# 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. I NTRODUCTION 

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

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

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

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

2. F ACILITY 

### O VERVIEW 

### ........................................................................................................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. S AMPLE 

### C OLLECTION 

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

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

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

3.1.2 Effluent from FGD Wa stewater System..................................................3-4

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

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

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

4. L ABORATORY 

### A NALYTICAL 

### R ESULTS AND 

### D ISCUSSION 

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

4.1 Measured and Calculated Results for In fluent to FGD Wastewater Treatment System Samples ...................................................................................................4-2

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

5. D ATA 

### Q UALITY 

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

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

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

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

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

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

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

6. R EFERENCES 

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

Appendix A: A NALYTICAL 

### R ESULTS



### Appendix B: D ATA 

### R EVIEW 

### N ARRATIVES



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

### C OUPLED 

### P LASMA 

### M ASS 

### S PECTROMETRY FOR



### T RACE 

### E LEMENT 

### A NALYSIS IN 

### F LUE 

### G AS 

### D ESULFURIZATION 

### W ASTEWATERS

### ii LIST OF TABLES

Page

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

Table 3-2. Sample Collection at Hatfie ld’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 Sa mpling Point and Day, Hatfield’s Ferry.......... 3-15

Table 3-5. Analytical Met hods, 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 Su mmary, Hatfield’s Ferry..................................................... 3-18

Table 3-8. Generating Unit Operating Character istics during Sample Co llection, 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 duri ng Sample Collection, Hatfield’s Ferry............. 3-23

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

Table 4-1. Influent to F GD 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 Polluta nt 4-Day Average Data Su mmary for FGD Wastewater Treatment System, Hatfield’s Ferry............................................................................... 4-15

Table 4-4. Metal Pollutant 4-Day Average Da ta Summary for FGD Wa stewater Treatment System, Hatfield’s Ferry ................................................................................................ 4-16

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

Table 5-2. Field Duplicate Re sults – Effluent fr om FGD Wastewater Treatment System, Hatfield’s Ferry............................................................................................................... . 5-6

Table A-1. Biphasic Sample Results for Cla ssicals and Total Meta ls, Influent to FGD Wastewater Treatment System, Day 1 Anal ytical Results, Hatfield’s Ferry.................. A-1

Table A-2. Biphasic Sample Results for Cla ssicals and Total Meta ls, Influent to FGD Wastewater Treatment System, Day 2 Anal ytical Results, Hatfield’s Ferry.................. A-3

### LIST OF TABLES (Continued)

Page

iii Table A-3. Biphasic Sample Results for Cla ssicals and Total Meta ls, Influent to FGD Wastewater Treatment System, Day 3 Anal ytical Results, Hatfield’s Ferry.................. A-5

Table A-4. Biphasic Sample Results for Cla ssicals and Total Meta ls, Influent to FGD Wastewater Treatment System, Day 4 Anal ytical 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 FG D Wastewater Treatment System, Day 1 Analytical Results, Hatfield’s Ferry............................................................................................................. A- 34

Table A-10. Effluent from FG D Wastewater Treatment System , Day 2 Analytical Results, Hatfield’s Ferry............................................................................................................. A- 37

Table A-11. Effluent from FG D Wastewater Treatment System , Day 3 Analytical Results, Hatfield’s Ferry............................................................................................................. A- 40

Table A-12. Effluent from FG D 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 Wast ewater Treatment System, Hatfield’s Ferry

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

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

Power Station.................................................................................................................. . 2-7

### 1-1 1. I NTRODUCTION



### The Engineering and Analysis Division (EAD) of the U.S. Environmental Protection Agency (EPA) is conducting a sampling program at steam electric power plants. The sampling program will characterize raw wastewaters generate d by coal-fired steam electric power plants and evaluate treatment technologi es and best management practic es used to reduce pollutant discharges. This Sampling Episode Report (SER ) describes the sampling activities that took place December 5-10, 2010, at Allegheny Energy’s Ha tfield’s Ferry Power Station (Hatfield’s Ferry), located in Masontown, Pennsylvania (S ampling Episode 6564). The focus of Episode 6564 was to characterize the purge stream ente ring the flue gas desulfurization (FGD) wastewater treatment system and the efflue nt from the chemical precipitation system.

1.1 Background of Detailed Study

During EPA’s recently completed detailed study of the steam electric industry, EPA identified metals and certain other constituents pr esent in the wastewater discharges from steam electric power plants that substantially cont ribute to the toxic load ings for the industry. Additionally, EPA determined that one of the wa ste streams contributing most of these toxic loadings are associated with wet flue gas desu lfurization (FGD) systems present at coal-fired power plants. Based on these findings, EPA ha s focused the sampling program on characterizing

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

wastewater.

1.2 Power Plant Site Selection

EPA selected seven coal-fired steam electric plants for FGD wast ewater 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 pow er plant that burns a ble nd 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/m etal 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-catal ytic reduction (SNCR) system on Unit 3.

### 1-1 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 fo llowing 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 sample s with the Utility Water Act Group (UWAG). UWAG is a trade asso ciation for the electric power generating industry. During the sampling episod e, UWAG acted as Hatfield’s Ferry’s representative and collected samples on behalf of the plant.

### 2-1 2. F ACILITY 

### O VERVIEW



### 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 ep isode the blend ranged from 58% bituminous

and 42% PRB to 84% bituminous and 16% PRB. Th e 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 retr ofitted all three un its with wet FGD scrubber systems to control the sulfur dioxide (SO 2 

### ) releases from the plant. The Unit 1 FGD system was installed in June 2009, and the Unit 2 and Unit 3 FGD systems we re both installed in October 2009. With the recent addition of the FGD scrubber systems, Hatfie ld’s Ferry also insta lled 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 (NO

x 

### ) 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 NO

x 

### burners on all three units to control NO

x 

### releases from the plant.

The electrostatic precipitators (ESPs) at Hatf ield’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 a nd other particulates are collected in hoppers and are pneumatically transfe rred to fly ash silos.

Units 1 has the following configuration:

 Boiler (Low NO

x 

### Burners with ROFA system located in boiler);

 Air heater;

 ESP; and

 FGD scrubber system.

Unit 2 has the following configuration:

 Boiler (Low NO

x 

### Burners located in boiler);

 Air heater;

 ESP; and

 FGD scrubber system.

Unit 3 has the following configuration:

 Boiler (Low NO

x 

### 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 oxida tion wet FGD scrubber systems (one per unit)

to control the emission of SO 2 

### from the units. The plant uses limes tone slurry as the sorbent for

SO 2 

### 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 reac tion tank of the FGD systems where the slurry is pumped to the various levels of the FGD scrubbe rs with the recycle pump s. All three absorbers have five spray levels, but the plant usually on ly 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 sl urry, the spray droplets of the limestone slurry contact the flue gas and absorb the SO 2 

### , which reacts with the limestone particles and produces calcium sulfite. The spray droplets flow downward until they settle on the first of two dual flow trays, forming a layer of sl urry that the flue gas must pass through to exit the FGD system. The tray has small holes in it that allow the flue ga s to bubble through the limestone slurry layered on the tray, which pr ovides 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 unt il it reaches the reaction tank. Hatfield’s Ferry bubbles air through the reaction tank to oxidize th e calcium sulfite to calcium sulfate (i.e., gypsum).

The source of up to 50% of the make-up wate r 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, othe rwise it is difficult for th e plant to control the pH within the FGD system. All wastewater generate d at the plant, except for FGD wastewater, is

transferred to the wastewater treatment lagoon, which includes bo ttom 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 pl ant also monitors the chloride level in the absorber; however, by maintaining the correct leve l 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 concen tration for the absorber is 12,500 ppm. For all three units, blowdown from the absorbers occurs in ten hou r 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 pr imary 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 a nd 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 de signed to be recycled back to the absorber, however, any leakage would be directed to the r eclaim 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 pl ant stated that although the syst em 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 co ntent of 10% after th e vacuum belt filters. Hatfield’s Ferry transfers the gypsum to an on-s ite 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 de signed 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 wa s 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/m etal hydroxide precipitation);

 Organosulfide addition;

 Ferric chloride addition;

 Polymer addition;

 Clarification;

 Hydrochloric acid additi on (pH adjustment); and

 Filtration (sand filters).

Figures 2-1 and 2-2 located at the end of this section, presen t 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 diag ram of the FGD wastewater treatment system. Figure 2-2 presents a more complex diagram provi ding more detail on the chemical precipitation treatment operations.

The secondary hydrocyclone overflow from the scrubbers is transfe rred to the purge tank and then sent to the equalization tank at the start of the wastew ater treatment system. During the sampling episode, the FGD influent wastewater was found to contain between 4 and 7 percent

### 2-4 solids, had a pH between 6 and 7 S.U., a nd a temperature between 40 and 50 °C. The equalization tank also receives water from the wa stewater treatment sump and off-specification

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

wastewater such as filter back wash and filtrate from the filter pr ess that dewater the sludge from the clarifiers. Sumps from the dewatering area ar e also transferred to the equalization tank; however, the sumps in the limestone preparati on 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 abso rber) 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 wh ere ferric chloride is added.

From reaction tank 2, the wastewater is split ev enly between two solids contact clarifiers. Right before this split, a polymer is added to the wastewater. As of th e time of the sampling episode, one clarifier was out of service and being repaired, and all wastewater was being

transferred to the second clarifie r. Hatfield’s Ferry personnel noted that at the low flow rate at which the system was operating during the samp ling episode, the clarif iers achieve better performance if only one clarifie r is operating because if both are operating, the flow does not provide enough hydraulic lift to k eep the sludge bed suspended. Bo th solids contact clarifiers contain a sludge bed that facilitates removal of the solids in the wast ewater. A portion of the sludge from the clarifiers can be recycled to r eaction tank 1, while the majo rity 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 r ecycling any of the clarifie r sludge to reaction tank 1.

The dewatered sludge, which contains approxima tely 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 eq ualization tank.

The clarifier overflow is transferred to the sa nd filters (gravity filtration); however, prior to reaching the sand filters, hydrochloric acid is in jected into the waste stream to decrease the pH

to 7.0 S.U. The backwash from the sand filters is transferred to the wast ewater treatment area sump, which is recycled b ack to the equalization tank.

After treatment with the sand filters, the wastew ater is collected in the treated wastewater storage tank. From this tank, the wa stewater is either recirculated back to the equalization tank or

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

Discharge from the wastewater treatment sy stem is continuous, unless the plant is recirculating the effluent because it is not mee ting specifications. The plant’s permit limit for its average monthly discharge flow rate is 160 gpm, th erefore the plant attempts to keep the average daily discharge at 160 gpm. The wastewater treatm ent system is designed for typical flow rates between 100 and 500 gpm. The hydraulic residen ce 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 Ha tfield’s Ferry sampling episode; they are

summarized below:

 A sample of the secondary hydrocycl one overflow from an individual unit 1 

### , 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 trea ted wastewater storage tank, before mixing

with the treated wastew ater lagoon effluent.

1 During each day of the sampling episode, ERG collected the secondary hydrocyclone ov erflow 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.

### 2-6Figure 2-1. Simplified Diagram ofthe FGD Wastewater Treatment System, Hatfield’s Ferry Power Station

### 2-7Figure 2-2. Detailed Diagram of the FGD Wastewater Treatment System, Hatfield’s Ferry Power Station

### 3-1 3. S AMPLE 

### C OLLECTION



### During the Hatfield’s Ferry sampling episode, the sampling team followed the collection protocols specified in the Sa mpling Plan. Section 3.1 describes the sampling points, sample collection methods, and field measurements. Secti on 3.2 describes the list of analytes and the sample preservation procedures. Section 3.3 discu sses the plant operational data collected during the sampling episode. Finally, Section 3.4 discusse s any deviations from the planned sampling

activities.

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

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

measurements. Additional details are available in Section 3 of the Sampling Plan. Figures 2-1 and 2-2 of this report present flow diagrams of the plant’s wastewater treatment system, including sampling point locations.

Table 3-1 lists the sampling points, sampli ng point descriptions, type of sample collection, and sample collection dates and times. Table 3-2 list s the sampling point numbers and descriptions, the number of samples collected, and the pollutant parameters for which the samples were analyzed. Table 3-3 presents th e field measurement data collected from each sampling point. Table 3-4 presents a crosswalk be tween the sample numbers used for laboratory sample identification and the sample points for each day.

The sampling points for this episode were:

 SP-1 Influent to FGD Wastewater Treatment System;

 SP-2 Effluent from FGD Wast ewater Treatment System;

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

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

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

For all the sampling points, EPA collected split samples with Hatfield’s Ferry’s representative by inserting a “Y” splitter into the sample tubi ng configuration at each sampling point to allow for split sample collection. EPA co llected all samples (other than mercury and cyanide) at all sampling points as “true” splits (i.e., samples for the same analyte were collected simultaneously). The mercury and cyanide samples were collected directly from a sample tap; therefore, for these samples, EPA and Hatfie ld’s Ferry’s representative collected duplicate samples, with one filling the bot tle immediately after the other.

At each of the sampling points, EPA collected metals sample fractions following EPA Method 1669 collection protocols. To collect these samples, EPA samplers donned Tyvek® coveralls and dust masks (dust masks were worn until all mercury samples had been collected). In addition, EPA set up a “cleanbox,” which consists of a portable plastic rectangular box with a shallow lip and a flip-top lid th at secures itself ope n with clips. The “cleanbox” is double-bagged with a clear inner bag, enclosed in a translu cent outer bag. The “cleanbo x” is handled using “clean hands / dirty hands” techniques, where by the inner bag is ha ndled only by the “clean hands” sampler. When the “cleanbox” is opened, the sampler is able to position his/her hands in the box and pull the bag over the open ing of the box, but is still able to see the sample bottles and

### 3-2 tubing. The “cleanbox” minimizes potential at mospheric contamination during sample

collection.

The metals sample bottles were also double-bagged. To collect the metals samples, EPA placed the sample bottles (while still in its seal ed inner bag) into the “cleanbox” following the protocols specified in Method 1669, also referred to as “clean hands / dirty hands” protocols. Sampling staff filled the sample container, then cl osed the sample bottle lid and sealed the inner bag as quickly as possible with in the “cleanbox.” The bagged sample bottles were then removed from the “cleanbox” and placed into the outer bag following the “clean hands / dirty hands” protocols.

3.1.1 Influent to FGD Wastewater Treatment System

The influent to the FGD wastewater treatment system (SP-1) was collected from a sample tap located on the wastewater piping on the ove rflow line from the secondary hydrocyclones. Because Hatfield’s Ferry does not have a sa mple tap located downstream from where the secondary hydrocyclone overflow for each unit is combined, one unit’s secondary hydrocyclone overflow was sampled each day 2 

### . 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 co llecting representative split samples using composite sampling techniques. This was not an issue for samples collec ted at SP-1 because the

characteristics of the influent to the wastewater treatment syst em are expected to be fairly consistent during the purge. The sampling poi nt was located inside the gypsum dewatering building, at the location of the secondary hydr ocyclones. Because the sampling point was located inside, there were no wind or rain concerns during the sample collection.

On Day 1 only, prior to collecting the sample s at the influent to the FGD wastewater treatment system (SP-1), the sampling team collected field blanks (SP-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 fe et off the ground and because the wastewater at the tap was not pressurized, the samples eith er 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, a nd carefully lowered the tubing through the opening in the secondary hydrocylones down to the level be low. The end of the silicone tubing was fitted with a “Y” splitter, with two addi tional lengths of silicone tubi ng 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 valv e 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-liter 3 

### 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 tr ansported to the staging area, put on ice, and

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

The sampling team collected an aliquot of sample for field testing. Sample pH and temperature were measured immediately at the sa mpling point using four-color pH paper, a pH meter, and a thermometer. Table 3-3 presents the field measurement data for the influent to the FGD wastewater treatment system.

The samplers then filled containe rs for biochemical oxygen demand (BOD 5 

### ), Group I, Group II, and total cyanide samples directly fr om the tubing without using a “cleanbox.” See Table 3-6 for a list of Group I and Group II analytes. BOD 5 

### , Group I, Group II, and total cyanide samples were immediately placed on ice after sa mple collection.

The total cyanide sample was immediately preserved. Lead acetate test strips and potassium-iodide starch test stri ps were used to measure for su lfides and oxidants, respectively. No sulfides or oxidants were detected during th e sampling episode. The samplers then preserved the total cyanide sample with sodium hydroxide to a pH >10 S.U. and placed it on ice.

Samples for the dissolved metals analyses we re pumped from the previously filled 10- liter container. The pump-off station consisted of a length of Teflon® tubing attached to a length of silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team attached a capsule filter to th e silicone tubing, which was a s hort distance downstream of the pump. They then attached another short length of silicone tubing to the capsule filter effluent, which was attached to a “Y” spli tter and two lengths of silicone tubing. This set-up allowed EPA to collect “true” split samples w ith 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. Approxi mately 0.5 liters of sample were pumped through the tubing/filter to purge th e line before collecting samples 4



### .

Samplers collected the following dissolved sa mples 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 repr esentatives 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, pu rged 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 immedi ately 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 wastewat er 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 transf er treated effluent to th e 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 occu rring. Hatfield’s Ferr y installed a three-way splitter on the sample tap, which had three separa te taps to collect samples from the sampling point. The sample tap was located inside the F GD wastewater treatment building (see Figure 2-2 for the sampling location for SP-2). 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 comp ositors 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 compos itor to collect sample volume for all classical analytes (i.e., BOD 5 

### , Group I, and Group II, excluding cy anide). In addition to collecting automatic composite samples for the analytes listed above, ERG collected total and dissolved mercury grab samples every six hours during ea ch compositing period. ERG also collected one grab sample for cyanide during each compositing period.

On day 1 only, ERG collected field blank samp les (SP-5) for hexavalent chromium, total and dissolved metals by 200.7, and total and di ssolved metals by 200.8. See Section 5.2.3 for a description of the field blank samp le collection procedures at the effluent of the FGD wastewater

treatment system.

Samplers set up the compositors by attaching tw o T-splitter tubing sets to two of the taps on the three-way splitter. The T-splitter tubing set consisted of three silicone tubes attached to a T-splitter. The tubing configura tion was set up such that one e nd was connected to the sample tap, one end was threaded through the automatic compositor, and connected to the large composite container, and one end was placed next to a sump/drain near the sampling point. The samplers attached the silicone tubing to the samp le tap, opened the valve, and allowed sample to flow through both sets of tubing before calibrati ng either of the automatic compositors. This ensured that the flow through the tubing during calibration would be the expected flow through the tubing during sample collection. The automatic compositors were calibrated such that they collected 830 mL every hour, so that the project ed complete volume would be 20 liters. After

5 On day 2, the samplers were unable to collect the he xavalent 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 a nd flowed directly to the sump/drain. The automatic compositor pulled sa mple from the flowing stream as dictated by the sampling program and was capable of purging th e line back to the flowing stream between each individual sample aliquot 6



### .

Both 20-liter composite containers were placed into plastic trash cans, and maintained on ice for the entire 24-hour compositing period. A plas tic bag was placed on t op of the trash cans

to minimize contamination.

Immediately after setting up the compositors, ERG collected the first set of the total and dissolved mercury grab samples. At the first gr ab sample every day, ERG collected field blanks for total mercury samples. See Section 5.2.3 for a de scription of the field blank sample collection procedures at the influent to the bioreactor system.

For mercury collection, samplers shrouded one of the three taps on the three-way splitter (the other two taps were being used by the two compositors) with a clean plastic bag by puncturing a hole in the bottom of the bag with the end of the tap and then securing it to the tap with a ziptie. Because the sample tap was located on the suction side of the effluent transfer pumps, the head from the wastewater storage ta nk level was the only pressure moving the water through the piping. Because of this reduced pres sure, when the samplers opened the third valve on the sample tap to collect the mercury sample s, no wastewater was drained. Therefore, to collect the mercury sample, the sa mpling team pinched the drain lin e 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 allo wed 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 tota l 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 fille d 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 thir d set of mercury grabs, ERG collected a total cyanide grab sample from the same tap on the three-way splitt er that was used for mercury sample collection. Because total cyanide samples were collected directly from the ta p, ERG was not able to collect split samples with Hatfield’s Ferry ’s representatives; therefore, duplicate samples were collected. The total cyanide sample was immediately preser ved with sodium hydroxide to a pH >10 S.U. and the samples placed on ice. Lead acetate test st rips and potassium-iodide starch test strips

were used to measure for sulfides and oxidant s, respectively. No sulfides or oxidants were detected during the sampling epis ode at effluent from the FGD wa stewater 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 co mpositors 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 co llected in the two composite containers 7 

### , ERG followed “clean hands / dirty hands” sampling tec hniques to disassemble the compositors from the sampling set up. Closed caps were placed on the two composite containers and the composite containers were moved to the pump-off area where they remained on ice until individual sample bottles were filled. The samplers then began setting up the compositors for the next day of samples using new tubing sets and composite containers. The automatic compositor was programmed to collect the same vol ume on each day of sample collection.

