and 9.0 S.U. Service water is 

used to create the hydrated lime. Hatfield’s Ferry also adds an organosulfide, Nalmet® 1689, to 

reaction tank 1 to encourage the formation of sulfide complexes. The overflow from reaction 

tank 1 flows to reaction tank 2 where ferric chloride is added. 

From reaction tank 2, the wastewater is split evenly between two solids contact clarifiers. 

Right before this split, a polymer is added to the wastewater. As of the time of the sampling 

episode, one clarifier was out of service and being repaired, and all wastewater was being 

transferred to the second clarifier. Hatfield’s Ferry personnel noted that at the low flow rate at 

which the system was operating during the sampling episode, the clarifiers achieve better 

performance if only one clarifier is operating because if both are operating, the flow does not 

provide enough hydraulic lift to keep the sludge bed suspended. Both solids contact clarifiers 

contain a sludge bed that facilitates removal of the solids in the wastewater. A portion of the 

sludge from the clarifiers can be recycled to reaction tank 1, while the majority is transferred to 

the sludge tank and then pumped to a filter press for dewatering. At the time of the sampling 

episode, the plant was not recycling any of the clarifier sludge to reaction tank 1. 

The dewatered sludge, which contains approximately 75% solids, is transferred to the onsite landfill, along with the gypsum. The filter press filtrate is transferred to the wastewater 

treatment area sump and recycled back to the equalization tank. 

The clarifier overflow is transferred to the sand filters (gravity filtration); however, prior 

to reaching the sand filters, hydrochloric acid is injected into the waste stream to decrease the pH 

to 7.0 S.U. The backwash from the sand filters is transferred to the wastewater treatment area 

sump, which is recycled back to the equalization tank. 

After treatment with the sand filters, the wastewater is collected in the treated wastewater 

storage tank. From this tank, the wastewater is either recirculated back to the equalization tank or 

mixed with the effluent from the treatment lagoon and discharged to the Monongahela River. 

Discharge from the wastewater treatment system is continuous, unless the plant is 

recirculating the effluent because it is not meeting specifications. The plant’s permit limit for its 

average monthly discharge flow rate is 160 gpm, therefore the plant attempts to keep the average 

daily discharge at 160 gpm. The wastewater treatment system is designed for typical flow rates 

between 100 and 500 gpm. The hydraulic residence time of the FGD wastewater treatment 

system is 24 hours.
2-5

2.2.1 Sampling Points 

Figure 2-2 shows the sampling points for the Hatfield’s Ferry sampling episode; they are 

summarized below: 

 A sample of the secondary hydrocyclone overflow from an individual unit1

, which 

is upstream of the equalization tank (i.e., the sample was collected prior to any 

chemical addition or mixing with recycle streams); and 

 A sample of the effluent from the treated wastewater storage tank, before mixing 

with the treated wastewater lagoon effluent. 

 

1

 During each day of the sampling episode, ERG collected the secondary hydrocyclone overflow from one unit. 

Over the course of the four-day sampling episode, ERG collected the secondary hydrocyclone overflow once from 

Unit 1, once from Unit 2, and twice from Unit 3. 
2-6 

Figure 2-1. Simplified Diagram of the FGD Wastewater Treatment System, Hatfield’s Ferry Power 
2-7 

Figure 2-2. Detailed Diagram of the FGD Wastewater Treatment System, Hatfield’s Ferry Power S
3-1

3. SAMPLE COLLECTION

During the Hatfield’s Ferry sampling episode, the sampling team followed the collection 

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

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

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

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

activities. 

3.1 Sampling Points, Sample Collection Methods, and Field Measurements

This section describes the sampling points, sample collection methods, and field 

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

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

including sampling point locations. 

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

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

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

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

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

sample identification and the sample points for each day. 

The sampling points for this episode were: 

 SP-1 Influent to FGD Wastewater Treatment System; 

 SP-2 Effluent from FGD Wastewater Treatment System; 

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

 SP-4 Influent of FGD Wastewater Treatment System (SP-1) Field Blank; and 

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

For all the sampling points, EPA collected split samples with Hatfield’s Ferry’s 

representative by inserting a “Y” splitter into the sample tubing configuration at each sampling 

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

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

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

therefore, for these samples, EPA and Hatfield’s Ferry’s representative collected duplicate 

samples, with one filling the bottle immediately after the other. 

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

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

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

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

shallow lip and a flip-top lid that secures itself open with clips. The “cleanbox” is double-bagged 

with a clear inner bag, enclosed in a translucent outer bag. The “cleanbox” is handled using 

“clean hands / dirty hands” techniques, whereby the inner bag is handled only by the “clean 

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

the box and pull the bag over the opening of the box, but is still able to see the sample bottles and 
3-2

tubing. The “cleanbox” minimizes potential atmospheric contamination during sample 

collection. 

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

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

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

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

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

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

protocols. 

3.1.1 Influent to FGD Wastewater Treatment System 

The influent to the FGD wastewater treatment system (SP-1) was collected from a sample 

tap located on the wastewater piping on the overflow line from the secondary hydrocyclones. 

Because Hatfield’s Ferry does not have a sample tap located downstream from where the 

secondary hydrocyclone overflow for each unit is combined, one unit’s secondary hydrocyclone 

overflow was sampled each day2

. Figure 2-2 identifies the sampling location for SP-1. This 

sample was collected as a grab sample. Due to the relatively high concentration of suspended 

solids, the FGD purge was not amenable to collecting representative split samples using 

composite sampling techniques. This was not an issue for samples collected at SP-1 because the 

characteristics of the influent to the wastewater treatment system are expected to be fairly 

consistent during the purge. The sampling point was located inside the gypsum dewatering 

building, at the location of the secondary hydrocyclones. Because the sampling point was 

located inside, there were no wind or rain concerns during the sample collection. 

On Day 1 only, prior to collecting the samples 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. See Section 5.2.3 for a description of 

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

system. 

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

system, a 3/8 inch hose barb was attached to the sample tap tubing to reduce the diameter of the 

sample tap. The sample tap was only a couple feet off the ground and because the wastewater at 

the tap was not pressurized, the samples either had to collected on the ground, or on the 

level/floor below the secondary hydrocyclones. Therefore, the samplers attached a 15-foot 

length of silicone tubing to the sample tap, and carefully lowered the tubing through the opening 

in the secondary hydrocylones down to the level below. The end of the silicone tubing was fitted 

with a “Y” splitter, with two additional lengths of silicone tubing attached to the “Y” splitter. 

The samplers attached the silicone tubing to the hose barb, opened the valve, and allowed sample 

to flow through the tubing and hose barb for two minutes before beginning to fill sample 

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

dissolved metals samples). 

 

2

 Secondary hydrocyclone overflow from Unit 3 was sampled on day 1 and day 4. Secondary hydrocyclone 

overflow from Unit 2 was sampled on day 2 and secondary hydrocyclone overflow from Unit 1 was sampled on day 

3. 
3-3

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

3.1: 

 Total and dissolved mercury; 

 Total metals by 200.8; and 

 Total metals by 200.7. 

Samplers then filled a 10-liter3 container with sample to be pumped off later for 

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

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

then left untouched to allow the solids in the wastewater to settle. 

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

temperature were measured immediately at the sampling point using four-color pH paper, 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 containers for biochemical oxygen demand (BOD5), Group I, 

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

Table 3-6 for a list of Group I and Group II analytes. BOD5, Group I, Group II, and total cyanide 

samples were immediately placed on ice after sample collection. 

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

potassium-iodide starch test strips were used to measure for sulfides and oxidants, respectively. 

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

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

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

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

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

attached a capsule filter to the silicone tubing, which was a short distance downstream of the 

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

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

to collect “true” split samples with Hatfield’s Ferry’s representatives. The sampling team placed 

the end of the Teflon® tubing into the 10-liter container filled with wastewater from the influent 

to the FGD wastewater treatment system. By this time, the solids in the wastewater had been 

settling for approximately 120 minutes. Approximately 0.5 liters of sample were pumped 

through the tubing/filter to purge the line before collecting samples4

. 

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

Section 3.1: 

 Dissolved metals by 200.8; 

 

3

 On day 3 and day 4, two (2) 10-liter containers were collected for the dissolved metals pump off because the 

sample collected on Day 2 did not result in enough supernatant to collect all sample fractions needed. ERG filled 

one 10-liter container while Hatfield’s Ferry’s representatives filled the other 10-liter container. 4

 On day 3 and 4, one 10-liter container was used to collect the 200.8 dissolved metals sample volumes. The sample 

tubing was then moved to the second 10-liter container, purged with 0.5 liters of sample, and the remaining sample 

volumes were collected. 
3-4

 Dissolved metals by 200.7; and 

 Dissolved hexavalent chromium5. 

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

3.1.2 Effluent from FGD Wastewater System 

The effluent from the FGD wastewater system (SP-2) was collected from a sample tap 

downstream of the treated wastewater storage tank on the suction side of the pump that directs 

the wastewater to the river for discharge. EPA decided to sample from the suction side of the 

pump because Hatfield’s Ferry does not always transfer treated effluent to the river; therefore, if 

the sample was located on the discharge side of the pump, then EPA would not be able to collect 

sample aliquots when the discharge was not occurring. Hatfield’s Ferry installed a three-way 

splitter on the sample tap, which had three separate taps to collect samples from the sampling 

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

for the sampling location for SP-2). Because the sampling point was located inside, there were 

no wind or rain concerns during the sample collection. 

ERG collected the effluent from the FGD wastewater treatment system composite 

samples using two automatic compositors which were programmed to collect individual sample 

volumes into two 20-liter containers. The compositors were programmed to collect 830 mL 

every hour during the 24-hour composite period. Following the composite period, ERG pumped 

off the specific sample volumes into the individual sample containers. 

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

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

analytes (i.e., BOD5, Group I, and Group II, excluding cyanide). In addition to collecting 

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

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

grab sample for cyanide during each compositing period. 

On day 1 only, ERG collected field blank samples (SP-5) for hexavalent chromium, total 

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

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

treatment system. 

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

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

T-splitter. The tubing configuration was set up such that one end was connected to the sample 

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

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

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

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

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

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

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

 

5

 On day 2, the samplers were unable to collect the hexavalent chromium sample because there was not enough 

supernatant in the 10-L container after allowing the solids to settle. 
3-5

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

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

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

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

each individual sample aliquot6

. 

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

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

to minimize contamination. 

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

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

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

procedures at the influent to the bioreactor system. 

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

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

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

with a ziptie. Because the sample tap was located on the suction side of the effluent transfer 

pumps, the head from the wastewater storage tank level was the only pressure moving the water 

through the piping. Because of this reduced pressure, when the samplers opened the third valve 

on the sample tap to collect the mercury samples, no wastewater was drained. Therefore, to 

collect the mercury sample, the sampling team pinched the drain line of the T-splitter tubing set 

for the both the metals and classical compositors to obtain flow through the tap used for mercury 

sampling. After purging the tap for two minutes, the samples were collected directly from the 

tap into the sample bottles. After the samples were collected the drain line in the T-splitter tubing 

sets for the compositors were released and allowed to flow normally. Because total mercury and 

dissolved mercury samples were collected directly from the tap, ERG was not able to collect split 

samples with Hatfield’s Ferry’s representatives; therefore, duplicate samples were collected. 

ERG collected another set of total and dissolved mercury samples every six hours thereafter over 

the 24-hour period. The plastic shroud was replaced for each set of mercury grab samples. After 

collecting each set of mercury grabs, ERG filled a field test bottle and tested for pH and 

temperature using four-colored pH paper, a pH meter, and a thermometer. Table 3-3 presents the 

field measurement data for the effluent of the FGD wastewater treatment system. 

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

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

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

split samples with Hatfield’s Ferry’s representatives; therefore, duplicate samples were collected. 

The total cyanide sample was immediately preserved with sodium hydroxide to a pH >10 S.U. 

and the samples placed on ice. Lead acetate test strips and potassium-iodide starch test strips 

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

detected during the sampling episode at effluent from the FGD wastewater treatment system. 

 

6

 On day 4 of sample collection, the samplers pinched the drain line of the T-splitter tubing set for the classical 

compositor so there was only a drain line from the metals compositor. This approach provided a more consistent 

flow for each of the compositors and still allowed both compositors to purge the line back to the flowing stream 

prior to each individual sample aliquot, the classical just had to purge all the way back to the sample tap. 
3-6

After the twenty-fourth aliquots were collected in the two composite containers7, ERG 

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

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

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

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

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

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

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

transferred the wastewater collected in the 20-liter containers into the individual sample 

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

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

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

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

concentrations in the dissolved metals fractions. 

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

previously filled 20-liter containers. The pump-off station consisted of a length of Teflon® 

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

pump. The sampling team attached a capsule filter to the silicone tubing, which was a short 

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

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

tubing. This set-up allowed EPA to collect “true” split samples with Hatfield’s Ferry’s 

representative. On Day 1 only, prior to collecting any samples of the effluent from the FGD 

wastewater treatment system, the samplers collected a field blank sample (SP-5) for dissolved 

and total metals. See Section 5.2.3 for a description of the dissolved metals field blank sample 

collection at the influent to the bioreactor system. 

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

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

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

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

 Dissolved metals by 200.8; 

 Dissolved metals by 200.7; and 

 Dissolved hexavalent chromium. 

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

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

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

described in Section 3.1: 

 

7

 The 20-liter metals and classical containers from day 1 were almost completely full at the end of the 24-hour 

compositing period. There was only a small amount of head space in the vented cap. On day 2 the 20-liter classical 

compositor was disconnected after only nine full aliquots because the 20-liter container was already full. On day 3 

the metals composite container collected 22 liters of sample (and did not overflow) and the classical composite 

container collected 21.5 liter of sample. On day 4 the metals and classical composite containers collected 

approximately 20 liters each. 
3-7

 Total metals by 200.8; and 

 Total metals by 200.7. 

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

Teflon® tubing into the other previously filled 20-liter container8

. Once the tubing was purged 

with 1-2 liters of sample, samplers filled containers for biochemical oxygen demand (BOD5), 

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

6 for a list of Group I and Group II analytes. BOD5, Group I, and Group II samples were 

immediately placed on ice after sample collection. 

For mercury, ERG collected QC samples at the effluent from the FGD wastewater 

treatment system (SP-2) on Day 3 of the sampling episode. ERG collected QC samples for all 

other analytes at the effluent from the FGD wastewater treatment system (SP-2) on Day 4 of the 

sampling episode. In addition, for mercury, ERG collected a duplicate sample of the effluent 

from the FGD wastewater treatment system (SP-3) on Day 2 of the sampling episode. For all 

other analytes, ERG collected a duplicate sample for the effluent from the FGD wastewater 

treatment system (SP-3) on Day 3. 

3.2 List of Analytes and Sample Preservation

Samples collected at Hatfield’s Ferry were analyzed for the following pollutants: 

 Classicals: 

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

— Chemical oxygen demand (COD), 

— Total suspended solids (TSS), 

— Total dissolved solids (TDS), 

— Sulfate, 

— Chloride, 

— Total Kjeldahl nitrogen (TKN), 

— Ammonia as nitrogen, 

— Nitrate/nitrite as nitrogen, 

— Total phosphorus, 

— Total cyanide; 

 Total Metals9

: 

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

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

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

titanium, vanadium, and zinc. 

 Dissolved Metals: 

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

 

8

 On day 1 of the sampling episode, there was sufficient volume in the metals container; therefore, samplers did not 

transfer the tubing to the other container. On day 2, because the classicals composite container was disconnected 

(due to overfilling), the samplers collected all the samples from the metals composite container. 

9

 In this report, EPA uses the terms “total metals” and “total recoverable metals” interchangeably. 
3-8

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

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

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

concentrations. 

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

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

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

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

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

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

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

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

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

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

hexavalent chromium samples were preserved with ammonium sulfate buffer solution 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 tested for sulfides and oxidants immediately after 

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

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

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

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

3.3 Plant Operational Data

During the EPA sampling episode, Hatfield’s Ferry plant personnel provided the 

sampling team with operational data for each of the generating units and the FGD scrubber 

system, as well as operational and flow data for the FGD wastewater treatment system. Table 3-8 

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

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

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

episode, and Table 3-12 presents the FGD wastewater treatment system operating characteristics. 

3.4 Deviations from the Sampling and Analysis Plan

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

described below: 

 Preservation of 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 ammonium sulfate buffer solution was not 

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

sulfate buffer solution, followed by as much ammonium hydroxide as necessary 

to reach the desired pH. 

 Collection of total and dissolved mercury samples at SP-2: Because the sample 

tap was located on the suction side of the effluent transfer pumps, the head from 

the wastewater storage tank level was the only pressure moving the water through 
3-9

the piping. Because of this reduced pressure, when the samplers opened the third 

valve on the sample tap to collect the mercury samples, no wastewater was 

drained. Therefore, to collect the mercury sample, the sampling team pinched the 

drain line of the T-splitter tubing set for the both the metals and classical 

compositors to obtain flow through the tap used for mercury sampling. 

 Metals and Classicals Composite Containers at SP-2 (Day 1): On day 1 of 

sample collection at the effluent from the FGD wastewater treatment system, the 

samplers after the first 24-hour compositing period at the effluent from the FGD 

wastewater treatment system (SP-2), samplers disconnected the 20-liter containers 

from the compositors and noted that both containers were completely full, filled 

to above the 20-liter level. The number of complete aliquots collected is not 

known. 

 Collection of classicals samples at SP-2 (Day 1): On day 1 of sample collection 

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

team collected the classicals samples from the same 20-liter container that was 

used to collect the metals samples. There was sufficient volume remaining in the 

metals composite container, after collecting the required dissolved and total 

metals samples, to collect the samples for BOD, Group I analytes, and Group II. 

 Collection of hexavalent chromium samples at SP-1 (Day 2): On day 2 of 

sample collection at the influent to the FGD wastewater treatment system (SP-1), 

the hexavalent chromium sample was not collected. After allowing the solids to 

settle for approximately two hours, the samplers collected the dissolved metals by 

200.8 and dissolved metals by 200.7. The samplers then began collecting the 

hexavalent chromium sample but stopped when the bottle was approximately half 

full because the filter became clogged with solids. Sampling activities were 

paused and the sample was allowed to continue settling. During this time the 

hexavalent chromium sample was capped and the inner bag was sealed and left 

inside the clean box. The outer bag around the clean box was closed. After 

approximately one hour and twenty minutes, the 10-liter container was checked 

for further settling. Due to the minimal supernatant present, EPA decided not to 

collect the hexavalent chromium sample. 

 Collection of classicals composite sample at SP-2 (Day 2) – On day 2 of sample 

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

classical compositor was disconnected after only 9 full aliquots. The container 

was almost filled with 20-liters of sample and samplers chose to disconnect the 

compositor prior to the sample completely filling the 20-liter container. 

 Collection of duplicate samples (SP-3) – As described above, on day 2 of 

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

classical compositor overfilled during the compositing period. ERG had planned 

to collect the duplicate samples of the effluent from the FGD wastewater 

treatment system (SP-3) on day 2; however, because only one 20-L container 

would have volume for the sample collection, the metals and classical duplicate 

samples were collected on day 3 instead. At the time the classical composite 
3-10

container issue was identified, two of the four mercury duplicate samples had 

already been collected; therefore, ERG continued collecting the mercury duplicate 

samples on day 2. 

 Collection of dissolved metals samples at SP-1 (Days 3 and 4) – On day 3 and 

day 4 of the sample collection at the influent of the FGD wastewater system (SP2), two 10-liter containers were filled and allowed to settle before collection of 

dissolved metals samples. ERG filled one of the 10-liter containers while 

Hatfield’s Ferry’s representatives simultaneously filled an additional 10-liter 

container. One container was used to collect all sample volumes needed for 

dissolved metals 200.8. The pump off tubing was then transferred to the second 

10-liter container, purged with approximately 250 mL of sample, and the 

remaining sample volumes were collected. 

 Collection of duplicate samples for total and dissolved metals, classicals, and 

hexavalent chromium at SP-2 (Day 3) – On day 3 of the sample collection at the 

effluent of the FGD wastewater system (SP-2), both classical and metals 

compositors again collected more than the desired 20 liters of sample, with the 

metals compositor collecting approximately 22 liters and the classicals 

compositor collecting approximately 21.5 liters. Samplers were present for the 

final composite sample collection cycle and were able to verify that both 

containers did not reach full capacity and were able to hold the full volume of the 

last sample. The sample volume collected on day 3 of sampling was used to 

collect duplicate samples (SP-3) for total metals, dissolved metals, classicals, and 

hexavalent chromium. 