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

transferred the wastewater coll ected in the 20-liter containe rs into the individual sample containers at the pump-off area. For this samp ling point, ERG used a sample pump-off approach to transfer the composite samples to the individual sample bottles. For this sample pump-off procedure, the dissolved metals samples were collected before the total metals and classical samples to prevent cross-contamination with in the tubing, which could lead to greater

concentrations in the dissolved metals fractions.

Samples for the dissolved and total metals analyses were pumped from one of the previously filled 20-liter cont ainers. The pump-off station cons isted of a length of Teflon® tubing attached to a length of silicone tubing, which was threaded throu gh an ISCO peristaltic pump. The sampling team attached a capsule fi lter to the silicone t ubing, which was a short distance downstream of the pump. They then attached another short length of silicone tubing to the capsule filter effluent, which was attached to a “Y” splitter and two lengths of silicone tubing. This set-up allowed EPA to collect “t rue” split samples with Hatfield’s Ferry’s representative. On Day 1 only, prior to collectin g any samples of the effluent from the FGD wastewater treatment system, the samplers collect ed a field blank sample (SP-5) for dissolved and total metals. See Section 5.2.3 for a descripti on 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 “cl eanbox,” as described in Section 3.1:

 Dissolved metals by 200.8;

 Dissolved metals by 200.7; and

 Dissolved hexavalent chromium.

Hexavalent chromium samples were immediat ely placed on ice after sample collection. After the dissolved metals had been collected, the filter was removed. Once the tubing was purged with 1-2 liters of sample, samplers coll ected the following samples using a “cleanbox,” as

described in Section 3.1:

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 be cause 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 previo usly filled 20-liter container 8 

### . Once the tubing was purged with 1-2 liters of sample, samplers fille d containers for biochemical oxygen demand (BOD 5 

### ), Group I, and Group II samples directly from the tubing without using a “cleanbox.” See Table 3- 6 for a list of Group I and Group II analytes. BOD 5 

### , Group I, and Group II samples were immediately placed on ice af ter sample collection.

For mercury, ERG collected QC samples at the effluent from the FGD wastewater treatment system (SP-2) on Day 3 of the sampli ng episode. ERG collected QC samples for all other analytes at the effluent from the FGD wastewater treatmen t system (SP-2) on Day 4 of the sampling episode. In addition, for mercury, ERG co llected 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 we re analyzed for the following pollutants:

 Classicals:

— Biochemical oxygen demand, 5-day (BOD 5 

### ),

— Chemical oxygen demand (COD),

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus,

— Total cyanide;

 Total Metals 9 

### :

— 

### Aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium, chromium, cobalt, copper , iron, lead, magnesium, manganese, mercury, molybdenum, nickel, selenium, silver, sodium, thallium, tin, titanium, vanadium, and zinc.

 Dissolved Metals:

— 

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

8 On day 1 of the sampling episode, ther e was sufficient volume in the metals co ntainer; 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 meta ls” and “total recoverable metals” interchangeably.

### 3-8 The analytes selected reflect the current understanding of coal-fired power plant air pollution control wastewaters, in cluding contributions from coal , scrubber sorb ents, treatment chemicals, and other sources. Table 3-5 lists the analytical methods used to determine pollutant

concentrations.

Table 3-6 lists the containers used for sample collection as well as the preservation requirements for each sample. Table 3-7 summarizes the chemical preservation for each of the samples that were preserved on site. The sampli ng team preserved samples in accordance with procedures described in Section 3.4 of the Sampling Plan. Immediately following sample collection, the samplers placed the BOD 5 

### , Group I, Group II, dissolved hexavalent chromium, and total cyanide samples on ice to cool the sa mples to <6°C. The sampling team did not place

the total and dissolved metals or the total and dissolved mercury samples on ice, which comports with the requirements of Methods 200.7, 200.8, and 1631E. All dissolved metals samples, except for mercury, were filtered in the field. The hexavalent chromium samples were preserved in the field, but all other metals samples were acid-pre served prior to extraction at the laboratory. The hexavalent chromium samples were preserve d with ammonium sulfate buffer solution and ammonium hydroxide to a pH between 9.3 and 9.5 S.U. The Group II samples were preserved with sulfuric acid to a pH of <2 S.U. in the staging area, and the pH was confirmed with fourcolor pH strips. Each total cyanide sample was te sted for sulfides and oxidants immediately after sample collection. Because sulfides and oxidants we re not detected at any of the sampling points during the sampling episode, the samplers did not need to dilute the samples or add sodium arsenite to the samples. After testing for sulf ides and oxidants, the total cyanide samples were preserved with sodium hydroxide to a pH >10 S.U. and placed on ice.

3.3 Plant Operational Data

During the EPA sampling episode, 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, Tabl e 3-9 presents the FGD scrubber system operating characteristics, Table 3-10 presents informati on on the coal burned during the sampling episode, Table 3-11 presents information on the FGD sc rubber slurry generation during the sampling episode, and Table 3-12 presents th e FGD wastewater treatment syst em operating characteristics.

3.4 Deviations from the Sampling and Analysis Plan

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

described below:

 Preservation of hexavalent chromium: ERG planned to preserve the hexavalent chromium samples to a pH between 9.3 and 9.7 S.U. using an ammonium sulfate buffer solution; however, since the amm onium sulfate buffer solution was not achieving the desired pH, the samplers added only 100 drops of ammonium sulfate buffer solution, followed by as mu ch ammonium hydroxide as necessary to reach the desired pH.

 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 th e only pressure moving the water through

### 3-9 the piping. Because of this reduced pre ssure, when the samplers opened the third valve on the sample tap to collect th e mercury samples, no wastewater was drained. Therefore, to collect the merc ury 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 compositi ng period at the effluent from the FGD wastewater treatment system (SP-2), samp lers 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 sy stem (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 sa mplers 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 w ith 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 ar ound the clean box was closed. After approximately one hour and twenty minut es, 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 compos ite 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 di sconnected after only 9 full aliquots. The container was almost filled with 20-liters of samp le and samplers chose to disconnect the compositor prior to the sample comple tely 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 th e compositing period. ERG had planned to collect the duplicate samples of th e effluent from the FGD wastewater treatment system (SP-3) on day 2; ho wever, because only one 20-L container would have volume for the sample collec tion, 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 infl uent of the FGD wastewater system (SP2), two 10-liter containers were filled a nd 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 tubi ng was then transferred to the second 10-liter container, purged with appr oximately 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 approxi mately 22 liters and the classicals compositor collecting approximately 21.5 liter s. Samplers were present for the final composite sample collection cycle and were able to verify that both containers did not reach full capacity and we re 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 wa stewater 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 Wa stewater Treatment System – Day 1 Grab 12/6/10 0907 a and 1049 b

Influent to FGD Wa stewater Treatment System – Day 2 Grab 12/7/10 0957 a and 1214 b

Influent to FGD Wa stewater Treatment System – Day 3 Grab 12/8/10 1048 a and 1325 b SP-1

Influent to FGD Wa stewater Treatment System – Day 4 Grab 12/9/10 0947 a and 1229 b

Composite 12/6/10

12/7/10 0722 c

0813 d Effluent from FGD Wastewater System – Day 1

Grab 12/6/10

12/7/10 0736 e , 1332 f , and 1943 g

0126 h

Composite 12/7/10

12/8/10 0622 c

0828 d Effluent from FGD Wastewater System – Day 2

Grab 12/7/10

12/8/10 0736 e , 1332 f , and 1940 g

0140 h

Composite 12/8/10

12/9/10 0759 c

0818 d Effluent from FGD Wastewater System – Day 3

Grab 12/8/10

12/9/10 0809 e , 1408 f , and 2007 g

0210 h

Composite 12/9/10

12/10/10 0747 c

0706 d SP-2

Effluent from FGD Wastewater System – Day 4

Grab 12/9/10

12/10/10 0800 e , 1359 f , and 2007 g

0205 h

Composite 12/8/10

12/9/10 0759 c

0819 d SP-3 Duplicate of Effluent from FGD Wastewater System – Day 3

Grab 12/7/10

12/8/10 0737 e , 1333 f , and 1944 g

0143 h

SP-4 Influent to FGD Wastewater Treatment System Field Blank Grab 12/6/10 0850 i and 1040 j

Composite 12/6/10

12/7/10 0627 k

0802 l Effluent from FGD Wastewater System Field Blank – Day 1

Grab 12/6/10 0730 m

Effluent from FGD Wastewater System Field Blank – Day 2 Grab 12/7/10 0731 m

Effluent from FGD Wastewater System Field Blank – Day 3 Grab 12/8/10 0804 m SP-5

Effluent from FGD Wastewater System Field Blank – Day 4 Grab 12/9/10 0755 m

a Start time for the collection of the total metals samples (total metals by 200.7 and total metals by 200.8) total and dissolved mercury, and classicals (BOD 5 , Group I, Group II, and total cyanide).

b Start time for the collection of the dissolved metals samples (dissolved metals by 200.7, dissolved metals by 200.8, and dissolved hexavalent chromium (except for hexavalent chromium on day 2)). Does not include dissolved

mercury.

### 3-12 c Started metals compositor. The classical compositor wa s started approximately two minutes after the metals compositor.

d Start time for the collection of dissolved metals samples (dissolved metals by 200.7, dissolved metals by 200.8, and dissolved hexavalent chromium), total metals samples (total metals by 200.7 and total metals by 200.8), and classicals (BOD 5 , Group I, and Group II).

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

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

g Start time for the collection of total and diss olved 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.

### 3-13Table 3-2. Sample Collection at Hatfield’s Ferry Steam Electric PlantSamplingPoint NumberSampling Point Name Total Metals (EPA Method 200.8 with collision cell) Total Metals (EPA Method 200.7) Dissolved Metals (EPA Method 200.8 with collision cell) Dissolved Metals (EPA Method 200.7) Total Mercury Dissolved Mercury Hexavalent Chromium BOD 5 Group I

a Group II
b Total CyanideSP-1 Influent to FGD Wastewater TreatmentSystem4 4 4 4 4 4 3c4 4 4 4SP-2 Effluent from FGDWastewater TreatmentSystem4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-3 Duplicate of Effluent from FGD WastewaterTreatment System1 1 1 1 1 1 1 1 1 1 1SP-4 Influent to FGD Wastewater TreatmentSystem Field Blank1 1 1 1 1 1SP-5 Effluent from FGDWastewater TreatmentSystem Field Blank1 1 1 1 4 1Total Number of Samples 11+1QC11+1QC 11+1QC 11+1QC 14+1QC 9+1QC 10+1QC 9+1QC 9+1QC 9+1QC 9+1QCaGroup I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate, and chloride.bGroup II includes ammonia as nitrogen, nitrate/nitrite as nitrogen, total Kjeldahlnitrogen (TKN), chemical oxygen demand (COD), and total phosphorus.cThe hexavalent chromium sample for the influent to the FGD wastewater treatment system was not collected on day 2. See Section 3.4 for more details.

### 3-14Table 3-3. Field Measurements, Hatfield’s FerrypH(S.U.)SamplingPointNumberSampling Point DescriptionDateTimeTemperature(°C)MeteraStripsWasteStream FlowRate(gpm)NotesInfluent to FGD Wastewater TreatmentSystem – Day 112/6/2010 0907475.92 6.5 171bInfluent to FGD Wastewater TreatmentSystem – Day 212/7/2010 0957496.06 7 171bInfluent to FGD Wastewater TreatmentSystem – Day 312/8/2010 1048496.11 7 171bSP-1Influent to FGD Wastewater TreatmentSystem – Day 412/9/2010 0947486.14 7 171bSamplers noted that the sampleshad a dark brown color andappeared to be high in solids.No detected sulfides or oxidantsin total cyanide grab.12/6/10 0743287.5 7 120c12/6/10 1335297.48 7 120c12/6/10 2000277.47 7 120Effluent from Wastewater TreatmentSystem – Day 112/7/10 0132287.48 7 12012/7/10 0742287.48 7 12012/7/10 1340287.46 7 12012/7/10 1954297.45 7.5 120Effluent from Wastewater TreatmentSystem – Day 212/8/10 0150297.46 7 12012/8/10 0810287.42 7 12012/8/10 1410297.61 7 11112/8/10 2015297.42 7 120Effluent from Wastewater TreatmentSystem – Day 312/9/10 0214297.49 7 12012/9/10 0802287.40 7 12012/9/10 1401297.42 7.5 12012/9/10 2014297.49 7.5 120SP-2Effluent from Wastewater TreatmentSystem – Day 412/10/10 0209287.46 7.5 120Samples were clear andcolorless and did not have anyobserved particulates. Nodetected sulfides or oxidants intotal cyanide grab.aThe pH meter was calibrated prior to the sampling episode and once every day during the sampling episode using prepackaged buffer solutions at pH 4.0, 7.0,and 10.0.bPlant does not monitor or record the flow at SP-1. Plant estimates flow based to be an average of 171 gpm during the samplingperiod.cDischarge flow monitoring was not functioning until 12/6/2010 at 1400 hrs. Flow rate at SP-2 prior to this time is estimated(from 0700 hrs to 1400 hrs).

### 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 (BOD 5 ) SM 5210 B Chemical oxygen demand (COD) EPA 410.4 Total suspended solids (TSS) SM 2540 D Total dissolved solids (TDS) SM 2540 C

Sulfate EPA 300.0

Chloride EPA 300.0 Ammonia as nitrogen EPA 350.1 Nitrate/nitrate as nitrogen EPA 353.2 Total Kjeldahl nitrogen (TKN) EPA 351.2 Total phosphorus EPA 365.1 Total cyanide SM 4500 CN E

Total and Dissolved Metals Mercury EPA 1631E Hexavalent chromium (dissolved only) EPA 218.6 Antimony, arsenic, cadmium, chromium, copper, lead, manganese, nickel, selenium, silver, thallium, and vanadium EPA 200.8 with collision cell 1

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

BOD 5 One 1-L plastic

bottle One 1-L plastic

bottle ≤ 6  C

Group I a One 1-L plastic

bottles One 1-L plastic

bottles ≤ 6  C

Group II b Two 1-L plastic

bottles Two 1-L plastic

bottles H 2 SO 4 to pH <2 S.U., ≤ 6  C

Total cyanide One 1-L plastic

bottle One 1-L plastic

bottles Dilution until sulfide is not detected,

NaAsO 2 until total chlorine is not present, NaOH to pH >10 S.U.,

≤ 6  C

Metals

Total metals (EPA Method 200.8 with collision cell) One 500-mL plastic bottle No additional

volume needed None (acid preserve at laboratory)

Total metals (EPA Method 200.7) One 500-mL plastic bottle No additional

volume needed None (acid preserve at laboratory)

Dissolved metals (EPA Method 200.8 with collision cell) One 500-mL plastic bottle No additional

volume needed 0.45-μm filter (performed in field) (acid preserve at laboratory)

Dissolved metals (EPA Method 200.7) One 500-mL plastic bottle No additional

volume needed 0.45-μm filter (performed in field) (acid preserve at laboratory)

Total mercury:

Manual composite grab samples Four 125-mL glass bottle No additional

volume needed

Influent samples and field blank samples Two 250-mL glass bottle No additional

volume needed None (acid preserve at laboratory)

Dissolved mercury:

Manual composite grab samples Four 125-mL glass bottle No additional

volume needed

Influent samples One 250-mL glass bottle No additional

volume needed None (filter and acid preserve at laboratory)

Hexavalent chromium One 250-mL plastic bottle No additional

volume needed 0.45-μm filter (performed in field)

Ammonium sulfate buffer to pH 9.3 – 9.7 S.U., ≤ 6  C

(a) Group I includes TSS, TD S, sulfate, and chloride. (b) Group II includes ammonia as nitrogen, COD, nitr ate/nitrite as nitrogen, TKN, and total phosphorus.

### 3-18 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 H 2 SO 4 7 2 175

71941 Group II Volume II 12/6/2010 H 2 SO 4 7 2 170

(NH 4 ) 2 SO 4

Buffer 6.5 8.5 100 71941 Hexavalent Chromium 12/6/2010

NH 4 OH 8.5 9.5 10

(NH 4 ) 2 SO 4

Buffer 6.5 9 100 71950 Hexavalent Chromium Field

Blank 12/6/2010

NH 4 OH 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 H 2 SO 4 6 2 200

71942 Group II Volume II 12/7/2010 H 2 SO 4 6 2 200

71945 Group II Volume I 12/7/2010 H 2 SO 4 7.5 2 40

71945 Group II Volume II 12/7/2010 H 2 SO 4 7.5 2 40

(NH 4 ) 2 SO 4

Buffer 7.1 8.1 100 71945 Hexavalent Chromium 12/7/2010

NH 4 OH 8.7 9.5 3

(NH 4 ) 2 SO 4

Buffer 6.5 9.0 100 71951 Hexavalent Chromium Field

Blank 12/7/2010

NH 4 OH 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 H 2 SO 4 6 2 200

71943 Group II Volume II 12/8/2010 H 2 SO 4 6 2 200

71946 Group II Volume I 12/8/2010 H 2 SO 4 7.5 2 40

71946 Group II Volume II 12/8/2010 H 2 SO 4 7.5 2 40

(NH 4 ) 2 SO 4

Buffer 6.5 8.1 100 71943 Hexavalent Chromium 12/8/2010

NH 4 OH 8.1 9.5 24

(NH 4 ) 2 SO 4

Buffer 7.4 8.7 200 71946 Hexavalent Chromium 12/8/2010

NH 4 OH 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 H 2 SO 4 6 2 240

71944 Group II Volume II 12/9/2010 H 2 SO 4 6 2 260

71947 Group II Volume I 12/9/2010 H 2 SO 4 7 2 40

71947 Group II Volume II 12/9/2010 H 2 SO 4 7 2 40

71955 Group II Volume I 12/9/2010 H 2 SO 4 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 H 2 SO 4 7 2 40

(NH 4 ) 2 SO 4

Buffer 7 8.3 100 71944 Hexavalent Chromium 12/9/2010

NH 4 OH 8.3 9.5 12

(NH 4 ) 2 SO 4

Buffer 7 8.5 100 71947 Hexavalent Chromium 12/9/2010

NH 4 OH 8.5 9.5 10

(NH 4 ) 2 SO 4

Buffer 7 8.5 100 71955 Hexavalent Chromium 12/9/2010

NH 4 OH 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 H 2 SO 4 7 2 30

71948 Group II Volume II 12/10/2010 H 2 SO 4 7 2 30

71948 Group II Volume I - QC 12/10/2010 H 2 SO 4 7 2 30

71948 Group II Volume II - QC 12/10/2010 H 2 SO 4 7 2 30

(NH 4 ) 2 SO 4

Buffer 7 8.5 100 71948 Hexavalent Chromium 12/10/2010

NH 4 OH 8.5 9.5 9

### 3-20 Table 3-8. Generating Unit Operating Characteri stics 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

### 3-21Table 3-9. FGD Scrubber System Operating Characteristics, Hatfield’s FerryUnit IDWet FGDSystem (Yes/No)Type ofScrubberForcedOxidation(Yes/No)SorbentAdditives (DBA,formic acid, etc.)FGD Make-upWater SourceSO2RemovalPercentageType of SolidsSeparation1 Yes B&W Yes Limestone NoneRiver and wastewater99% Hydrocyclone2 Yes B&W Yes Limestone NoneRiver and wastewater99% Hydrocyclone3 Yes B&W Yes Limestone NoneRiver and wastewater99% HydrocycloneB&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

Coal a (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 2.55 NA 1

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 2.91 NA 2

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 2.92 NA 3

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 3.24 NA 4

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 dur ing 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%

### 3-24Table 3-12. FGD Wastewater Treatment SystemOperation Information, Hatfield’s FerryScrubber PurgeChemical UsageDay ofSamplingFlow Rate(gpm)Duration(hr)Lime (tons)Ferric Chloride(liters)OrganosulfideNalco 1689(liters)Polymer:Nalco 1404(liters)HCl(liters)1 47 24 1.2 63 17 29 2632 120 24 3.198 17 43 6783 118 24 3.192 17 43 6784 120 24 3.186 17 43 678

### 4-1 4. L ABORATORY 

### A NALYTICAL 

### R ESULTS AND 

### D ISCUSSION



### This section summarizes the laboratory results of analyses of samples for the influent to the FGD wastewater treatment system and the effluent from the FGD wastewater treatment system. Section 4.1 discusses the methods used by the laboratories for th e biphasic analysis of SP-1. Section 4.2 presents the laborat ory analytical data for the infl uent to and effluent from the FGD wastewater treatment system.

The total and dissolved mercury samples we re analyzed by Frontier Global Sciences (Frontier). The dissolved mercury samples were vacuum filtered through acid-cleaned cellulose nitrate membrane filters contained in disposab le polystyrene filtration units at the Frontier laboratory under clean room conditions on the day of sample receipt. Samples with elevated solids were filtered through multiple filtration units until the entire sample was filtered. The mercury samples were subjected to a room temp erature bromine monochlor ide digestion prior to analysis using a method-compliant bubbler system.

For the total and dissolved mercury samples from SP-2, EPA collected four individual grab samples that were composited by Frontier a nd analyzed as one sample. Frontier composited these samples by combining the entire sample bo ttle for each of four i ndividual grab samples prior to digestion and an alysis; however, if one or more of th e grab samples were received with limited volume, equal volumes from each individual grab sample were combined for the composite analysis.

The total and dissolved metals by EPA Method 200.7 were analyzed by TestAmerica Laboratories – Denver (TestAmerica). As describe d in Section 3, the dissolved metals samples

were filtered in the field. The dissolved metals samples were preserved to a pH <2 at least 24 hours prior to being subjected to a heated ni tric acid digestion according to SW846 Method 3005A. The total metals samples were preserved to a pH <2 at least 24 hours prior to being subjected to a heated nitric acid dige stion according to SW846 Method 3010A.

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

TestAmerica. Similar to the metals anal yzed by EPA Method 200.7, the dissolved metals analyzed by EPA Method 200.8 were also filtered in the field. The total and dissolved metals samples were preserved to a pH <2 at least 24 hou rs prior to being subjected to a closed vessel, heated nitric acid and hydrochloric ac id digestion according to EPA Method 1638.

The classical analytes were analyzed by Te stAmerica and were di gested, prepared, and analyzed according to the me thods specified in Table 3-5.

Appendix A provides all analytical results for all samples collected at Hatfield’s Ferry, including all qualified results a nd all results that were measur ed above the method detection limit, but below the quantitation limit (i.e., J-values).

For EPA Method 200.7, some of the quantitat ion limits provided are TestAmerica’s standard routine quantitation limits; these limits are used for most of TestAmerica’s projects and were not optimized for FGD wastewater or the EPA sampling program. The quantitation limits are established using not only the results of the MDL studies, but also are based on the results of TestAmerica’s long term blank st udies. If the typical back ground blank levels for a given element are variable or frequently elevated, th en the quantitation limit may be raised to prevent

### 4-2 the reporting of false positives. This resulted in some analytes (e.g., manganese, sodium) having a QL/MDL ratio greater than five, wher e three to five is the normal range.

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

The samples of the influent to the FGD wast ewater treatment system were expected to contain significant amounts of r eadily settleable solids, to a large degree consisting of gypsum, unreacted limestone, and fly ash. Because of th is, EPA was concerned that there could be analytical interferences for the metals analyses, since the acid digestion procedures used may not be sufficiently rigorous for samples with high solid s loads. Therefore, ERG directed its contract laboratories to separate the aque ous and solid phases of the samp le prior to conducting certain analyses, where allowed by the analytical method a nd if necessary to obtain acceptable analytical results. This biphasic approach provides EPA with measured or calculated pollutant

concentrations for the follo wing phases of the sample:

 Aqueous phase;

 Solid phase; and

 Total sample.

The metals and classicals laboratory, Test America Laboratories - Denver (TestAmerica), and the mercury laboratory, Frontier, used two different approaches for the biphasic analysis. This section describes the approaches used by ea ch laboratory and presen ts the results of the analyses.

Metals and Classicals Analyses

TestAmerica used EPA Methods 200.7 and 200.8 to analyze the wastewater samples for metals. Both EPA Methods 200.7 and 200.8 state, “Aqueous samples containing total suspended

solids ≥ 1% (w/v) should be extracted as a solid type sample.” [3, 4] Because EPA expected the solids content to be greater than one percent, TestAmerica developed an approach for the analysis of the FGD influent samples that consiste d of performing a pressure filtration to separate the solids from the sample and analyzing the solid and aqueous phases separately.

Once the FGD influent samples were separa ted into solid and aqueous phases, the aqueous portion was analyzed using EPA Method 200.7 or Method 200.8, depending on the analyte. The solid portion of the samples asso ciated with the 200.7 analys is were prepared and analyzed according to SW846 Method 6010B, while the solid portion of the samples associated with the 200.8 analysis were prepared and analyzed according to SW846 Method 6020.

For solid phase analyses of n itrate/nitrite and ammonia, the analytical methods (i.e., EPA Method 353.2 and EPA Method 350.1, respectively) do not include proce dures for analyzing solid solids. Therefore, TestAmerica determin ed the concentration of nitrate/nitrite and ammonia in the FGD influent solid samples by perf orming a deionized leach of the solid sample. TestAmerica achieved this by placing a specified amount of the solid sample with an amount of deionized water and shaking the mixture for one hour. TestAmerica than separated the leachate from the solids using a centrifuge and then preser ved the leachate to a pH <2 S.U. and analyzed the leachate according the specified methods.

### 4-3 TestAmerica also dried the solids prior to an alysis, so the solid c oncentration is on a dryweight basis. To calculate the total sample concentration from the solid and aqueous phase results, the laboratory also needed to measure the original sample volum e, solid phase weight, and filtrate volume. EPA developed the following e quation to calculate the individual metal total concentrations for the sample.

Sample Solid Solid Filtrate Filtrate 

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

 (4-1)

where:

C Filtrate 

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

V Filtrate 

### = volume of the filtrate;

C Solid 

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

Wt Solid 

### = weight of the solids in the sample; and

V Sample 

### = volume of the original sample.

TestAmerica used the same approach for the se ven classical pollutants that were analyzed as biphasic samples: ammonia as nitrogen, chloride, sulfate, nitrate/nitrite, total cyanide, total Kjeldahl nitrogen (TKN), and total phosphorus.

Mercury Analyses

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

Method 1631E does not contain a ny language stating how wastewat er samples with high solid concentrations should be analyzed ; therefore, Frontier developed an approach for the analysis of the FGD influent samples that minimized potenti al contamination to the samples. Frontier’s approach consisted of using a centr ifuge to separate the solids from the sample and analyzing the solid and aqueous phases separately.

Once the FGD influent samples were separa ted into solid and aqueous phases, the aqueous portion was analyzed using EPA Method 1631E , just like all the other mercury samples. The solid portion was analyzed according to the Appendix to 1631: Total Mercury in Tissue, Sludge, Sediment, and Soil by Acid Digestion and BrCl Oxidation , which was associated with EPA Method 1631B. Frontier digested th e samples with aqua regia (HCl/HNO 3 

### ) and then analyzed the samples using EPA Method 1631E.

Frontier did not dry the solids prior to analysis, so the solid concentration is on a wetweight basis. To calculate the total sample concentration from the solid and aqueous phase results, the laboratory also needed to measure the original sample volum e, solid phase weight, and filtrate volume. EPA used Equation 4-1 to calculate the individual total mercury concentrations for the sample.

Appendix Tables A-1 through A-4 present th e results of the biphasic analysis for ammonia as nitrogen, nitrate/nitrit e, chloride, sulfate, nitrate/nitrite, total cyanide, TKN, total phosphorus, total metals, and total mercury for each of the four days of sampling. Results are rounded to three significant figures.

### 4-4 4.2 FGD Wastewater Treatment System

Table 4-1 presents the analytical results for all classical and metal analytes for the four days of sampling at the influent to the FGD wast ewater treatment system (SP-1), as well as the calculated 4-day average result for each analyte for the sampling point. The total metal results presented in Table 4-1 represent the calculated total result for all analytes for which biphasic separation was performed. Table 4-2 presents the analytical results for all classical and metal analytes for the four days of sampling at the e ffluent from the FGD wast ewater treatment system (SP-2).

Tables 4-1 and 4-2 include the analytical results for all anal ytes for which EPA conducted analyses. Results are rounded to three signifi cant digits. If an analyte was not detected in a sample above the method detection limit, the resu lt is reported as “ND” followed by the samplespecific quantitation limit in parentheses. If an analyte was measured above the method detection limit, but below the quantitation limit, the result is reported as “NQ” followed by the sample-specific quantitation limit in parentheses.

For Table 4-2 (effluent from the FGD wastew ater treatment system), a duplicate sample for mercury was collected on Day 2 of the samp ling episode and duplicate samples for all other analytes were collected on Day 3. The Day 2 re sult for mercury presented in Table 4-2 represent the average of the original and the duplicate samp le 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 resu lts for the original and duplicate mercury results from Day 2 and the calculated relative percen t difference (RPD). Table 5-3 presents the analytical results for the original and duplicate re sults 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 quantitati on limit, then all results were averaged together;

 If at least one result was above the quan titation limit, then 1⁄2 the quantitation limit was used in the average calculation for all results that were less than the quantitation limit and the result is repo rted with a less than sign (“<”);

 If all results were below the quantitation limit, but at least one result was above the method detection limit (i.e., J-value), then the sample-specific quantitation limits for all results were averaged and the result is reported as “NQ” followed by the average of the sample-specific quantitation limits; and

 If all results were below the method de tection limit, then the sample-specific quantitation limits for all results were aver aged and the result is reported as “ND” followed by the average of the sample-specific quantitation limits.

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

the FGD wastewater treatment system (SP-1) and the efflue nt from the FGD wastewater treatment system (SP-2). Table 4-4 presents th e 4-day average results for all metal analytes, including total and dissolved analyses, for the in fluent to the FGD wastewater treatment system (SP-1) and the effluent from th e FGD wastewater treatment system (SP-2). The results presented

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

### 4-6Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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 FerryInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmonia mg/L 350.1NQ(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)F(H, P) –S(H, P, Est)NQ(4.22)Nitrate Nitriteas Nmg/L 353.2 129F(H, P, Est) –S(H, P, Est)208F(H, P, Est) –S(H, P, Est)157F(H, P, Est) –S(H, P, Est)129F(H, P, Est) –S(H, P, Est)156Nitrogen,TotalKjeldahl mg/L 351.2 45.6F(B, H, P, Est)– S(H, P, Est) 57.4F(B, H, P, Est) –S(H, P, Est) 38.3F(B, H, P, Est) –S(H, P, Est) 47.0F(B, H, P, Est)– S(H, P, Est) 47.1BiochemicalOxygenDemandmg/L 5210B 3.00 B NQ (5.00) 3.80 2.50 < 2.95ChemicalOxygenDemandmg/L 410.4 250 F,G,Est 520 350 G,Est 280 G,Est 350Chloride mg/L 300.0, 9056 5,610F(H, Est) –S(H, Est) 8,510F(H, Est) –S(H, Est) 8,000F(H, Est) –S(H, Est) 6,250F(H, Est) –S(H, Est) 7,090Sulfate mg/L 300.0, 9056 10,400F(H, Est) –S(H, Est)11,800F(H, Est) –S(H, Est)10,100F(H, Est) –S(H, Est)10,300F(H, Est) –S(H, Est)10,700Cyanide,Total mg/L 4500 CN ENQ(0.119)F(H, P) –S(H, P, Est) 0.216F(H, P, Est) –S(H, P, Est) 0.195F(H, P, Est) – S(H,P, Est) 0.136F(H, P) –S(H, P, Est) < 0.152TotalDissolvedSolidsmg/L 2540C 25,000 41,000 31,000 26,000 30,800

### 4-7Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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 FerryInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageTotalSuspendedSolidsmg/L 2540D 54,000 67,000 66,000 47,000 58,500Phosphorus,Total mg/L 365.1NQ(0.345)F(B, H, P, Est)– S(H, P) 17.8F(B, H, P, Est) –S(H, P, Est) 13.3F(B, H, P, Est)– S(H, P, Est)NQ(0.322)F(B, H, P,Est) – S(H, P)< 7.86Total MetalsAluminum ug/L 200.7, 6010B 1,760,000 2,550,000 2,080,000 2,000,0002,100,000Antimony ug/L 200.8, 6020 24.1 NQ (29.3) NQ (26.7) NQ (21.2) < 15.7Arsenic ug/L 200.8, 6020 2,300 4,610 2,150 2,830 2,970Barium ug/L 200.7, 6010B 13,000 S(B) 21,300 S(B) 12,500 S(B) 13,400 S(B) 15,100Beryllium ug/L 200.7, 6010B 59.9 136 54.9 73.7 81.1Boron ug/L 200.7, 6010B 233,000 S(B) 364,000 F(B) – S(B) 309,000 F(B) – S(B) 262,000 F(B) – S(B) 292,000Cadmium ug/L 200.8, 6020 425 595 589 451 515Calcium ug/L 200.7, 6010B 8,230,000 6,730,000 9,700,000 6,740,0007,850,000Chromium ug/L 200.8, 6020 6,460 8,490 6,920 6,660 7,130Cobalt ug/L 200.7, 6010B 556 869 637 597 665Copper ug/L 200.8, 6020 1,900 3,130 2,090 2,200 2,330Iron ug/L 200.7, 6010B 1,470,000 2,050,000 1,800,000 1,770,0001,770,000Lead ug/L 200.8, 6020 1,170 S(B) 2,120 S(B) 1,310 S(B) 1,390 S(B) 1,500

### 4-8Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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 FerryInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageMagnesium ug/L 200.7, 6010B 5,070,000 6,830,000 6,150,000 5,120,0005,790,000Manganese ug/L 200.7, 6010B 71,100 98,300 96,200 80,400 86,500Mercury ng/L1631E, FGS069521,000 654,000 789,000 624,000 647,000Molybdenum ug/L 200.7, 6010B 675 1,350 680 760 866Nickel ug/L 200.8, 6020 2,970 4,360 3,710 3,280 3,580Selenium ug/L 200.8, 6020 2,680 3,920 3,550 2,740 3,220Silver ug/L 200.8, 6020 NQ (12.4) NQ (15.2) NQ (14.3) NQ (11.8)NQ(13.4)Sodium ug/L 200.7, 6010B 377,000 607,000 465,000 373,000 456,000Thallium ug/L 200.8, 6020 96.8 195 99.9 116 127Tin ug/L 200.7, 6010B NQ (757) NQ (785) NQ (769) NQ (651) NQ (741)Titanium ug/L 200.7, 6010B 14,100 29,700 11,100 16,100 17,800Vanadium ug/L 200.8, 6020 5,900 10,700 6,530 7,230 7,590Zinc ug/L 200.7, 6010B 15,000 F(B) 19,100 F(B) 16,200 F(B) 15,400 F(B) 16,400Dissolved MetalsAluminum ug/L 200.7 NQ (200) 250 ND (200) NQ (200) < 138Antimony ug/L 200.8 5.40 13.0 5.60 6.30 7.58Arsenic ug/L 200.8 5.20 11.0 5.10 7.70 7.25Barium ug/L 200.7 140 160 160 160 155Beryllium ug/L 200.7 3.00 3.60 NQ (2.00) 3.10 < 2.68

### 4-9Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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 FerryInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageBoron ug/L 200.7 250,000 B 410,000 B 340,000 B 290,000 B 323,000Cadmium ug/L 200.8 300 450 420 290 365Calcium ug/L 200.7 730,000 800,000 860,000 780,000 793,000Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.00)ND(8.00)Chromium(VI)ug/L 218.6 ND (10.0) NA ND (10.0) ND (10.0)ND(10.0)Cobalt ug/L 200.7 310 370 380 330 348Copper ug/L 200.8 14.0 14.0 14.0 11.0 13.3Iron ug/L 200.7 ND (200) 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)ND(2.00)Magnesium ug/L 200.7 4,400,000 6,300,000 5,300,000 4,800,0005,200,000Manganese ug/L 200.7 69,000 94,000 96,000 82,000 85,300Mercury ng/L 1631E 131 382 236 187 234Molybdenum ug/L 200.7 320 960 360 420 515Nickel ug/L 200.8 1,000 1,200 1,200 1,100 1,130Selenium ug/L 200.8 340 1,100 350 400 548Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)ND(2.00)Sodium ug/L 200.7 370,000 590,000 470,000 360,000 448,000

### 4-10Note: The total metals results and the results for certain classical analytes (i.e., ammonia as nitrogen, chloride, nitrate/nitrite sulfate, total cyanide, TKN, total phosphorus)represent the total result that was calculated based on the resultsof the solid and aqueous phase of the samples. See Section4.1 for more details. Sample qualifiers denoted withan ‘F( )’ are qualifiers associated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associated with the solid portion of the sample.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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 FerryInfluent to FGD Wastewater Treatment System (SP-1)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageThallium ug/L 200.8 20.0 45.0 21.0 24.0 27.5Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)ND(20.0)Vanadium ug/L 200.8 35.0 97.0 37.0 45.0 53.5Zinc ug/L 200.7 2,600 2,200 2,400 2,100 2,330

### 4-11Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.* - LCS or LCSD is outside the laboratory control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table 4-2. Effluent from FGD Wastewater Treatment System, Hatfield’s FerryEffluent from FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageClassicalsAmmonia mg/L 350.1 NQ (1.00) B NQ (1.00) B 1.10 1.00 < 0.775Nitrate Nitrite as N mg/L 353.2 130 140 140 130 135Nitrogen, Kjeldahl mg/L 351.2 19.0 16.0 17.5 17.0 4 17.4Biochemical Oxygen Demand mg/L 5210B ND (2.00) NQ (2.50) NQ (2.50) 2.60 *,Min < 1.53Chemical Oxygen Demand mg/L 410.4 240 240 230 230 F 235Chloride mg/L 300.0 6,500 6,700 6,700 6,500 6,600Sulfate mg/L 300.0 5,800 5,000 4,700 5,500 5,250Cyanide, Total mg/L 4500 CN E 0.110 0.180 0.195 0.170 F 0.164Total Dissolved Solids mg/L 2540C 16,00016,000 12,500 15,000 D,Est 14,900Total Suspended Solids mg/L 2540D NQ (4.00) NQ (4.00) NQ (4.00) 4.00 D,Est < 2.50Phosphorus, Total mg/L 365.1 0.0670 B 0.230 B 0.0620 NQ (0.0500) B,F < 0.096Total MetalsAluminum ug/L 200.7 ND (200) NQ (200) B NQ (200) NQ (200) B NQ (200)Antimony ug/L 200.8 7.40 8.20 8.65 8.80 8.26Arsenic ug/L 200.8 5.40 4.60 6.40 7.60 6.00Barium ug/L 200.7 100 120 130 110 115Beryllium ug/L 200.7 ND (2.00) ND (2.00)ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 180,000 B,4 190,000 B 185,000 190,000 B,4 186,000Cadmium ug/L 200.8 5.60 7.00 8.65 8.70 7.49Calcium ug/L 200.7 1,200,000 B,4 1,400,000 B 1,400,000 1,200,000 B,4 1,300,000Chromium ug/L 200.8 11.0 11.0 10.5 10.0 10.6

### 4-12Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.* - LCS or LCSD is outside the laboratory control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table 4-2. Effluent from FGD Wastewater Treatment System, Hatfield’s FerryEffluent from FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageCobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) NQ (20.0) NQ (20.0)Copper ug/L 200.8 NQ (4.00) 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) B < 125Lead ug/L 200.8 ND (2.00) 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 B,4 2,880,000Manganese ug/L 200.7 2,400 B,4 1,900 B 2,050 6,400 B,4 3,190Mercury ng/L 1631E 35.3 38.4 31.8 37.0 33.6Molybdenum ug/L 200.7 430 420 465 460 444Nickel ug/L 200.8 6.50 4.50 4.95 13.0 7.24Selenium ug/L 200.8 570 4 540 595 620 4 581Silver ug/L 200.8 ND (2.00) F ND (2.00) ND (2.00) ND (2.00) F ND (2.00)Sodium ug/L 200.7 410,000 4 420,000 415,000 380,000 4 406,000Thallium ug/L 200.8 7.00 7.40 8.55 7.80 7.69Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) ND (20.0)Vanadium ug/L 200.8 27.0 B 23.0 B 30.0 47.0 B 31.8Zinc ug/L 200.7 ND (40.0) ND (40.0) ND (40.0) NQ (40.0) NQ (40.0)Dissolved MetalsAluminum ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Antimony ug/L 200.8 6.90 7.50 8.10 7.90 7.60Arsenic ug/L 200.8 5.10 4.30 6.25 8.60 6.06Barium ug/L 200.7 100 F 120 130 100 F 113