 Collection of QC samples at SP-2 – The QC samples for total and dissolved 

mercury at the effluent from the FGD wastewater treatment system (SP-2) were 

collected on day 2, as planned; however, because the duplicate samples for total 

and dissolved metals and classicals were collected on day 3 instead of day 2 (as 

described above), ERG collected the QC samples for these analytes on day 4 

instead of day 3. 
3-11

Table 3-1. Sample Collection Information, Hatfield’s Ferry

Sampling 

Point 

Number Sampling Point Description 

Type of 

Sample 

Sample Collection 

Date 

Sample Collection 

Time 

Influent to FGD Wastewater Treatment 

System – Day 1 

Grab 12/6/10 0907a and 1049b

Influent to FGD Wastewater Treatment 

System – Day 2 

Grab 12/7/10 0957a and 1214b

Influent to FGD Wastewater Treatment 

System – Day 3 

Grab 12/8/10 1048a and 1325b

SP-1 

Influent to FGD Wastewater Treatment 

System – Day 4 

Grab 12/9/10 0947a and 1229b

Composite 12/6/10 

12/7/10

0722c 

0813d

Effluent from FGD Wastewater System – 

Day 1 

Grab 12/6/10 

 12/7/10 

0736e

, 1332f , and 1943 g 

0126 h 

Composite 12/7/10 

 12/8/10 

0622c 

0828d 

Effluent from FGD Wastewater System – 

Day 2 

Grab 12/7/10 

 12/8/10 

0736e

, 1332f , and 1940 g 

0140 h 

Composite 12/8/10 

 12/9/10 

0759c 

0818d 

Effluent from FGD Wastewater System – 

Day 3 

Grab 12/8/10 

 12/9/10 

0809e

, 1408f , and 2007 g 

0210 h 

Composite 12/9/10 

 12/10/10 

0747c 

0706d 

SP-2 

Effluent from FGD Wastewater System – 

Day 4 

Grab 12/9/10 

 12/10/10 

0800e

, 1359f , and 2007 g 

0205 h 

Composite 12/8/10 

 12/9/10 

0759c 

0819d 

SP-3 Duplicate of Effluent from FGD 

Wastewater System – Day 3 

Grab 12/7/10 

 12/8/10 

0737e

, 1333f , and 1944 g 

0143 h 

SP-4 Influent to FGD Wastewater Treatment 

System Field Blank 

Grab 12/6/10 0850 i and 1040j

Composite 12/6/10 

12/7/10

0627k

0802l

Effluent from FGD Wastewater System 

Field Blank – Day 1 

Grab 12/6/10 0730m

Effluent from FGD Wastewater System 

Field Blank – Day 2 

Grab 12/7/10 0731m

Effluent from FGD Wastewater System 

Field Blank – Day 3 

Grab 12/8/10 0804m

SP-5 

Effluent from FGD Wastewater System 

Field Blank – Day 4 

Grab 12/9/10 0755m

a

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

dissolved mercury, and classicals (BOD5, Group I, Group II, and total cyanide). 

b

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

and dissolved hexavalent chromium (except for hexavalent chromium on day 2)). Does not include dissolved 

mercury. 
3-12

c Started metals compositor. The classical compositor was started approximately two minutes after the metals 

compositor. 

d

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

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

classicals (BOD5, Group I, and Group II). e

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

f

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

g

 Start time for the collection of total and dissolved mercury Grab 3 and total cyanide samples. h

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

i

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

j

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

field blank samples. 

k

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

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

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

m Start time for the collection of total mercury field blank samples. 
3-13 

Table 3-2. Sample Collection at Hatfield’s Ferry Steam Electric Plant

Sampling 

Point Number Sampling Point Name 

Total Metals 

(EPA Method 200.8 with 

collision cell)

Total Metals 

(EPA Method 200.7) 

Dissolved Metals 

(EPA Method 200.8 with 

collision cell) 

Dissolved Metals 

(EPA Method 200.7) 

Total Mercury 

Dissolved Mercury 

Hexavalent Chromium 

BOD

5

SP-1 Influent to FGD Wastewater Treatment 

System 

4 4 4 4 4 4 3c 4 

SP-2 Effluent from FGD Wastewater Treatment 

System 

4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+

SP-3 Duplicate of Effluent from FGD Wastewater 

Treatment System 

1 1 1 1 1 1 1 1 

SP-4 Influent to FGD Wastewater Treatment 

System Field Blank 

1 1 1 1 1 1 

SP-5 Effluent from FGD Wastewater Treatment 

System Field Blank 

1 1 1 1 4 1 

Total Number of Samples 11+1QC 11+1QC 11+1QC 11+1QC 14+1QC 9+1QC 10+1QC 9+1QC 9+

a Group I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate, and chloride. b Group II includes ammonia as nitrogen, nitrate/nitrite as nitrogen, total Kjeldahl nitrogen (TKN), chemical oxygen demand (COD), and total phosphc The hexavalent chromium sample for the influent to the FGD wastewater treatment system was not collected on day 2. See Section 3.4 for more deta
3-14 

Table 3-3. Field Measurements, Hatfield’s Ferry

pH 

(S.U.) Sampling Point 

Number Sampling Point Description Date Time 

Temperature 

(°C) Metera Strips 

Waste 

Stream Flow 

Rate 

(gpm) 

Influent to FGD Wastewater Treatment System – Day 1

12/6/2010 0907 47 5.92 6.5 171b 

Influent to FGD Wastewater Treatment System – Day 2 

12/7/2010 0957 49 6.06 7 171b 

Influent to FGD Wastewater Treatment System – Day 3 

12/8/2010 1048 49 6.11 7 171b 

SP-1 

Influent to FGD Wastewater Treatment System – Day 4 

12/9/2010 0947 48 6.14 7 171b 

Samplhad a appeaNo dein tota

12/6/10 0743 28 7.5 7 120c 12/6/10 1335 29 7.48 7 120c 12/6/10 2000 27 7.47 7 120 

Effluent from Wastewater Treatment System – Day 1

12/7/10 0132 28 7.48 7 120 12/7/10 0742 28 7.48 7 120 12/7/10 1340 28 7.46 7 120 12/7/10 1954 29 7.45 7.5 120 

Effluent from Wastewater Treatment System – Day 2 

12/8/10 0150 29 7.46 7 120 

12/8/10 0810 28 7.42 7 120 12/8/10 1410 29 7.61 7 111 12/8/10 2015 29 7.42 7 120 

Effluent from Wastewater Treatment System – Day 3 

12/9/10 0214 29 7.49 7 120 

12/9/10 0802 28 7.40 7 120 12/9/10 1401 29 7.42 7.5 120 12/9/10 2014 29 7.49 7.5 120 

SP-2 

Effluent from Wastewater Treatment System – Day 4 

12/10/10 0209 28 7.46 7.5 120 

Samplcolorlobservdetecttotal c

a The pH meter was calibrated prior to the sampling episode and once every day during the sampling episode using prepackaged buffer 

and 10.0. 

b Plant does not monitor or record the flow at SP-1. Plant estimates flow based to be an average of 171 gpm during the sampling periodc Discharge flow monitoring was not functioning until 12/6/2010 at 1400 hrs. Flow rate at SP-2 prior to this time is estimated (from 07
3-15 

Table 3-4. Crosswalk of Sample Number to Sampling Point and Day, Hatfield’s Ferry

Sample Number Sample Point Sample Description 

71941 SP-1, Day 1 Influent to FGD Wastewater Treatment System - Day 1 

71942 SP-1, Day 2 Influent to FGD Wastewater Treatment System - Day 2 

71943 SP-1, Day 3 Influent to FGD Wastewater Treatment System - Day 3 

71944 SP-1, Day 4 Influent to FGD Wastewater Treatment System - Day 4 

71945 SP-2, Day 1 Effluent to FGD Wastewater Treatment System - Day 1 

71946 SP-2, Day 2 Effluent to FGD Wastewater Treatment System - Day 2 

71947 SP-2, Day 3 Effluent to FGD Wastewater Treatment System - Day 3 

71948 SP-2, Day 4 Effluent to FGD Wastewater Treatment System - Day 4 

71949 SP-3, Day 2 Duplicate of Effluent to FGD Wastewater Treatment System - Day 2 

71950 SP-4, Day 1 Influent to FGD Wastewater Treatment System Field Blank - Day 1 

71951 SP-5, Day 1 Effluent to FGD Wastewater Treatment System Field Blank - Day 1 

71952 SP-5, Day 2 Effluent to FGD Wastewater Treatment System Field Blank - Day 2 

71953 SP-5, Day 3 Effluent to FGD Wastewater Treatment System Field Blank - Day 3 

71954 SP-5, Day 4 Effluent to FGD Wastewater Treatment System Field Blank - Day 4 

71955 SP-3, Day 3 Duplicate of Effluent to FGD Wastewater Treatment System - Day 3 
3-16 

Table 3-5. Analytical Methods, Hatfield’s Ferry

Parameter Method Number 

Classicals

Biochemical oxygen demand (BOD5) SM 5210 B 

Chemical oxygen demand (COD) EPA 410.4 

Total suspended solids (TSS) SM 2540 D 

Total dissolved solids (TDS) SM 2540 C 

Sulfate EPA 300.0 

Chloride EPA 300.0 

Ammonia as nitrogen EPA 350.1 

Nitrate/nitrate as nitrogen EPA 353.2 

Total Kjeldahl nitrogen (TKN) EPA 351.2 

Total phosphorus EPA 365.1 

Total cyanide SM 4500 CN E 

Total and Dissolved Metals

Mercury EPA 1631E 

Hexavalent chromium (dissolved only) EPA 218.6 

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

nickel, selenium, silver, thallium, and vanadium 

EPA 200.8 with collision cell1

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

molybdenum, sodium, tin, titanium, and zinc. 

EPA 200.7 

1

 EPA used an SOP developed specifically for analyzing FGD wastewater (see Appendix C).
3-17 

Table 3-6. Summary of Sample Container and Planned Preservation, Hatfield’s Ferry 

Parameter 

Sample 

Container and 

Volume 

QC Sample 

Container and 

Volume On-Site Preservation 

Classicals 

BOD5 One 1-L plastic 

bottle 

One 1-L plastic 

bottle 

≤6C 

Group I a One 1-L plastic 

bottles 

One 1-L plastic 

bottles 

≤6C 

Group II b Two 1-L plastic 

bottles 

Two 1-L plastic 

bottles 

H2SO4 to pH <2 S.U., ≤6C 

Total cyanide One 1-L plastic 

bottle 

One 1-L plastic 

bottles 

Dilution until sulfide is not detected, 

NaAsO2 until total chlorine is not 

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

≤6C 

Metals 

Total metals (EPA Method 200.8 with 

collision cell) 

One 500-mL 

plastic bottle 

No additional 

volume needed 

None 

(acid preserve at laboratory) 

Total metals (EPA Method 200.7) One 500-mL 

plastic bottle 

No additional 

volume needed 

None 

(acid preserve at laboratory) 

Dissolved metals (EPA Method 200.8 

with collision cell) 

One 500-mL 

plastic bottle 

No additional 

volume needed 

0.45-μm filter (performed in field) 

(acid preserve at laboratory) 

Dissolved metals (EPA Method 200.7) One 500-mL 

plastic bottle 

No additional 

volume needed 

0.45-μm filter (performed in field) 

(acid preserve at laboratory) 

Total mercury: 

Manual composite grab samples Four 125-mL 

glass bottle 

No additional 

volume needed 

Influent samples and field blank 

samples 

Two 250-mL 

glass bottle 

No additional 

volume needed 

None 

(acid preserve at laboratory) 

Dissolved mercury: 

Manual composite grab samples Four 125-mL 

glass bottle 

No additional 

volume needed 

Influent samples One 250-mL 

glass bottle 

No additional 

volume needed 

None 

(filter and acid preserve at 

laboratory) 

Hexavalent chromium One 250-mL 

plastic bottle 

No additional 

volume needed 

0.45-μm filter (performed in field) 

Ammonium sulfate buffer to 

pH 9.3 – 9.7 S.U., ≤6C 

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

(b) Group II includes ammonia as nitrogen, COD, nitrate/nitrite as nitrogen, TKN, and total phosphorus.
3-18 

Table 3-7. Sample Preservation Summary, Hatfield’s Ferry

Sampling Point 

Number Analysis Date 

Chemical 

Added 

Initial pH 

(S.U.) 

Final pH 

(S.U.) 

Amount 

Added 

(drops) 

71941 Group II Volume I 12/6/2010 H2SO4 7 2 175 

71941 Group II Volume II 12/6/2010 H2SO4 7 2 170 

(NH4)2SO4

Buffer 

71941 Hexavalent Chromium 12/6/2010 6.5 8.5 100 

NH4OH 8.5 9.5 10 

(NH4)2SO4

Buffer 

71950 Hexavalent Chromium Field 6.5 9 100 

Blank 

12/6/2010 

NH4OH 9 9.5 6 

71941 Total Cyanide 12/6/2010 NaOH 6.5 10 210 

71945 Total Cyanide 12/6/2010 NaOH 8.0 10 25 

71942 Group II Volume I 12/7/2010 H2SO4 6 2 200 

71942 Group II Volume II 12/7/2010 H2SO4 6 2 200 

71945 Group II Volume I 12/7/2010 H2SO4 7.5 2 40 

71945 Group II Volume II 12/7/2010 H2SO4 7.5 2 40 

(NH4)2SO4

Buffer 

71945 Hexavalent Chromium 12/7/2010 7.1 8.1 100 

NH4OH 8.7 9.5 3 

(NH4)2SO4

Buffer 

71951 Hexavalent Chromium Field 6.5 9.0 100 

Blank 

12/7/2010 

NH4OH 9.0 9.5 5 

71942 Total Cyanide 12/7/2010 NaOH 6.5 10 350 

71946 Total Cyanide 12/7/2010 NaOH 7 10 20 

71949 Total Cyanide 12/7/2010 NaOH 7 10 25 

71943 Group II Volume I 12/8/2010 H2SO4 6 2 200 

71943 Group II Volume II 12/8/2010 H2SO4 6 2 200 

71946 Group II Volume I 12/8/2010 H2SO4 7.5 2 40 

71946 Group II Volume II 12/8/2010 H2SO4 7.5 2 40 

(NH4)2SO4

Buffer 

71943 Hexavalent Chromium 12/8/2010 6.5 8.1 100 

NH4OH 8.1 9.5 24 

(NH4)2SO4

Buffer 

71946 Hexavalent Chromium 12/8/2010 7.4 8.7 200 

NH4OH 8.7 9.5 6 

71943 Total Cyanide 12/8/2010 NaOH 6.5 10 275 

71947 Total Cyanide 12/8/2010 NaOH 7.5 10 20 

71955 Total Cyanide 12/8/2010 NaOH 7.5 10 20 

71944 Group II Volume I 12/9/2010 H2SO4 6 2 240 

71944 Group II Volume II 12/9/2010 H2SO4 6 2 260 

71947 Group II Volume I 12/9/2010 H2SO4 7 2 40 

71947 Group II Volume II 12/9/2010 H2SO4 7 2 40 

71955 Group II Volume I 12/9/2010 H2SO4 7 2 40 
3-19 

Table 3-7. Sample Preservation Summary, Hatfield’s Ferry

Sampling Point 

Number Analysis Date 

Chemical 

Added 

Initial pH 

(S.U.) 

Final pH 

(S.U.) 

Amount 

Added 

(drops) 

71955 Group II Volume II 12/9/2010 H2SO4 7 2 40 

(NH4)2SO4

Buffer 

71944 Hexavalent Chromium 12/9/2010 7 8.3 100 

NH4OH 8.3 9.5 12 

(NH4)2SO4

Buffer 

71947 Hexavalent Chromium 12/9/2010 7 8.5 100 

NH4OH 8.5 9.5 10 

(NH4)2SO4

Buffer 

71955 Hexavalent Chromium 12/9/2010 7 8.5 100 

NH4OH 8.5 9.5 10 

71944 Total Cyanide 12/9/2010 NaOH 6.5 10 206 

71948 Total Cyanide 12/9/2010 NaOH 7 10 20 

71948 Total Cyanide - QC 12/9/2010 NaOH 7 10 20 

71948 Group II Volume I 12/10/2010 H2SO4 7 2 30 

71948 Group II Volume II 12/10/2010 H2SO4 7 2 30 

71948 Group II Volume I - QC 12/10/2010 H2SO4 7 2 30 

71948 Group II Volume II - QC 12/10/2010 H2SO4 7 2 30 

(NH4)2SO4

Buffer 

71948 Hexavalent Chromium 12/10/2010 7 8.5 100 

NH4OH 8.5 9.5 9 
3-20 

Table 3-8. Generating Unit Operating Characteristics during Sample Collection, Hatfield’s Ferry

Unit ID Boiler Type 

Capacity 

(MW) 

Electricity Production 

(MW) 

(or Percent Capacity %)

SNCR 

(No, On, Off) 

Particulate Control System 

(HS/CS ESP, or BH) 

1 

Once Thru 

Supercritical 

Opposing Wall 

Fired 

570 91% No ESP 

2 

Once Thru 

Supercritical 

Opposing Wall 

Fired 

570 87% No ESP 

3 

Once Thru 

Supercritical 

Opposing Wall 

Fired 

570 89% Off ESP 
3-21 

Table 3-9. FGD Scrubber System Operating Characteristics, Hatfield’s Ferry 

Unit ID 

Wet FGD 

System (Yes/No) 

Type of 

Scrubber 

Forced 

Oxidation 

(Yes/No) Sorbent 

Additives (DBA, 

formic acid, etc.) 

FGD Make-up 

Water Source 

SO2 Re

Percen

1 Yes B&W Yes Limestone None River and waste water 992 Yes B&W Yes Limestone None River and waste water 993 Yes B&W Yes Limestone None River and waste water 99

B&W – Babcock and Wilcox Company
3-22

Table 3-10. Coal Usage during Sample Collection, Hatfield’s Ferry 

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 

Coala

(ppm) 

1 E Bit at 84% 

PRB at 16% 4,435 

Eastern 

Bituminous 

WY 

2.55 NA 

2 E Bit at 84% 

PRB at 16% 4,685 

Eastern 

Bituminous 

WY 

1 2.55 NA 

3 E Bit at 84% 

PRB at 16% 5,409 

Eastern 

Bituminous 

WY 

2.55 NA 

1 E Bit at 73% 

PRB at 27% 4,879 

Eastern 

Bituminous 

WY 

2.91 NA 

2 E Bit at 73% 

PRB at 27% 5,042 

Eastern 

Bituminous 

WY 

2 2.91 NA 

3 E Bit at 73% 

PRB at 27% 4,239 

Eastern 

Bituminous 

WY 

2.91 NA 

1 E Bit at 70% 

PRB at 30% 3,868 

Eastern 

Bituminous 

WY 

2.92 NA 

2 E Bit at 70% 

PRB at 30% 4,015 

Eastern 

Bituminous 

WY 

3 2.92 NA 

3 E Bit at 70% 

PRB at 30% 5,899 

Eastern 

Bituminous 

WY 

2.92 NA 

1 E Bit at 58% 

PRB at 42%b 4,556 

Eastern 

Bituminous 

WY 

3.24 NA 

2 E Bit at 58% 

PRB at 42%b 3,829 

Eastern 

Bituminous 

WY 

4 3.24 NA 

3 E Bit at 58% 

PRB at 42%b 5,179 

Eastern 

Bituminous 

WY 

3.24 NA 

a

 Data on chlorine content of coal is not available. 

b A 42% blend of PBR is ver a typical for Hatfield’s Ferry. Normal PBR fuel blends typically run around 20% 

PBR/80% Eastern Bituminous.

 
3-23

Table 3-11. Scrubber Slurry Information during Sample Collection, Hatfield’s Ferry

Scrubber Slurry 

Blowdown Flow Rate 

Day of 

Sampling 

FGD 

System ID 

Associated 

Unit IDs 

Flow Rate 

(gpm) Duration 

Scrubber 

Slurry 

Percent 

Solids 

Time of 

Dewatering 

During 

Sampling Day 

Percent 

Filtrate 

Recycled 

Back to 

Scrubber 

1 1 1400 11 hrs 

30min 21% 2:00am – 11:00am 

9:30pm – 12:00am 97% 

2 2 1400 12 hrs 

20 min 

21% 12:00am – 2:20am 

12:00pm – 4:00pm 

6:00pm – 12:00am 

97%

1 

3 3 1400 12 hrs 

15 min 

21% 12:00am – 3:30am 

12:30pm – 3:30pm 

5:15pm – 11:00pm 

97%

1 1 1400 16 hrs 21% 12:00am – 7:30am 

3:30pm – 12:00am 

93%

2 2 1400 12 hrs 21% 12:30am – 4:30am 

11:45am – 7:45pm 

93% 2 

3 3 1400 12 hrs 

40 min 

21% 3:20am – 2:00pm 

10:00pm –12:00am 

93%

1 1 1400 7 hrs 

20 min 

21% 12:00am – 2:00am 

1:00pm – 6:20pm 

91%

2 2 1400 9 hrs 

20 min 

21% 3:00am – 9:00am 

8:40pm – 12:00am 

91% 3 

3 3 1400 13 hrs 

10 min 

21% 12:00am – 5:00am 

1:50pm – 12:00am 

91%

1 1 1400 14 hrs 

45 min 

21% 4:00am – 1:00pm 

6:15pm – 12:00am 

93%

2 2 1400 13 hrs 

30 min 

21% 12:00am – 6:30am 

11:00am – 6:00pm 

93% 4 

3 3 1400 12 hrs 

30 min 

21% 12:00am – 4:30am 

1:30pm – 9:30pm 

93%
3-24 

Table 3-12. FGD Wastewater Treatment System Operation Information, Hatfield’s Ferry

Scrubber Purge Chemical Usage 

Day of 

Sampling 

Flow Rate 

(gpm) 

Duration 

(hr) Lime (tons) 

Ferric Chloride 

(liters) 

Organosulfide 

Nalco 1689 

(liters) 

Polymer

Nalco 140

(liters) 

1 47 24 1.2 63 17 29 2 120 24 3.1 98 17 43 3 118 24 3.1 92 17 43 4 120 24 3.1 86 17 43 
4-1 

4. LABORATORY ANALYTICAL RESULTS AND DISCUSSION

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

the FGD wastewater treatment system and the effluent from the FGD wastewater treatment 

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

SP-1. Section 4.2 presents the laboratory analytical data for the influent to and effluent from the 

FGD wastewater treatment system. 

The total and dissolved mercury samples were analyzed by Frontier Global Sciences 

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

nitrate membrane filters contained in disposable polystyrene filtration units at the Frontier 

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

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

mercury samples were subjected to a room temperature bromine monochloride digestion prior to 

analysis using a method-compliant bubbler system. 

For the total and dissolved mercury samples from SP-2, EPA collected four individual 

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

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

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

limited volume, equal volumes from each individual grab sample were combined for the 

composite analysis. 

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

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

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

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

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

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

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

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

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

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

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

The classical analytes were analyzed by TestAmerica and were digested, prepared, and 

analyzed according to the methods specified in Table 3-5. 

Appendix A provides all analytical results for all samples collected at Hatfield’s Ferry, 

including all qualified results and all results that were measured above the method detection 

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

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

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

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

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

TestAmerica’s long term blank studies. If the typical background blank levels for a given 

element are variable or frequently elevated, then the quantitation limit may be raised to prevent 
4-2 

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

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

4.1 Measured and Calculated Results for Influent to FGD Wastewater Treatment 

System Samples

The samples of the influent to the FGD wastewater treatment system were expected to 

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

unreacted limestone, and fly ash. Because of this, 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 solids loads. Therefore, ERG directed its contract 

laboratories to separate the aqueous and solid phases of the sample 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 following phases of the sample: 

 Aqueous phase; 

 Solid phase; and 

 Total sample. 

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

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

This section describes the approaches used by each laboratory and presents 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 consisted 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 separated 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 associated with the 200.7 analysis 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 nitrate/nitrite and ammonia, the analytical methods (i.e., EPA 

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

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

ammonia in the FGD influent solid samples by performing 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 preserved 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 analysis, so the solid concentration 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 volume, solid phase weight, 

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

concentrations for the sample. 

Sample

Filtrate Filtrate Solid Solid

V

(C V ) (C Wt ) TotalSampleConcentration     (4-1) 

where: 

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

VFiltrate = volume of the filtrate; 

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

WtSolid = weight of the solids in the sample; and 

VSample = volume of the original sample. 

TestAmerica used the same approach for the seven 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 any language stating how wastewater samples with high solid 

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

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

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

solid and aqueous phases separately. 

Once the FGD influent samples were separated 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 the samples with aqua regia (HCl/HNO3) 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 volume, 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 the results of the biphasic analysis for 

ammonia as nitrogen, nitrate/nitrite, 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 wastewater 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 effluent from the FGD wastewater treatment system 

(SP-2). 

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

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

sample above the method detection limit, the result is reported as “ND” followed by the 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 wastewater treatment system), a duplicate sample 

for mercury was collected on Day 2 of the sampling episode and duplicate samples for all other 

analytes were collected on Day 3. The Day 2 result for mercury presented in Table 4-2 represent 

the average of the original and the duplicate sample results and the Day 3 results for all analytes 

other than mercury in Table 4-2 represent the average of the original and duplicate sample 

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

from Day 2 and the calculated relative percent difference (RPD). Table 5-3 presents the 

analytical results for the original and duplicate results for all analytes other than mercury for Day 

3 and the calculated RPD. 

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

averages, ERG used the following methodology: 

 If all results were above the quantitation limit, then all results were averaged 

together; 

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

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

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

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

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

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

the average of the sample-specific quantitation limits; and 

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

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

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

Table 4-3 presents the 4-day average results for all classical analytes for the influent to 

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

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

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

(SP-1) and the effluent from the FGD wastewater treatment system (SP-2). The results presented 
4-5 

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

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

system. 