### 4-13Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.* - LCS or LCSD is outside the laboratory control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table 4-2. Effluent from FGD Wastewater Treatment System, Hatfield’s FerryEffluent from FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageBeryllium ug/L 200.7 ND (2.00) ND (2.00)ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 190,000 B,4 190,000 B 175,000 190,000 B,4 186,000Cadmium ug/L 200.8 4.60 7.20 9.10 7.80 7.18Calcium ug/L 200.7 1,200,000 4 1,400,000 1,450,000 1,200,000 4 1,310,000Chromium ug/L 200.8 8.50 9.10 9.75 8.60 8.99Chromium (VI) ug/L 218.6 4.08 3.93 3.86 2.96 3.71Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) NQ (20.0) NQ (20.0)Copper ug/L 200.8 NQ (4.00) 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) ND (200)Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00) ND (2.00)Magnesium ug/L 200.7 3,000,000 4 2,900,000 2,800,000 2,800,000 4 2,880,000Manganese ug/L 200.7 2,400 4 1,900 2,000 6,200 4 3,130Mercury ng/L 1631E NQ (0.500) 7.98 8.90 16.5 < 8.50Molybdenum ug/L 200.7 430 430 465 450 444Nickel ug/L 200.8 5.30 4.00 5.15 13.0 6.86Selenium ug/L 200.8 610 4 560 620 630 4 605Silver ug/L 200.8 ND (2.00) F ND (2.00) ND (2.00) ND (2.00) F ND (2.00)Sodium ug/L 200.7 410,000 4 400,000 415,000 370,000 4 399,000Thallium ug/L 200.8 7.50 7.10 8.70 7.60 7.73Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0) ND (20.0)Vanadium ug/L 200.8 26.0 22.0 29.5 44.0 30.4

### 4-14Note: The Day 2 results represent the average of the original sample and the field duplicate (SP-3). See Section 5.2.4 for theanalytical results for the individual samples.< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.* - LCS or LCSD is outside the laboratory control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table 4-2. Effluent from FGD Wastewater Treatment System, Hatfield’s FerryEffluent from FGD Wastewater Treatment System (SP-2)AnalyteUnitsMethodDay 1Day 2Day 3Day 44-DayAverageZinc ug/L 200.7 ND (40.0) NQ (40.0) ND (40.0) ND (40.0) NQ (40.0)

### 4-15< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-3. Classical Pollutant 4-Day Average Data Summary for FGD Wastewater Treatment System, Hatfield’s FerryAnalyteUnitsMethodInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent from FGDWastewater TreatmentSystem (SP-2)4-Day AverageClassicalsAmmonia mg/L 350.1 NQ (4.22) < 0.775Nitrate Nitrite as N mg/L 353.2 156 135Nitrogen, Total Kjeldahl mg/L 351.2 47.1 17.4Biochemical Oxygen Demand mg/L 5210B < 2.95 < 1.53Chemical Oxygen Demand mg/L 410.4 350 235Chloride mg/L 300.0, 9056 7,090 6,600Sulfate mg/L 300.0, 9056 10,700 5,250Cyanide, Total mg/L 4500 CN E < 0.152 0.164Total Dissolved Solids mg/L 2540C 30,800 14,900Total Suspended Solids mg/L 2540D 58,500 < 2.50Phosphorus, Total mg/L 365.1 < 7.86 < 0.096

### 4-16< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-4. Metal Pollutant 4-Day Average Data Summary for FGD Wastewater Treatment System, Hatfield’s FerryInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent from FGDWastewater TreatmentSystem (SP-2)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedMetalsAluminum ug/L 200.7 2,100,000 < 138 NQ (200) ND (200)Antimony ug/L 200.8 < 15.7 7.58 8.26 7.60Arsenic ug/L 200.8 2,970 7.25 6.00 6.06Barium ug/L 200.7 15,100 155 115 113Beryllium ug/L 200.7 81.1 < 2.68 ND (2.00) ND (2.00)Boron ug/L 200.7 292,000 323,000 186,000 186,000Cadmium ug/L 200.8 515 365 7.49 7.18Calcium ug/L 200.7 7,850,000 793,000 1,300,000 1,310,000Chromium ug/L 200.8 7,130 ND (8.00) 10.6 8.99Chromium (VI) ug/L 218.6 NA ND (10.0) NA 3.71Cobalt ug/L 200.7 665 348 NQ (20.0) NQ (20.0)Copper ug/L 200.8 2,330 13.3 NQ (4.00) NQ (4.00)Iron ug/L 200.7 1,770,000 ND (200) < 125 ND (200)Lead ug/L 200.8 1,500 ND (2.00) ND (2.00) ND (2.00)Magnesium ug/L 200.7 5,790,000 5,200,000 2,880,000 2,880,000Manganese ug/L 200.7 86,500 85,300 3,190 3,130Mercury ng/L 1631E 647,000 234 33.6 < 8.50Molybdenum ug/L 200.7 866 515 444 444Nickel ug/L 200.8 3,580 1,130 7.24 6.86Selenium ug/L 200.8 3,220 548 581 605Silver ug/L 200.8 NQ (13.4) ND (2.00) ND (2.00) ND (2.00)Sodium ug/L 200.7 456,000 448,000 406,000 399,000Thallium ug/L 200.8 127 27.5 7.69 7.73Tin ug/L 200.7 NQ (741) ND (200) ND (200) ND (200)

### 4-17< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).NA – Not analyzed.ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-4. Metal Pollutant 4-Day Average Data Summary for FGD Wastewater Treatment System, Hatfield’s FerryInfluent to FGDWastewater TreatmentSystem (SP-1)4-Day AverageEffluent from FGDWastewater TreatmentSystem (SP-2)4-Day AverageAnalyteUnitsMethodTotalDissolvedTotalDissolvedTitanium ug/L 200.7 17,800 ND (20.0) ND (20.0) ND (20.0)Vanadium ug/L 200.8 7,590 53.5 31.8 30.4Zinc ug/L 200.7 16,400 2,330 NQ (40.0) NQ (40.0)

### 5-1 5. D ATA 

### Q UALITY



### Quality assurance/quality control (QA/QC) pro cedures 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 pr ocedures used to assess the precision and accuracy of the analytical data presented in Section 4 and Appendix A. QC practices used for this sampling episode include the analysis of matrix spikes, blanks, duplicate samples, and QC standard checks.

5.1 Analytical Quality Control

ERG contracted directly with analytical labor atories for the analysis of samples collected during this episode. ERG verified that the pe rformance of the laboratories selected was acceptable by conducting QC checks of the analytical data. Data review chemists at ERG prepared written data review narr atives describing any qualifications of the analytical data from this episode. The data review narrat ives are included in Appendix B.

5.2 Field Quality Control

This subsection discusses the bottle blanks , equipment blanks, field blanks, and field duplicate sample results. Section 3.8 of the Samp ling Plan discusses field QC specifications.

5.2.1 Bottle Blanks

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

bottles. Bottle blanks were collected and analyzed for metals (EPA Method 200.8, 200.7, and 1631E) by the supplier of the precleaned bottl es, Frontier Global Sciences (Frontier).

Frontier collected the bottle blanks for the meta ls sample bottles by filling the precleaned bottle with reagent water, preserving the sample w ith nitric acid to a pH <2 S.U. Frontier then analyzed the samples using EPA Method 1638.

Frontier collected the bottle blanks for the mercury sample bottles by filling the precleaned bottle with reagent water, preserving the sample with bromine monochloride. Frontier then analyzed the samples using EPA Method 1631E.

Albion Environmental collected the bottle bl anks for the 10- and 20-liter composite containers by filling the container with approx imately two liters of ASTM Type 1 water and allowing it to soak for approximately 24 hours. During this period, th e laboratory shook the container periodically and changed its orientation to expose all surfaces of the container to the ASTM Type 1 water. Albion Environmental th en shook the 10- and 20-liter containers and poured a representative sample into a precleaned LDPE sample bottle. The blank samples were then preserved and analyzed according to the analytical methods (i.e., EPA Method 1638).

No metals were detected in the bottle bla nks. 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 (a s described in Section 5.2.3) include the sampling equipment and ther efore would identify whether the sampling equipment was introducing contamination. In addition, Frontier collected and analyzed equipment blanks for metals (EPA Met hod 1638 and 1631E) for each type of precleaned equipment supplied for the episode.

Frontier collected the equipment blanks for th e capsule filters and fabricated tubing sets by pumping reagent water through the cleaned and fully assemble d equipment sets (with the filter attached) into a cleaned bottle (an HDPE bottl e for metals and a glass bottle for mercury). The blank samples were then preserved and anal yzed according to the analytical methods (EPA Method 1638 and 1631E), as described in Sectio n 5.2.1 for the bottle blank samples.

No other metals were detected in the equi pment 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. Calciu m was detected in the pu mp off tubing set at 40 ug/L, and all calcium results for the sampling ep isode were more than 2,000 times greater than the equipment blank detection. Appendix Table A-15 presents all of the an alytical results from the bottle blank and equipment blank analyses for all of the equipment used for the collection of metals and mercury samples.

5.2.3 Field Blanks

The sampling team collected field blanks (SP-4, and SP-5) to evaluate possible contamination from sampling equipment, samp ling equipment decontamination procedures, sample collection procedures, or atmospheric contamination. EPA analyzed the field blank samples for the total and dissolved metals and total and dissolved mercury samples 10



### .

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

for the influent to the FGD wastewater treatm ent system (SP-4) were collected by pouring ASTM Type 1 water through a precle aned funnel attached to the si licone tubing used for sample collection. To prevent potential atmospheric deposition, the sampling team shrouded the blank water and funnel with a plastic bag while pouring the blank water into the funnel and placed the sample bottles in a “cleanbox.” Prior to filli ng the sample bottles, the tubing was purged with approximately 1 liter of blank water. The ASTM Type 1 water flowed through the funnel, tubing, and “Y” splitter, and was poured into the sample bottles. EPA collected the field blank samples as “true” split samples with Hatfield’s Ferry ’s representative, usi ng the same procedure discussed in the sample collec tion description (Section 3.1).

The dissolved metals by 200.8, dissolved metals by 200.7, and dissolved hexavalent chromium field blank samples for the influent to the FGD wastew ater treatment system (SP-4) were collected by pouring ASTM Type 1 water th rough the funnel and tubi ng and into a 10-liter

10 EPA did not collect a dissolved mercury field blank samp le because the sample filtration was performed at the laboratory to minimize potential mercury contamination. The laboratory performed a filtration blank prior to filtering the sample, which is assessed as the field bl ank for the dissolved mercury sample. Mercury was not detected above the method detection limit (0.24 ng/L) in the filtration blanks performed 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 bo ttles. EPA collected the field blank samples as “true” split samples with Hatfield’s Ferry’s repr esentative, using the same procedure discussed in the sample collection desc ription (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 th e three taps on the sample tap splitter with a clear plastic bag. Before purgi ng 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 me tals by 200.8 field blank samples for the effluent from the FGD wastewater treatment sy stem (SP-5) were collected by filling a 20-liter composite container with ASTM Ty pe 1 water. The same T-splitter tubing used to fill the metals composite container was used with a pump to f ill the 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 othe r 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. Th e vented cap used for the field blank collection was the same cap that was late r used for the metals composite container.

After 24 hours, the ASTM Type 1 water in th e 20-liter field bla nk composite container was pumped off into the individual sample bottles. The sample bottles were placed in a “cleanbox” and the ASTM Type 1 water was pump ed through the tubing and “Y” splitter, and into the sample bottles. EPA collected the fiel d blank samples as “true” split samples with Hatfield’s Ferry’s representative, using the same procedure discussed in the sample collection description (Section 3.1). Prior to filling the sample bot tles, the tubing was purged with approximately 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 approxim ately 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 analyt ical results for SP-4 and SP-5. Only those analytes that were detected in the field blank samples at levels above the quantitation limit are

included in the table. Results are rounded to three significant digits . Appendix Tables A-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 dupl icate samples are separate samp les collected from the same location as the original sample. The duplicate is filled immediately after the original sample and is stored and analyzed independently. The RPD be tween the two sample results is examined to

### 5-4 determine the precision of the data. EPA used the following equation to calculate the RPD for the duplicate sample results.

100

2 D S D S (%) RPD         

 

### (5-1)

where: S = concentration of the analyte from original sample analysis; D = concentration of the analyte from the duplicate sample analysis; and RPD = relative percent difference between the original and duplicate sample

result.

During this sampling episode, EPA collected du plicate 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 Tabl es A-10, A-13 and A-14 present all the analytical results for the

effluent from the FGD wa stewater treatment system (SP-2) Day 2 for mercury and Day 3 for all other analytes and the duplicate of the effluentfrom the FGD wastewater treatment system (SP3) sample analyses, including all qualified results and all results that we re measured above the method detection limit, but below the quantitation limit (i.e., J-values).

### 5-5Table 5-1. Field Blank Analytical Results, Hatfield’s FerryAnalyteSample DescriptionMethodUnitsConcentrationTotal MetalsMercury Influent to FGD Wastewater Treatment System Field Blank - Day 1 1631E ng/L 1.69

### 5-6aOriginal 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, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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 FerryAnalyteMethodUnitsOriginal Effluentfrom FGDWastewaterTreatment System,Day 3 Concentration(SP-2)Duplicate Effluentfrom FGDWastewaterTreatment SystemConcentration (SP-3)AverageResultRelativePercentDifferenceClassicalsAmmonia 350.1 mg/L 1.10 1.10 1.10 0.00Nitrate Nitrite as N 353.2 mg/L 140 140 140 0.00Nitrogen, Total Kjeldahl 351.2 mg/L 19.0 16.0 17.5 17.1Biochemical Oxygen Demand 5210B mg/L NQ (2.50) NQ (2.50) NQ (2.50) NCChemical Oxygen Demand 410.4 mg/L 230 230 230 0.00Chloride 300.0 mg/L 6,900 6,500 6,700 5.97Sulfate 300.0 mg/L 4,800 4,600 4,700 4.26Cyanide, Total 4500 CN E mg/L 0.240 0.150 F 0.195 46.2Total Dissolved Solids 2540C mg/L 14,000 11,000 12,500 24.0Total Suspended Solids 2540D mg/L NQ (4.00) NQ (4.00) NQ (4.00) NCPhosphorus, Total 365.1 mg/L 0.0630 B 0.0610 B 0.0620 3.23Total MetalsAluminum 200.7 ug/L NQ (200) B ND (200) NQ (200) NCAntimony 200.8 ug/L 8.60 8.70 8.65 1.16Arsenic 200.8 ug/L 6.00 6.80 6.40 12.5Barium 200.7 ug/L 130 130 130 0.00Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.00) NCBoron 200.7 ug/L 190,000 B 180,000 B 185,000 5.41Cadmium 200.8 ug/L 8.70 8.60 8.65 1.16Calcium 200.7 ug/L 1,400,000 B 1,400,000 B 1,400,000 0.00Chromium 200.8 ug/L 11.0 10.0 10.5 9.52Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20.0) NC

### 5-7aOriginal 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, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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 FerryAnalyteMethodUnitsOriginal Effluentfrom FGDWastewaterTreatment System,Day 3 Concentration(SP-2)Duplicate Effluentfrom FGDWastewaterTreatment SystemConcentration (SP-3)AverageResultRelativePercentDifferenceCopper 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.00) NCIron 200.7 ug/L NQ (200) B NQ (200) B NQ (200) NCLead 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCMagnesium 200.7 ug/L 2,800,000 B 2,800,000 B 2,800,000 0.00Manganese 200.7 ug/L 2,000B 2,100 B 2,050 4.88Mercurya1631E ng/L 46.4 30.3 38.4 42.0Molybdenum 200.7 ug/L 450 480 465 6.45Nickel 200.8 ug/L 4.70 5.20 4.95 10.1Selenium 200.8 ug/L 580 610 595 5.04Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCSodium 200.7 ug/L 400,000 430,000 415,000 7.23Thallium 200.8 ug/L 8.20 8.90 8.55 8.19Tin 200.7 ug/L ND (200) ND (200) ND (200) NCTitanium 200.7 ug/L ND (20.0) ND (20.0) ND (20.0) NCVanadium 200.8 ug/L 30.0 B 30.0 B 30.0 0.00Zinc 200.7 ug/L ND (40.0) ND (40.0) ND (40.0) NCDissolved MetalsAluminum 200.7 ug/L ND (200) ND (200) ND (200) NCAntimony 200.8 ug/L 7.70 8.50 8.10 9.88Arsenic 200.8 ug/L 5.90 6.60 6.25 11.2Barium 200.7 ug/L 130 130 130 0.00Beryllium 200.7 ug/L ND (2.00) ND (2.00) ND (2.00) NCBoron 200.7 ug/L 170,000 B 180,000 B 175,000 5.71

### 5-8aOriginal 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, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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 FerryAnalyteMethodUnitsOriginal Effluentfrom FGDWastewaterTreatment System,Day 3 Concentration(SP-2)Duplicate Effluentfrom FGDWastewaterTreatment SystemConcentration (SP-3)AverageResultRelativePercentDifferenceCadmium 200.8 ug/L 9.70 8.50 9.10 13.2Calcium 200.7 ug/L 1,500,000 1,400,000 1,450,000 6.90Chromium 200.8 ug/L 10.0 9.50 9.75 5.13Chromium (VI) 218.6 ug/L 3.70 4.02 3.86 8.29Cobalt 200.7 ug/L ND (20.0) ND (20.0) ND (20.0) NCCopper 200.8 ug/L NQ (4.00) NQ (4.00) NQ (4.00) NCIron 200.7 ug/L ND (200) ND (200) ND (200) NCLead 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCMagnesium 200.7 ug/L 2,900,000 2,700,000 2,800,000 7.14Manganese 200.7 ug/L 2,0002,000 2,000 0.00Mercurya1631E ng/L 7.60 8.35 7.98 9.40Molybdenum 200.7 ug/L 470 460 465 2.15Nickel 200.8 ug/L 5.30 5.00 5.15 5.83Selenium 200.8 ug/L 620 620 620 0.00Silver 200.8 ug/L ND (2.00) ND (2.00) ND (2.00) NCSodium 200.7 ug/L 420,000 410,000 415,000 2.41Thallium 200.8 ug/L 8.60 8.80 8.70 2.30Tin 200.7 ug/L ND (200) ND (200) ND (200) NCTitanium 200.7 ug/L ND (20.0) ND (20.0) ND (20.0) NCVanadium 200.8 ug/L 29.0 30.0 29.5 3.39Zinc 200.7 ug/L ND (40.0) ND (40.0) ND (40.0) NC

### 6-1 6. R EFERENCES



### 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 C oupled Plasma – Atomic Emission Spectrometry. Revision

4.4.

4. U.S. EPA. 1994. Method 200.7: Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma - Mass Spectrometry. Revision 5.4.

### Appendix A

ANALYTICAL RESULTS

### A-1Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).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 Treatment System,Day 1 Analytical Results, Hatfield’s FerryAnalyteAqueous Phase Result(mg/L for Classicals;ug/L for Metals; and ng/Lfor Mercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)ClassicalsAmmonia 1.7 J,H,P 15 H,P,Est 2.42 F(J, H, P) – S(H, P, Est)Nitrate Nitrite as N 140 H,P,Est 34 H,P,Est 129 F(H, P, Est) – S(H, P, Est)Nitrogen, Total Kjeldahl 14 B,H,P,Est 560 H,P,Est 45.6 F(B, H, P, Est) – S(H, P, Est)Chloride 6,100 H,Est 1,500 H,Est 5,610 F(H, Est) – S(H, Est)Sulfate 9,700 H,Est 27,000 H,Est 10,400 F(H, Est) – S(H, Est)Cyanide, Total 0.079 J,H,P 0.54 H,P,Est 0.103 F(J, H, P) – S(H, P, Est)Phosphorus, Total 0.12 B,H,P,Est ND (5.1) U,H,P 0.109 F(B, H, P, Est) – S(U, H, P)Total MetalsAluminum ND (200) U 30,000 1,760,000 F(U)Antimony 5.2 0.33 J 24.1 S(J)Arsenic 7.3 39 2,300Barium 64 220 B 13,000 S(B)Beryllium 1.3 J 1 59.9 F(J)Boron 240,000 B 270 B 233,000 F(B) – S(B)Cadmium 230 3.7 425Calcium 660,000 130,000 8,230,000Chromium ND (8) U 110 6,460 F(U)Cobalt 270 5.3 556Copper 23 32 1,900Iron ND (200) U 25,000 1,470,000 F(U)Lead ND (2) U 20 B 1,170 F(U) – S(B)Magnesium 4,500,000 17,000 5,070,000

### A-2Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).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 Treatment System,Day 1 Analytical Results, Hatfield’s FerryAnalyteAqueous Phase Result(mg/L for Classicals;ug/L for Metals; and ng/Lfor Mercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)Manganese 65,000 210 71,100Mercury 202,000 10,200 521,000Molybdenum 350 6.1 675Nickel 950 36 2,970Selenium 430 39 2,680Silver ND (2) U 0.12 J 7.05 F(U) – S(J)Sodium 370,000 720 377,000Thallium 9.6 1.5 96.8Tin ND (200) U 2.4 J 141 F(U) – S(J)Titanium ND (20) U 240 14,100 F(U)Vanadium 27 100 5,900Zinc 1,600 B 230 15,000 F(B)

### A-3Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).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 forClassicals and Total Metals, Influent toFGD Wastewater Treatment System, Day 2Analytical Results, Hatfield’s FerryAnalyteAqueous Phase Result(mg/L for Classicals;ug/L for Metals;and ng/L for Mercury)Solid Phase Result(mg/kg for Classicals andMetals and ng/g forMercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)ClassicalsAmmonia 1.6 J,H,P 12 H,P,Est 2.26 F(J, H, P) – S(H, P, Est)Nitrate Nitrite as N 230 H,P,Est 69 H,P,Est 208 F(H, P, Est) – S(H, P, Est)Nitrogen, Total Kjeldahl 25 B,H,P,Est 500 H,P,Est 57.4 F(B, H, P, Est) – S(H, P, Est)Chloride 9,400 H,Est 3,000 H,Est 8,510 F(H, Est) – S(H, Est)Sulfate 11,000 H,Est 29,000 H,Est 11,800 F(H, Est) – S(H, Est)Cyanide, Total 0.19 H,P,Est 0.69 H,P,Est 0.216 F(H, P, Est) – S(H, P, Est)Phosphorus, Total 0.14 B,H,P,Est 250 H,P,Est 17.8 F(B, H, P, Est) – S(H, P, Est)Total MetalsAluminum 32 J 36,000 2,550,000 F(J)Antimony 12 0.24 J 27.6 S(J)Arsenic 14 65 4,610Barium 75 300 B 21,300 S(B)Beryllium 1.9 J 1.9 136 F(J)Boron 380,000 B 400 B 364,000 F(B) – S(B)Cadmium 370 3.8 595Calcium 740,000 86,000 6,730,000Chromium 5.4 J 120 8,490 F(J)Cobalt 320 8.3 869Copper 19 44 3,130Iron ND (200) U 29,000 2,050,000 F(U)Lead ND (2) U 30 B 2,120 F(U) – S(B)Magnesium 6,300,000 18,000 6,830,000

### A-4Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).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 forClassicals and Total Metals, Influent toFGD Wastewater Treatment System, Day 2Analytical Results, Hatfield’s FerryAnalyteAqueous Phase Result(mg/L for Classicals;ug/L for Metals;and ng/L for Mercury)Solid Phase Result(mg/kg for Classicals andMetals and ng/g forMercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)Manganese 89,000 280 98,300Mercury 1,440 19,100 654,000Molybdenum 980 6.8 1,350Nickel 1,100 48 4,360Selenium 1,000 43 3,920Silver ND (2) U 0.12 J 8.49 F(U) – S(J)Sodium 600,000 1,100 607,000Thallium 21 2.5 195Tin ND (200) U 3.2 J 226 F(U) – S(J)Titanium ND (20) U 420 29,700 F(U)Vanadium 60 150 10,700Zinc 1,600 B 250 19,100 F(B)

### A-5Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).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 forClassicals and Total Metals, Influent toFGD Wastewater Treatment System, Day 3Analytical Results, Hatfield’s FerryAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/g forMercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)ClassicalsAmmonia 1.7 J,H,P 11 H,P,Est 2.3 F(J, H, P) – S(H, P, Est)Nitrate Nitrite as N 170 H,P,Est 39 H,P,Est 157 F(H, P, Est) – S(H, P, Est)Nitrogen, Total Kjeldahl 36 B,H,P,Est 83 H,P,Est 38.3 F(B, H, P, Est) – S(H, P, Est)Chloride 8,700 H,Est 1,900 H,Est 8,000 F(H, Est) – S(H, Est)Sulfate 9,300 H,Est 24,000 H,Est 10,100 F(H, Est) – S(H, Est)Cyanide, Total 0.16 H,P,Est 0.73 H,P,Est 0.195 F(H, P, Est) – S(H, P, Est)Phosphorus, Total 0.13 B,H,P,Est 190 H,P,Est 13.3 F(B, H, P, Est) – S(H, P, Est)Total MetalsAluminum ND (200) U 30,000 2,080,000 F(U)Antimony 5.6 0.19 J 18.2 S(J)Arsenic 5.2 31 2,150Barium 77 180 B 12,500 S(B)Beryllium 1.1 J 0.78 54.9 F(J)Boron 320,000 B 280 B 309,000 F(B) – S(B)Cadmium 360 3.8 589Calcium 780,000 130,000 9,700,000Chromium ND (8) U 100 6,920 F(U)Cobalt 360 4.5 637Copper 22 30 2,090Iron 44 J 26,000 1,800,000 F(J)Lead ND (2) U 19 B 1,310 F(U) – S(B)Magnesium 5,500,000 17,000 6,150,000

### A-6Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).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 forClassicals and Total Metals, Influent toFGD Wastewater Treatment System, Day 3Analytical Results, Hatfield’s FerryAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/g forMercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)Manganese 91,000 200 96,200Mercury 1,520 21,900 789,000Molybdenum 400 4.6 680Nickel 1,200 38 3,710Selenium 560 44 3,550Silver ND (2) U 0.097 J 6.71 F(U) – S(J)Sodium 470,000 580 465,000Thallium 11 1.3 99.9Tin ND (200) U 2.1 J 145 F(U) – S(J)Titanium ND (20) U 160 11,100 F(U)Vanadium 28 94 6,530Zinc 1,900 B 210 16,200 F(B)

### A-7Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).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 forClassicals and Total Metals, Influent toFGD Wastewater Treatment System, Day 4Analytical Results, Hatfield’s FerryAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)ClassicalsAmmonia 1.7 J,H,P 15 H,P,Est 2.36 F(J, H, P) – S(H, P, Est)Nitrate Nitrite as N 140 H,P,Est 49 H,P,Est 129 F(H, P, Est) – S(H, P, Est)Nitrogen, Total Kjeldahl 14 B,H,P,Est 620 H,P,Est 47 F(B, H, P, Est) – S(H, P, Est)Chloride 6,800 H,Est 2,200 H,Est 6,250 F(H, Est) – S(H, Est)Sulfate 9,800 H,Est 27,000 H,Est 10,300 F(H, Est) – S(H, Est)Cyanide, Total 0.092 J,H,P 0.96 H,P,Est 0.136 F(J, H, P) – S(H, P, Est)Phosphorus, Total 0.11 B,H,P,Est 1.3 J,H,P 0.171 F(B, H, P, Est) – S(J, H, P)Total MetalsAluminum ND (200) U 36,000 2,000,000 F(U)Antimony 6.6 0.26 J 20.4 S(J)Arsenic 6.8 51 2,830Barium 77 240 B 13,400 S(B)Beryllium 1.8 J 1.3 73.7 F(J)Boron 270,000 B 340 B 262,000 F(B) – S(B)Cadmium 230 4.4 451Calcium 710,000 110,000 6,740,000Chromium 4.7 J 120 6,660 F(J)Cobalt 300 5.9 597Copper 40 39 2,200Iron ND (200) U 32,000 1,770,000 F(U)Lead ND (2) U 25 B 1,390 F(U) – S(B)Magnesium 4,700,000 16,000 5,120,000

### A-8Note: Sample qualifiers denoted with an ‘F( )’ are qualifiersassociated with the filtrate portion of the sample and sample qualifiers denoted with an ‘S( )’ are qualifiers associatedwith the solid portion of the sample.ND – Not detected (number in parentheses is the quantitation limit).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 forClassicals and Total Metals, Influent toFGD Wastewater Treatment System, Day 4Analytical Results, Hatfield’s FerryAnalyteAqueous Phase Result(mg/L for Classicals; ug/Lfor Metals; and ng/L forMercury)Solid Phase Result(mg/kg for Classicalsand Metals and ng/gfor Mercury)Calculated Total Sample Result(mg/L for Classicals; ug/Lfor Metals; and ng/L for Mercury)Manganese 75,000 230 80,400Mercury 1,360 22,300 624,000Molybdenum 450 6.4 760Nickel 990 43 3,280Selenium 460 42 2,740Silver ND (2) U 0.085 J 4.71 F(U) – S(J)Sodium 370,000 720 373,000Thallium 12 1.9 116Tin ND (200) U 2.8 J 155 F(U) – S(J)Titanium ND (20) U 290 16,100 F(U)Vanadium 30 130 7,230Zinc 1,700 B 250 15,400 F(B)

### A-9NA – 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 TreatmentSystem, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassical Pollutants - TotalAmmonia 350.1 mg/L NA 0.44 4.2 2.42Nitrate Nitrite as N 353.2 mg/L NA 0.365 2.4 129Nitrogen, Total Kjeldahl 351.2 mg/L NA 3.66 16.5 45.6Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 3 BChemical Oxygen Demand 410.4 mg/L 2 8.1 40 250 F,G,EstChloride 300.0, 9056 mg/L NA 46.7 552 5,610Sulfate 300.0, 9056 mg/L NA 51.6 1,200 10,400Cyanide, Total 4500 CN E mg/L NA 0.024 0.119 0.103Total Dissolved Solids 2540C mg/L 1 160 330 25,000Total Suspended Solids 2540D mg/L 1 110 400 54,000Phosphorus, Total 365.1 mg/L NA 0.0545 0.345 0.109Classicals Pollutants - Solid (dry weight)Ammonia 350.1 mg/Kg 1 4.1 9.9 15 H,P,EstNitrate Nitrite as N 353.2 mg/Kg 1 0.36 10 34 H,P,EstNitrogen, Total Kjeldahl 351.2 mg/Kg 5 60 250 560 H,P,EstChloride 9056 mg/Kg 5 9.8 150 1,500 H,EstSulfate 9056 mg/Kg 100 170 5,000 27,000 H,EstCyanide, Total 4500 CN E mg/Kg 1 0.1 0.49 0.54 H,P,EstPhosphorus, Total 365.1 mg/Kg 1 0.85 5.1 ND (5.1) U,H,PClassicals Pollutants -Filtered AqueousAmmonia 350.1 mg/L 1 0.22 4 1.7 J,H,PNitrate Nitrite as N 353.2 mg/L 20 0.38 2 140 H,P,EstNitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 14 B,H,P,EstChloride 300.0 mg/L 200 51 600 6,100 H,Est

### A-10NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationSulfate 300.0 mg/L 200 46 1,000 9,700 H,EstCyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.079 J,H,PPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.12 B,H,P,EstMetals - Calculated TotalAluminum 200.7, 6010B ug/L NA 890 5,820 1,760,000Antimony 200.8, 6020 ug/L NA 2.18 23.5 24.1Arsenic 200.8, 6020 ug/L NA 6.55 68.2 2,300Barium 200.7, 6010B ug/L NA 6.55 74.5 13,000Beryllium 200.7, 6010B ug/L NA 2.52 30 59.9Boron 200.7, 6010B ug/L NA 706 10,200 233,000Cadmium 200.8, 6020 ug/L NA 2.08 14.2 425Calcium 200.7, 6010B ug/L NA 8,290 28,600 8,230,000Chromium 200.8, 6020 ug/L NA 11.2 29 6,460Cobalt 200.7, 6010B ug/L NA 6.63 74.5 556Copper 200.8, 6020 ug/L NA 8.5 30.6 1,900Iron 200.7, 6010B ug/L NA 2,200 8,400 1,470,000Lead 200.8, 6020 ug/L NA 2.6 18.3 1,170Magnesium 200.7, 6010B ug/L NA 700 10,200 5,070,000Manganese 200.7, 6010B ug/L NA 17.4 509 71,100Mercury 1631E, FGS-069 ng/L NA 7,090 32,200 521,000Molybdenum 200.7, 6010B ug/L NA 16.1 148 675Nickel 200.8, 6020 ug/L NA 3.51 20.1 2,970Selenium 200.8, 6020 ug/L NA 71.9 279 2,680Silver 200.8, 6020 ug/L NA 2.71 12.4 7.05Sodium 200.7, 6010B ug/L NA 3,510 37,200 377,000

### A-11NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationThallium 200.8, 6020 ug/L NA 0.801 12.4 96.8Tin 200.7, 6010B ug/L NA 56.6 757 141Titanium 200.7, 6010B ug/L NA 9.08 74.5 14,100Vanadium 200.8, 6020 ug/L NA 5.71 63.1 5,900Zinc 200.7, 6010B ug/L NA 30.6 207 15,000Metals - DissolvedAluminum 200.7 ug/L 2 9.4 200 95 JAntimony 200.8 ug/L 2 0.72 2 5.4Arsenic 200.8 ug/L 2 1.2 4 5.2Barium 200.7 ug/L 2 2.5 20 140Beryllium 200.7 ug/L 2 0.71 2 3Boron 200.7 ug/L 50 170 5,000 250,000 BCadmium 200.8 ug/L 2 1.2 4 300Calcium 200.7 ug/L 2 69 400 730,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) UCobalt 200.7 ug/L 2 1.1 20 310Copper 200.8 ug/L 2 0.96 4 14Iron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 4,400,000Manganese 200.7 ug/L 50 13 500 69,000Mercury 1631E ng/L 100 24.8 52 131Molybdenum 200.7 ug/L 2 1.6 40 320Nickel 200.8 ug/L 2 0.89 4 1,000

### A-12NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationSelenium 200.8 ug/L 5 1.6 10 340Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 370,000Thallium 200.8 ug/L 2 0.47 2 20Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 35Zinc 200.7 ug/L 2 9.1 40 2,600Metals - Filtered AqueousAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 5.2Arsenic 200.8 ug/L 2 1.2 4 7.3Barium 200.7 ug/L 2 2.5 20 64Beryllium 200.7 ug/L 2 0.71 2 1.3 JBoron 200.7 ug/L 50 170 5,000 240,000 BCadmium 200.8 ug/L 2 1.2 4 230Calcium 200.7 ug/L 2 69 400 660,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 270Copper 200.8 ug/L 2 0.96 4 23Iron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 4,500,000Manganese 200.7 ug/L 50 13 500 65,000Mercury 1631E ng/L 20,000 5,210 10,900 202,000

### A-13NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMolybdenum 200.7 ug/L 2 1.6 40 350Nickel 200.8 ug/L 2 0.89 4 950Selenium 200.8 ug/L 5 1.6 10 430Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 370,000Thallium 200.8 ug/L 2 0.47 2 9.6Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 27Zinc 200.7 ug/L 2 9.1 40 1,600 BMetals - Solid (dry weight)Aluminum 6010B mg/kg 10 15 96 30,000Antimony 6020 mg/kg 2 0.026 0.37 0.33 JArsenic 6020 mg/kg 2 0.093 1.1 39Barium 6010B mg/kg 1 0.073 0.96 220 BBeryllium 6010B mg/kg 1 0.032 0.48 1Boron 6010B mg/kg 10 9.4 96 270 BCadmium 6020 mg/kg 2 0.017 0.18 3.7Calcium 6010B mg/kg 10 140 480 130,000Chromium 6020 mg/kg 2 0.14 0.37 110Cobalt 6010B mg/kg 1 0.096 0.96 5.3Copper 6020 mg/kg 2 0.13 0.46 32Iron 6010B mg/kg 10 37 140 25,000Lead 6020 mg/kg 2 0.033 0.28 20 BMagnesium 6010B mg/kg 1 3.6 19 17,000

### A-14NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese 6010B mg/kg 1 0.096 0.96 210Mercury FGS-069 ng/g 4,000 73.7 671 10,200Molybdenum 6010B mg/kg 1 0.25 1.9 6.1Nickel 6020 mg/kg 2 0.046 0.28 36Selenium 6020 mg/kg 10 1.2 4.6 39Silver 6020 mg/kg 2 0.037 0.18 0.12 JSodium 6010B mg/kg 1 57 480 720Thallium 6020 mg/kg 2 0.0064 0.18 1.5Tin 6010B mg/kg 1 0.89 9.8 2.4 JTitanium 6010B mg/kg 1 0.13 0.96 240Vanadium 6020 mg/kg 2 0.071 0.92 100Zinc 6010B mg/kg 1 0.38 2.9 230

### A-15NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassical Pollutants - TotalAmmonia 350.1 mg/L NA 0.484 4.22 2.26Nitrate Nitrite as N 353.2 mg/L NA 0.696 4.24 208Nitrogen, Total Kjeldahl 351.2 mg/L NA 2.1 11.5 57.4Biochemical Oxygen Demand 5210B mg/L 1 0.59 5 3.6 JChemical Oxygen Demand 410.4 mg/L 5 20 100 520Chloride 300.0, 9056 mg/L NA 116 1,340 8,510Sulfate 300.0, 9056 mg/L NA 118 2,560 11,800Cyanide, Total 4500 CN E mg/L NA 0.0247 0.124 0.216Total Dissolved Solids 2540C mg/L 1 470 1,000 41,000Total Suspended Solids 2540D mg/L 1 140 500 67,000Phosphorus, Total 365.1 mg/L NA 0.301 1.81 17.8Classicals Pollutants - Solid (dry weight)Ammonia 350.1 mg/Kg 1 4.1 9.8 12 H,P,EstNitrate Nitrite as N 353.2 mg/Kg 1 0.36 10 69 H,P,EstNitrogen, Total Kjeldahl 351.2 mg/Kg 2 25 100 500 H,P,EstChloride 9056 mg/Kg 10 20 300 3,000 H,EstSulfate 9056 mg/Kg 100 170 5,000 29,000 H,EstCyanide, Total 4500 CN E mg/Kg 1 0.1 0.5 0.69 H,P,EstPhosphorus, Total 365.1 mg/Kg 5 4.2 25 250 H,P,EstClassicals Pollutants -Filtered AqueousAmmonia 350.1 mg/L 1 0.22 4 1.6 J,H,PNitrate Nitrite as N 353.2 mg/L 40 0.76 4 230 H,P,EstNitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 25 B,H,P,EstChloride 300.0 mg/L 500 130 1,500 9,400 H,EstSulfate 300.0 mg/L 500 120 2,500 11,000 H,EstCyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.19 H,P,Est

### A-16NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.14 B,H,P,EstMetals - Calculated TotalAluminum 200.7, 6010B ug/L NA 998 6,540 2,550,000Antimony 200.8, 6020 ug/L NA 2.54 29.3 27.6Arsenic 200.8, 6020 ug/L NA 7.99 88.4 4,610Barium 200.7, 6010B ug/L NA 7.01 81.3 21,300Beryllium 200.7, 6010B ug/L NA 2.75 33.6 136Boron 200.7, 6010B ug/L NA 772 10,800 364,000Cadmium 200.8, 6020 ug/L NA 2.33 17 595Calcium 200.7, 6010B ug/L NA 9,250 32,200 6,730,000Chromium 200.8, 6020 ug/L NA 13.5 34.6 8,490Cobalt 200.7, 6010B ug/L NA 7.33 81.3 869Copper 200.8, 6020 ug/L NA 10.7 38.2 3,130Iron 200.7, 6010B ug/L NA 2,430 10,100 2,050,000Lead 200.8, 6020 ug/L NA 3.12 22.3 2,120Magnesium 200.7, 6010B ug/L NA 710 10,100 6,830,000Manganese 200.7, 6010B ug/L NA 17.8 505 98,300Mercury 1631E, FGS-069 ng/L NA 3,170 28,500 654,000Molybdenum 200.7, 6010B ug/L NA 17.7 163 1,350Nickel 200.8, 6020 ug/L NA 4.25 24 4,360Selenium 200.8, 6020 ug/L NA 93.3 355 3,920Silver 200.8, 6020 ug/L NA 3.28 15.2 8.49Sodium 200.7, 6010B ug/L NA 3,910 40,600 607,000Thallium 200.8, 6020 ug/L NA 0.896 15.2 195Tin 200.7, 6010B ug/L NA 60.1 785 226Titanium 200.7, 6010B ug/L NA 10.6 81.3 29,700Vanadium 200.8, 6020 ug/L NA 6.8 77.4 10,700