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

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

system (SP-2), and the duplicate of the effluent from the FGD wastewater treatment system (SP3) sample analyses, including J-values. 
4-6 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKNrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. H – Sample was prepared/analyzed beyond the specified holding time. P – Sample was not preserved immediately following collection. 

Table 4-1. Influent to FGD Wastewater Treatment System, Hatfield’s Ferry 

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Classicals Ammonia mg/L 350.1 

NQ 

(4.20) 

F(H, P) – 

S(H, P, Est) 

NQ 

(4.22) 

F(H, P) – 

S(H, P, Est) 

NQ 

(4.31) 

F(H, P) – S(H, 

P, Est) 

NQ 

(4.15) 

Nitrate Nitrite as N mg/L 353.2 129 

F(H, P, Est) – 

S(H, P, Est) 208 

F(H, P, Est) – 

S(H, P, Est) 157 

F(H, P, Est) – 

S(H, P, Est) 129 

Nitrogen, Total Kjeldahl mg/L 351.2 45.6 

F(B, H, P, Est) 

– S(H, P, Est) 57.4 

F(B, H, P, Est) – 

S(H, P, Est) 38.3 

F(B, H, P, Est) – 

S(H, P, Est) 47.0 

Biochemical Oxygen Demand mg/L 5210B 3.00 B NQ (5.00) 3.80 2.50 Chemical Oxygen Demand mg/L 410.4 250 F,G,Est 520 350 G,Est 280 Chloride mg/L 300.0, 9056 5,610 

F(H, Est) – 

S(H, Est) 8,510 

F(H, Est) – 

S(H, Est) 8,000 

F(H, Est) – 

S(H, Est) 6,250 

Sulfate mg/L 300.0, 9056 10,400 

F(H, Est) – 

S(H, Est) 11,800 

F(H, Est) – 

S(H, Est) 10,100 

F(H, Est) – 

S(H, Est) 10,300 

Cyanide, Total mg/L 4500 CN E 

NQ 

(0.119) 

F(H, P) – 

S(H, P, Est) 0.216 

F(H, P, Est) – 

S(H, P, Est) 0.195 

F(H, P, Est) – S(H, 

P, Est) 0.136 

Total Dissolved Solids mg/L 2540C 25,000 41,000 31,000 26,000 
4-7 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKNrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. H – Sample was prepared/analyzed beyond the specified holding time. P – Sample was not preserved immediately following collection. 

Table 4-1. Influent to FGD Wastewater Treatment System, Hatfield’s Ferry 

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Total Suspended Solids mg/L 2540D 54,000 67,000 66,000 47,000 Phosphorus, Total mg/L 365.1 

NQ 

(0.345) 

F(B, H, P, Est) 

– S(H, P) 17.8 

F(B, H, P, Est) – 

S(H, P, Est) 13.3 

F(B, H, P, Est) 

– S(H, P, Est)

NQ 

(0.322) 

Total Metals Aluminum ug/L 200.7, 6010B 1,760,000 2,550,000 2,080,000 2,000,0Antimony ug/L 200.8, 6020 24.1 NQ (29.3) NQ (26.7) NQ (21Arsenic ug/L 200.8, 6020 2,300 4,610 2,150 2,830 Barium ug/L 200.7, 6010B 13,000 S(B) 21,300 S(B) 12,500 S(B) 13,400 Beryllium ug/L 200.7, 6010B 59.9 136 54.9 73.7 Boron ug/L 200.7, 6010B 233,000 S(B) 364,000 F(B) – S(B) 309,000 F(B) – S(B) 262,000 Cadmium ug/L 200.8, 6020 425 595 589 451 Calcium ug/L 200.7, 6010B 8,230,000 6,730,000 9,700,000 6,740,0Chromium ug/L 200.8, 6020 6,460 8,490 6,920 6,660 Cobalt ug/L 200.7, 6010B 556 869 637 597 Copper ug/L 200.8, 6020 1,900 3,130 2,090 2,200 Iron ug/L 200.7, 6010B 1,470,000 2,050,000 1,800,000 1,770,0Lead ug/L 200.8, 6020 1,170 S(B) 2,120 S(B) 1,310 S(B) 1,390 
4-8 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKNrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. H – Sample was prepared/analyzed beyond the specified holding time. P – Sample was not preserved immediately following collection. 

Table 4-1. Influent to FGD Wastewater Treatment System, Hatfield’s Ferry 

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Magnesium ug/L 200.7, 6010B 5,070,000 6,830,000 6,150,000 5,120,0Manganese ug/L 200.7, 6010B 71,100 98,300 96,200 80,400 Mercury ng/L 

1631E, FGS069 521,000 654,000 789,000 624,00

Molybdenum ug/L 200.7, 6010B 675 1,350 680 760 Nickel ug/L 200.8, 6020 2,970 4,360 3,710 3,280 Selenium ug/L 200.8, 6020 2,680 3,920 3,550 2,740 Silver ug/L 200.8, 6020 NQ (12.4) NQ (15.2) NQ (14.3) NQ (11Sodium ug/L 200.7, 6010B 377,000 607,000 465,000 373,00Thallium ug/L 200.8, 6020 96.8 195 99.9 116 Tin ug/L 200.7, 6010B NQ (757) NQ (785) NQ (769) NQ (65Titanium ug/L 200.7, 6010B 14,100 29,700 11,100 16,100 Vanadium ug/L 200.8, 6020 5,900 10,700 6,530 7,230 Zinc ug/L 200.7, 6010B 15,000 F(B) 19,100 F(B) 16,200 F(B) 15,400 Dissolved MetalsAluminum ug/L 200.7 NQ (200) 250 ND (200) NQ (2Antimony ug/L 200.8 5.40 13.0 5.60 6.30 Arsenic ug/L 200.8 5.20 11.0 5.10 7.70 Barium ug/L 200.7 140 160 160 160 Beryllium ug/L 200.7 3.00 3.60 NQ (2.00) 3.10 
4-9 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKNrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. H – Sample was prepared/analyzed beyond the specified holding time. P – Sample was not preserved immediately following collection. 

Table 4-1. Influent to FGD Wastewater Treatment System, Hatfield’s Ferry 

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Boron ug/L 200.7 250,000 B 410,000 B 340,000 B 290,00Cadmium ug/L 200.8 300 450 420 290 Calcium ug/L 200.7 730,000 800,000 860,000 780,00Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.Chromium (VI) ug/L 218.6 ND (10.0) NA ND (10.0) ND (10Cobalt ug/L 200.7 310 370 380 330 Copper ug/L 200.8 14.0 14.0 14.0 11.0 Iron ug/L 200.7 ND (200) ND (200) ND (200) ND (20Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.Magnesium ug/L 200.7 4,400,000 6,300,000 5,300,000 4,800,0Manganese ug/L 200.7 69,000 94,000 96,000 82,000 Mercury ng/L 1631E 131 382 236 187 Molybdenum ug/L 200.7 320 960 360 420 Nickel ug/L 200.8 1,000 1,200 1,200 1,100 Selenium ug/L 200.8 340 1,100 350 400 Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.Sodium ug/L 200.7 370,000 590,000 470,000 360,00
4-10 

Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKNrepresent the total result that was calculated based on the results of the solid and aqueous phase of the samples. See Section 4.1 for more details. Saman ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the s< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. H – Sample was prepared/analyzed beyond the specified holding time. P – Sample was not preserved immediately following collection. 

Table 4-1. Influent to FGD Wastewater Treatment System, Hatfield’s Ferry 

Influent to FGD Wastewater Treatment System (SP-1) 

Analyte Units Method Day 1 Day 2 Day 3 

Thallium ug/L 200.8 20.0 45.0 21.0 24.0 Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (20Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20Vanadium ug/L 200.8 35.0 97.0 37.0 45.0 Zinc ug/L 200.7 2,600 2,200 2,400 2,100 
4-11 

Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for the analytical results for the < - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. * - LCS or LCSD is outside the laboratory control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. Min – Minimum value. 

Table 4-2. Effluent from FGD Wastewater Treatment System, Hatfield’s Ferry 

Effluent from FGD Wastewater Treatment System 

Analyte Units Method Day 1 Day 2 Day 3 Day 

Classicals Ammonia mg/L 350.1 NQ (1.00) B NQ (1.00) B 1.10 1.00 Nitrate Nitrite as N mg/L 353.2 130 140 140 130 Nitrogen, Kjeldahl mg/L 351.2 19.0 16.0 17.5 17.0 Biochemical Oxygen Demand mg/L 5210B ND (2.00) NQ (2.50) NQ (2.50) 2.60 Chemical Oxygen Demand mg/L 410.4 240 240 230 230 Chloride mg/L 300.0 6,500 6,700 6,700 6,500 Sulfate mg/L 300.0 5,800 5,000 4,700 5,500 Cyanide, Total mg/L 4500 CN E 0.110 0.180 0.195 0.170 Total Dissolved Solids mg/L 2540C 16,000 16,000 12,500 15,000 Total Suspended Solids mg/L 2540D NQ (4.00) NQ (4.00) NQ (4.00) 4.00 Phosphorus, Total mg/L 365.1 0.0670 B 0.230 B 0.0620 NQ (0.0500Total Metals Aluminum ug/L 200.7 ND (200) NQ (200) B NQ (200) NQ (200) Antimony ug/L 200.8 7.40 8.20 8.65 8.80 Arsenic ug/L 200.8 5.40 4.60 6.40 7.60 Barium ug/L 200.7 100 120 130 110 Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Boron ug/L 200.7 180,000 B,4 190,000 B 185,000 190,000 Cadmium ug/L 200.8 5.60 7.00 8.65 8.70 Calcium ug/L 200.7 1,200,000 B,4 1,400,000 B 1,400,000 1,200,000 Chromium ug/L 200.8 11.0 11.0 10.5 10.0 
4-12 

Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for the analytical results for the < - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. * - LCS or LCSD is outside the laboratory control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. Min – Minimum value. 

Table 4-2. Effluent from FGD Wastewater Treatment System, Hatfield’s Ferry 

Effluent from FGD Wastewater Treatment System 

Analyte Units Method Day 1 Day 2 Day 3 Day 

Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) NQ (20.0) Copper ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) Iron ug/L 200.7 200 B,F NQ (200) B NQ (200) NQ (200) Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Magnesium ug/L 200.7 2,800,000 B,4 2,900,000 B 2,800,000 3,000,000 Manganese ug/L 200.7 2,400 B,4 1,900 B 2,050 6,400 Mercury ng/L 1631E 35.3 38.4 31.8 37.0 Molybdenum ug/L 200.7 430 420 465 460 Nickel ug/L 200.8 6.50 4.50 4.95 13.0 Selenium ug/L 200.8 570 4 540 595 620 Silver ug/L 200.8 ND (2.00) F ND (2.00) ND (2.00) ND (2.00) Sodium ug/L 200.7 410,000 4 420,000 415,000 380,000 Thallium ug/L 200.8 7.00 7.40 8.55 7.80 Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) Vanadium ug/L 200.8 27.0 B 23.0 B 30.0 47.0 Zinc ug/L 200.7 ND (40.0) ND (40.0) ND (40.0) NQ (40.0) Dissolved Metals Aluminum ug/L 200.7 ND (200) ND (200) ND (200) ND (200) Antimony ug/L 200.8 6.90 7.50 8.10 7.90 Arsenic ug/L 200.8 5.10 4.30 6.25 8.60 Barium ug/L 200.7 100 F 120 130 100 
4-13 

Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for the analytical results for the < - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. * - LCS or LCSD is outside the laboratory control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. Min – Minimum value. 

Table 4-2. Effluent from FGD Wastewater Treatment System, Hatfield’s Ferry 

Effluent from FGD Wastewater Treatment System 

Analyte Units Method Day 1 Day 2 Day 3 Day 

Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Boron ug/L 200.7 190,000 B,4 190,000 B 175,000 190,000 Cadmium ug/L 200.8 4.60 7.20 9.10 7.80 Calcium ug/L 200.7 1,200,000 4 1,400,000 1,450,000 1,200,000 Chromium ug/L 200.8 8.50 9.10 9.75 8.60 Chromium (VI) ug/L 218.6 4.08 3.93 3.86 2.96 Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) NQ (20.0) Copper ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00) Iron ug/L 200.7 ND (200) ND (200) ND (200) ND (200) Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) Magnesium ug/L 200.7 3,000,000 4 2,900,000 2,800,000 2,800,000 Manganese ug/L 200.7 2,400 4 1,900 2,000 6,200 Mercury ng/L 1631E NQ (0.500) 7.98 8.90 16.5 Molybdenum ug/L 200.7 430 430 465 450 Nickel ug/L 200.8 5.30 4.00 5.15 13.0 Selenium ug/L 200.8 610 4 560 620 630 Silver ug/L 200.8 ND (2.00) F ND (2.00) ND (2.00) ND (2.00) Sodium ug/L 200.7 410,000 4 400,000 415,000 370,000 Thallium ug/L 200.8 7.50 7.10 8.70 7.60 Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) Vanadium ug/L 200.8 26.0 22.0 29.5 44.0 
4-14 

Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for the analytical results for the < - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the qu

ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. * - LCS or LCSD is outside the laboratory control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. Min – Minimum value. 

Table 4-2. Effluent from FGD Wastewater Treatment System, Hatfield’s Ferry 

Effluent from FGD Wastewater Treatment System 

Analyte Units Method Day 1 Day 2 Day 3 Day 

Zinc ug/L 200.7 ND (40.0) NQ (40.0) ND (40.0) ND (40.0) 
4-15 

< - Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quNQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. 

Table 4-3. Classical Pollutant 4-Day Average Data Summary for FGD Wastewater Treatment System, Ha

Analyte Units Method 

Influent to FGD 

Wastewater Treatment 

System (SP-1) 

4-Day Average 

Effluent f

Wastewate

System 

4-Day A

Classicals Ammonia mg/L 350.1 NQ (4.22) < 0Nitrate Nitrite as N mg/L 353.2 156 1Nitrogen, Total Kjeldahl mg/L 351.2 47.1 17Biochemical Oxygen Demand mg/L 5210B < 2.95 < 1Chemical Oxygen Demand mg/L 410.4 350 2Chloride mg/L 300.0, 9056 7,090 6,6Sulfate mg/L 300.0, 9056 10,700 5,2Cyanide, Total mg/L 4500 CN E < 0.152 0.Total Dissolved Solids mg/L 2540C 30,800 14,Total Suspended Solids mg/L 2540D 58,500 < 2Phosphorus, Total mg/L 365.1 < 7.86 < 0
4-16 

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

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

value. 

Table 4-4. Metal Pollutant 4-Day Average Data Summary for FGD Wastewater Treatment System, Hatf

Influent to FGD 

Wastewater Treatment 

System (SP-1) 

4-Day Average 

Effluen

Wastewa

Syst

4-Da

Analyte Units Method Total Dissolved Total 

Metals Aluminum ug/L 200.7 2,100,000 < 138 NQ (200) Antimony ug/L 200.8 < 15.7 7.58 8.26 Arsenic ug/L 200.8 2,970 7.25 6.00 Barium ug/L 200.7 15,100 155 115 Beryllium ug/L 200.7 81.1 < 2.68 ND (2.00) Boron ug/L 200.7 292,000 323,000 186,000 Cadmium ug/L 200.8 515 365 7.49 Calcium ug/L 200.7 7,850,000 793,000 1,300,000 Chromium ug/L 200.8 7,130 ND (8.00) 10.6 Chromium (VI) ug/L 218.6 NA ND (10.0) NA Cobalt ug/L 200.7 665 348 NQ (20.0) Copper ug/L 200.8 2,330 13.3 NQ (4.00) Iron ug/L 200.7 1,770,000 ND (200) < 125 Lead ug/L 200.8 1,500 ND (2.00) ND (2.00) Magnesium ug/L 200.7 5,790,000 5,200,000 2,880,000 Manganese ug/L 200.7 86,500 85,300 3,190 Mercury ng/L 1631E 647,000 234 33.6 Molybdenum ug/L 200.7 866 515 444 Nickel ug/L 200.8 3,580 1,130 7.24 Selenium ug/L 200.8 3,220 548 581 Silver ug/L 200.8 NQ (13.4) ND (2.00) ND (2.00) Sodium ug/L 200.7 456,000 448,000 406,000 Thallium ug/L 200.8 127 27.5 7.69 Tin ug/L 200.7 NQ (741) ND (200) ND (200) 
4-17 

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

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

value. 

Table 4-4. Metal Pollutant 4-Day Average Data Summary for FGD Wastewater Treatment System, Hatf

Influent to FGD 

Wastewater Treatment 

System (SP-1) 

4-Day Average 

Effluen

Wastewa

Syst

4-Da

Analyte Units Method Total Dissolved Total 

Titanium ug/L 200.7 17,800 ND (20.0) ND (20.0) Vanadium ug/L 200.8 7,590 53.5 31.8 Zinc ug/L 200.7 16,400 2,330 NQ (40.0) 
5-1

5. DATA QUALITY

Quality assurance/quality control (QA/QC) procedures applicable to the Hatfield’s Ferry 

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

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

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

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

QC standard checks. 

5.1 Analytical Quality Control

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

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

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

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

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

5.2 Field Quality Control

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

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

5.2.1 Bottle Blanks 

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

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

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

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

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

analyzed the samples using EPA Method 1638. 

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

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

Frontier then analyzed the samples using EPA Method 1631E. 

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

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

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

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

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

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

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

No metals were detected in the bottle blanks. Appendix Table A-15 presents all of the 

analytical results from the bottle blank analyses for the bottles used to collect the metals and 

mercury samples. 
5-2

5.2.2 Equipment Blanks 

EPA collects equipment blanks to evaluate possible contamination from the equipment 

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

5.2.3) include the sampling equipment and therefore would identify whether the sampling 

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

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

equipment supplied for the episode. 

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

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

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

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

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

No other metals were detected in the equipment blanks, except for aluminum in the 

sample tap tubing set and calcium in the pump off tubing set. Because the sample tap tubing sets 

were only used for the collection of the influent samples, the aluminum contamination did not 

affect the results of the sampling episode. Calcium was detected in the pump off tubing set at 40 

ug/L, and all calcium results for the sampling episode were more than 2,000 times greater than 

the equipment blank detection. Appendix Table A-15 presents all of the analytical results from 

the bottle blank and equipment blank analyses for all of the equipment used for the collection of 

metals and mercury samples. 

5.2.3 Field Blanks 

The sampling team collected field blanks (SP-4, and SP-5) to evaluate possible 

contamination from sampling equipment, sampling equipment decontamination procedures, 

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

samples for the total and dissolved metals and total and dissolved mercury samples10. 

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

for the influent to the FGD wastewater treatment system (SP-4) were collected by pouring 

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

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

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

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

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

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

as “true” split samples with Hatfield’s Ferry’s representative, using the same procedure 

discussed in the sample collection description (Section 3.1). 

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

chromium field blank samples for the influent to the FGD wastewater treatment system (SP-4) 

were collected by pouring ASTM Type 1 water through the funnel and tubing and into a 10-liter 

 

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

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

filtering the sample, which is assessed as the field blank for the dissolved mercury sample. Mercury was not 

detected above the method detection limit (0.24 ng/L) in the filtration blanks performed for each day of samples. 
5-3

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 was purged with approximately one liter of blank water. The sample bottles were 

placed in a “cleanbox” and the ASTM Type 1 water was pumped through the tubing, capsule 

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

“true” split samples with Hatfield’s Ferry’s representative, using the same procedure discussed in 

the sample collection description (Section 3.1). 

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

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

clear plastic bag. Before purging the sample tap, ASTM Type 1 water was poured directly into 

the sample bottles under the clear plastic bag. 

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

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

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

composite container was used with a pump to fill the 20-liter field blank composite container. 

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

container holding ASTM Type 1 water. The other end of the tubing was attached to the vented 

cap on top of the 20-liter field blank composite container. After enough volume was pumped into 

the 20-liter field blank composite container, the vented cap was replaced with a closed cap and 

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

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

After 24 hours, the ASTM Type 1 water in the 20-liter field blank composite container 

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

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

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

Hatfield’s Ferry’s representative, using the same procedure discussed in the sample collection 

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

approximately 1.5 liters of ASTM Type 1 water. First the samplers collected the total metals by 

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

the tubing set and purged the tubing with approximately 0.5 liters of ASTM Type 1 water. The 

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

hexavalent chromium field blank samples. 

Table 5-1 presents the field blank analytical results 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-16 

through A-20 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). 

5.2.4 Field Duplicates 

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

precision for the episode. Field duplicate samples are separate samples collected from the same 

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

is stored and analyzed independently. The RPD between the two sample results is examined to 
5-4

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

the duplicate sample results. 

100

2

S D

S D

RPD (%) 





 



 

  (5-1) 

where: 

S = concentration of the analyte from original sample analysis; 

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

RPD = relative percent difference between the original and duplicate sample 

result. 