### A-17NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationZinc 200.7, 6010B ug/L NA 33.5 226 19,100Metals - DissolvedAluminum 200.7 ug/L 2 9.4 200 250Antimony 200.8 ug/L 2 0.72 2 13Arsenic 200.8 ug/L 2 1.2 4 11Barium 200.7 ug/L 2 2.5 20 160Beryllium 200.7 ug/L 2 0.71 2 3.6Boron 200.7 ug/L 50 170 5,000 410,000 BCadmium 200.8 ug/L 2 1.2 4 450Calcium 200.7 ug/L 2 69 400 800,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 370Copper 200.8 ug/L 2 0.96 4 14Iron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 6,300,000Manganese 200.7 ug/L 50 13 500 94,000Mercury 1631E ng/L 100 24.8 52 382Molybdenum 200.7 ug/L 2 1.6 40 960Nickel 200.8 ug/L 2 0.89 4 1,200Selenium 200.8 ug/L 5 1.6 10 1,100Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 590,000Thallium 200.8 ug/L 2 0.47 2 45Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 97

### A-18NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationZinc 200.7 ug/L 2 9.1 40 2,200Metals - Filtered AqueousAluminum 200.7 ug/L 2 9.4 200 32 JAntimony 200.8 ug/L 2 0.72 2 12Arsenic 200.8 ug/L 2 1.2 4 14Barium 200.7 ug/L 2 2.5 20 75Beryllium 200.7 ug/L 2 0.71 2 1.9 JBoron 200.7 ug/L 50 170 5,000 380,000 BCadmium 200.8 ug/L 2 1.2 4 370Calcium 200.7 ug/L 2 69 400 740,000Chromium 200.8 ug/L 2 3.3 8 5.4 JCobalt 200.7 ug/L 2 1.1 20 320Copper 200.8 ug/L 2 0.96 4 19Iron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 6,300,000Manganese 200.7 ug/L 50 13 500 89,000Mercury 1631E ng/L 200 52.1 109 1,440Molybdenum 200.7 ug/L 2 1.6 40 980Nickel 200.8 ug/L 2 0.89 4 1,100Selenium 200.8 ug/L 5 1.6 10 1,000Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 600,000Thallium 200.8 ug/L 2 0.47 2 21Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 60

### A-19NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationZinc 200.7 ug/L 2 9.1 40 1,600 BMetals - Solid (dry weight)Aluminum 6010B mg/kg 10 14 90 36,000Antimony 6020 mg/kg 2 0.027 0.39 0.24 JArsenic 6020 mg/kg 2 0.098 1.2 65Barium 6010B mg/kg 1 0.068 0.9 300 BBeryllium 6010B mg/kg 1 0.03 0.45 1.9Boron 6010B mg/kg 10 8.8 90 400 BCadmium 6020 mg/kg 2 0.018 0.19 3.8Calcium 6010B mg/kg 10 130 450 86,000Chromium 6020 mg/kg 2 0.15 0.39 120Cobalt 6010B mg/kg 1 0.09 0.9 8.3Copper 6020 mg/kg 2 0.14 0.49 44Iron 6010B mg/kg 10 34 140 29,000Lead 6020 mg/kg 2 0.035 0.29 30 BMagnesium 6010B mg/kg 1 3.3 18 18,000Manganese 6010B mg/kg 1 0.09 0.9 280Mercury FGS-069 ng/g 4,000 91.4 832 19,100Molybdenum 6010B mg/kg 1 0.23 1.8 6.8Nickel 6020 mg/kg 2 0.049 0.29 48Selenium 6020 mg/kg 10 1.3 4.9 43Silver 6020 mg/kg 2 0.039 0.19 0.12 JSodium 6010B mg/kg 1 53 450 1,100Thallium 6020 mg/kg 2 0.0068 0.19 2.5Tin 6010B mg/kg 1 0.79 8.6 3.2 JTitanium 6010B mg/kg 1 0.13 0.9 420Vanadium 6020 mg/kg 2 0.075 0.97 150

### A-20NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationZinc 6010B mg/kg 1 0.36 2.7 250

### A-21NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 3 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassical Pollutants - TotalAmmonia 350.1 mg/L NA 0.483 4.31 2.3Nitrate Nitrite as N 353.2 mg/L NA 0.369 2.5 157Nitrogen, Total Kjeldahl 351.2 mg/L NA 1.17 7.84 38.3Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 3.8Chemical Oxygen Demand 410.4 mg/L 5 20 100 350 G,EstChloride 300.0, 9056 mg/L NA 46.8 553 8,000Sulfate 300.0, 9056 mg/L NA 53.4 1,250 10,100Cyanide, Total 4500 CN E mg/L NA 0.025 0.126 0.195Total Dissolved Solids 2540C mg/L 1 240 500 31,000Total Suspended Solids 2540D mg/L 1 280 1,000 66,000Phosphorus, Total 365.1 mg/L NA 0.302 1.84 13.3Classicals Pollutants - Solid (dry weight)Ammonia 350.1 mg/Kg 1 4.1 10 11 H,P,EstNitrate Nitrite as N 353.2 mg/Kg 1 0.36 10 39 H,P,EstNitrogen, Total Kjeldahl 351.2 mg/Kg 1 12 48 83 H,P,EstChloride 9056 mg/Kg 5 9.8 150 1,900 H,EstSulfate 9056 mg/Kg 100 170 5,000 24,000 H,EstCyanide, Total 4500 CN E mg/Kg 1 0.1 0.51 0.73 H,P,EstPhosphorus, Total 365.1 mg/Kg 5 4.3 26 190 H,P,EstClassicals Pollutants -Filtered AqueousAmmonia 350.1 mg/L 1 0.22 4 1.7 J,H,PNitrate Nitrite as N 353.2 mg/L 20 0.38 2 170 H,P,EstNitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 36 B,H,P,EstChloride 300.0 mg/L 200 51 600 8,700 H,EstSulfate 300.0 mg/L 200 46 1,000 9,300 H,Est

### A-22NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 3 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.16 H,P,EstPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.13 B,H,P,EstMetals - Calculated TotalAluminum 200.7, 6010B ug/L NA 1,050 6,960 2,080,000Antimony 200.8, 6020 ug/L NA 2.38 26.7 18.2Arsenic 200.8, 6020 ug/L NA 7.38 79.7 2,150Barium 200.7, 6010B ug/L NA 7.45 85.9 12,500Beryllium 200.7, 6010B ug/L NA 2.86 35.7 54.9Boron 200.7, 6010B ug/L NA 818 11,300 309,000Cadmium 200.8, 6020 ug/L NA 2.26 16.1 589Calcium 200.7, 6010B ug/L NA 9,750 34,300 9,700,000Chromium 200.8, 6020 ug/L NA 12.7 32.1 6,920Cobalt 200.7, 6010B ug/L NA 7.77 85.9 637Copper 200.8, 6020 ug/L NA 9.86 34.7 2,090Iron 200.7, 6010B ug/L NA 2,590 10,600 1,800,000Lead 200.8, 6020 ug/L NA 2.94 20.5 1,310Magnesium 200.7, 6010B ug/L NA 738 10,400 6,150,000Manganese 200.7, 6010B ug/L NA 18.5 520 96,200Mercury 1631E, FGS-069 ng/L NA 3,170 28,600 789,000Molybdenum 200.7, 6010B ug/L NA 18.7 175 680Nickel 200.8, 6020 ug/L NA 3.99 22.3 3,710Selenium 200.8, 6020 ug/L NA 84.4 320 3,550Silver 200.8, 6020 ug/L NA 3.09 14.3 6.71Sodium 200.7, 6010B ug/L NA 4,170 42,900 465,000Thallium 200.8, 6020 ug/L NA 0.861 14.3 99.9Tin 200.7, 6010B ug/L NA 58.3 769 145

### A-23NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 3 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTitanium 200.7, 6010B ug/L NA 11.1 85.9 11,100Vanadium 200.8, 6020 ug/L NA 6.31 71.3 6,530Zinc 200.7, 6010B ug/L NA 35.2 237 16,200Metals - DissolvedAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 5.6Arsenic 200.8 ug/L 2 1.2 4 5.1Barium 200.7 ug/L 2 2.5 20 160Beryllium 200.7 ug/L 2 0.71 2 1.7 JBoron 200.7 ug/L 50 170 5,000 340,000 BCadmium 200.8 ug/L 2 1.2 4 420Calcium 200.7 ug/L 2 69 400 860,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) UCobalt 200.7 ug/L 2 1.1 20 380Copper 200.8 ug/L 2 0.96 4 14Iron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 5,300,000Manganese 200.7 ug/L 50 13 500 96,000Mercury 1631E ng/L 20 4.83 10.1 236Molybdenum 200.7 ug/L 2 1.6 40 360Nickel 200.8 ug/L 2 0.89 4 1,200Selenium 200.8 ug/L 5 1.6 10 350Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 470,000

### A-24NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 3 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationThallium 200.8 ug/L 2 0.47 2 21Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 37Zinc 200.7 ug/L 2 9.1 40 2,400Metals - Filtered AqueousAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 5.6Arsenic 200.8 ug/L 2 1.2 4 5.2Barium 200.7 ug/L 2 2.5 20 77Beryllium 200.7 ug/L 2 0.71 2 1.1 JBoron 200.7 ug/L 50 170 5,000 320,000 BCadmium 200.8 ug/L 2 1.2 4 360Calcium 200.7 ug/L 2 69 400 780,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 360Copper 200.8 ug/L 2 0.96 4 22Iron 200.7 ug/L 2 32 200 44 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 5,500,000Manganese 200.7 ug/L 50 13 500 91,000Mercury 1631E ng/L 200 52.1 109 1,520Molybdenum 200.7 ug/L 2 1.6 40 400Nickel 200.8 ug/L 2 0.89 4 1,200Selenium 200.8 ug/L 5 1.6 10 560Silver 200.8 ug/L 2 0.59 2 ND (2) U

### A-25NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 3 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationSodium 200.7 ug/L 2 180 10,000 470,000Thallium 200.8 ug/L 2 0.47 2 11Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 28Zinc 200.7 ug/L 2 9.1 40 1,900 BMetals - Solid (dry weight)Aluminum 6010B mg/kg 10 15 98 30,000Antimony 6020 mg/kg 2 0.025 0.36 0.19 JArsenic 6020 mg/kg 2 0.091 1.1 31Barium 6010B mg/kg 1 0.075 0.98 180 BBeryllium 6010B mg/kg 1 0.032 0.49 0.78Boron 6010B mg/kg 10 9.6 98 280 BCadmium 6020 mg/kg 2 0.017 0.18 3.8Calcium 6010B mg/kg 10 140 490 130,000Chromium 6020 mg/kg 2 0.14 0.36 100Cobalt 6010B mg/kg 1 0.098 0.98 4.5Copper 6020 mg/kg 2 0.13 0.45 30Iron 6010B mg/kg 10 37 150 26,000Lead 6020 mg/kg 2 0.033 0.27 19 BMagnesium 6010B mg/kg 1 3.6 20 17,000Manganese 6010B mg/kg 1 0.098 0.98 200Mercury FGS-069 ng/g 4,000 87.1 793 21,900Molybdenum 6010B mg/kg 1 0.25 2 4.6Nickel 6020 mg/kg 2 0.046 0.27 38Selenium 6020 mg/kg 10 1.2 4.5 44

### A-26NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 3 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationSilver 6020 mg/kg 2 0.037 0.18 0.097 JSodium 6010B mg/kg 1 58 490 580Thallium 6020 mg/kg 2 0.0063 0.18 1.3Tin 6010B mg/kg 1 0.78 8.5 2.1 JTitanium 6010B mg/kg 1 0.14 0.98 160Vanadium 6020 mg/kg 2 0.069 0.9 94Zinc 6010B mg/kg 1 0.39 2.9 210

### A-27NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassical Pollutants - TotalAmmonia 350.1 mg/L NA 0.426 4.15 2.36Nitrate Nitrite as N 353.2 mg/L NA 0.362 2.36 129Nitrogen, Total Kjeldahl 351.2 mg/L NA 3.57 16.2 47Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 2.5Chemical Oxygen Demand 410.4 mg/L 2 8.1 40 280 G,EstChloride 300.0, 9056 mg/L NA 46.5 549 6,250Sulfate 300.0, 9056 mg/L NA 50.9 1,180 10,300Cyanide, Total 4500 CN E mg/L NA 0.0236 0.117 0.136Total Dissolved Solids 2540C mg/L 1 240 500 26,000Total Suspended Solids 2540D mg/L 1 92 330 47,000Phosphorus, Total 365.1 mg/L NA 0.05 0.322 0.171Classicals Pollutants - Solid (dry weight)Ammonia 350.1 mg/Kg 1 4.1 9.9 15 H,P,EstNitrate Nitrite as N 353.2 mg/Kg 1 0.36 10 49 H,P,EstNitrogen, Total Kjeldahl 351.2 mg/Kg 5 62 260 620 H,P,EstChloride 9056 mg/Kg 5 9.8 150 2,200 H,EstSulfate 9056 mg/Kg 100 170 5,000 27,000 H,EstCyanide, Total 4500 CN E mg/Kg 1 0.1 0.49 0.96 H,P,EstPhosphorus, Total 365.1 mg/Kg 1 0.82 5 1.3 J,H,PClassicals Pollutants -Filtered AqueousAmmonia 350.1 mg/L 1 0.22 4 1.7 J,H,P

### A-28NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationNitrate Nitrite as N 353.2 mg/L 20 0.38 2 140 H,P,EstNitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 14 B,H,P,EstChloride 300.0 mg/L 200 51 600 6,800 H,EstSulfate 300.0 mg/L 200 46 1,000 9,800 H,EstCyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.092 J,H,PPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.11 B,H,P,EstMetals - Calculated TotalAluminum 200.7, 6010B ug/L NA 785 5,060 2,000,000Antimony 200.8, 6020 ug/L NA 2.03 21.2 20.4Arsenic 200.8, 6020 ug/L NA 6.02 64.6 2,830Barium 200.7, 6010B ug/L NA 5.97 66.8 13,400Beryllium 200.7, 6010B ug/L NA 2.25 26.2 73.7Boron 200.7, 6010B ug/L NA 630 9,390 262,000Cadmium 200.8, 6020 ug/L NA 1.97 13.6 451Calcium 200.7, 6010B ug/L NA 6,710 24,800 6,740,000Chromium 200.8, 6020 ug/L NA 10.2 26.6 6,660Cobalt 200.7, 6010B ug/L NA 5.87 66.8 597Copper 200.8, 6020 ug/L NA 7.52 28 2,200Iron 200.7, 6010B ug/L NA 1,860 7,390 1,770,000Lead 200.8, 6020 ug/L NA 2.43 16.2 1,390Magnesium 200.7, 6010B ug/L NA 664 10,000 5,120,000Manganese 200.7, 6010B ug/L NA 16.6 499 80,400

### A-29NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMercury 1631E, FGS-069 ng/L NA 2,810 25,300 624,000Molybdenum 200.7, 6010B ug/L NA 14.2 136 760Nickel 200.8, 6020 ug/L NA 3.24 18 3,280Selenium 200.8, 6020 ug/L NA 68 253 2,740Silver 200.8, 6020 ug/L NA 2.53 11.8 4.71Sodium 200.7, 6010B ug/L NA 3,040 33,400 373,000Thallium 200.8, 6020 ug/L NA 0.767 11.8 116Tin 200.7, 6010B ug/L NA 47.6 651 155Titanium 200.7, 6010B ug/L NA 8.09 66.8 16,100Vanadium 200.8, 6020 ug/L NA 5.3 57.8 7,230Zinc 200.7, 6010B ug/L NA 27.6 180 15,400Metals - DissolvedAluminum 200.7 ug/L 2 9.4 200 82 JAntimony 200.8 ug/L 2 0.72 2 6.3Arsenic 200.8 ug/L 2 1.2 4 7.7Barium 200.7 ug/L 2 2.5 20 160Beryllium 200.7 ug/L 2 0.71 2 3.1Boron 200.7 ug/L 50 170 5,000 290,000 BCadmium 200.8 ug/L 2 1.2 4 290Calcium 200.7 ug/L 2 69 400 780,000Chromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 5 1.96 10 ND (10) U

### A-30NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationCobalt 200.7 ug/L 2 1.1 20 330Copper 200.8 ug/L 2 0.96 4 11Iron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 4,800,000Manganese 200.7 ug/L 50 13 500 82,000Mercury 1631E ng/L 20 4.97 10.4 187Molybdenum 200.7 ug/L 2 1.6 40 420Nickel 200.8 ug/L 2 0.89 4 1,100Selenium 200.8 ug/L 5 1.6 10 400Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 360,000Thallium 200.8 ug/L 2 0.47 2 24Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 45Zinc 200.7 ug/L 2 9.1 40 2,100Metals - Filtered AqueousAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 6.6Arsenic 200.8 ug/L 2 1.2 4 6.8Barium 200.7 ug/L 2 2.5 20 77

### A-31NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationBeryllium 200.7 ug/L 2 0.71 2 1.8 JBoron 200.7 ug/L 50 170 5,000 270,000 BCadmium 200.8 ug/L 2 1.2 4 230Calcium 200.7 ug/L 2 69 400 710,000Chromium 200.8 ug/L 2 3.3 8 4.7 JCobalt 200.7 ug/L 2 1.1 20 300Copper 200.8 ug/L 2 0.96 4 40Iron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 4,700,000Manganese 200.7 ug/L 50 13 500 75,000Mercury 1631E ng/L 200 52.1 109 1,360Molybdenum 200.7 ug/L 2 1.6 40 450Nickel 200.8 ug/L 2 0.89 4 990Selenium 200.8 ug/L 5 1.6 10 460Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 370,000Thallium 200.8 ug/L 2 0.47 2 12Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 30Zinc 200.7 ug/L 2 9.1 40 1,700 B

### A-32NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMetals - Solid (dry weight)Aluminum 6010B mg/kg 10 14 88 36,000Antimony 6020 mg/kg 2 0.025 0.35 0.26 JArsenic 6020 mg/kg 2 0.089 1.1 51Barium 6010B mg/kg 1 0.067 0.88 240 BBeryllium 6010B mg/kg 1 0.029 0.44 1.3Boron 6010B mg/kg 10 8.6 88 340 BCadmium 6020 mg/kg 2 0.016 0.18 4.4Calcium 6010B mg/kg 10 120 440 110,000Chromium 6020 mg/kg 2 0.13 0.35 120Cobalt 6010B mg/kg 1 0.088 0.88 5.9Copper 6020 mg/kg 2 0.12 0.44 39Iron 6010B mg/kg 10 33 130 32,000Lead 6020 mg/kg 2 0.032 0.26 25 BMagnesium 6010B mg/kg 1 3.2 18 16,000Manganese 6010B mg/kg 1 0.088 0.88 230Mercury FGS-069 ng/g 4,000 99.1 902 22,300Molybdenum 6010B mg/kg 1 0.23 1.8 6.4Nickel 6020 mg/kg 2 0.044 0.26 43Selenium 6020 mg/kg 10 1.2 4.4 42Silver 6020 mg/kg 2 0.036 0.18 0.085 JSodium 6010B mg/kg 1 52 440 720

### A-33NA – Not applicable. Total results is based on calculated result from solid and aqueous phases.ND – Not detected (number in parentheses is the quantitation limit).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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationThallium 6020 mg/kg 2 0.0062 0.18 1.9Tin 6010B mg/kg 1 0.78 8.5 2.8 JTitanium 6010B mg/kg 1 0.12 0.88 290Vanadium 6020 mg/kg 2 0.068 0.88 130Zinc 6010B mg/kg 1 0.35 2.6 250

### A-34ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-9. Effluent from FGD Wastewater TreatmentSystem, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 0.78 J,BNitrate Nitrite as N 353.2 mg/L 20 0.38 2 130Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 19Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 ND (2) UChemical Oxygen Demand 410.4 mg/L 2 8.1 40 240Chloride 300.0 mg/L 200 51 600 6,500Sulfate 300.0 mg/L 200 46 1,000 5,800Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.11Total Dissolved Solids 2540C mg/L 1 94 200 16,000Total Suspended Solids 2540D mg/L 1 1.1 4 1.2 JPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.067 BTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 7.4Arsenic 200.8 ug/L 2 1.2 4 5.4Barium 200.7 ug/L 2 2.5 20 100Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 180,000 B,4Cadmium 200.8 ug/L 2 1.2 4 5.6Calcium 200.7 ug/L 50 1,700 10,000 1,200,000 B,4Chromium 200.8 ug/L 2 3.3 8 11Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 1.2 JIron 200.7 ug/L 2 32 200 200 B,FLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,800,000 B,4Manganese 200.7 ug/L 2 0.51 20 2,400 B,4Mercury 1631E ng/L 20 4.78 10 35.3