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

FGD wastewater treatment system (SP-3). The samplers collected the duplicate for mercury on 

day 2, while the duplicate for all other analytes was collected on day 3. Table 5-2 presents 

analytical results and the RPD for all analytes for SP-2 and SP-3. Results are rounded to three 

significant digits. Appendix Tables A-10, A-13 and A-14 present all the analytical results for the 

effluent from the FGD wastewater treatment system (SP-2) Day 2 for mercury and Day 3 for all 

other analytes and the duplicate of the effluent from the FGD wastewater treatment system (SP3) sample analyses, including all qualified results and all results that were measured above the 

method detection limit, but below the quantitation limit (i.e., J-values). 
5-5 

Table 5-1. Field Blank Analytical Results, Hatfield’s Ferry 

Analyte Sample Description Method Units C

Total Metals Mercury Influent to FGD Wastewater Treatment System Field Blank - Day 1 1631E ng/L 
5-6 

a Original and duplicate mercury samples were collected on Day 2. NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 

Table 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Hatfield’s 

Analyte Method Units

Original Effluent 

from FGD 

Wastewater 

Treatment System, 

Day 3 Concentration 

(SP-2) 

Duplicate Effluent 

from FGD 

Wastewater 

Treatment System 

Concentration (SP-3) 

Avera

Resul

Classicals Ammonia 350.1 mg/L 1.10 1.10 1.10 Nitrate Nitrite as N 353.2 mg/L 140 140 140 Nitrogen, Total Kjeldahl 351.2 mg/L 19.0 16.0 17.5 Biochemical Oxygen Demand 5210B mg/L NQ (2.50) NQ (2.50) NQ (2.5Chemical Oxygen Demand 410.4 mg/L 230 230 230 Chloride 300.0 mg/L 6,900 6,500 6,700 Sulfate 300.0 mg/L 4,800 4,600 4,700 Cyanide, Total 4500 CN E mg/L 0.240 0.150 F 0.195 Total Dissolved Solids 2540C mg/L 14,000 11,000 12,50Total Suspended Solids 2540D mg/L NQ (4.00) NQ (4.00) NQ (4.0Phosphorus, Total 365.1 mg/L 0.0630 B 0.0610 B 0.062Total Metals Aluminum 200.7 ug/L NQ (200) B ND (200) NQ (20Antimony 200.8 ug/L 8.60 8.70 8.65 Arsenic 200.8 ug/L 6.00 6.80 6.40 Barium 200.7 ug/L 130 130 130 Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.0Boron 200.7 ug/L 190,000 B 180,000 B 185,00Cadmium 200.8 ug/L 8.70 8.60 8.65 Calcium 200.7 ug/L 1,400,000 B 1,400,000 B 1,400,0Chromium 200.8 ug/L 11.0 10.0 10.5 Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20
5-7 

a Original and duplicate mercury samples were collected on Day 2. NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 

Table 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Hatfield’s 

Analyte Method Units

Original Effluent 

from FGD 

Wastewater 

Treatment System, 

Day 3 Concentration 

(SP-2) 

Duplicate Effluent 

from FGD 

Wastewater 

Treatment System 

Concentration (SP-3) 

Avera

Resul

Copper 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.0Iron 200.7 ug/L NQ (200) B NQ (200) B NQ (20Lead 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Magnesium 200.7 ug/L 2,800,000 B 2,800,000 B 2,800,0Manganese 200.7 ug/L 2,000 B 2,100 B 2,050 Mercurya 1631E ng/L 46.4 30.3 38.4 Molybdenum 200.7 ug/L 450 480 465 Nickel 200.8 ug/L 4.70 5.20 4.95 Selenium 200.8 ug/L 580 610 595 Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Sodium 200.7 ug/L 400,000 430,000 415,00Thallium 200.8 ug/L 8.20 8.90 8.55 Tin 200.7 ug/L ND (200) ND (200) ND (20Titanium 200.7 ug/L ND (20.0) ND (20.0) ND (20Vanadium 200.8 ug/L 30.0 B 30.0 B 30.0 Zinc 200.7 ug/L ND (40.0) ND (40.0) ND (40Dissolved Metals Aluminum 200.7 ug/L ND (200) ND (200) ND (20Antimony 200.8 ug/L 7.70 8.50 8.10 Arsenic 200.8 ug/L 5.90 6.60 6.25 Barium 200.7 ug/L 130 130 130 Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.0Boron 200.7 ug/L 170,000 B 180,000 B 175,00
5-8 

a Original and duplicate mercury samples were collected on Day 2. NC – Not calculated. ND – Not detected (number in parentheses is the quantitation limit). NQ – Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the quantitation limit

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

value. B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 

Table 5-2. Field Duplicate Results – Effluent from FGD Wastewater Treatment System, Hatfield’s 

Analyte Method Units

Original Effluent 

from FGD 

Wastewater 

Treatment System, 

Day 3 Concentration 

(SP-2) 

Duplicate Effluent 

from FGD 

Wastewater 

Treatment System 

Concentration (SP-3) 

Avera

Resul

Cadmium 200.8 ug/L 9.70 8.50 9.10 Calcium 200.7 ug/L 1,500,000 1,400,000 1,450,0Chromium 200.8 ug/L 10.0 9.50 9.75 Chromium (VI) 218.6 ug/L 3.70 4.02 3.86 Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20Copper 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.0Iron 200.7 ug/L ND (200) ND (200) ND (20Lead 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Magnesium 200.7 ug/L 2,900,000 2,700,000 2,800,0Manganese 200.7 ug/L 2,000 2,000 2,000 Mercurya 1631E ng/L 7.60 8.35 7.98 Molybdenum 200.7 ug/L 470 460 465 Nickel 200.8 ug/L 5.30 5.00 5.15 Selenium 200.8 ug/L 620 620 620 Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.0Sodium 200.7 ug/L 420,000 410,000 415,00Thallium 200.8 ug/L 8.60 8.80 8.70 Tin 200.7 ug/L ND (200) ND (200) ND (20Titanium 200.7 ug/L ND (20.0) ND (20.0) ND (20Vanadium 200.8 ug/L 29.0 30.0 29.5 Zinc 200.7 ug/L ND (40.0) ND (40.0) ND (40
6-1

6. REFERENCES

1. Eastern Research Group, Inc., 2010. Sampling Plan, Allegheny Energy’s Hatfield’s Ferry 

Steam Electric Plant. October 27. DCN SE00507. 

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 Coupled 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-1 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). 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-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatm

Day 1 Analytical Results, Hatfield’s Ferry 

Analyte 

Aqueous Phase Result 

(mg/L for Classicals; 

ug/L for Metals; and ng/L 

for Mercury) 

Solid Phase Result 

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury) 

Calculated Total Samp

(mg/L for Classical

for Metals; and ng/L fo

Classicals Ammonia 1.7 J,H,P 15 H,P,Est 2.42 F(J, H, P) – Nitrate Nitrite as N 140 H,P,Est 34 H,P,Est 129 F(H, P, Est) – Nitrogen, Total Kjeldahl 14 B,H,P,Est 560 H,P,Est 45.6 F(B, H, P, Est) Chloride 6,100 H,Est 1,500 H,Est 5,610 F(H, Est) – Sulfate 9,700 H,Est 27,000 H,Est 10,400 F(H, Est) – Cyanide, Total 0.079 J,H,P 0.54 H,P,Est 0.103 F(J, H, P) – Phosphorus, Total 0.12 B,H,P,Est ND (5.1) U,H,P 0.109 F(B, H, P, EstTotal Metals Aluminum ND (200) U 30,000 1,760,000 F(UAntimony 5.2 0.33 J 24.1 S(Arsenic 7.3 39 2,300 Barium 64 220 B 13,000 S(BBeryllium 1.3 J 1 59.9 F(Boron 240,000 B 270 B 233,000 F(B) – Cadmium 230 3.7 425 Calcium 660,000 130,000 8,230,000 Chromium ND (8) U 110 6,460 F(UCobalt 270 5.3 556 Copper 23 32 1,900 Iron ND (200) U 25,000 1,470,000 F(ULead ND (2) U 20 B 1,170 F(U) – Magnesium 4,500,000 17,000 5,070,000 
A-2 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). 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-1. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatm

Day 1 Analytical Results, Hatfield’s Ferry 

Analyte 

Aqueous Phase Result 

(mg/L for Classicals; 

ug/L for Metals; and ng/L 

for Mercury) 

Solid Phase Result 

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury) 

Calculated Total Samp

(mg/L for Classical

for Metals; and ng/L fo

Manganese 65,000 210 71,100 Mercury 202,000 10,200 521,000 Molybdenum 350 6.1 675 Nickel 950 36 2,970 Selenium 430 39 2,680 Silver ND (2) U 0.12 J 7.05 F(U) – Sodium 370,000 720 377,000 Thallium 9.6 1.5 96.8 Tin ND (200) U 2.4 J 141 F(U) – Titanium ND (20) U 240 14,100 F(UVanadium 27 100 5,900 Zinc 1,600 B 230 15,000 F(B
A-3 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). 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 Total Metals, Influent to FGD Wastewater Treatmen

Analytical Results, Hatfield’s Ferry 

Analyte 

Aqueous Phase Result 

(mg/L for Classicals; 

ug/L for Metals; 

and ng/L for Mercury) 

Solid Phase Result 

(mg/kg for Classicals and 

Metals and ng/g for 

Mercury) 

Calculated Total S

(mg/L for Class

for Metals; and ng/L 

Classicals Ammonia 1.6 J,H,P 12 H,P,Est 2.26 F(J, HNitrate Nitrite as N 230 H,P,Est 69 H,P,Est 208 F(H, P, Nitrogen, Total Kjeldahl 25 B,H,P,Est 500 H,P,Est 57.4 F(B, H, PChloride 9,400 H,Est 3,000 H,Est 8,510 F(H, Sulfate 11,000 H,Est 29,000 H,Est 11,800 F(H, Cyanide, Total 0.19 H,P,Est 0.69 H,P,Est 0.216 F(H, P, Phosphorus, Total 0.14 B,H,P,Est 250 H,P,Est 17.8 F(B, H, PTotal Metals Aluminum 32 J 36,000 2,550,000 Antimony 12 0.24 J 27.6 Arsenic 14 65 4,610 Barium 75 300 B 21,300 Beryllium 1.9 J 1.9 136 Boron 380,000 B 400 B 364,000 FCadmium 370 3.8 595 Calcium 740,000 86,000 6,730,000 Chromium 5.4 J 120 8,490 Cobalt 320 8.3 869 Copper 19 44 3,130 Iron ND (200) U 29,000 2,050,000 Lead ND (2) U 30 B 2,120 FMagnesium 6,300,000 18,000 6,830,000 
A-4 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). 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 Total Metals, Influent to FGD Wastewater Treatmen

Analytical Results, Hatfield’s Ferry 

Analyte 

Aqueous Phase Result 

(mg/L for Classicals; 

ug/L for Metals; 

and ng/L for Mercury) 

Solid Phase Result 

(mg/kg for Classicals and 

Metals and ng/g for 

Mercury) 

Calculated Total S

(mg/L for Class

for Metals; and ng/L 

Manganese 89,000 280 98,300 Mercury 1,440 19,100 654,000 Molybdenum 980 6.8 1,350 Nickel 1,100 48 4,360 Selenium 1,000 43 3,920 Silver ND (2) U 0.12 J 8.49 Sodium 600,000 1,100 607,000 Thallium 21 2.5 195 Tin ND (200) U 3.2 J 226 Titanium ND (20) U 420 29,700 Vanadium 60 150 10,700 Zinc 1,600 B 250 19,100 
A-5 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). 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-3. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatmen

Analytical Results, Hatfield’s Ferry 

Analyte 

Aqueous Phase Result 

(mg/L for Classicals; ug/L 

for Metals; and ng/L for 

Mercury) 

Solid Phase Result 

(mg/kg for Classicals 

and Metals and ng/g for 

Mercury) 

Calculated Total Sam

(mg/L for Classica

for Metals; and ng/L f

Classicals Ammonia 1.7 J,H,P 11 H,P,Est 2.3 F(J, H, Nitrate Nitrite as N 170 H,P,Est 39 H,P,Est 157 F(H, P, ENitrogen, Total Kjeldahl 36 B,H,P,Est 83 H,P,Est 38.3 F(B, H, P, Chloride 8,700 H,Est 1,900 H,Est 8,000 F(H, ESulfate 9,300 H,Est 24,000 H,Est 10,100 F(H, ECyanide, Total 0.16 H,P,Est 0.73 H,P,Est 0.195 F(H, P, EPhosphorus, Total 0.13 B,H,P,Est 190 H,P,Est 13.3 F(B, H, P, Total Metals Aluminum ND (200) U 30,000 2,080,000 Antimony 5.6 0.19 J 18.2 Arsenic 5.2 31 2,150 Barium 77 180 B 12,500 Beryllium 1.1 J 0.78 54.9 Boron 320,000 B 280 B 309,000 FCadmium 360 3.8 589 Calcium 780,000 130,000 9,700,000 Chromium ND (8) U 100 6,920 Cobalt 360 4.5 637 Copper 22 30 2,090 Iron 44 J 26,000 1,800,000 Lead ND (2) U 19 B 1,310 FMagnesium 5,500,000 17,000 6,150,000 
A-6 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). 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-3. Biphasic Sample Results for Classicals and Total Metals, Influent to FGD Wastewater Treatmen

Analytical Results, Hatfield’s Ferry 

Analyte 

Aqueous Phase Result 

(mg/L for Classicals; ug/L 

for Metals; and ng/L for 

Mercury) 

Solid Phase Result 

(mg/kg for Classicals 

and Metals and ng/g for 

Mercury) 

Calculated Total Sam

(mg/L for Classica

for Metals; and ng/L f

Manganese 91,000 200 96,200 Mercury 1,520 21,900 789,000 Molybdenum 400 4.6 680 Nickel 1,200 38 3,710 Selenium 560 44 3,550 Silver ND (2) U 0.097 J 6.71 FSodium 470,000 580 465,000 Thallium 11 1.3 99.9 Tin ND (200) U 2.1 J 145 FTitanium ND (20) U 160 11,100 Vanadium 28 94 6,530 Zinc 1,900 B 210 16,200 
A-7 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). 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 Treatmen

Analytical Results, Hatfield’s Ferry 

Analyte 

Aqueous Phase Result 

(mg/L for Classicals; ug/L 

for Metals; and ng/L for 

Mercury) 

Solid Phase Result 

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury) 

Calculated Total Sam

 (mg/L for Classica

for Metals; and ng/L fo

Classicals Ammonia 1.7 J,H,P 15 H,P,Est 2.36 F(J, H, PNitrate Nitrite as N 140 H,P,Est 49 H,P,Est 129 F(H, P, EsNitrogen, Total Kjeldahl 14 B,H,P,Est 620 H,P,Est 47 F(B, H, P, EChloride 6,800 H,Est 2,200 H,Est 6,250 F(H, EsSulfate 9,800 H,Est 27,000 H,Est 10,300 F(H, EsCyanide, Total 0.092 J,H,P 0.96 H,P,Est 0.136 F(J, H, PPhosphorus, Total 0.11 B,H,P,Est 1.3 J,H,P 0.171 F(B, H, P, Total Metals Aluminum ND (200) U 36,000 2,000,000 Antimony 6.6 0.26 J 20.4 Arsenic 6.8 51 2,830 Barium 77 240 B 13,400 Beryllium 1.8 J 1.3 73.7 Boron 270,000 B 340 B 262,000 F(BCadmium 230 4.4 451 Calcium 710,000 110,000 6,740,000 Chromium 4.7 J 120 6,660 Cobalt 300 5.9 597 Copper 40 39 2,200 Iron ND (200) U 32,000 1,770,000 Lead ND (2) U 25 B 1,390 F(UMagnesium 4,700,000 16,000 5,120,000 
A-8 

Note: Sample qualifiers denoted with an ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘Swith the solid portion of the sample. ND – Not detected (number in parentheses is the quantitation limit). 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 Treatmen

Analytical Results, Hatfield’s Ferry 

Analyte 

Aqueous Phase Result 

(mg/L for Classicals; ug/L 

for Metals; and ng/L for 

Mercury) 

Solid Phase Result 

(mg/kg for Classicals 

and Metals and ng/g 

for Mercury) 

Calculated Total Sam

 (mg/L for Classica

for Metals; and ng/L fo

Manganese 75,000 230 80,400 Mercury 1,360 22,300 624,000 Molybdenum 450 6.4 760 Nickel 990 43 3,280 Selenium 460 42 2,740 Silver ND (2) U 0.085 J 4.71 F(USodium 370,000 720 373,000 Thallium 12 1.9 116 Tin ND (200) U 2.8 J 155 F(UTitanium ND (20) U 290 16,100 Vanadium 30 130 7,230 Zinc 1,700 B 250 15,400 
A-9 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. 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-5. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Classical Pollutants - Total Ammonia 350.1 mg/L NA 0.44 4.2 Nitrate Nitrite as N 353.2 mg/L NA 0.365 2.4 Nitrogen, Total Kjeldahl 351.2 mg/L NA 3.66 16.5 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0, 9056 mg/L NA 46.7 552 Sulfate 300.0, 9056 mg/L NA 51.6 1,200 Cyanide, Total 4500 CN E mg/L NA 0.024 0.119 Total Dissolved Solids 2540C mg/L 1 160 330 Total Suspended Solids 2540D mg/L 1 110 400 Phosphorus, Total 365.1 mg/L NA 0.0545 0.345 Classicals Pollutants - Solid (dry weight) Ammonia 350.1 mg/Kg 1 4.1 9.9 Nitrate Nitrite as N 353.2 mg/Kg 1 0.36 10 Nitrogen, Total Kjeldahl 351.2 mg/Kg 5 60 250 Chloride 9056 mg/Kg 5 9.8 150 Sulfate 9056 mg/Kg 100 170 5,000 Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.49 Phosphorus, Total 365.1 mg/Kg 1 0.85 5.1 NClassicals Pollutants -Filtered Aqueous Ammonia 350.1 mg/L 1 0.22 4 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Chloride 300.0 mg/L 200 51 600 
A-10 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. 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-5. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Sulfate 300.0 mg/L 200 46 1,000 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Metals - Calculated Total Aluminum 200.7, 6010B ug/L NA 890 5,820 1,Antimony 200.8, 6020 ug/L NA 2.18 23.5 Arsenic 200.8, 6020 ug/L NA 6.55 68.2 Barium 200.7, 6010B ug/L NA 6.55 74.5 Beryllium 200.7, 6010B ug/L NA 2.52 30 Boron 200.7, 6010B ug/L NA 706 10,200 2Cadmium 200.8, 6020 ug/L NA 2.08 14.2 Calcium 200.7, 6010B ug/L NA 8,290 28,600 8,Chromium 200.8, 6020 ug/L NA 11.2 29 Cobalt 200.7, 6010B ug/L NA 6.63 74.5 Copper 200.8, 6020 ug/L NA 8.5 30.6 Iron 200.7, 6010B ug/L NA 2,200 8,400 1,Lead 200.8, 6020 ug/L NA 2.6 18.3 Magnesium 200.7, 6010B ug/L NA 700 10,200 5,Manganese 200.7, 6010B ug/L NA 17.4 509 Mercury 1631E, FGS-069 ng/L NA 7,090 32,200 5Molybdenum 200.7, 6010B ug/L NA 16.1 148 Nickel 200.8, 6020 ug/L NA 3.51 20.1 Selenium 200.8, 6020 ug/L NA 71.9 279 Silver 200.8, 6020 ug/L NA 2.71 12.4 Sodium 200.7, 6010B ug/L NA 3,510 37,200 3
A-11 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. 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-5. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Thallium 200.8, 6020 ug/L NA 0.801 12.4 Tin 200.7, 6010B ug/L NA 56.6 757 Titanium 200.7, 6010B ug/L NA 9.08 74.5 Vanadium 200.8, 6020 ug/L NA 5.71 63.1 Zinc 200.7, 6010B ug/L NA 30.6 207 Metals - Dissolved Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 2Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 7Chromium 200.8 ug/L 2 3.3 8 NChromium (VI) 218.6 ug/L 5 1.96 10 NCobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 50 540 10,000 4,Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 100 24.8 52 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 
A-12 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. 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-5. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 3Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Metals - Filtered Aqueous Aluminum 200.7 ug/L 2 9.4 200 NAntimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 2Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 6Chromium 200.8 ug/L 2 3.3 8 NCobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 50 540 10,000 4,Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 20,000 5,210 10,900 2
A-13 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. 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-5. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 3Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Metals - Solid (dry weight) Aluminum 6010B mg/kg 10 15 96 Antimony 6020 mg/kg 2 0.026 0.37 Arsenic 6020 mg/kg 2 0.093 1.1 Barium 6010B mg/kg 1 0.073 0.96 Beryllium 6010B mg/kg 1 0.032 0.48 Boron 6010B mg/kg 10 9.4 96 Cadmium 6020 mg/kg 2 0.017 0.18 Calcium 6010B mg/kg 10 140 480 1Chromium 6020 mg/kg 2 0.14 0.37 Cobalt 6010B mg/kg 1 0.096 0.96 Copper 6020 mg/kg 2 0.13 0.46 Iron 6010B mg/kg 10 37 140 Lead 6020 mg/kg 2 0.033 0.28 Magnesium 6010B mg/kg 1 3.6 19 
A-14 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. F – MS and/or MSD not within laboratory control limits. G – pH upon receipt greater than 2 S.U. 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-5. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Manganese 6010B mg/kg 1 0.096 0.96 Mercury FGS-069 ng/g 4,000 73.7 671 Molybdenum 6010B mg/kg 1 0.25 1.9 Nickel 6020 mg/kg 2 0.046 0.28 Selenium 6020 mg/kg 10 1.2 4.6 Silver 6020 mg/kg 2 0.037 0.18 Sodium 6010B mg/kg 1 57 480 Thallium 6020 mg/kg 2 0.0064 0.18 Tin 6010B mg/kg 1 0.89 9.8 Titanium 6010B mg/kg 1 0.13 0.96 Vanadium 6020 mg/kg 2 0.071 0.92 Zinc 6010B mg/kg 1 0.38 2.9 
A-15 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Classical Pollutants - Total Ammonia 350.1 mg/L NA 0.484 4.22 Nitrate Nitrite as N 353.2 mg/L NA 0.696 4.24 Nitrogen, Total Kjeldahl 351.2 mg/L NA 2.1 11.5 Biochemical Oxygen Demand 5210B mg/L 1 0.59 5 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0, 9056 mg/L NA 116 1,340 Sulfate 300.0, 9056 mg/L NA 118 2,560 Cyanide, Total 4500 CN E mg/L NA 0.0247 0.124 Total Dissolved Solids 2540C mg/L 1 470 1,000 Total Suspended Solids 2540D mg/L 1 140 500 Phosphorus, Total 365.1 mg/L NA 0.301 1.81 Classicals Pollutants - Solid (dry weight) Ammonia 350.1 mg/Kg 1 4.1 9.8 Nitrate Nitrite as N 353.2 mg/Kg 1 0.36 10 Nitrogen, Total Kjeldahl 351.2 mg/Kg 2 25 100 Chloride 9056 mg/Kg 10 20 300 Sulfate 9056 mg/Kg 100 170 5,000 Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.5 Phosphorus, Total 365.1 mg/Kg 5 4.2 25 Classicals Pollutants -Filtered Aqueous Ammonia 350.1 mg/L 1 0.22 4 Nitrate Nitrite as N 353.2 mg/L 40 0.76 4 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chloride 300.0 mg/L 500 130 1,500 Sulfate 300.0 mg/L 500 120 2,500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 
A-16 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Metals - Calculated Total Aluminum 200.7, 6010B ug/L NA 998 6,540 2,Antimony 200.8, 6020 ug/L NA 2.54 29.3 Arsenic 200.8, 6020 ug/L NA 7.99 88.4 Barium 200.7, 6010B ug/L NA 7.01 81.3 Beryllium 200.7, 6010B ug/L NA 2.75 33.6 Boron 200.7, 6010B ug/L NA 772 10,800 3Cadmium 200.8, 6020 ug/L NA 2.33 17 Calcium 200.7, 6010B ug/L NA 9,250 32,200 6,Chromium 200.8, 6020 ug/L NA 13.5 34.6 Cobalt 200.7, 6010B ug/L NA 7.33 81.3 Copper 200.8, 6020 ug/L NA 10.7 38.2 Iron 200.7, 6010B ug/L NA 2,430 10,100 2,Lead 200.8, 6020 ug/L NA 3.12 22.3 Magnesium 200.7, 6010B ug/L NA 710 10,100 6,Manganese 200.7, 6010B ug/L NA 17.8 505 Mercury 1631E, FGS-069 ng/L NA 3,170 28,500 6Molybdenum 200.7, 6010B ug/L NA 17.7 163 Nickel 200.8, 6020 ug/L NA 4.25 24 Selenium 200.8, 6020 ug/L NA 93.3 355 Silver 200.8, 6020 ug/L NA 3.28 15.2 Sodium 200.7, 6010B ug/L NA 3,910 40,600 6Thallium 200.8, 6020 ug/L NA 0.896 15.2 Tin 200.7, 6010B ug/L NA 60.1 785 Titanium 200.7, 6010B ug/L NA 10.6 81.3 Vanadium 200.8, 6020 ug/L NA 6.8 77.4 
A-17 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Zinc 200.7, 6010B ug/L NA 33.5 226 Metals - Dissolved Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 4Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 8Chromium 200.8 ug/L 2 3.3 8 NCobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 50 540 10,000 6,Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 100 24.8 52 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 5Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 
A-18 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Zinc 200.7 ug/L 2 9.1 40 Metals - Filtered Aqueous Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 3Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 7Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 50 540 10,000 6,Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 200 52.1 109 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 6Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 
A-19 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Zinc 200.7 ug/L 2 9.1 40 Metals - Solid (dry weight) Aluminum 6010B mg/kg 10 14 90 Antimony 6020 mg/kg 2 0.027 0.39 Arsenic 6020 mg/kg 2 0.098 1.2 Barium 6010B mg/kg 1 0.068 0.9 Beryllium 6010B mg/kg 1 0.03 0.45 Boron 6010B mg/kg 10 8.8 90 Cadmium 6020 mg/kg 2 0.018 0.19 Calcium 6010B mg/kg 10 130 450 Chromium 6020 mg/kg 2 0.15 0.39 Cobalt 6010B mg/kg 1 0.09 0.9 Copper 6020 mg/kg 2 0.14 0.49 Iron 6010B mg/kg 10 34 140 Lead 6020 mg/kg 2 0.035 0.29 Magnesium 6010B mg/kg 1 3.3 18 Manganese 6010B mg/kg 1 0.09 0.9 Mercury FGS-069 ng/g 4,000 91.4 832 Molybdenum 6010B mg/kg 1 0.23 1.8 Nickel 6020 mg/kg 2 0.049 0.29 Selenium 6020 mg/kg 10 1.3 4.9 Silver 6020 mg/kg 2 0.039 0.19 Sodium 6010B mg/kg 1 53 450 Thallium 6020 mg/kg 2 0.0068 0.19 Tin 6010B mg/kg 1 0.79 8.6 Titanium 6010B mg/kg 1 0.13 0.9 Vanadium 6020 mg/kg 2 0.075 0.97 
A-20 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Zinc 6010B mg/kg 1 0.36 2.7 
A-21 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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-7. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Classical Pollutants - Total Ammonia 350.1 mg/L NA 0.483 4.31 Nitrate Nitrite as N 353.2 mg/L NA 0.369 2.5 Nitrogen, Total Kjeldahl 351.2 mg/L NA 1.17 7.84 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 5 20 100 Chloride 300.0, 9056 mg/L NA 46.8 553 Sulfate 300.0, 9056 mg/L NA 53.4 1,250 1Cyanide, Total 4500 CN E mg/L NA 0.025 0.126 Total Dissolved Solids 2540C mg/L 1 240 500 3Total Suspended Solids 2540D mg/L 1 280 1,000 6Phosphorus, Total 365.1 mg/L NA 0.302 1.84 Classicals Pollutants - Solid (dry weight) Ammonia 350.1 mg/Kg 1 4.1 10 Nitrate Nitrite as N 353.2 mg/Kg 1 0.36 10 Nitrogen, Total Kjeldahl 351.2 mg/Kg 1 12 48 Chloride 9056 mg/Kg 5 9.8 150 Sulfate 9056 mg/Kg 100 170 5,000 2Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.51 Phosphorus, Total 365.1 mg/Kg 5 4.3 26 Classicals Pollutants -Filtered Aqueous Ammonia 350.1 mg/L 1 0.22 4 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 200 46 1,000 
A-22 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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-7. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Metals - Calculated Total Aluminum 200.7, 6010B ug/L NA 1,050 6,960 2,0Antimony 200.8, 6020 ug/L NA 2.38 26.7 Arsenic 200.8, 6020 ug/L NA 7.38 79.7 Barium 200.7, 6010B ug/L NA 7.45 85.9 1Beryllium 200.7, 6010B ug/L NA 2.86 35.7 Boron 200.7, 6010B ug/L NA 818 11,300 3Cadmium 200.8, 6020 ug/L NA 2.26 16.1 Calcium 200.7, 6010B ug/L NA 9,750 34,300 9,7Chromium 200.8, 6020 ug/L NA 12.7 32.1 Cobalt 200.7, 6010B ug/L NA 7.77 85.9 Copper 200.8, 6020 ug/L NA 9.86 34.7 Iron 200.7, 6010B ug/L NA 2,590 10,600 1,8Lead 200.8, 6020 ug/L NA 2.94 20.5 Magnesium 200.7, 6010B ug/L NA 738 10,400 6,Manganese 200.7, 6010B ug/L NA 18.5 520 9Mercury 1631E, FGS-069 ng/L NA 3,170 28,600 7Molybdenum 200.7, 6010B ug/L NA 18.7 175 Nickel 200.8, 6020 ug/L NA 3.99 22.3 Selenium 200.8, 6020 ug/L NA 84.4 320 Silver 200.8, 6020 ug/L NA 3.09 14.3 Sodium 200.7, 6010B ug/L NA 4,170 42,900 4Thallium 200.8, 6020 ug/L NA 0.861 14.3 Tin 200.7, 6010B ug/L NA 58.3 769 
A-23 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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-7. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Titanium 200.7, 6010B ug/L NA 11.1 85.9 1Vanadium 200.8, 6020 ug/L NA 6.31 71.3 Zinc 200.7, 6010B ug/L NA 35.2 237 1Metals - Dissolved Aluminum 200.7 ug/L 2 9.4 200 ND Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 3Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 8Chromium 200.8 ug/L 2 3.3 8 NChromium (VI) 218.6 ug/L 5 1.96 10 NCobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 ND Lead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 50 540 10,000 5,3Manganese 200.7 ug/L 50 13 500 9Mercury 1631E ng/L 20 4.83 10.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 4
A-24 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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-7. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 ND Titanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Metals - Filtered Aqueous Aluminum 200.7 ug/L 2 9.4 200 ND Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 3Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 7Chromium 200.8 ug/L 2 3.3 8 NCobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 50 540 10,000 5,5Manganese 200.7 ug/L 50 13 500 9Mercury 1631E ng/L 200 52.1 109 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 N
A-25 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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-7. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Sodium 200.7 ug/L 2 180 10,000 4Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 ND Titanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Metals - Solid (dry weight) Aluminum 6010B mg/kg 10 15 98 3Antimony 6020 mg/kg 2 0.025 0.36 Arsenic 6020 mg/kg 2 0.091 1.1 Barium 6010B mg/kg 1 0.075 0.98 Beryllium 6010B mg/kg 1 0.032 0.49 Boron 6010B mg/kg 10 9.6 98 Cadmium 6020 mg/kg 2 0.017 0.18 Calcium 6010B mg/kg 10 140 490 1Chromium 6020 mg/kg 2 0.14 0.36 Cobalt 6010B mg/kg 1 0.098 0.98 Copper 6020 mg/kg 2 0.13 0.45 Iron 6010B mg/kg 10 37 150 2Lead 6020 mg/kg 2 0.033 0.27 Magnesium 6010B mg/kg 1 3.6 20 1Manganese 6010B mg/kg 1 0.098 0.98 Mercury FGS-069 ng/g 4,000 87.1 793 2Molybdenum 6010B mg/kg 1 0.25 2 Nickel 6020 mg/kg 2 0.046 0.27 Selenium 6020 mg/kg 10 1.2 4.5 
A-26 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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-7. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Silver 6020 mg/kg 2 0.037 0.18 Sodium 6010B mg/kg 1 58 490 Thallium 6020 mg/kg 2 0.0063 0.18 Tin 6010B mg/kg 1 0.78 8.5 Titanium 6010B mg/kg 1 0.14 0.98 Vanadium 6020 mg/kg 2 0.069 0.9 Zinc 6010B mg/kg 1 0.39 2.9 
A-27 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Classical Pollutants - Total Ammonia 350.1 mg/L NA 0.426 4.15 Nitrate Nitrite as N 353.2 mg/L NA 0.362 2.36 Nitrogen, Total Kjeldahl 351.2 mg/L NA 3.57 16.2 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0, 9056 mg/L NA 46.5 549 Sulfate 300.0, 9056 mg/L NA 50.9 1,180 Cyanide, Total 4500 CN E mg/L NA 0.0236 0.117 Total Dissolved Solids 2540C mg/L 1 240 500 Total Suspended Solids 2540D mg/L 1 92 330 Phosphorus, Total 365.1 mg/L NA 0.05 0.322 Classicals Pollutants - Solid (dry weight) Ammonia 350.1 mg/Kg 1 4.1 9.9 Nitrate Nitrite as N 353.2 mg/Kg 1 0.36 10 Nitrogen, Total Kjeldahl 351.2 mg/Kg 5 62 260 Chloride 9056 mg/Kg 5 9.8 150 Sulfate 9056 mg/Kg 100 170 5,000 Cyanide, Total 4500 CN E mg/Kg 1 0.1 0.49 Phosphorus, Total 365.1 mg/Kg 1 0.82 5 Classicals Pollutants -Filtered Aqueous Ammonia 350.1 mg/L 1 0.22 4 
A-28 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 200 46 1,000 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Metals - Calculated Total Aluminum 200.7, 6010B ug/L NA 785 5,060 2,Antimony 200.8, 6020 ug/L NA 2.03 21.2 Arsenic 200.8, 6020 ug/L NA 6.02 64.6 Barium 200.7, 6010B ug/L NA 5.97 66.8 Beryllium 200.7, 6010B ug/L NA 2.25 26.2 Boron 200.7, 6010B ug/L NA 630 9,390 2Cadmium 200.8, 6020 ug/L NA 1.97 13.6 Calcium 200.7, 6010B ug/L NA 6,710 24,800 6,Chromium 200.8, 6020 ug/L NA 10.2 26.6 Cobalt 200.7, 6010B ug/L NA 5.87 66.8 Copper 200.8, 6020 ug/L NA 7.52 28 Iron 200.7, 6010B ug/L NA 1,860 7,390 1,Lead 200.8, 6020 ug/L NA 2.43 16.2 Magnesium 200.7, 6010B ug/L NA 664 10,000 5,Manganese 200.7, 6010B ug/L NA 16.6 499 
A-29 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Mercury 1631E, FGS-069 ng/L NA 2,810 25,300 6Molybdenum 200.7, 6010B ug/L NA 14.2 136 Nickel 200.8, 6020 ug/L NA 3.24 18 Selenium 200.8, 6020 ug/L NA 68 253 Silver 200.8, 6020 ug/L NA 2.53 11.8 Sodium 200.7, 6010B ug/L NA 3,040 33,400 3Thallium 200.8, 6020 ug/L NA 0.767 11.8 Tin 200.7, 6010B ug/L NA 47.6 651 Titanium 200.7, 6010B ug/L NA 8.09 66.8 Vanadium 200.8, 6020 ug/L NA 5.3 57.8 Zinc 200.7, 6010B ug/L NA 27.6 180 Metals - Dissolved Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 2Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 7Chromium 200.8 ug/L 2 3.3 8 NChromium (VI) 218.6 ug/L 5 1.96 10 N
A-30 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 50 540 10,000 4,Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 20 4.97 10.4 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 3Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Metals - Filtered Aqueous Aluminum 200.7 ug/L 2 9.4 200 NAntimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 
A-31 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 2Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 7Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 NLead 200.8 ug/L 2 0.73 2 NMagnesium 200.7 ug/L 50 540 10,000 4,Manganese 200.7 ug/L 50 13 500 Mercury 1631E ng/L 200 52.1 109 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 NSodium 200.7 ug/L 2 180 10,000 3Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
A-32 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Metals - Solid (dry weight) Aluminum 6010B mg/kg 10 14 88 Antimony 6020 mg/kg 2 0.025 0.35 Arsenic 6020 mg/kg 2 0.089 1.1 Barium 6010B mg/kg 1 0.067 0.88 Beryllium 6010B mg/kg 1 0.029 0.44 Boron 6010B mg/kg 10 8.6 88 Cadmium 6020 mg/kg 2 0.016 0.18 Calcium 6010B mg/kg 10 120 440 1Chromium 6020 mg/kg 2 0.13 0.35 Cobalt 6010B mg/kg 1 0.088 0.88 Copper 6020 mg/kg 2 0.12 0.44 Iron 6010B mg/kg 10 33 130 Lead 6020 mg/kg 2 0.032 0.26 Magnesium 6010B mg/kg 1 3.2 18 Manganese 6010B mg/kg 1 0.088 0.88 Mercury FGS-069 ng/g 4,000 99.1 902 Molybdenum 6010B mg/kg 1 0.23 1.8 Nickel 6020 mg/kg 2 0.044 0.26 Selenium 6020 mg/kg 10 1.2 4.4 Silver 6020 mg/kg 2 0.036 0.18 Sodium 6010B mg/kg 1 52 440 
A-33 

NA – Not applicable. Total results is based on calculated result from solid and aqueous phases. ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. Est – Estimated value. G – pH upon receipt greater than 2 S.U. 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, Hatfield’s F

Analyte Method Units 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Thallium 6020 mg/kg 2 0.0062 0.18 Tin 6010B mg/kg 1 0.78 8.5 Titanium 6010B mg/kg 1 0.12 0.88 Vanadium 6020 mg/kg 2 0.068 0.88 Zinc 6010B mg/kg 1 0.35 2.6 
A-34 

ND – Not detected (number in parentheses is the quantitation limit). 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 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, Hatfield’s 

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific Q

Classicals Ammonia 350.1 mg/L 1 0.055 1 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 200 46 1,000 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 94 200 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.78 10 
A-35 

ND – Not detected (number in parentheses is the quantitation limit). 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 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, Hatfield’s 

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific Q

Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 
A-36 

ND – Not detected (number in parentheses is the quantitation limit). 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. 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, Hatfield’s 

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific Q

Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
A-37 

ND – 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-10. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Hatfield’

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific 

Classicals Ammonia 350.1 mg/L 1 0.055 1 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 94 200 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.97 10.4 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 
A-38 

ND – 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-10. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Hatfield’

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific 

Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 5 1.24 2.6 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 
A-39 

ND – 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-10. Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Hatfield’

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific 

Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
A-40 

ND – 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-11. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Hatfield’

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific 

Classicals Ammonia 350.1 mg/L 1 0.055 1 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 94 200 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.97 10.4 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 
A-41 

ND – 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-11. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Hatfield’

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific 

Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 10 2.48 5.2 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 
A-42 

ND – 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-11. Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Hatfield’

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific 

Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
A-43 

ND – Not detected (number in parentheses is the quantitation limit). * - LCS or LCSD is outside the laboratory control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. 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-12. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Hatfield’

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific Q

Classicals Ammonia 350.1 mg/L 1 0.055 1 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 200 46 1,000 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 94 200 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 
A-44 

ND – Not detected (number in parentheses is the quantitation limit). * - LCS or LCSD is outside the laboratory control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. 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-12. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Hatfield’

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific Q

Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 20 4.97 10.4 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 5 4.2 25 Zinc 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
A-45 

ND – Not detected (number in parentheses is the quantitation limit). * - LCS or LCSD is outside the laboratory control limits. 4 – MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are 

B – Analyte was found in the blank and sample. D – Laboratory duplicate RPD greater than method-specified criteria. Est – Estimated value. 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-12. Effluent from FGD Wastewater Treatment System, Day 4 Analytical Results, Hatfield’

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific Q

Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 10 2.48 5.2 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
A-46 

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

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific QL 

Total Metals Mercury 1631E ng/L 20 4.97 10.4 Dissolved Metals Mercury 1631E ng/L 5 1.24 2.6 
A-47 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-14. Duplicate of Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Ha

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific 

Classicals Ammonia 350.1 mg/L 1 0.055 1 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 100 23 500 Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 Total Dissolved Solids 2540C mg/L 1 94 200 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 
A-48 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-14. Duplicate of Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Ha

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific 

Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 50 540 10,000 Manganese 200.7 ug/L 2 0.51 20 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 5 1.6 10 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 
A-49 

ND – Not detected (number in parentheses is the quantitation limit). B – Analyte was found in the blank and sample. F – MS and/or MSD not within laboratory control limits. J – Result measured above the MDL, but less than the quantitation limit. U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-14. Duplicate of Effluent from FGD Wastewater Treatment System, Day 3 Analytical Results, Ha

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific 

Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
a

 Aluminum was detected in one equipment blank for the sample tap tubing set at 5.3 ug/L. 

b

 Calcium was detected in one equipment blank for the pump-off tubing set at 40 ug/L. 

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

A-50 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Hatfield’s Ferry

Analyte Method Process Units Concentration 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

 Aluminum was detected in one equipment blank for the sample tap tubing set at 5.3 ug/L. 

b

 Calcium was detected in one equipment blank for the pump-off tubing set at 40 ug/L. 

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

A-51 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Hatfield’s Ferry

Analyte Method Process Units Concentration 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Aluminum EPA 1638 Dissolved ug/L ND (2.0) 

Antimony EPA 1638 Dissolved ug/L ND (0.50) 

Arsenic EPA 1638 Dissolved ug/L ND (0.50) 

Barium EPA 1638 Dissolved ug/L ND (0.10) 

Beryllium EPA 1638 Dissolved ug/L ND (0.10) 

Cadmium EPA 1638 Dissolved ug/L ND (0.10) 

Chromium EPA 1638 Dissolved ug/L ND (1.0) 

Cobalt EPA 1638 Dissolved ug/L ND (0.10) 

Copper EPA 1638 Dissolved ug/L ND (0.30) 

Lead EPA 1638 Dissolved ug/L ND (0.050) 

Manganese EPA 1638 Dissolved ug/L ND (0.50) 

Molybdenum EPA 1638 Dissolved ug/L ND (0.50) 

Nickel EPA 1638 Dissolved ug/L ND (0.50) 

Selenium EPA 1638 Dissolved ug/L ND (2.0) 

Silver EPA 1638 Dissolved ug/L ND (0.10) 

Thallium EPA 1638 Dissolved ug/L ND (0.050) 

Vanadium EPA 1638 Dissolved ug/L ND (1.0) 

Zinc EPA 1638 Dissolved ug/L ND (0.50) 

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

 Aluminum was detected in one equipment blank for the sample tap tubing set at 5.3 ug/L. 

b

 Calcium was detected in one equipment blank for the pump-off tubing set at 40 ug/L. 

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

A-52 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Hatfield’s Ferry

Analyte Method Process Units Concentration 

Aluminum EPA 1638 Dissolved ug/L ND (2.0) 

Antimony EPA 1638 Dissolved ug/L ND (0.50) 

Arsenic EPA 1638 Dissolved ug/L ND (0.50) 

Barium EPA 1638 Dissolved ug/L ND (0.10) 

Beryllium EPA 1638 Dissolved ug/L ND (0.10) 

Cadmium EPA 1638 Dissolved ug/L ND (0.10) 

Chromium EPA 1638 Dissolved ug/L ND (1.0) 

Cobalt EPA 1638 Dissolved ug/L ND (0.10) 

Copper EPA 1638 Dissolved ug/L ND (0.30) 

Lead EPA 1638 Dissolved ug/L ND (0.050) 

Manganese EPA 1638 Dissolved ug/L ND (0.50) 

Molybdenum EPA 1638 Dissolved ug/L ND (0.50) 

Nickel EPA 1638 Dissolved ug/L ND (0.50) 

Selenium EPA 1638 Dissolved ug/L ND (2.0) 

Silver EPA 1638 Dissolved ug/L ND (0.10) 

Thallium EPA 1638 Dissolved ug/L ND (0.050) 

Vanadium EPA 1638 Dissolved ug/L ND (1.0) 

Zinc EPA 1638 Dissolved ug/L ND (0.50) 

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

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

Aluminum EPA 1638 Total Recoverable ug/L 5.3a 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

 Aluminum was detected in one equipment blank for the sample tap tubing set at 5.3 ug/L. 

b

 Calcium was detected in one equipment blank for the pump-off tubing set at 40 ug/L. 

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

A-53 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Hatfield’s Ferry

Analyte Method Process Units Concentration 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Calcium EPA 1638 Total Recoverable ug/L 40b 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

 Aluminum was detected in one equipment blank for the sample tap tubing set at 5.3 ug/L. 

b

 Calcium was detected in one equipment blank for the pump-off tubing set at 40 ug/L. 

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

A-54 

Table A-15. Bottle Blank and Equipment Blank Analytical Data, Hatfield’s Ferry

Analyte Method Process Units Concentration 

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Zinc EPA 1638 Total Recoverable ug/L ND (0.20) 
A-55 

ND – 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-16. Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, Hatf

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific QL 

Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 
A-56 

ND – 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-16. Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, Hatf

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific QL 

Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
A-57 

ND – 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-17. Effluent from FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, Ha

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific QL C

Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 NBeryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 NChromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 NCopper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 NManganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 NMolybdenum 200.7 ug/L 2 1.6 40 NNickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 Dissolved Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 
A-58 

ND – 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-17. Effluent from FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, Ha

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific QL C

Barium 200.7 ug/L 2 2.5 20 NBeryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 NChromium 200.8 ug/L 2 3.3 8 Chromium (VI) 218.6 ug/L 1 0.39 2 Cobalt 200.7 ug/L 2 1.1 20 NCopper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Molybdenum 200.7 ug/L 2 1.6 40 NNickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 NZinc 200.7 ug/L 2 9.1 40 N
A-59 

ND – Not detected (number in parentheses is the quantitation limit). U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-18. Effluent from FGD Wastewater Treatment System Field Blank, Day 2 Analytical Results, 

Ferry 

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific QL Con

Total Metals Mercury 1631E ng/L 1 0.24 0.5 ND 
A-60 

ND – Not detected (number in parentheses is the quantitation limit). U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-19. Effluent from FGD Wastewater Treatment System Field Blank, Day 3 Analytical Results, 

Ferry 

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific QL Con

Total Metals Mercury 1631E ng/L 1 0.24 0.5 ND 
A-61 

ND – Not detected (number in parentheses is the quantitation limit). U – Result below the MDL. (Number shown in parentheses is the quantitation limit). 

Table A-20. Effluent from FGD Wastewater Treatment System Field Blank, Day 4 Analytical Results, 

Ferry 

Analyte Method Units Dilution Factor Sample-Specific MDL Sample-Specific QL Con

Total Metals Mercury 1631E ng/L 1 0.24 0.5 ND 
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: Donna Tedder, ERG

Date: 9/1/2011

Subject: FGS Data Review Narrative for Total & Dissolved Mercury – Episode 6564

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

The samples were analyzed according to EPA Method 1631E for total mercury by Cold 

Vapor Atomic Fluorescence Spectrometry (CVA-FS) analysis.

Table 1 summarizes the 27 samples (excluding laboratory filter blanks) FGS extracted

and analyzed for total and dissolved mercury. 