### A-35ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-9. Effluent from FGD Wastewater TreatmentSystem, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationMolybdenum 200.7 ug/L 2 1.6 40 430Nickel 200.8 ug/L 2 0.89 4 6.5Selenium 200.8 ug/L 5 1.6 10 570 4Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 410,000 4Thallium 200.8 ug/L 2 0.47 2 7Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 27 BZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 6.9Arsenic 200.8 ug/L 2 1.2 4 5.1Barium 200.7 ug/L 2 2.5 20 100 FBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 190,000 B,4Cadmium 200.8 ug/L 2 1.2 4 4.6Calcium 200.7 ug/L 50 1,700 10,000 1,200,000 4Chromium 200.8 ug/L 2 3.3 8 8.5Chromium (VI) 218.6 ug/L 1 0.39 2 4.08Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 1.6 JIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 3,000,000 4Manganese 200.7 ug/L 2 0.51 20 2,400 4Mercury 1631E ng/L 1 0.24 0.5 0.24 JMolybdenum 200.7 ug/L 2 1.6 40 430

### A-36ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-9. Effluent from FGD Wastewater TreatmentSystem, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationNickel 200.8 ug/L 2 0.89 4 5.3Selenium 200.8 ug/L 5 1.6 10 610 4Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 410,000 4Thallium 200.8 ug/L 2 0.47 2 7.5Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 26Zinc 200.7 ug/L 2 9.1 40 ND (40) U

### A-37ND – 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 TreatmentSystem, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 0.98 J,BNitrate Nitrite as N 353.2 mg/L 20 0.38 2 140Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 16Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 1.7 JChemical Oxygen Demand 410.4 mg/L 2 8.1 40 240Chloride 300.0 mg/L 200 51 600 6,700Sulfate 300.0 mg/L 100 23 500 5,000Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.18Total Dissolved Solids 2540C mg/L 1 94 200 16,000Total Suspended Solids 2540D mg/L 1 1.1 4 1.6 JPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.23 BTotal MetalsAluminum 200.7 ug/L 2 9.4 200 81 J,BAntimony 200.8 ug/L 2 0.72 2 8.2Arsenic 200.8 ug/L 2 1.2 4 4.6Barium 200.7 ug/L 2 2.5 20 120Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 190,000 BCadmium 200.8 ug/L 2 1.2 4 7Calcium 200.7 ug/L 50 1,700 10,000 1,400,000 BChromium 200.8 ug/L 2 3.3 8 11Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 2.4 JIron 200.7 ug/L 2 32 200 160 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,900,000 BManganese 200.7 ug/L 2 0.51 20 1,900 BMercury 1631E ng/L 20 4.97 10.4 46.4Molybdenum 200.7 ug/L 2 1.6 40 420Nickel 200.8 ug/L 2 0.89 4 4.5

### A-38ND – 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 TreatmentSystem, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationSelenium 200.8 ug/L 5 1.6 10 540Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 420,000Thallium 200.8 ug/L 2 0.47 2 7.4Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 23 BZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 7.5Arsenic 200.8 ug/L 2 1.2 4 4.3Barium 200.7 ug/L 2 2.5 20 120Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 190,000 BCadmium 200.8 ug/L 2 1.2 4 7.2Calcium 200.7 ug/L 50 1,700 10,000 1,400,000Chromium 200.8 ug/L 2 3.3 8 9.1Chromium (VI) 218.6 ug/L 1 0.39 2 3.93Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 2.9 JIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,900,000Manganese 200.7 ug/L 2 0.51 20 1,900Mercury 1631E ng/L 5 1.24 2.6 7.6Molybdenum 200.7 ug/L 2 1.6 40 430Nickel 200.8 ug/L 2 0.89 4 4Selenium 200.8 ug/L 5 1.6 10 560Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 400,000

### A-39ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-10. Effluent from FGD Wastewater TreatmentSystem, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationThallium 200.8 ug/L 2 0.47 2 7.1Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 22Zinc 200.7 ug/L 2 9.1 40 14 J

### A-40ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-11. Effluent from FGD Wastewater TreatmentSystem, Day 3 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 1.1Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 140Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 19Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 2 JChemical Oxygen Demand 410.4 mg/L 2 8.1 40 230Chloride 300.0 mg/L 200 51 600 6,900Sulfate 300.0 mg/L 100 23 500 4,800Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.24Total Dissolved Solids 2540C mg/L 1 94 200 14,000Total Suspended Solids 2540D mg/L 1 1.1 4 2 JPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.063 BTotal MetalsAluminum 200.7 ug/L 2 9.4 200 26 J,BAntimony 200.8 ug/L 2 0.72 2 8.6Arsenic 200.8 ug/L 2 1.2 4 6Barium 200.7 ug/L 2 2.5 20 130Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 190,000 BCadmium 200.8 ug/L 2 1.2 4 8.7Calcium 200.7 ug/L 50 1,700 10,000 1,400,000 BChromium 200.8 ug/L 2 3.3 8 11Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 2.8 JIron 200.7 ug/L 2 32 200 190 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,800,000 BManganese 200.7 ug/L 2 0.51 20 2,000 BMercury 1631E ng/L 20 4.97 10.4 31.8Molybdenum 200.7 ug/L 2 1.6 40 450Nickel 200.8 ug/L 2 0.89 4 4.7

### A-41ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-11. Effluent from FGD Wastewater TreatmentSystem, Day 3 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationSelenium 200.8 ug/L 5 1.6 10 580Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 400,000Thallium 200.8 ug/L 2 0.47 2 8.2Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 30 BZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 7.7Arsenic 200.8 ug/L 2 1.2 4 5.9Barium 200.7 ug/L 2 2.5 20 130Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 170,000 BCadmium 200.8 ug/L 2 1.2 4 9.7Calcium 200.7 ug/L 50 1,700 10,000 1,500,000Chromium 200.8 ug/L 2 3.3 8 10Chromium (VI) 218.6 ug/L 1 0.39 2 3.7Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 2.7 JIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,900,000Manganese 200.7 ug/L 2 0.51 20 2,000Mercury 1631E ng/L 10 2.48 5.2 8.9Molybdenum 200.7 ug/L 2 1.6 40 470Nickel 200.8 ug/L 2 0.89 4 5.3Selenium 200.8 ug/L 5 1.6 10 620Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 420,000

### A-42ND – 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 TreatmentSystem, Day 3 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationThallium 200.8 ug/L 2 0.47 2 8.6Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 29Zinc 200.7 ug/L 2 9.1 40 ND (40) U

### A-43ND – 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 laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 1Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 130Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 17 4Biochemical Oxygen Demand 5210Bmg/L 1 0.3 2.5 2.6 *,MinChemical Oxygen Demand 410.4 mg/L 2 8.1 40 230 FChloride 300.0 mg/L 200 51 600 6,500Sulfate 300.0 mg/L 200 46 1,000 5,500Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.17 FTotal Dissolved Solids 2540C mg/L 1 94 200 15,000 D,EstTotal Suspended Solids 2540D mg/L 1 1.1 4 4 D,EstPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.036 J,B,FTotal MetalsAluminum 200.7 ug/L 2 9.4 200 48 J,BAntimony 200.8 ug/L 2 0.72 2 8.8Arsenic 200.8 ug/L 2 1.2 4 7.6Barium 200.7 ug/L 2 2.5 20 110Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 190,000 B,4Cadmium 200.8 ug/L 2 1.2 4 8.7Calcium 200.7 ug/L 50 1,700 10,000 1,200,000 B,4Chromium 200.8 ug/L 2 3.3 8 10Cobalt 200.7 ug/L 2 1.1 20 2.1 JCopper 200.8 ug/L 2 0.96 4 2.5 JIron 200.7 ug/L 2 32 200 180 J,BLead 200.8 ug/L 2 0.73 2 ND (2) U

### A-44ND – 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 laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationMagnesium 200.7 ug/L 50 540 10,000 3,000,000 B,4Manganese 200.7 ug/L 2 0.51 20 6,400 B,4Mercury 1631E ng/L 20 4.97 10.4 37Molybdenum 200.7 ug/L 2 1.6 40 460Nickel 200.8 ug/L 2 0.89 4 13Selenium 200.8 ug/L 5 1.6 10 620 4Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 380,000 4Thallium 200.8 ug/L 2 0.47 2 7.8Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 5 4.2 25 47 BZinc 200.7 ug/L 2 9.1 40 9.1 JDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 7.9Arsenic 200.8 ug/L 2 1.2 4 8.6Barium 200.7 ug/L 2 2.5 20 100 FBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 190,000 B,4Cadmium 200.8 ug/L 2 1.2 4 7.8Calcium 200.7 ug/L 50 1,700 10,000 1,200,000 4Chromium 200.8 ug/L 2 3.3 8 8.6Chromium (VI) 218.6 ug/L 1 0.39 2 2.96Cobalt 200.7 ug/L 2 1.1 20 1.4 JCopper 200.8 ug/L 2 0.96 4 2.5 J

### A-45ND – 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 laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.D – Laboratory duplicate RPD greater than method-specified criteria.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.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 TreatmentSystem, Day 4 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,800,000 4Manganese 200.7 ug/L 2 0.51 20 6,200 4Mercury 1631E ng/L 10 2.48 5.2 16.5Molybdenum 200.7 ug/L 2 1.6 40 450Nickel 200.8 ug/L 2 0.89 4 13Selenium 200.8 ug/L 5 1.6 10 630 4Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 370,000 4Thallium 200.8 ug/L 2 0.47 2 7.6Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 44Zinc 200.7 ug/L 2 9.1 40 ND (40) U

### A-46Table A-13. Duplicate of Effluent from FGD Wastewater Treatment System, Day 2 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 20 4.97 10.4 30.3Dissolved MetalsMercury 1631E ng/L 5 1.24 2.6 8.35

### A-47ND – 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, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 1.1Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 140Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 16Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 2 JChemical Oxygen Demand 410.4 mg/L 2 8.1 40 230Chloride 300.0 mg/L 200 51 600 6,500Sulfate 300.0 mg/L 100 23 500 4,600Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.15 FTotal Dissolved Solids 2540C mg/L 1 94 200 11,000Total Suspended Solids 2540D mg/L 1 1.1 4 2 JPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.061 BTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 8.7Arsenic 200.8 ug/L 2 1.2 4 6.8Barium 200.7 ug/L 2 2.5 20 130Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 180,000 BCadmium 200.8 ug/L 2 1.2 4 8.6Calcium 200.7 ug/L 50 1,700 10,000 1,400,000 BChromium 200.8 ug/L 2 3.3 8 10Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 2.8 JIron 200.7 ug/L 2 32 200 78 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,800,000 BManganese 200.7 ug/L 2 0.51 20 2,100 BMolybdenum 200.7 ug/L 2 1.6 40 480Nickel 200.8 ug/L 2 0.89 4 5.2

### A-48ND – 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, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationSelenium 200.8 ug/L 5 1.6 10 610Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 430,000Thallium 200.8 ug/L 2 0.47 2 8.9Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 30 BZinc 200.7 ug/L 2 9.1 40 ND (40) UDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 8.5Arsenic 200.8 ug/L 2 1.2 4 6.6Barium 200.7 ug/L 2 2.5 20 130Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 180,000 BCadmium 200.8 ug/L 2 1.2 4 8.5Calcium 200.7 ug/L 50 1,700 10,000 1,400,000Chromium 200.8 ug/L 2 3.3 8 9.5Chromium (VI) 218.6 ug/L 1 0.39 2 4.02Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 3.4 JIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 2,700,000Manganese 200.7 ug/L 2 0.51 20 2,000Molybdenum 200.7 ug/L 2 1.6 40 460Nickel 200.8 ug/L 2 0.89 4 5Selenium 200.8 ug/L 5 1.6 10 620Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 410,000

### A-49ND – 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, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationThallium 200.8 ug/L 2 0.47 2 8.8Tin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 30Zinc 200.7 ug/L 2 9.1 40 ND (40) Ua 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 Reco verable ug/L ND (0.040)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Copper EPA 1638 Total Recoverable ug/L ND (0.10)a Aluminum was detected in 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 Reco verable ug/L ND (0.040)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Aluminum 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-sp litter, and two pieces of 5 feet of #24 silicone tubing for sample collect ion for mercury and metals from sample taps)

Aluminum EPA 1638 Total Recoverable ug/L 5.3 a

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)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 Blan k (Three feet of Teflon® tubing, 10 feet of #73 silicone tubing, Ysplitter, and two pieces of 5 feet of #24 silicone tubing for total and di ssolved sample collection for metals)

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

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

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

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

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

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

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

Calcium EPA 1638 Total Recoverable ug/L 40 b

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

T-Splitter Tubing Set – Equipment Blank (Ten feet of #7 3 silicone tubing, T-splitter, six feet of #73 silicone tubing, and 15 feet of #73 silicone tubing for total and dissolved sample collect ion for metal composites)

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

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)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 Reco verable ug/L ND (0.040)

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

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

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

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

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

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

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

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

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

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

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

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

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

### A-55ND – 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 SystemField Blank, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 100 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 140 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 2.6 JIron 200.7 ug/L 2 32 200 180 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 19 J,BMercury 1631E ng/L 1 0.24 0.5 1.69Molybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 ND (10,000) UThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 3.8 J,BVanadium 200.8 ug/L 2 1.7 10 2.4 J,BZinc 200.7 ug/L 2 9.1 40 10 JDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 11 JAntimony 200.8 ug/L 2 0.72 2 ND (2) U

### A-56ND – 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 SystemField Blank, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 31 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 1 0.39 2 ND (2) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 1.8 JIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 33 JManganese 200.7 ug/L 2 0.51 20 1.1 JMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 ND (10,000) UThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 ND (40) U

### A-57ND – 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 SystemField Blank, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 95 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 140 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 130 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 19 J,BMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 620 JThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 3.3 J,BVanadium 200.8 ug/L 2 1.7 10 2.9 J,BZinc 200.7 ug/L 2 9.1 40 11 JDissolved MetalsAluminum 200.7 ug/L 2 9.4 200 39 JAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) U

### A-58ND – 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 SystemField Blank, Day 1 Analytical Results, Hatfield’s FerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 38 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UChromium (VI) 218.6 ug/L 1 0.39 2 ND (2) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 36 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 45 JManganese 200.7 ug/L 2 0.51 20 1.8 JMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 230 JThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 12 JTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 ND (40) U

### A-59ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-18. Effluent from FGD Wastewater Treatment System Field Blank, Day 2 Analytical Results, Hatfield’sFerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

### A-60ND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-19. Effluent from FGD Wastewater Treatment System Field Blank, Day 3 Analytical Results, Hatfield’sFerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

### A-61ND – 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, Hatfield’sFerryAnalyteMethodUnitsDilution FactorSample-Specific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

### Appendix B

DATA REVIEW NARRATIVES

### 1 

## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD Deb Bartram, ERG TJ Finseth, ERG

From: Donna Tedder, ERG

Date: 9 / 1/2011 Subject: FGS Data R eview Narrative for Total & Diss olved Mercury

– Episode 6564

Frontier Global Sciences (FGS) generated analytical data for total and dissolved mercury.
T he samples were analyzed according to E PA Method 1631E for total mercury by Cold Vapor Atomic Fluorescence Spectrometry (CVA

- FS) analy sis.

Table 1 summarizes the 27 s amples (excluding laboratory filter blanks) FG S extracted and analyzed for total and dissolved mercury

.

Table 1. 

### EPA Episode 6564 Total & Dissolved Mercury

– Sample Identification

EPA Sample # Lab Sample

ID # Sample

M atrix 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 /201 0 1/7/2011

71942 1012070

- 03 Aqueous FGD Inf luent, Day 2 12/ 7 /2010 1/6/2011

71942 1012070

- 04 Aqueous Dissolved FGD In fluent, Day 2 12/ 7 /2010 1/6/2011

71942 1012070

- 13 Solid FGD Influent, Day 2 (Solid s ) 12/ 7 /2010 1/ 7 /2011

71943 1012100

- 03 Aqueous FGD In f luent, Day 3 12/ 8 /2010 1/6/2011

71943 1012100

- 04 Aqueous Dissolved FGD Influent, Day 3 12/ 8 /2010 12/2 3 /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 101 2110

- 05 Aqueous Dissolved FGD Influent, Day 4 12/9/2010 12/2 8 /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 Ef fluent, 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

71 9 48 1012120

- 06 Aqueous FGD Effluent, Day 4 12/9/2010 12/28/2010

71 9 48 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

M atrix 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 In fluent Field Blank

, Day 1 12/6/2010 12/22/2010

71951 1012060

- 06 Aqueous FGD Effluent Field Blank, Day 1 12/6/201 0 12/22/2010

71952 1012070

- 07 Aqueous FGD Effluent Field Blank, Day 2 12/ 7 /2010 12/22/2010

71953 1012100

- 11 Aqueous F GD Effluent Field Blank , Day 3 12/ 8 /2010 12/2 3 /2010

71954 1012110

- 08 Aqueous FGD Ef fluent Field Blank , Day 4 12/9/2010 12/28/2010



### SUMM ARY

The samples were prepared according to EPA Method 1631 E 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 qua lifiers in this

dataset.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no s ample receipt issues in this data package

.

I NITIAL CAL IBRATION

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

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

coefficient ≥0.995

. All method specified criteria were met.

INITIAL AND C ONTINUING C ALIBRATION V ERIFICATION S

All initial and c ontinuing c alib ration v erifications ( ICVs, CCVs ) met method

- specified

criteria

.

BLANK S

All instrument and preparation blanks met method s pecified criteria. Preparation Blanks

F0 12184

- BLK 1, F0 12184

- BLK 5, F0 12215

- BLK 5, F0 12215

– BLK 6, F0 12243

– BLK 6,

F 101058

– BLK 1, F 101058

– BLK 4, and F 101058

- BLK 5 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 bla nk 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 f ield duplicate

, Sample 71949 w a s collected on the S ample 71 9 46

. 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%.

L aboratory duplicates were performed on samples 71941

, 71 9 4 1 ( solid )

, 71 9 4 2, and

71 9 4 7. 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 t he 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, 71 9 4 1 ( solid ) , 71 9 4 2, and 71 9 4 7 for the total mercury analyse s

. MS and MSDs were performed on sample 71947 for the dissolved mercury analyse s. All aqueous MS/MSD recoveries were within method specifications of 70

- 125%

. All RPDs met

method

- specified criteria

.

Two sets of M S / MSD w ere performed on the solid sample 71941 f rom this episode.

MS/MSD1 did not me e t 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

- specifie d 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 R eview Narrative for Total and Dissolved Metals by 200.8

– Episode 65 64

Test America generated analytical data for total and dissolved metals ( antimony, arsenic, cadmium, chromium, copper, lead, nickel, selenium, silver, thallium and v anadium ) for Sample Episode 6564

. T he samples were analyzed according to EPA Method 200.8

.

Tabl e 1 summarizes the samples Test America 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

– S olid 280

- 10453

- 3 Solid 12/06/2010 12/07/2010

71941 FGD Influent, Day 1

– F iltrate 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

– S olid 280

- 10513

- 4 Solid 12/07/2010 12/08/2010

71942 FGD Influent, Day 2

– F iltrate 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

– S olid 280

- 10583

- 3 Solid 12/08/2010 12/09/2010

71943 FGD Influent, Day 3

– F iltrate 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

- S olid 280

- 10656

- 4 Solid 12/09/2010 12/10/2010

71944 FGD Influent, Day 4

- F iltrate 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

– D uplicate 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 ph ase 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 STANDARDIZA TION

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

### 3 INITIAL CALIBRATION

Test America performed the initial calibrations on each analysis day

. The initial

calibration for the ICP

- MS analysis consisted of a blank and four calibration standards

.

I NITIAL 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 BLANK S

All the m ethod b lanks were less than the r eporting l imit ; however, some elements were above the MDL and flagged with a “J” qualifier

. No additiona l qualifiers were required

for m eth od b lanks.

All i nstrument b lanks ( ICB and CCB) were less tha n the r eporting l imit ; however, some elements were above the MDL and flagged with a “J” qualifier. No additional qua lifiers were required for i nstrument b lanks.

REPORTING LIMIT VERIFICATION STANDARD ( CRI )

A ll CRI samples passed Test America’s SOP control limits of 50

– 150%.