Table 1. EPA Episode 6564 Total & Dissolved Mercury – Sample Identification

EPA 

Sample #

Lab Sample 

ID #

Sample 

Matrix Sample Description

Sampling 

Date

Analysis 

Date

71941 1012060-03 Aqueous FGD Influent, Day 1 12/6/2010 1/6/2011

71941 1012060-08 Aqueous Dissolved FGD Influent, Day 1 12/6/2010 12/22/2010

71941 1012060-10 Solid FGD Influent, Day 1 (Solids) 12/6/2010 1/7/2011

71942 1012070-03 Aqueous FGD Influent, Day 2 12/7/2010 1/6/2011

71942 1012070-04 Aqueous Dissolved FGD Influent, Day 2 12/7/2010 1/6/2011

71942 1012070-13 Solid FGD Influent, Day 2 (Solids) 12/7/2010 1/7/2011

71943 1012100-03 Aqueous FGD Influent, Day 3 12/8/2010 1/6/2011

71943 1012100-04 Aqueous Dissolved FGD Influent, Day 3 12/8/2010 12/23/2010

71943 1012100-13 Solid FGD Influent, Day 3 (Solids) 12/8/2010 1/7/2011

71944 1012110-04 Aqueous FGD Influent, Day 4 12/9/2010 1/6/2011

71944 1012110-05 Aqueous Dissolved FGD Influent, Day 4 12/9/2010 12/28/2010

71944 1012110-12 Solid FGD Influent, Day 4 (Solids) 12/9/2010 1/7/2011

71945 1012070-05 Aqueous FGD Effluent, Day 1 12/7/2010 12/22/2010

71945 1012070-06 Aqueous Dissolved FGD Effluent, Day 1 12/6/2010 12/22/2010

71946 1012100-05 Aqueous FGD Effluent, Day 2 12/7/2010 12/23/2010

71946 1012100-06 Aqueous Dissolved FGD Effluent, Day 2 12/7/2010 12/23/2010

71947 1012110-06 Aqueous FGD Effluent, Day 3 12/8/2010 12/28/2010

71947 1012110-07 Aqueous Dissolved FGD Effluent, Day 3 12/8/2010 12/28/2010

71948 1012120-06 Aqueous FGD Effluent, Day 4 12/9/2010 12/28/2010

71948 1012120-07 Aqueous Dissolved FGD Effluent, Day 4 12/9/2010 12/28/2010
2

Table 1. EPA Episode 6564 Total & Dissolved Mercury – Sample Identification

EPA 

Sample #

Lab Sample 

ID #

Sample 

Matrix Sample Description

Sampling 

Date

Analysis 

Date

71949 1012100-07 Aqueous FGD Effluent Duplicate, Day 2 12/7/2010 12/23/2010

71949 1012100-08 Aqueous Dissolved FGD Effluent Duplicate, Day 2 12/7/2010 12/23/2010

71950 1012060-04 Aqueous FGD Influent Field Blank, Day 1 12/6/2010 12/22/2010

71951 1012060-06 Aqueous FGD Effluent Field Blank, Day 1 12/6/2010 12/22/2010

71952 1012070-07 Aqueous FGD Effluent Field Blank, Day 2 12/7/2010 12/22/2010

71953 1012100-11 Aqueous FGD Effluent Field Blank, Day 3 12/8/2010 12/23/2010

71954 1012110-08 Aqueous FGD Effluent Field Blank, Day 4 12/9/2010 12/28/2010

SUMMARY

The samples were prepared according to EPA Method 1631E to be analyzed by CVAFS.

Due to TSS values greater than 1%, samples 71941, 71942, 71943, and 71944 were phase 

separated. 

There were no findings from the data review that required additional qualifiers in this 

dataset.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INITIAL CALIBRATION

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

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

coefficient ≥0.995. All method specified criteria were met.

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

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

criteria.

BLANKS

All instrument and preparation blanks met method specified criteria. Preparation Blanks 

F012184-BLK1, F012184-BLK5, F012215-BLK5, F012215–BLK6, F012243–BLK6, 

F101058–BLK1, F101058–BLK4, and F101058-BLK5 had mercury levels of 0.13, 0.19, 

0.08, 0.09, 0.15, 0.15, 0.08, and 0.20 ng/L, respectively. These blank results were greater 

than the MDL (0.08 ng/L), but less than the RL (0.50 ng/L). Because all of the blank 

results were less than the RL, no samples were qualified based on these preparation blank 

results.
3

DUPLICATES

A field duplicate, Sample 71949 was collected on the Sample 71946. The total mercury 

relative percent difference (RPD) was 42% and the dissolved mercury RPD was 9.4%.

The method-suggested RPD criterion between field duplicates is 20%.

Laboratory duplicates were performed on samples 71941, 71941 (solid), 71942, and 

71947. All RPDs were less than 20% (the method-suggested RPD criterion between field 

duplicates; the method does not require the analysis of laboratory duplicates), except for 

sample 71947, which had an RPD of 79.7%. Because the method does not require the 

analysis of laboratory duplicates, this result was not qualified.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

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

71941, 71941 (solid), 71942, and 71947 for the total mercury analyses. MS and MSDs 

were performed on sample 71947 for the dissolved mercury analyses. All aqueous 

MS/MSD recoveries were within method specifications of 70-125%. All RPDs met 

method-specified criteria.

Two sets of MS/MSD were performed on the solid sample 71941 from this episode.

MS/MSD1 did not meet method-specified criteria for recovery or RPD. The laboratory 

does state that the sample concentration was more than two times the spike amount. 

MS/MSD2 did meet method-specified criteria for recovery and RPD. 
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 6564

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

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

Sample Episode 6564. 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 6563 Total & Dissolved Metals – Sample Identification

EPA 

Sample 

# EPA Sample Description

Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71941 FGD Influent, Day 1 280-10453-1 Aqueous 12/06/2010 12/07/2010

71941 FGD Influent, Day 1 – Solid 280-10453-3 Solid 12/06/2010 12/07/2010

71941 FGD Influent, Day 1 – Filtrate 280-10453-4 Aqueous 12/06/2010 12/07/2010

71942 FGD Influent, Day 2 280-10513-1 Aqueous 12/07/2010 12/08/2010

71942 FGD Influent, Day 2 – Solid 280-10513-4 Solid 12/07/2010 12/08/2010

71942 FGD Influent, Day 2 – Filtrate 280-10513-5 Aqueous 12/07/2010 12/08/2010

71943 FGD Influent, Day 3 280-10583-1 Aqueous 12/08/2010 12/09/2010

71943 FGD Influent, Day 3 – Solid 280-10583-3 Solid 12/08/2010 12/09/2010

71943 FGD Influent, Day 3 – Filtrate 280-10583-4 Aqueous 12/08/2010 12/09/2010

71944 FGD Influent, Day 4 280-10656-1 Aqueous 12/09/2010 12/10/2010

71944 FGD Influent, Day 4 - Solid 280-10656-4 Solid 12/09/2010 12/10/2010

71944 FGD Influent, Day 4 - Filtrate 280-10656-5 Aqueous 12/09/2010 12/10/2010

71945 FGD Effluent, Day 1 280-10513-2 Aqueous 12/07/2010 12/08/2010

71946 FGD Effluent, Day 2 280-10583-2 Aqueous 12/08/2010 12/09/2010

71947 FGD Effluent, Day 3 280-10656-2 Aqueous 12/09/2010 12/10/2010

71948 FGD Effluent, Day 4 280-10724-1 Aqueous 12/10/2010 12/11/2010

71950 FGD Influent Field Blank, Day 1 280-10453-2 Aqueous 12/06/2010 12/07/2010
2

Table 1. EPA Episode 6563 Total & Dissolved Metals – Sample Identification

EPA 

Sample 

# EPA Sample Description

Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71951 FGD Effluent Filed Blank, Day 1 280-10513-3 Aqueous 12/07/2010 12/08/2010

71955 FGD Effluent – Duplicate 280-10656-3 Aqueous 12/09/2010 12/10/2010

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 Element Analysis in Flue Gas Desulfurization Wastewaters,” dated October 6, 

2010, based on EPA Method 200.8, by ICP/MS analysis.

Any significant findings are summarized below. No additional data qualifiers were 

required.

• The matrix spike (MS) and matrix spike duplicate (MSD) recoveries that failed 

the EPA Method 200.8 control limits of 70–130% are as follows: total and 

dissolved silver (71945 MS/MSD); and total and dissolved silver (71948

MS/MSD).

• The MS/MSD relative percent difference (RPD) for dissolved silver for samples 

71945 and 71948 failed TestAmerica’s SOP control limits of ±20%.

• The MS/MSD RPD for total silver for sample 71945 failed TestAmerica’s SOP 

control limits of ±20%.

• The post digestion spikes (PDS) for total and dissolved silver for sample 71945 

failed the method criteria of 85–115%.

• The PDS for silver in the filtrate phase for sample 71944 failed the method 

criteria of 85–115%.

• The PDS for silver in the solid phase for sample 71944 failed the method criteria 

of 85–115%.

• The PDS for total cadmium and total nickel in the aqueous sample for sample 

71944 failed the method criteria of 85–115%.

INTERNAL STANDARDIZATION

All internal standards used by TestAmerica were within the method criteria. 
3

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial 

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

INITIAL AND CONTINUING CALIBRATION VERIFICATION (ICV/CCV)

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

performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit; however, some elements were 

above the MDL and flagged with a “J” qualifier. No additional qualifiers were required 

for method blanks.

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

elements were above the MDL and flagged with a “J” qualifier. No additional qualifiers 

were required for instrument blanks.

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 QC limits of 85–115%.

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION (ICSA)

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

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

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

ICS.

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

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

SERIAL DILUTION (SRD)

The serial dilution performed for the total and dissolved sample 71945 FGD Effluent, 

Day 1 (280-10513-2) met Test America’s requirement of ±10% difference.
4

FIELD DUPLICATES

The RPD of the field duplicates 71947/71955 for total and dissolved results were less

than ±20% for all values equal to or greater than the reporting limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

MS and MSDs were performed on samples 71945 FGD Effluent, Day 1 and 71948 FGD 

Effluent, Day 4 for total and dissolved analytes. The total and dissolved selenium results 

in the MS and MSD samples for samples 71945 and 71948 failed the 70–130% method 

control limits and were flagged with a “4” qualifier indicating concentrations in the 

parent samples were greater than four times the spike amounts. Otherwise, the MS/MSD 

spike recoveries were always within the control limits of 70-130% with the exception of 

total and dissolved silver for the MS and MSD samples for both 71945 and 71948, which 

were flagged with an “F” qualifier. The RPD for all MS/MSD samples passed the 

method-specified criteria of ±20%, except for dissolved silver for samples 71945 and 

71948 and total silver for 71945. The poor recoveries and RPD of silver are probably due 

to high sulfates in this episode’s samples that could form insoluble silver sulfide and/or 

silver sulfate.

POST DIGESITON SPIKES

PDSs were performed on sample 71945 FGD Effluent, Day 1 (280-10513-2 PDS) and the 

solid and aqueous sample of 71944 FGD Influent, Day 4 (280-10656-4 PDS; 280-10656-

5 PDS respectively). Total and dissolved silver failed TestAmerica’s aqueous control 

limits of 85–115% for sample 71945, total silver failed the filtrate of sample 71944, and 

total silver failed the solid control limits of 75–115% for sample 71944. All failures were

all flagged “W”. The poor recoveries of silver are probably due to high sulfates in this 

episode’s samples that could form insoluble silver sulfide and/or silver sulfate. The 

aqueous sample 71944 also failed TestAmerica’s 85-115% control limits for total 

cadmium and total nickel, which were flagged “W”.

DETECTION LIMITS

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

of reagent water.
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

Deb Bartram, ERG

TJ Finseth, ERG

From: Randy Mercurio, ERG

Date: 9/1/2011

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

Episode 6564

TestAmerica generated analytical data for total and dissolved metals (aluminum, boron, 

barium, beryllium, calcium, cobalt, iron, magnesium, manganese, molybdenum, sodium, 

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

Table 1 summarizes the samples TestAmerica extracted and analyzed for total and 

dissolved metals by EPA Method 200.7.

Table 1. EPA Episode 6564 Total & Dissolved Metals – Sample Identification

EPA 

Sample 

# EPA Sample Description

Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71941 FGD Influent, Day 1 280-10453-1 Aqueous 12/06/2010 12/07/2010

71941 FGD Influent, Day 1 – Solid 280-10453-3 Solid 12/06/2010 12/07/2010

71941 FGD Influent, Day 1 - Filtrate 280-10453-4 Aqueous 12/06/2010 12/07/2010

71942 FGD Influent, Day 2 280-10513-1 Aqueous 12/07/2010 12/08/2010

71942 FGD Influent, Day 2 – Solid 280-10513-4 Solid 12/07/2010 12/08/2010

71942 FGD Influent, Day 2 – Filtrate 280-10513-5 Aqueous 12/07/2010 12/08/2010

71943 FGD Influent, Day 3 280-10583-1 Aqueous 12/08/2010 12/09/2010

71943 FGD Influent, Day 3 – Solid 280-10583-3 Solid 12/08/2010 12/09/2010

71943 FGD Influent, Day 3 – Filtrate 280-10583-4 Aqueous 12/08/2010 12/09/2010

71944 FGD Influent, Day 4 280-10656-1 Aqueous 12/09/2010 12/10/2010

71944 FGD Influent, Day 4 – Solid 280-10656-4 Solid 12/09/2010 12/10/2010

71944 FGD Influent, Day 4 - Filtrate 280-10656-5 Aqueous 12/09/2010 12/10/2010

71945 FGD Effluent, Day 1 280-10513-2 Aqueous 12/07/2010 12/08/2010

71946 FGD Effluent, Day 2 280-10583-2 Aqueous 12/08/2010 12/09/2010

71947 FGD Effluent, Day 3 280-10656-2 Aqueous 12/09/2010 12/10/2010

71948 FGD Effluent, Day 4 280-10724-1 Aqueous 12/10/2010 12/11/2010

71950 FGD Influent Field Blank, Day 1 280-10453-2 Aqueous 12/06/2010 12/07/2010
2

Table 1. EPA Episode 6564 Total & Dissolved Metals – Sample Identification

EPA 

Sample 

# EPA Sample Description

Lab Sample 

ID #

Sample 

Matrix

Sampling 

Date

Receipt 

Date

71951 FGD Effluent Filed Blank, Day 1 280-10513-3 Aqueous 12/07/2010 12/08/2010

71955 FGD Effluent – Duplicate 280-10656-3 Aqueous 12/09/2010 12/10/2010

SUMMARY

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

TestAmerica’s SOP for ICP Analysis for Trace Metals by Method 200.7. Any significant 

findings are summarized below. No additional data qualifiers were required.

• The serial dilution analysis for dissolved manganese, dissolved molybdenum, and 

dissolved sodium for sample 71945 did not meet TestAmerica’s requirement of 

±10% difference.

• The serial dilution analysis for barium, cobalt, magnesium, manganese, titanium, 

and zinc in the solid phase of sample 71944 did not meet TestAmerica’s 

requirement of ±10% difference.

• The matrix spike (MS) and matrix spike duplicate (MSD) recoveries that failed 

the EPA Method 200.7 control limits of 70–130% are as follows: dissolved 

barium (71945 MS/MSD); dissolved barium (71948 MS/MSD); and total iron 

(71945 MSD).

• The MS/MSD relative percent difference (RPD) for dissolved barium for samples 

71945 and 71948 failed TestAmerica’s SOP control limits of ±20%.

• The post digestion spikes (PDS) for total barium for sample 71945 failed the 

method criteria of 85–115%.

• The PDS for magnesium and tin in the solid phase for sample 71944 failed the 

method criteria of 85–115%.

• The PDS for titanium and zinc in the filtrate phase for sample 71944 failed the 

method criteria of 85–115%.

SAMPLE RECEIPT, HANDLING, AND STORAGE

There were no issues associated with receipt, handling and storage.
3

INTERNAL STANDARDIZATION

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

ISTD recoveries in the ±30% criterion of the calibration blank as per Section 9.11 of the 

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

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial 

calibration for the ICP analysis consisted of a blank and one calibration standard.

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

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

performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANKS

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

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

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

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

REPORTING LIMIT VERIFICATION STANDARD (CRI)

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

LABORATORY CONTROL SAMPLES (LCS)

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

INTERFERENCE CHECK SOLUTIONS

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

recoveries met the method-specified criteria.

SERIAL DILUTION (SRD)

Serial dilutions were performed for each batch of total and dissolved samples. The serial 

dilution results for dissolved manganese, dissolved molybdenum and dissolved sodium 

for sample 71945 FGD Effluent, Day 1 (280-10513-2) had percent differences of 25%, 

22% and 20% respectively, which were appropriately flagged. The serial dilution results 

for total barium, total cobalt, total magnesium, total manganese, total titanium and total 

zinc of the solid fraction for sample 71944 FGD Influent, Day 4 (280-10656-4) had 
4

percent differences of 41%, 53%, 51%, 50%, 44% and 43% respectively, which were also 

appropriately flagged. No additional qualifiers were required.

FIELD DUPLICATES

The total and dissolved RPDs of the field duplicate (71955) to parent sample (71947) 

were less than 20% for values greater than the reporting limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

MS and MSD were performed on the total and dissolved samples of 71945 FGD Effluent, 

Day1 (280-10513-2) and 71948 FGD Effluent, Day 4 (280-10724-1). Some elements 

with high concentrations frequently failed the EPA 200.7 Method spike recovery control 

limits of 70–130% but were flagged with a “4” qualifier indicating that the concentration 

in the parent sample was greater than 4 times the spike and could not be reliably 

calculated. Otherwise, the MS/MSD spike recoveries were always within the control 

limits of 70-130% with the exception of dissolved barium for both the MS and MSD for 

samples 71945 and 71948 and the total iron MSD for sample 71945. All relative percent 

differences (RPDs) were within ± 20% with the exception of dissolved barium for both 

samples 71945 and 71948. No additional data qualifiers were needed.

POST DIGESTION SPIKE

The PDS of sample 71945 FGD Effluent, Day 1 (280-10513-2 PDS) failed the method 

criteria of 85–115% for total barium, which was flagged. The solid fraction PDS of 

sample 71944 FGD Influent, Day 4 (280-10656-4 PDS) failed for magnesium and tin, 

which were flagged. The filtrate fraction PDS of sample 71944 FGD Influent, Day 5 

(280-10656-5 PDS) failed for titanium and zinc, which were flagged. No additional 

qualifiers were required.

DETECTION LIMITS

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

of reagent water.
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

Deb Bartram, ERG

TJ Finseth, ERG

From: Donna Tedder, ERG

Date: 9/1/2011

Subject: FGS Data Review Narrative for Dissolved Hexavalent Chromium – Episode 

6564

Frontier Global Sciences (FGS) generated analytical data for dissolved hexavalent 

chromium for Sample Episode 6564. The samples were analyzed according to a 

modified EPA Method 218.6 for dissolved hexavalent chromium by Liquid 

Chromatography – Inductively Coupled Plasma Mass Spectrometry (LC-ICP-MS).

Table 1 summarizes the samples FGS prepared and analyzed for dissolved hexavalent 

chromium.

Table 1. EPA Episode 6564 Dissolved Hexavalent Chromium – Sample 

Identification

EPA 

Sample #

Sample 

Matrix Sample Description

Sampling 

Date

Analysis 

Date

71941 Aqueous FGD Influent Day 1 12/6/10 12/29/10

71943 Aqueous FGD Influent Day 3 12/8/10 12/29/10

71944 Aqueous FGD Influent Day 4 12/9/10 12/29/10

71945 Aqueous FGD Effluent Day 1 12/7/10 12/29/10

71946 Aqueous FGD Effluent Day 2 12/8/10 12/29/10

71947 Aqueous FGD Effluent Day 3 12/9/10 12/29/10

71950 Aqueous FGD Influent Field Blank Day 1 12/6/10 12/29/10

71951 Aqueous FGD Effluent Field Blank Day 1 12/7/10 12/29/10

71955 Aqueous FGD Effluent Dup Day 3 12/9/10 12/29/10

SUMMARY

The samples were prepared for dissolved hexavalent chromium analysis according to 

FGS-129.01 Standard Operating Procedure (SOP), a modified EPA Method 218.6.

Samples 71941, 71943, and 71944 were diluted prior to analysis due to the presence of 

high levels of nontarget chloride interferences. There were no issues requiring additional 

data qualifiers for the hexavalent chromium data in this episode.
2

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

The collection date and time were not recorded on the chain of custody for samples 

71945 and 71951.

INITIAL PRECISION AND ACCURACY/RECOVERY

The initial precision and recovery (IPR) performed by FGS had recoveries within the 

method criteria.

INITIAL CALIBRATION

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

the LC-ICP-MS analysis consisted of a blank and eight calibration standards with a 

correlation factor ≥ 0.995 as required by the method.

A secondary source initial calibration verification (ICV) was analyzed and passed ± 10% 

of true value required by the analytical method.

CONTINUING CALIBRATION VERIFICATION

All CCVs met method-specified criteria, ± 10% of true value with recoveries ranging 

from 94.9 to 95.5%.

BLANK

All of the preparation blanks/laboratory reagent blanks (LRBs) and the continuing 

calibration blanks (CCBs) met method-specified requirements. 

OTHER CHECKS

The laboratory control sample/duplicate (LCS/LCSD) or laboratory fortified 

blank/duplicate (LFB/LFBD) passed method criteria of ± 10% of true value with 

recoveries of 96% and 95%. The method suggested that a second source quality control 

sample (QCS) must be analyzed by the laboratory at least once a quarter. The second 

source ICV meets this recommendation.

DETECTION LIMITS

The laboratory method detection limit (MDL) in the synthetic matrix was 0.392 ug/L. 

Results below this MDL were reported as not detected.
3

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 was collected and analyzed. Sample 71955, was a duplicate of 

effluent sample 71947, with an RPD of 8%. 

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The MS and matrix spike duplicate (MSD) were performed using a secondary source 

spike on sample 71948. Two set of MS/MSD were performed at two different 

concentration levels. The MS/MSD1 (spiked at 50 ug/L) recoveries were within criteria, 

92.5% and 91.0%, with an RPD of 1.59%. The MS/MSD2 (spiked at 250 ug/L) 

recoveries were within criteria, 96.2% and 96.8%, with an RPD of 0.56%.
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

Deb Bartram, ERG

TJ Finseth, ERG

From: Donna Tedder, ERG

Date: 9/1/2011

Subject: TestAmerica Data Review Narrative for Classicals Analyses – Episode 6564

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry 

analyses for Sample Episode 6564. All samples were tested for the following analytes:

• Ammonia by EPA method 350.1, 

• Biochemical Oxygen Demand – 5 day (BOD5) by SM 5210B, 

• Chloride and Sulfate by EPA method 300.0, 

• Chemical Oxygen Demand (COD) by EPA method 410.4, 

• Cyanide (total) by SM 4500 CN- E, 

• Nitrate/Nitrite by EPA method 353.2

• Phosphorus (total) by EPA method 365.1, 

• Total Dissolved Solids (TDS) by SM 2540C, 

• Total Kjeldakl Nitrogen (TKN) by EPA method 351.2, and 

• Total Suspended Solids (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 

analyzed both portions separately for the following analytes:

• Ammonia, 

• Chloride

• Cyanide, 

• Nitrate/Nitrite, 

• Phosphorus,

• Sulfate, and

• TKN. 

Table 1 summarizes the nine field samples analyzed by TestAmerica and particularly 

highlights how the laboratory split and analyzed the influent samples.
2

Table 1. EPA Episode 6564 Classical Analytes – Sample Identification

EPA

Sample #

Sample 

Description

Sampling

Date

Sample

Matrix

Portion of 

Sample

Analytes 

71941 FGD Influent, 

Day 1 12/06/10

Water Entire 

Fraction

BOD5, COD, TDS, and 

TSS

Water Filtrate

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Phosphorus, Sulfate, and 

TKN

Solids Solids

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Phosphorus, Sulfate, and 

TKN

71942 FGD Influent, 

Day 2 12/07/10

Water Entire 

Fraction

BOD5, COD, TDS, and 

TSS

Water Filtrate

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Phosphorus, Sulfate, and 

TKN

Solids Solids

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Phosphorus, Sulfate, and 

TKN

71943 FGD Influent, 

Day 3 12/08/10

Water Entire 

Fraction

BOD5, COD, TDS, and 

TSS

Water Filtrate

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Phosphorus, Sulfate, and 

TKN

Solids Solids

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Phosphorus, Sulfate, and 

TKN

71944 FGD Influent, 

Day 4 12/09/10

Water Entire 

Fraction

BOD5, COD, TDS, and 

TSS

Water Filtrate

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite, 

Phosphorus, Sulfate, and 

TKN

Solids Solids

Ammonia, Chloride, 

Cyanide, Nitrate/Nitrite,

Phosphorus, Sulfate, and 

TKN

71945 FGD Effluent, 

Day 1 12/07/10 Water Entire Fraction All analytes
3

EPA

Sample #

Sample 

Description

Sampling

Date

Sample

Matrix

Portion of 

Sample

Analytes 

71946 FGD Effluent, 

Day 2 12/08/10 Water Entire Fraction All analytes

71947 FGD Effluent, 

Day 3 12/09/10 Water Entire Fraction All analytes

71948 FGD Effluent, 

Day 4 12/10/10 Water Entire Fraction All analytes

71955 FGD Effluent -

Duplicate 12/09/10 Water Entire Fraction All analytes

SUMMARY

All samples were analyzed within the holding time specified in 40 CFR 136 Table II

unless otherwise noted below.

TestAmerica could not use a preserved sample volume for phase separation. Therefore, 

they combined two of the unpreserved 250 mL metal sample volumes and phase 

separated this volume. After phase separation, TestAmerica preserved the samples 

accordingly. Because of this process, ammonia, nitrate/nitrite, TKN, phosphorus, and 

cyanide influent samples were not preserved immediately following sample collection as 

required by the method. 

One field duplicate sample was collected and analyzed for each analyte. The relative 

percent difference (RPD) between the sample and its duplicate was less than 20% unless 

otherwise noted below. 

If applicable, the appropriate number of standards was used to create a calibration curve. 

If sample results were above the highest standard used to create the curve, the sample was 

diluted and reanalyzed. All sample results were between the lowest and highest standards

unless noted below. Additionally, all calibration blanks and calibration verification 

samples met the criteria specified in the method.

If required by the method, the quality control sample (QCS), a secondary source standard 

used to verify calibration, was always within the control limits specified by the method. 

As described below, the analyte of interest was detected above the method detection limit 

(MDL) in some laboratory reagent blanks (LRB). However, the analyte of interest was 

never detected above the reporting limit (RL) in the LRBs. If required by the method, all 

laboratory fortified blanks (LFB) met the criteria specified in the method unless specified 

below.

If required by the method, a matrix spike (MS) analysis was run on sample 71948 (FGD 

effluent) for each analyte to check for matrix interferences. For some analytes, 

TestAmerica spiked more than one sample. 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 samples 71941 - 71944 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

phase separation. The filtrate volume of samples 71941 - 71944 were already qualified by 

TestAmerica 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 solid aliquot 

of samples 71941 - 71944 were qualified as estimated values because the samples were 

not preserved immediately following sample collection.

The filtrate and solid aliquots of samples 71941, 71942, 71943, and 71944 were analyzed 

9, 8, 7, and 6 days, respectively, after the 28-day hold time. These samples were already 

qualified as estimated values either because their result was less than the RL or because 

they were not preserved immediately following sample collection, so no further action 

was necessary.

Ammonia was detected at 0.0610 mg/L in the LRB associated with samples 71945 and 

71946. The blank result was above the MDL (0.055 mg/L), but below the RL (1.0 mg/L), 

so these samples were not qualified based on this LRB result.

BOD5

TestAmerica analyzed five dilutions, but no dilutions had a dissolved oxygen (DO) 

depletion greater than 2.0 mg/L for sample 71945. Therefore, BOD5 was reported as not 

detected for this 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. 

BOD was not detected above the RL in any method blanks. However, for batch 44128, 

the results for the three water/unseeded blanks were 0.23 mg/L, 0.21 mg/L, and 0.19 

mg/L. Two of these water blanks were above the method control criteria of 0.20 mg/L.

Because of these blank results, sample 71941 was qualified with a “B” meaning the 

analyte was detected in the sample and the blank. 

The glucose-glutamic acid (GGA) standards associated with sample 71948 had percent 

recoveries of 84% and 86%. The percent recovery of the first GGA standard was below

the method and laboratory criteria of 85-115%. TestAmerica flagged sample 71948 with 

a “*” meaning the laboratory control sample was not within laboratory control limits. 

Sample 71948 was additionally qualified as a minimum value.
5

Chloride and Sulfate

Solid aliquots of samples 71941, 71942, 71943, and 71944 were analyzed 9, 8, 7, and 6 

days, respectively, after the 28-day hold time. Additionally, filtrate aliquots of samples 

71941, 71942, 71943, and 71944 were analyzed 8, 7, 6, and 5 days, respectively, outside 

of the 28-day hold time. These samples were qualified as estimated values.

The laboratory diluted the MS and MSD samples for 71941 and 71948 by 200, but the 

diluted results for sulfate and chloride were still above the highest calibration standard. 

The laboratory did not reanalyze these samples with a higher dilution factor, because the 

MS and MSD percent recoveries were within the control limits specified by EPA method 

300.0. Therefore, if the MS and MSD results for sample 71941 for chloride and sulfate 

are reported, they will be qualified as estimated values. The results for samples 71941 

and 71948 were within the calibration range, so there was no need to qualify these 

samples. The LFB associated with sample 71941 and 71948 met the method criteria.

COD

Samples 71941, 71943, and 71944 were preserved to pH less than 2 S.U. after sample 

collection. However, when the laboratory received the samples, the pH was neutral. The 

samples were preserved again by the laboratory. These samples were qualified as 

estimated values.

The percent recoveries for the MS and MSD samples associated with 71948 were 93% 

and 79%, respectively. Only the MS sample was within the control limits of 90 - 110%

specified in the method. However, since the method does not require an MSD analysis,

sample 71948 was not qualified because of the low MSD percent recovery. Also, the MS

and MSD results associated with sample 71948 were above 150 mg/L. COD is calculated 

using a reverse curve meaning that the 200 mg/L calibration point represents the zero in 

the curve and the 0 mg/L calibration point represents the highest absorbance. 

TestAmerica has noticed that results in the 150-200 mg/L range yield inconsistent results, 

so typically the lab dilutes these samples and reanalyzes. The MS and MSD samples 

associated with 71948 were not diluted further and reanalyzed, so TestAmerica flagged 

them with an “E” meaning that the results exceeded the calibration range. If reported, the 

MS and MSD results for sample 71948 will be qualified as estimated values. 

The percent recoveries for the MS and MSD samples associated with 71941 were 68% 

and 71%, respectively. Both the MS and MSD sample results for this sample were not 

within the control limits specified in the method. Sample 71941 was already qualified as 

an estimated value because the sample was not preserved appropriately, so there was no 

need to further qualify the sample as a minimum value. The LFB associated with sample 

71941 and 71948 met the method criteria. 
6

Cyanide 

As stated above, filtrate and solid aliquots of samples 71941-71944 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

phase separation. Filtrate aliquots of samples 71941 and 71944 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. Because the 

filtrate aliquots of samples 71942 and 71943 and the solid aliquots of samples 71941 -

71944 were not preserved immediately following sample collection as required by the 

method, these samples were qualified as estimated values.

Solid and filtrate aliquots of samples 71941, 71942, 71943, and 71944 were analyzed 25, 

24, 23, and 22 days, respectively, outside of the 14-day holding time. These samples were 

already qualified as estimated values because they were not preserved immediately

following sample collection as required by the method, so no further qualification was 

necessary.

All aqueous samples were diluted prior to distillation by a factor of 10 due to matrix 

interferences. The laboratory stated that the samples foamed during preparation and in 

order to protect the instruments, the samples needed to be diluted. The diluted results for

the filtrate aliquot of samples 71941 and 71944 were less than the lowest calibration 

standard. However, these samples were already qualified by the laboratory with a “J” 

meaning the sample result was an estimated value because it was less than the RL, so 

there was no need to further qualify these samples.

The percent recoveries for the MS and MSD samples associated with sample 71948 were 

79% and 78%, respectively. These percent recoveries were not within the laboratory 

control criteria of 90-110%. Additionally, the percent recoveries for the MS and MSD 

samples associated with sample 71955 were 67% and 69%, respectively. These percent 

recoveries were also not within the laboratory control criteria. Since there are no MS or 

MSD criteria specified in SM 4500 CN- E, samples 71948 and 71955 were not qualified 

based on the low MS and MSD percent recoveries. The LFBs associated with samples 

71948 and 71955 met the method criteria.

The RPD between sample 71947 and its field duplicate 71955 for cyanide was 46.2%. 

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 samples 71941 - 71944 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

phase separation. Because these samples were not preserved immediately following 

sample collection as required by the method, these samples were qualified as estimated 

values.
7

The filtrate and solid aliquots of samples 71941, 71942, 71943, and 71944 were analyzed 

11, 10, 9, and 8 days, respectively, outside of 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.

TestAmerica diluted the MS and MSD samples for 71948 by 20 fold, but the analyzed 

result was still above the highest calibration standard. The samples were not diluted and 

reanalyzed because the percent recoveries were within the control limits specified in the 

method. If the MS and MSD results are reported, they will be qualified as estimated 

values. The result for sample 71948 was within the calibration range, so there was no 

need to qualify this sample. The LFB associated with sample 71948 met the method 

criteria. 

Phosphorus 

As stated above, filtrate and solid aliquots of samples 71941 - 71944 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

phase separation. The solid aliquot of sample 71944 was already qualified by the 

laboratory with a “J” meaning the sample result was an estimated value because it was 

less than the RL, so there was no need to further qualify this sample. Phosphorus was not 

detected in the solid aliquot for sample 71941, so there was no need to further qualify this 

sample. Solid samples 71942 and 71943 and filtrate samples 71941 - 71944 were 

qualified as estimated values because they were not preserved immediately following 

sample collection as required by the method.

Filtrate and solid aliquots of samples 71941, 71942, 71943, and 71944 were analyzed 10, 

9, 8, and 7 days, respectively, past the 28-day hold time. These samples were not 

detected, already qualified with a “J”, or qualified as estimated values because they were 

not preserved immediately following sample collection, so no further action was 

necessary.

Phosphorus was detected at 0.0114 mg/L in the LRB associated with the filtrate aliquot

of samples 71941 - 71944. Phosphorus was also detected at 0.0103 mg/L in the LRB

associated with sample 71948. Additionally, phosphorus was detected at 0.0103 mg/L in 

the LRB associated with samples 71945, 71946, 71947, and 71955. Since all of these 

blank results were less than the RL (0.050 mg/L), no samples were qualified based on 

these LRB results.

The percent recoveries for the MS and MSD analyses for sample 71948 were not within 

the method control limits of 90-110% or within the laboratory control limits of 71-128%. 

The percent recoveries for the MS and MSD samples were 28% and 24%, respectively.

Sample 71948 was already qualified by the laboratory with a “J” meaning the sample 

result was an estimated value because it was less than the RL, so there was no need to 

further qualify this sample as a minimum value. The LFB associated with sample 71948 

met the method criteria.
8

TDS

One laboratory duplicate was analyzed on sample 71948. The RPD between this sample 

and its laboratory duplicate was 14%. This RPD was not less than 10% as required by the 

method, so sample 71948 was qualified as an estimated value.

Samples 71941, 71942, 71943, 71945, 71946, 71947, 71948, and 71955 did not achieve a 

constant weight after three drying cycles. The weight increased from the first weighing to 

the second weighing for sample 71948. SM 2540C warns that samples that contain high 

levels of calcium, magnesium, chloride, and sulfate may be hygroscopic, meaning they 

absorb moisture from the air. FGD wastewater contains high concentrations of all of 

these species, so this may be the cause for the inconsistent weight calculations. These 

samples were not qualified, but results may be biased high.

The RPD between sample 71947 and its field duplicate 71955 for TDS was 24%. 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 2540C. 

TKN

As stated above, filtrate and solid aliquots of samples 71941 - 71944 were not preserved 

immediately after sample collection. Instead, TestAmerica preserved the sample after 

phase separation. Because these samples were not preserved immediately following 

sample collection as required by the method, these samples were qualified as estimated 

values.

Filtrate and solid aliquots of samples 71941, 71942, 71943, and 71944 were analyzed 10, 

9, 8, and 7 days, respectively, past 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. 

TKN was detected at 0.264 mg/L in the laboratory reagent blank associated with the 

filtrate aliquot of samples 71941 - 71944. Because this blank result was less than the RL

(1.0 mg/L), no samples were qualified based on this LRB result.

TestAmerica preformed MS and MSD analysis on sample 71948. The percent recoveries

for the MS and MSD samples were 77% and 76%. The samples did 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. Sample 71948 was not qualified because it is not possible to 

determine if the MS and MSD failures were a result of matrix interferences or the low 

spiking level. The LFB associated with sample 71948 met the method criteria.
9

TSS 

Two laboratory duplicates were analyzed for TSS. The RPD for sample 71941 and its 

duplicate was less than 10% as required by the method; however, the RPD for sample 

71948 and its duplicate was 50%. The result for 71948 was at the RL (4.0 mg/L) and the 

result for the laboratory duplicate was 2.40 mg/L, which was less than the RL. The low 

concentration of TSS was likely the cause for the high RPD value. Sample 71948 was 

qualified as an estimated value.
10

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71941 (solid) Ammonia H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 9 

days past holding 

time.

15 mg/Kg

71942 (solid) Ammonia H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 8 

days past holding 

time.

12 mg/Kg

71943 (solid) Ammonia H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 7 

days past holding 

time.

11 mg/Kg

71944 (solid) Ammonia H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 6 

days past holding 

time.

15 mg/Kg

71941 BOD B Unseeded water blank 

> method-specified 

criteria

3.0 mg/L

71948 BOD Minimum Value GGA % recovery 

below methodspecified criteria

2.6 mg/L

71941 (solid) Chloride H, Estimated

Value

Analyzed 9 days past 

holding time.

1,500 

mg/Kg

71942 (solid) Chloride H, Estimated

Value

Analyzed 8 days past 

holding time.

3,000 

mg/Kg

71943 (solid) Chloride H, Estimated

Value

Analyzed 7 days past 

holding time.

1,900 

mg/Kg

71944 (solid) Chloride H, Estimated

Value

Analyzed 6 days past 

holding time.

2,200 

mg/Kg

71941 (filtrate) Chloride H, Estimated

Value

Analyzed 8 days past 

holding time.

6,100 mg/L

71942 (filtrate) Chloride H, Estimated

Value

Analyzed 7 days past 

holding time.

9,400 mg/L

71943 (filtrate) Chloride H, Estimated

Value

Analyzed 6 days past 

holding time.

8,700 mg/L
11

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71944 (filtrate) Chloride H, Estimated

Value

Analyzed 5 days past 

holding time.

6,800 mg/L

71941 (solid) Sulfate H, Estimated

Value

Analyzed 9 days past 

holding time.

27,000 

mg/Kg

71942 (solid) Sulfate H, Estimated

Value

Analyzed 8 days past 

holding time.

29,000 

mg/Kg

71943 (solid) Sulfate H, Estimated

Value

Analyzed 7 days past 

holding time.

24,000 

mg/Kg

71944 (solid) Sulfate H, Estimated

Value

Analyzed 6 days past 

holding time.

27,000 

mg/Kg

71941 (filtrate) Sulfate H, Estimated

Value

Analyzed 8 days past 

holding time.

9,700 mg/L

71942 (filtrate) Sulfate H, Estimated

Value

Analyzed 7 days past 

holding time.

11,000 

mg/L

71943 (filtrate) Sulfate H, Estimated

Value

Analyzed 6 days past 

holding time.

9,300 mg/L

71944 (filtrate) Sulfate H, Estimated

Value

Analyzed 5 days past 

holding time.

9,800 mg/L

71941 COD Estimated Value pH upon receipt > 2

S.U., MS % recovery 

below methodspecified criteria 

250 mg/L

71943 COD Estimated Value pH upon receipt > 2

S.U.

350 mg/L

71944 COD Estimated Value pH upon receipt > 2

S.U.

280 mg/L

71942 (filtrate) Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

24 days past holding 

time.

0.19 mg/L

71943 (filtrate) Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

23 days past holding 

time.

0.16 mg/L

71941 (solid) Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

25 days past holding 

time.

0.54 

mg/Kg
12

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71942 (solid) Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

24 days past holding 

time.

0.69 

mg/Kg

71943 (solid) Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

23 days past holding 

time.

0.73 

mg/Kg

71944 (solid) Cyanide H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

22 days past holding 

time.

0.96 

mg/Kg

71941 (solid) Nitrate/Nitrite H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

11 days past holding 

time.

34 mg/Kg

71942 (solid) Nitrate/Nitrite H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

10 days past holding 

time.

69 mg/Kg

71943 (solid) Nitrate/Nitrite H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 9

days past holding 

time.

39 mg/Kg

71944 (solid) Nitrate/Nitrite H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 8

days past holding 

time.

49 mg/Kg

71941 (filtrate) Nitrate/Nitrite H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

11 days past holding 

time.

140 mg/L
13

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71942 (filtrate) Nitrate/Nitrite H, Estimated 

Value

Sample not preserved

immediately following 

collection. Analyzed 

10 days past holding 

time.

230 mg/L

71943 (filtrate) Nitrate/Nitrite H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 9

days past holding 

time.

170 mg/L

71944 (filtrate) Nitrate/Nitrite H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 8

days past holding 

time.

140 mg/L

71942 (solid) Phosphorus H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 9

days past holding

time.

250 mg/Kg

71943 (solid) Phosphorus H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 8

days past holding 

time.

190 mg/Kg

71941 (filtrate) Phosphorus H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

10 days past holding 

time.

0.12 mg/L

71942 (filtrate) Phosphorus H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 9

days past holding 

time.

0.14 mg/L

71943 (filtrate) Phosphorus H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 8

days past holding 

time.

0.13 mg/L
14

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71944 (filtrate) Phosphorus H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 7

days past holding 

time.

0.11 mg/L

71948 TDS Estimated Value Laboratory duplicate 

RPD > methodspecified criteria

15,000 

mg/L

71941 (solid) TKN H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

10 days past holding 

time.

560 mg/Kg

71942 (solid) TKN H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 9

days past holding 

time.

500 mg/Kg

71943 (solid) TKN H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 8

days past holding 

time.

83 mg/Kg

71944 (solid) TKN H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 7

days past holding 

time.

620 mg/Kg

71941 (filtrate) TKN H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 

10 days past holding 

time.

14 mg/L

71942 (filtrate) TKN H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 9

days past holding 

time.

25 mg/L
15

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level 

Detected

71943 (filtrate) TKN H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 8

days past holding 

time.

36 mg/L

71944 (filtrate) TKN H, Estimated 

Value

Sample not preserved 

immediately following 

collection. Analyzed 7

days past holding 

time.

14 mg/L

71948 TSS Estimated Value Laboratory duplicate 

RPD > methodspecified criteria

4.0 mg/L
Appendix C 

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

ELEMENT ANALYSIS IN FLUE GAS DESULFURIZATION WASTEWATERS
C-1 

FGD ICP/MS SOP: Inductively Coupled Plasma Mass Spectrometry for 

Trace Element Analysis in Flue Gas Desulfurization Wastewaters 

1.0 Scope and Application

1.1 This document describes procedures used to measure elements in Flue Gas 

Desulfurization, FGD, wastewaters. Inductively coupled plasma-mass 

spectrometry (ICP/MS), as described in EPA Methods 200.8 and 1638, was used 

with a collision cell to mitigate the effects of interferences in the samples. These 

procedures are intended for use by analysts experienced with applying ICP/MS 

to complex wastewater samples. 

1.2 These procedures are applicable to the analysis of acid digested FGD 

wastewater, and have been evaluated for the analysis of 13 elements of interest. 

These are Al, As, Cd, Cr, Cu, Pb, Mn, Ni, Se, Ag, Tl, V and Zn. Additional 

elements may be included provided that the performance criteria presented in 

Sections 9 and 12 are met. 

1.3 Flue Gas Desulfurization wastewaters frequently have very high levels of 

calcium, sodium, magnesium, manganese, chloride and sulfate (up to thousands 

of ppm). The use of instrument configurations and/or accessories designed to 

accommodate samples with high dissolved solids levels is highly recommended. 

2.0 Summary

2.1 Aqueous samples, digestates, or leachates are nebulized into a spray chamber 

where a stream of argon carries the sample aerosol through the quartz torch and 

injects it into an RF plasma. There the sample is decomposed and desolvated. 

2.2 The ions produced are entrained in the plasma gas and by means of a watercooled, differentially pumped interface, introduced into a high-vacuum chamber 

that houses a quadrupole mass spectrometer capable of providing a resolution 

better than or equal to 0.9 amu peak width at 10% of the peak height. The ions 

are separated according to their mass-to-charge ratio and measured with a 

detector, such as an electron multiplier. 

2.3 A collision/reaction cell utilizing He and (optionally) H2 gases is used to remove 

molecular interferences. 

2.4 Interferences not eliminated by the collision/reaction cell must be assessed and 

valid corrections applied, or the data flagged to indicate problems. Interference 

correction must include compensation for interferences not removed by the 

collision / reaction cell. Recommended elemental equations are listed in 

Attachment 1. Use of the internal standard technique is required to compensate 

for suppressions and enhancements caused by sample matrices. 

3.0 Definitions

3.1 Batch – A group of samples which behave similarly with respect to the sampling 

or the testing procedures being employed and which are processed as a unit. 

For QC purposes, if the number of samples in a group is greater than 20, then 

each group of 20 samples or less will all be handled as a separate batch 
C-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. 
C-3 

4.0 Interferences

4.1 Isobaric Interferences 

Isobaric interferences in the ICP/MS are caused by isotopes of different elements 

forming ions with the same nominal mass-to-charge ratio (m/z). The 

recommended ions used for the elements in this procedure do not have 

elemental isobaric interferences, except for a very small interference from 

krypton on 78Se, which can be avoided by using argon free of krypton. 

4.2 Isobaric Molecular 

Isobaric molecular interferences are caused by ions consisting of more than one 

atom. These molecular interferences are minimized by use of the collision cell 

utilizing He and/or H2 gases. Common examples are potential interferences from 

40Ar35Cl or 40Ca35Cl on 75As, or 35Cl16O on 51V, or 40Ar12C on 52Cr. Collision cell 

interference removal works both by causing the interfering molecular ion to 

dissociate and by reducing the kinetic energy of the ion. The latter is termed 

Kinetic Energy Discrimination (KED), and is the primary mechanism for 

interference removal. Polyatomic ions are larger than elemental ions and so 

collide with the helium atoms in the collision cell more frequently than the smaller 

elemental ions. Each collision reduces the energy of the ion, so the molecular 

ions lose energy more quickly. At the end of the collision cell a positive voltage 

plate prevents passage of the now low energy molecular ions. Thus, the 

interference is eliminated because the molecular ions do not reach the detector. 

4.3 Doubly Charged Ion Interferences 

Doubly charged elemental ions are possible in cases where the second 

ionization potential of the element is significantly below the fist ionization 

potential for argon (15.7eV). If a doubly charged ion is formed, it will cause a 

response at half of its elemental mass, potentially causing an interference. 

Fortunately, most elements have high enough second ionization potentials that 

formation of doubly charged ions is not an issue. For the target analytes in this 

procedure, a significant potential for interference is from 150Nd and 150Dy 

(potential interference on 75As and from 156Gd (potential interference on 78Se). To 

check for these potential interferences, monitor the response for mass 150 and 

156. If the cps for these masses is > 5 times the cps for the quantitation limit for 

arsenic (in the case of mass 150) or selenium (in the case of mass 156) an 

interference is possible. In this case analyze a 100ppb standard of Nd and Dy (if 

mass 150 is observed) or Gd (if mass 156 is observed) and measure the 

response at 150 and 75 (or 156 and 78). This ratio can then be used to create an 

interference correction equation. For example, if the response for a 100ppb Gd 

standard at mass 156 is 10,000 cps, and the observed response for the same 

standard at mass 78 is 1,000 counts, then the equation for 78Se would be: 

78Se = 78Se – (156Gd/10) 

4.4 Physical Interferences 

 Physical interferences are associated with the transport and nebulization 

process. Internal standards are used to compensate for these types of 

interferences. 

 Internal standards should be added at a level to give approximately 

50,000 - 800,000 counts of raw signal intensity. The mass of the internal 

standard should ideally be within 50 amu of the mass of the measured 
C-4 

analyte. Consideration should also be given to matching internal 

standards to analytes with similar ionization potentials. 

 Matrix effects are monitored by comparing the internal standard intensity 

in the sample to the internal standard intensity of the calibration blank. 

The internal standards must be between 60% and 125% of the calibration 

blank. If they are outside this window the sample is diluted by a factor of 

2 (1:1) and is reanalyzed. 

 Memory effects are dependent on the relative concentration differences 

between samples and/or standards which are analyzed sequentially. The 

rinse period between samples must be long enough to eliminate 

significant memory interference (see section 10.3.6). 

5.0 Safety 

This procedure may involve hazardous material, operations and equipment. This 

procedure does not purport to address all of the safety problems associated with its use. 

It is the responsibility of the user of the method to follow appropriate safety, waste 

disposal and health practices under the assumption that all samples and reagents are 

potentially hazardous. Safety glasses, gloves, lab coats and closed-toe, nonabsorbent 

shoes are required. 

5.1 Specific Safety Concerns or Requirements 

5.1.1 Eye protection that satisfies ANSI Z87.1, laboratory coat, and 

nonpowdered nitrile or latex gloves must be worn while handling 

samples, standards, solvents, and reagents. Disposable gloves that 

have been contaminated must be removed and discarded; nondisposable gloves must be cleaned immediately. 

5.1.2 The ICP plasma emits strong UV light and is harmful to vision. All 

analysts must avoid looking directly at the plasma. The RF Generator 

produces strong radio frequency waves, most of which are unshielded. 

People with pacemakers should not go near the instrument while in 

operation. 

5.2 Primary Materials Used 

The following is a list of the materials used in this method, which have a serious 

or significant hazard rating. Note: This list does not include all materials 

used in the method. The table contains a summary of the primary hazards 

listed in the MSDS for each of the materials listed in the table. 
C-5 

Material (1) Hazards Exposure 

Limit (2) Signs and Symptoms of Exposure 

Nitric Acid Corrosive 

Oxidizer 

Poison 

2 ppmTWA 

4 ppmSTEL 

Nitric acid is extremely hazardous; it is corrosive, reactive, 

an oxidizer, and a poison. Inhalation of vapors can cause 

breathing difficulties and lead to pneumonia and pulmonary 

edema, which may be fatal. Other symptoms may include 

coughing, choking, and irritation of the nose, throat, and 

respiratory tract. Can cause redness, pain, and severe skin 

burns. Concentrated solutions cause deep ulcers and stain 

skin a yellow or yellow-brown color. Vapors are irritating and 

may cause damage to the eyes. Contact may cause severe 

burns and permanent eye damage. 

Material (1) 

Hazards 

Exposure 

Limit (2) Signs and Symptoms of Exposure 

Hydrochloric 

Acid

Corrosive 

Poison 

5 ppmCeiling Inhalation of vapors can cause coughing, choking, 

inflammation of the nose, throat, and upper respiratory tract, 

and in severe cases, pulmonary edema, circulatory failure, 

and death. Can cause redness, pain, and severe skin burns. 

Vapors are irritating and may cause damage to the eyes. 

Contact may cause severe burns and permanent eye 

damage. 

1 – Always add acid to water to prevent violent reactions. 

2 – Exposure limit refers to the OSHA regulatory exposure limit. 

6.0 Equipment and Supplies

6.1 Instrumentation 

 Inductively Coupled Plasma Mass Spectrometer (ICP/MS) capable of providing 

resolution, less than or equal to 0.9 amu at 10% peak height from 6-253 amu 

and 1.0 amu at 5% peak height from 6-253 amu with a data system that allows 

corrections for isobaric interferences and the application of the internal standard 

technique. The ICP/MS must be equipped with a collision cell for the removal of 

molecular interferences. This procedure was developed using an Agilent 7500 

or 7700 instrument equipped with a high matrix interface. The interface extends 

the amounts of total dissolved solids that may be measured into the percent 

concentration range. Any collision cell instrumentation that meets the 

specifications in this procedure may be used. 

 A discrete sample introduction system enables the use of only the exact amount 

of sample volume required for data acquisition. 

 Accessories and configuration that are designed to accommodate samples with 

high levels of dissolved solids should be used. 

 This sampling system results in less matrix being deposited in the system 

during analysis and minimizes the rinse times normally needed for difficult 

matrices. 

 Autosampler with autosampler tubes. 

 Appropriate water cooling device. 

 Block digester with tubes. 
C-6 

6.2 Supplies 

 Argon gas: High purity grade (99.99%). 

 Helium gas: High purity grade (99.99%). 

 Hydrogen gas: High purity grade (99.99%). 

 Calibrated automatic pipettes or Class A glass volumetric pipettes. 

7.0 Reagents and Standards

7.1 Storage and Shelf-Life 

7.1.1 All standards must be stored in glass, FEP fluorocarbon or previously 

unused polyethylene or polypropylene bottles. Standards stored at 

concentrations as received from the vendor and mid-level dilutions must 

be replaced prior to the expiration date assigned by the vendor. If no 

expiration date is provided, the stocks and mid-level standards may be 

stored for up to one year. They must be replaced sooner if verification 

from an independent source indicates a problem (See section 10.3.5 for 

initial calibration verification acceptance criteria). 

7.1.2 Working standards, i.e., all standards at concentrations ready to 

analyze on the ICP/MS (all except tuning mixes, ICSA and ICSAB 

mixes, which are received at ready-to-use concentrations), are prepared 

fresh daily. 

7.2 Standards

7.2.1 Tuning Solution, 10 ppb 

The tuning solution stock is purchased as a custom multi-element mix. 

The concentrations of the constituents are shown in Attachment 5. 

Prepare the Tuning Solution as detailed below. 

 Obtain a clean 100 mL volumetric flask. 

 Place 50 mL of reagent water and 2 mL of conc. HNO3 and 0.5 

mL of conc. HCl in the flask. 

 Swirl to mix. 

 Pipet 0.1mL of the Tuning Solution Stock into the flask. 

 Dilute to volume with reagent water. Stopper and mix. 

7.2.2 PA Tuning Solution 

The dual detector solution may be commercially purchased as a custom 

multi-element mix. 

Prepare the PA Tuning Solution as detailed below. 

 Add approximately 50 mL of the 2% HNO3 / 0.5% HCl to a 100 

mL volumetric flask. 

 Prepare at a concentration recommended by the instrument 

manufacturer. 
C-7 

7.2.3 Calibration Standards 

Stock calibration standards are purchased as custom multi-element 

mixes or as single element solutions. Each day of analysis, the 

standards are diluted to working levels using 2% nitric acid and 0.5% 

HCl acid matrix. Suggested concentrations are given in Attachment 8, 

but the laboratory may adjust calibration standard concentrations as 

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 
C-8 

7.2.6 Initial Calibration Verification (ICV) Standard 

The ICV stock is from a source different than the source for the 

calibration standards. Each day of analysis, the ICV standard is 

prepared in 2% HNO3 and 0.5 % HCl acid to the concentrations shown 

in Attachment 8. 

7.2.7 Continuing Calibration Verification (CCV) Standard 

The CCV is prepared from the same source as the calibration 

standards. The CCV standards are prepared fresh each day of analysis 

in 2% HNO3/0.5% HCl. The concentrations are shown in Attachment 8. 

Prepare the Working CCV as detailed below. 

 Dilute by 2X a known volume of the Working Calibration 

Standard in the 2% HNO3 / 0.5% HCl acid matrix. 

7.2.8 Spiking Stock Solution 

The spike stock solution is prepared from the same stocks as the 

calibration standards using the 2% HNO3 / 0.5% HCl acid matrix. Spike 

concentrations are listed in Attachment 8. 

7.3 Reagents

7.3.1 Reagent Water - ASTM Type I or equivalent for the elements of 

interest, generated using an ion-exchange water polishing system 

capable of achieving 18.0 megohm-cm.

7.3.2 Blank Matrix 2% HNO3 and 0.5% HCl. 

8.0 Sample Collection, Preservation, Shipment and Storage

Sample container, preservation techniques and holding times may vary and are 

dependent on sample matrix, method of choice, regulatory compliance, and/or specific 

contract or client requests. Listed below are the holding times and the references that 

include preservation requirements. 

Matrix Sample 

Container 

Min. Sample 

Size Preservation Holding Time Reference 

Waters HDPE 50 mLs HNO3, pH < 2 180 Days 40 CFR Part 136.3

Soils Glass or 

HDPE 

4 oz Cool 4 + 2oC 180 Days N/A 

9.0 Quality Control 

9.1 Quality control requirements are also summarized in Attachment 7. 

9.2 Ongoing data quality checks are compared with established performance criteria 

to determine if the results of analyses meet the performance characteristics of 
C-9 

the method. Any QC result that fails to meet control criteria must be 

documented. 

9.3 Individual interference check solutions 

The individual interference check solutions listed in section 7.2.6 are analyzed 

prior to initiating sample analysis, and at least once per quarter while FGD 

wastewaters are being analyzed, and after any major changes to instrument 

operating conditions. Concentrations of target elements observed should be less 

than their reporting limits. In some cases it may not be possible to obtain 

interference check solutions that are completely free of contamination. In this 

case, results up to 5X the reporting limit are acceptable if it is possible to 

demonstrate that the isotopic ratios correspond to natural abundances. For 

example, the natural abundances of zinc isotopes are Zn64 48.6%; Zn66 27.9%; 

Zn67 4.1%; Zn68 18.8%; Zn70 0.6%. The measured ratios are not expected to be 

exact, especially for low abundance isotopes, and some isotope may be masked 

by other elements in the solution, (for example Zn70 in the above example will be 

masked by Ge70) but it must be possible to explain the observed ratios. 

Because Arsenic, Manganese and Aluminum are monoisotopic, this 

demonstration is not possible and the level of interference observed must be less 

than the reporting limit. 

9.4 Synthetic FGD interference check solution 

The synthetic FGD matrix solution listed in section 7.2.7 is analyzed prior to 

initiating sample analysis, and at least once per day (immediately after 

calibration) while FGD wastewaters are being analyzed, and after any major 

changes to instrument operating conditions. Internal standard recovery must 

meet method criteria (Section 9.9) and concentrations of target elements 

observed should be less than their reporting limits. In some cases it may not be 

possible to obtain interference check solutions that are completely free of 

contamination. In this case, results up to 5X the reporting limit are acceptable if it 

is possible to demonstrate that the isotopic ratios correspond to natural 

abundances. For example, the natural abundances of zinc isotopes are Zn64

48.6%; Zn66 27.9%; Zn67 4.1%; Zn68 18.8%; Zn70 0.6%. The measured ratios are 

not expected to be exact, and some isotopes may be masked by other elements 

in the solution, (for example Zn70 in the above example will be masked by Ge70) 

but it must be possible to explain the observed ratios. Because Arsenic, 

Manganese and Aluminum are monoisotopic, this demonstration is not possible, 

and the level of interference observed must be less than the reporting limit. 

If the Synthetic FGD solution has to be diluted in order to analyze it 

effectively on the ICP/MS, then all samples and QC (including the MDL 

replicates) must be diluted by at least the same factor. 

9.4.1 Laboratory fortified Synthetic FGD solution 

The synthetic FGD solution is spiked with 40ppb of each of the target 

elements (400ppb for zinc and 4000ppb for aluminum) and analyzed 

once per day, immediately after the synthetic FGD check in section 9.4. 

All target elements must be recovered within 70-130% of the true value. 

If the Laboratory Fortified Synthetic FGD solution has to be diluted 

in order to analyze it effectively on the ICP/MS, then all samples 

and QC (including the MDL replicates) must be diluted by at least 

the same factor. 
C-10 

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. 

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. 
C-11 

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 

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. 
C-12 

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. 

10.2.5 The total volume of the solution in the tube is now greater than 50 mLs. 

The final volume will be 50 ml following the procedure to eliminate the 

discrepancy in the initial and final volumes. 

10.2.6 Tightly cap each digestion vessel. 

10.2.7 Place the digestion tube into a block digester adjusted to achieve a 

temperature of approximately 85o

C. 

10.2.8 Heat for 2 hours after 85o

C is obtained. 

10.2.9 Remove from the block and allow to cool. 

10.3 Calibration 

10.3.1 Instrument Start Up 

Set up the instrument according to manufacturer’s operating instructions. 

Allow the instrument to become thermally stable for at least 30 minutes 

before tuning. 

10.3.2 Instrument Tuning / Mass Calibration 

Tune the instrument with a solution containing elements representing all 

of the mass regions of interest. The relative standard deviations must be 

less than 5% for a minimum of 4 integrations of the solution. Mass 

calibration and resolution checks using the tuning solution must be 

completed at the beginning of every day. 

Mass Calibration Check – The mass calibration results must be within 

0.1 amu from the true value. If this criterion 

is not met, the mass calibration must be 

adjusted before running samples. 

Mass Resolution Check - The resolution must be verified to be less 

than 0.9 amu full width at 10% peak height. 

10.3.3 Mass 75 interference check 

The concentration determined for arsenic (mass 75) must be less than 

0.25 x the reporting limit when the blank matrix (2% nitric acid / 0.5% 

hydrochloric acid) is infused (using the collision gas mode used for 

arsenic). 

10.3.4 Initial Calibration 

The ICP/MS is calibrated each day of operation using a blank and at 

least 3 standards (see Section 7.2.3). Report the average of at least 

three integrations. 
C-13 

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 

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 
C-14 

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. 

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 
C-15 

ICV 

ICB 

RL verification standard 

Synthetic FGD matrix 

Spiked synthetic FGD matrix 

Carryover check 

CCV 

CCB 

10 Samples (which can include all sample types) 

CCV 

CCB 

11.0 Calculations / Data Reduction

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. 

100%

LCSTrue Value

LCS Found Value - LRB Found Value % 



 



 R 

100%

ICV True Value

ICV Found Value % 



 



 R 

100%

CCV True Value

CCV Found Value % 



 



 R 

100%

SA

SSR - SR % 



 



 R 
C-16 

11.5 The relative percent difference (RPD) between sample duplicates is 

calculated according to the following equation:

Where: 

DU1 = Sample result 

DU2 = Sample duplicate result 

11.6 The final concentration for an aqueous sample is calculated as follows:

2

1 Result ( g/L) V

C V  D

 

Where: 

C = Concentration from instrument readout, ppb 

D = Instrument dilution factor 

V1 = Final volume in liters after sample preparation 

V2 = Initial volume of sample digested in liters 

12.0 Method Performance 

12.1 Method Detection Limit Study (MDL) 

An initial method detection limit study must be performed on each instrument 

before samples can be analyzed. MDL studies are conducted annually as 

follows: 

 Prepare seven samples at three to five times the estimated MDL 

concentration. The MDL samples are prepared in the Synthetic FGD 

wastewater matrix and in reagent water. 

 Prepare and analyze the MDL standards as described in Section 10. 

 Calculate the average concentration found in μg/L, and the standard 

deviation of the concentration(s) in μg/L, for each analyte. 

 The MDL is calculated as Students t for the 99th percentile times the standard 

deviation of the MDL replicate results, following the procedure at 40CFR Part 

136, Appendix B. 

NOTE1: Perform the MDL study in the synthetic FGD 

wastewater matrix. Spiking this matrix provides detection 

limits that are better matched to the complex matrix 

typical of FGD wastewater. These limits can be 

significantly higher than those obtained in a reagent water 

matrix. In some cases (zinc in particular), the level of 

contamination in the synthetic FGD solution may be high 

enough to result in somewhat elevated MDLs. 

NOTE2: An FGD-MDL may be less than the MDL observed in 

method blanks. If this occurs frequently, the FGD-MDL 

  100

1 2 2

1

/ 1 2/





















  DU DUDU DU RPD
C-17 

should be elevated to the mean of the method blanks plus 

the Student t factor times the standard deviation of the 

method blanks. 

12.2 Instrument Detection Limit Study 

Instrument detection limit (IDL) studies are conducted quarterly for each 

instrument and each mass used for analysis. 

 Prepare ten blanks. 

 Analyze the IDL blanks on three non-consecutive days. 

 The IDL is equal to three times the standard deviation of the blank results.

12.3 Demonstration of Capabilities

All personnel are required to perform an initial demonstration of proficiency 

(IDOC) on the instrument they will be using for analysis prior to testing samples. 

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. 
C-18 

15.0 References / Cross-References

15.1 EPA Method 200.8, “Determination of Trace Elements in Waters and Wastes 

by Inductively Coupled Plasma - Mass Spectrometry”, Revision 5.4, EMMC 

Version. 

15.2 EPA Method 1638, “Determination of Trace Elements in Ambient Waters by 

Inductively Coupled Plasma – Mass Spectrometry, January 1996 

16.0 Attachments

Attachment 1: Recommended Elemental Equations 

Attachment 2: Internal Standards and Corresponding Metals 

Attachment 3: Sample Preservation and Holding Times 

Attachment 4: Suggested Mass Choices 

Attachment 5: Tuning Solution 

Attachment 6: Suggested Tuning and Response Factor Criteria 

Attachment 7: Summary of Quality Control Requirements 

Attachment 8: Calibration, Calibration Verification, and Spike Concentrations
C-19 

Attachment 1 

Recommended Elemental Equations 

Element 

Isobaric 

Correction Mathematical Equation 

Pb None (1.0000)(208M) + (1.0000)(207M) + (1.0000)(206M) 

6Li Li (natural) (1.0000)(6M) - (0.0813)(7M) 

In Sn (1.0000)(115M) - (0.0149)(118M) 

The 6

Li correction equation is only needed if 6Li is used as an internal standard for low mass elements. 

Attachment 2: Internal Standards and Corresponding Metals 

Internal Std. Associated elements1,2

Sc Na, Mg, Al, K, Ca, V, Cr, Mn 

Ge Fe, Ni, Cu, Zn, As, Se 

In Ag, Cd 

Ho Tl, Pb 

Footnote: (1) Na, Mg, K, Ca and Fe are included in the synthetic FGD wastewater but their 

analytical determination is optional – the interferences caused by these elements are more 

important than the determination of their exact concentration. 

(2) Other internal standards may be used. For example, 6

Li, Ga, Rh, Bi, Ho and Tb may be 

considered for use as internal standards. 
C-20 

Attachment 3: Sample Preservation and Holding Times 

Measurement 

Parameter

Container (1) Preservative (2) Maximum Holding 

Time (3)

Waters: 

Metals (4) P,G HNO3 to pH < 2 6 months 

Soils/Sediments/Wastes: 

The preservation required for soil/sediment/waste samples is maintenance at 4°C ( ± 2°C) until 

digestion. 

Footnotes: (1) Polyethylene (P) or glass (G). 

 (2) Sample preservation is performed by the sampler immediately upon sample 

collection or shipped to the laboratory unpreserved for preservation at the 

laboratory. 

 (3) Samples must be analyzed as soon as possible after collection. The times listed 

are the maximum times that sample may be held before analysis and still 

considered valid. Holding times are calculated from the date when the sample 

was collected. 

 (4) Samples are filtered immediately on-site by the sampler before adding 

preservative for dissolved elements. 
C-21 

Attachment 4: Suggested Mass Choices 

Masses listed indicate the masses which have the most impact on data quality and the elemental 

equations used to collect the data. 

Mass Element of Interest Analysis mode 

27 Aluminum No gas 

75 Arsenic He 

111 Cadmium He 

52 Chromium He 

63 Copper He 

208, 207, 206 Lead No gas or He 

24 Magnesium No gas 

55 Manganese He 

60 Nickel He 

39 Potassium No gas or He 

78 Selenium He (H2) 

107 Silver He 

23 Sodium No gas or He 

205 Thallium No gas or He 

51 Vanadium He 

66 Zinc He 

NOTE: It is strongly recommended that elements other than those of interest be 

monitored to indicate other potential molecular interferences which could 

affect the data quality. 
C-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 
C-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 
C-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. 
C-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. 
C-26 

Attachment 8: Calibration, Calibration Verification, and Spike Concentrations 

Element 

Initial Calibration 

(g/L) 

ICV 

(g/L)

CCV 

(g/L)

LCS

(g/L)

MS/MSD 

(g/L)

Aluminum 100, 1,000, 10,000 4000 5000 4000 4000 

Arsenic 1, 10, 100 40 50 40 40 

Cadmium 1, 10, 100 40 50 40 40 

Chromium 1, 10, 100 40 50 40 40 

Copper 1, 10, 100 40 50 40 40 

Lead 1, 10, 100 40 50 40 40 

Manganese 1, 10, 100 40 50 40 40 

Nickel 1, 10, 100 40 50 40 40 

Selenium 1, 10, 100 40 50 40 40 

Silver 1, 10, 100 40 50 40 40 

Thallium 1, 10, 100 40 50 40 40 

Vanadium 1, 10, 100 40 50 40 40 

Zinc 1, 10, 100 40 50 40 40 

Additional elements may be included in the calibration solution at the above levels. Levels 

may be adjusted to meet specific requirements. 

####