LABORATORY CONTROL SAMPLE S (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 che ck sample B (ICSAB) synthetic s pikes 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 71 945 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 l imits and were flagged with a “4” qualifier indicating concentration s in the parent sample s were greater than four times the spike amount s

. Otherwise, the MS/MSD spike recoveries were always within the control limits of 70

- 13 0 % with the exception of

total and dissolved s ilver 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 tot al silver for 71945. The poor recoveries and RPD of s ilver ar e probably due to high sulfates in this episode’s samples t hat could form insoluble silver sulfide and/or

silver s ulfate.

POST DIGESITON SPIKE S

PDSs were performed on sample 71945 FGD Ef fluent, Day 1 (280

- 10513

- 2 PD S ) and the

solid and aqueous sample of 71944 FGD Influent, Day 4 (280

- 10656

- 4 PDS ; 280

- 10656

- 5 PDS respectively ). Total and dissolved s ilver fail ed Test America’s aqueous control

limits of 8 5

– 11 5% 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 s ilver ar e probably due to high sulfates in this episode’s sam ples that could form insoluble silver sulfide and/or silver s ulfate. The

aqueous s ample 71944 also failed Test America’s 85

- 115% control limits for total

cadm ium and total nickel, which were flagged “W”.

D ETECTION 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 R eview Narrative for Total and Dissolved Metals by 200.7

– Episode 65 64

Test America generated analytical data for total and dissolved metals ( aluminum, boron, barium, beryllium, calcium, cobalt, iron, magnesium, manganese, molybdenum, sodium, tin, titanium

, and z inc)

. T he samples were analyzed according to EPA Method 200. 7

.

Table 1 summarizes the s ample s Test America extracted and analy zed 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

7 1941 FGD Influent, Day 1

– Solid 280

- 10453

- 3 Solid 12/06/2010 12/07/2010

7 1941 FGD Influent, Day 1

- Filtrate 280

- 10453

- 4 Aqueous 12/06/2010 12/07/2010

7 1942 FGD Influent, Day 2 280

- 10513

- 1 Aqueous 12/07 /2010 12/ 08 /2010

7 1942 FGD Influent, Day 2

– Solid 280

- 10513

- 4 Solid 12/07 /2010 12/ 08 /2010

7 1942 FGD Influent, Day 2

– Filtrate 28 0

- 10513

- 5 Aqueous 12/07 /2010 12/ 08 /2010

71943 FGD Influent , Day 3 2 80

- 10583

- 1 Aqueous 12/08 /2010 12/ 0 9 /2010

7 1943 FGD Influent, Day 3

– S olid 280

- 10583

- 3 Solid 12/08 /2010 12/ 0 9 /2010

7 1943 FGD Influent, Day 3

– F iltrate 280

- 10583

- 4 Aqueous 12/08 /2010 12/ 0 9 /2010

7 1944 FGD Influent

, Day 4 280

- 10656

- 1 Aqueous 12/ 0 9 /2010 12 /1 0 /2010

71944 FGD Influent

, Day 4

– Solid 280

- 10656

- 4 Solid 12/ 0 9 /2010 12 /1 0 /2010

71944 FGD Influent

, Day 4

- Filtrate 280

- 10656

- 5 Aqueous 12/ 0 9 /2010 12 /1 0 /2010

7 1945 FGD Effluent, Day 1 280

- 10513

- 2 Aqueous 12/07 /2010 12/ 08 /2010

7 1946 FGD Effluent, Day 2 280

- 10583

- 2 Aqueous 12/08 /2010 12/ 0 9 /2010

71947 FGD Effluent, Day 3 280

- 10656

- 2 Aqueous 12/ 0 9 /2010 12 /1 0 /2010

71948 FGD Effluent, Day 4 280

- 10724

- 1 Aqueous 12/10 /2010 12 /1 1 /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

7 1951 FGD Effluent Filed Blank

, Day 1 280

- 10513

- 3 Aqueous 12/07 /2010 12/ 08 /2010

71955 FGD Ef fluent

– D uplicate 280

- 10656

- 3 Aqueous 12/ 0 9 /2010 12 /1 0 /2010



### SUMMARY

The sample s were prepared for total and dissolved metals analysis according to

Test America’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 soli d 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 sample s 71945 and 71948 failed TestAmerica’s SOP control limits of ±20%.

• The post digestion spikes (PDS) for total barium for sample 71 945 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 crite ria of 85

– 115%.

SAMPLE RECEIPT, HANDLING, AND STORAGE

There were no issues associated with receipt, handling and storage.

### 3 INTERNAL STANDARDIZA TION

While the internal standard (ISTD) Yttrium was used for these analyses, no checks on the ISTD recoveries in the ±30% criterion of the calibration blank as per Section 9.11 of the

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

I NITIAL CAL IBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial

calibration for the ICP analysis consisted of a blank and one calibration standard.

I NITIAL AND CONTINUING CALIBRATION VERIFICATION S

The initial c alibration v erifications (ICV) and c ontinuing c alibration v erifications (CCV) performed by Test America all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANK S

All the m ethod b lanks were less than the r eporting l imit ; however, some had levels above

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

All i nstrument b lanks ( ICB and CCB) were less than the r eporting l imit; 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 SOLUTION S

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 sodi um 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 a nd 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 RPD s 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 sample s 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 tha t 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 d issolved barium for both the MS and MSD for sample s 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

. N o 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.

D ETECTION LIMITS

The laboratory performed an MDL study in the synthetic FGD wastewater matrix, instead of reagent water.

### 1 

## MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

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

Deb Bartram

, ERG

TJ Finseth

, ERG

From: Donna Tedder, ERG

Date: 9 / 1 /201 1 Subject: FGS Data R eview Narrative for Dissolved Hexavalent Chromium

– Episode

65 6 4

Frontier Global Sciences (FGS) generated analytical data for dissolved hexavalent

chromium for Sample Episode 6564

. T he samples were analyzed according to a

m odified EPA Method 2 18. 6 for dissolved hexavalent chromium by Liquid Chromatography

– Inductively Coupled Plasma Mass Spectrometry (LC

- ICP

- MS)

.

Table 1 summarizes the s amples 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

71 9 4 1 Aqueous FGD Influent Day 1 12 / 6 / 10 1 2 / 29 /10

7 1943 Aqueous FGD Influent Day 3 12/8/10 12/29/10

7 1944 Aqueous FGD Influent Day 4 12/9/10 12/29/10

7 1945 Aqueous FGD Effluent Day 1 12/7/10 12/29/10

7 1946 Aqueous FGD Effluent Day 2 12/8/10 12/29/10

71947 Aqueous FGD Effluent Day 3 12/9/10 12/29/10

7 1950 Aqueous FGD In fluent Field Blank Day 1 12/6/10 12/29/10

71951 Aqueous FGD Effluent Field Blank Day 1 12/7/10 12/29/10

7 1955 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

. S amples 71 9 4 1, 71 9 4 3, and 71 9 4 4 were diluted prior to analysis due to the presence of high levels of nontarget chloride interferences

. T here were no issues requiring additional

data qualifiers for the hexavalent chromium data in this episode.

### 2 SAMPLE REC E IPT, HANDLING, AND STORAGE ISSUES

The collection date and time were not recorded on the chain of custody for s ample s 71945 and 71951

.

I NITIAL P RECISION AND ACCURACY/ R ECOVERY

The initial precision and recovery ( IPR ) performed by FGS had recoveries within the

method criteria.

I NITIAL CAL IBRATION

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

the LC

- ICP

- MS analysis consisted of a blank and eight calibration standards with a

correlation factor ≥ 0.995 as re quired by the method

.

A secondary source initial calibration verification (ICV) was analyzed and passed ± 10 %

of true value required by the analytical method

.

C ONTINUING C ALIBRATION V ERIFICATION

All CCVs met method

- specified criteria

, ± 10% of true value with recoveries ranging

from 9 4.9 to 95.5 %.

BLANK

All of the prep aration blanks /laboratory reagent blanks (LRBs) and the continuing calibration blanks (CCBs) met method

- specified requirements

.

OTHER CHECKS

The l aboratory c ontrol s ample /duplicate (LCS /LCSD ) or laboratory fortified

blank /duplicate (LFB /LFBD ) passed method criteria of ± 10% of true value with

recoveries of 96 % and 95 %

. The method suggested that a second source quality control sample (QCS) must be analyzed by the laborator y at least once a quarter. The second

source ICV meets this recommendation

.

D ETECTION 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 w as collected and analyzed. Sample 719 55

, was a duplicate of

effluent sample 719 47

, with an RPD of 8 %.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The M S and matrix spike duplicate ( MSD ) were performed using a secondary source spike on sample 71 9 48

. Two set of MS/MSD were performed at two different

concentration levels. The MS/MSD 1 (spiked at 50 ug /L) r ecoveries were within criteria,

9 2

. 5 % and 91.0 %, with an RPD of 1.59 %. The MS/MSD 2 (spiked at 250 ug/L)

r ecoveries were within criteria

, 96. 2 % and 9 6

. 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 / 20 11 Subject: TestAmerica Data Review Narrative for Cla ssicals Analyses

– Episode 65 64

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry analyses for Sample Episode 65 64

. All samples were tested for the following analytes:

• Ammonia by EPA method 350.1,

• Biochemical Oxygen De mand

– 5 day (BOD 5 

### ) by SM 5210B,

• Chloride and S ulfate by EPA method 300.0,

• Chemical Oxygen Demand (COD) by EPA method 410.4,

• Cyanide (total) by SM 4500 CN - 

### E,

• Nitrate/ Nitrite by EPA method 353.2

• Phosphorus (total) by EPA method 365.1,

• Total D issolved S olids (TDS) by SM 2540C,

• Total K jeldakl N itrogen (TKN) by EPA method 351 .2

, and

• Total S uspended S olids (TSS) by SM 2540D

.

The TSS concentration of the influent samples was greater than one percent, so as requested

, the laboratory separated the solid an d liquid portions of the samples and

a nalyzed both portion s separately for the following analytes :

• Ammonia,

• Chloride

• Cyanide,

• Nitrate/Nitrite,

• Phosphorus,

• Sulfate, and

• TKN.

Table 1 summarizes the nine field sampl es analyzed by TestAmerica and partic ularly highlights how the laboratory split and analyzed the influent samples

.

### 2 Table 1. EPA Episode 65 6 4 Classical Analytes

– Sample Identification

EPA Sample # Sample Description Sampling

Date Sample

Matrix Portion of Sample Analytes

719 41 FGD Influen t, Day 1 12/06 /10 Water Entire

Fraction BOD 5 

### , 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

719 42 FGD Influent, Day 2 12/07 /10 Water Entire

Fraction BOD 5 

### , 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

719 43 FGD Influent, Day 3 12/08 /10 Water Entire

Fraction BOD 5 

### , 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

719 44 FGD Influent, Day 4 12/09 /10 Water Entire

Fraction BOD 5 

### , 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

719 45 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

719 46 FGD Effluent, Day 2 12/08 /10 Water Entire

Fraction All analytes

719 47 FGD Effluent, Day 3 12/09 /10 Water Entire

Fraction All analytes

719 48 FGD Ef fluent, 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 analyt e. The r elative

p ercent d ifference (RPD) between the sample and its duplicate was less than 20% unless

otherwise noted below.

If applicab le, the appropriate number of standards was used to create a calibration curve. If sample results were above the high est standard used to create the curve, the sample was diluted and reanalyzed. All sample results were between t he lowest and highest standards

unless noted below. Additionally, all calibration blanks and calibration verification samples met the criteria sp ecified 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 det ected 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 c riteria specified in the method unless specified

below

.

If required by the method, a matrix spike (M S) analysis was run on sample 71 948 (FGD

effluent ) for each analyte to check for matrix interferences

. For some analytes,

TestAmerica s piked 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 71 9 41

- 71 9 44 were not preserved immediately after sample collection. Ins tead

, 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 n eed to further qualify these samples. The solid aliquot

of s amples 71941

- 71944 were qualified as estimated value s because the samples were not preserved immediately following sample collection

.

The filtrate and solid aliquots of sample s 71 9 41 , 71 9 42, 71 9 43, and 71 9 44 were analyzed 9, 8, 7, and 6 day s , 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 s ample 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.

BOD 5



### TestAmerica analyzed five dilutions, but no dilutions had a dissolved oxygen (DO) depletion greater than 2.0 mg/L for sample 71 945

. Therefore, BOD 5 

### was reported as not

detect ed for th is sample

. The rest of the samples had at least one dilution with a DO depletion greater than 2.0 mg/L. As required in the method, the final result was calculated by taking the average of the results for all dilutions with a DO depletion greater than 2.0 mg/L and a final DO greater than 1.0 mg /L.

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 th ese blank results, sample 71 9 4 1 was qualified with a “B” meaning the analyte was detected in the sample and the blank.

The glucose

- glutamic acid (GGA) s tandards associated with sample 71948 h ad percent

recover ies of 8 4% and 86 %

. The perce nt recovery of the first GGA standard was below

the meth od and laboratory criteria of 85

- 115%. TestAmerica flagged sample 71948 with a “*” meaning the laboratory control sample was not within laboratory control limits. Sample 71 94 8 w as additionally qualifi ed as a minimum value.

### 5 Chloride and Sulfate

Solid aliquots of samples 71941, 71942, 71943, and 71944 were analyzed 9, 8, 7, and 6

d ays, respectively, after the 28

- day hold time. Additionally, f iltrate aliquots of samples
71941, 71942, 71943, and 71944 we r e 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 sample s for 71 941 and 71948 by 200 , but the

diluted result s for sulfate and chloride w e re still above the highest calibration standard. The laboratory did not reanalyze these sample s with a higher dilution factor, because the

MS and MSD percent recover ies w ere within the control limits specified by EPA method 300.0. Therefore, if the MS and MSD result s for sample 71 941 for chloride and sulfate

are reported, they will be qualified as estimated value s

. The results for samples 71941 and 71948 were within the calibration range, so there was no need to qualify these samples. The LFB associated wit h sample 71941 and 71948 met the method criteria.

COD

Sample s 71941, 71943, and 71944 were preserved to pH less than 2 S.U. after sample collection. However, when the laboratory received the sample s
, the p H was neutral. The sample s w ere preserved again b y the laboratory. These samples were qualified as

estimated values.

T he percent recoveries for the MS and MSD samples associated with 71 948 were 93%

and 79%

, respectively. Only the MS sample was within the control limits of 90

- 11 0% specified in the meth od. 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 m eaning 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.

T he 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 specifi ed 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 met hod criteria.

### 6 Cyanide

As stated above, filtrate and solid aliquots of samples 71 941

- 719 44 were not preserved immediately after sample collection. Instead

, TestAmerica preserved the sample after phase separation. Filtrate aliquots of samples 71 9 41 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 71 9 41

- 71 9 44 were not preserved immediately following sample collection as required by the method, these samples were qualified as estimated values.

Solid and filtrate aliquots of s ample s 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 qu alification was

necessary.

All aqueous samples w ere 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 t o be diluted. T he diluted result s for the filtrate aliquot of sample s 71 941 and 71944 w ere less than the lowe st calibration

standard. However , these samples were already qualified by the laboratory with a “J” meaning the sample result was an estimated valu e 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 laborator y control criteria of 90

- 110%. Additionally, t he 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 d uplicate 71 9 55 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 aliqu ots of samples 71 9 41

- 71 9 44 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 metho d, these samples were qualified as estimated

values.

### 7 The filtrate and solid aliquots of s amples 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 esti mated 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 stan dard. The samples were not diluted and reanalyzed because the percent recoveries were within the control limits spe cified in the

method. If the MS and MSD results are reported, they will be qualified as estimated

values. The result for sample 71948 was wit hin 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 71 9 41

- 71 9 44 were not preserved immediately after sample collection. Instead

, TestAmerica preserved the sample after phase separation. The solid aliquot of sample 719 44 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 t here wa s 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 719 42 and 71943 and filtrate samples 71941

- 71944 were qualified as esti mated values because they were not preserved immediately following sample collection as required by the method

.

Filtrate and solid aliquots of s amples 71941, 71942, 71943, and 71944 were analyzed 10, 9, 8, and 7 days, respectively, past the 28

- day ho ld ti me. These samples were not
detect ed

, 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, p hosphorus was detected at 0.0103 mg/L in

the LRB associated with sample s 71945, 71946, 71 947, 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 anal ys e s 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 71 948 was already qualified by the laboratory with a “J” meaning the sample

result was an estimated value beca use 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 l aboratory 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 thr ee 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 d uplicate 71 9 55 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 71 941

- 71 9 44 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 qua lified 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 p reserved 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 th e RL (1.0 mg/L) , no samples were qualified based on th is LRB result.

TestAmerica preformed MS and MSD analysis on sample 71 948 . T he percent recoveries

for the MS and MSD samples were 77% and 76 %. The samples d id not meet the method

control limits of 90

- 11 0% , 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 71 9 48 was not qualified because it is not possible to

determine if the MS and MSD failure s w ere a result of matrix interferences or the low spiking level. The LFB associated with sample 71948 met the method criteria.

### 9 TSS

Two laboratory du plicates were anal yzed for TSS . The RPD for sample 71941 and its duplicate was less than 10% as required by the method ; h owever, 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

Detecte d 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

co llection. 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 method

specified criteria 2.6 mg/L

71941 (solid) Chloride H, Estimate d

Value Analyze d 9 days past holding time. 1,500 mg/Kg 71942 (solid) Chloride H, Estimate d

Value Analyzed 8 days past holding time. 3,000 mg/Kg 71943 (solid) Chloride H, Estimate d

Value Analyzed 7 days past holding time. 1,900 mg/Kg 71944 (solid) Chloride H, Estimate d

Value Analyzed 6 days past holding time. 2,200 mg/Kg 71941 (filtrate) Chloride H, Estimate d

Value Analyzed 8 days past holding time. 6,100 mg/L

71942 (filtrate) Chloride H, Estimate d

Value Analyzed 7 days past holding time. 9,400 mg/L

71943 (filtrate) Chloride H, Estimate d

Value Analyzed 6 days past holding time. 8,700 mg/L

### 11 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detecte d 71944 (filtrate) Chloride H, Estimate d

Value Analyzed 5 days past holding time. 6,800 mg/L

71941 (solid) Sulfate H, Estimate d

Value Analyzed 9 days past holding time. 27,000 mg/Kg 71942 (solid) Sulfate H, Estimate d

Value Analyzed 8 days past holding time. 29,000 mg/Kg 71943 (solid) Sulfate H, Estimate d

Value Analyzed 7 days past holding time. 24,000 mg/Kg 71944 (solid) Sulfate H, Estimate d

Value Analyzed 6 days past holding time. 27,000 mg/Kg 71941 (filtrate) Sulfate H, Estimate d

Value Analyzed 8 days past holding time. 9,700 mg/L

71942 (filtrate) Sulfate H, Estimate d

Value Analyzed 7 days past holding time. 11,000 mg/L 71943 (filtrate) Sulfate H, Estimate d

Value Analyzed 6 day s past holding time. 9,300 mg/L

71944 (filtrate) Sulfate H, Estimate d

Value Analyzed 5 days past holding time. 9,800 mg/L

71941 COD Estimated Value pH upon receipt > 2

S.U. , MS % recovery

below method

specified criteria 250 mg/L

71943 COD Estimated Val ue 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 (fi ltrate) 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 h olding

time. 0.54 mg/Kg

### 12 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detecte d 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

col lection. 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 (soli d) 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 day s 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

Detecte d 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) Nitrat e/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

col lection. 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 Sampl e 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

Detecte d 71944 (filtrate) Phosphorus H, Estimated

Value Sample not preserved immediately following

collection. Analyzed 7 days past holding

time. 0.11 mg/L

71948 TDS Es timated Value Laboratory duplicate

RPD > method

specified 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

Detecte d 71943 (filtrate) TKN H, Estimated

Value Sample not preserved immediately following

collection. Analyzed 8 days pa st 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 > method

specified criteria 4.0 mg/L

### Appendix C

FGD ICP/MS SOP: I NDUCTIVELY 

### C OUPLED 

### P LASMA 

### M ASS 

### S PECTROMETRY FOR 

### T RACE


### E LEMENT 

### A NALYSIS IN 

### F LUE 

### G AS 

### D ESULFURIZATION 

### W ASTEWATERS

### C-1 

## FGD ICP/MS SOP: Inductively Co upled Plasma Mass Spectrometry for Trace Element Analysis in Flue Gas Desulfurization Wastewaters

1.0 Scope and Application

1.1 This document describes procedures used to measure elements in Flue Gas Desulfurization, FGD, wastewaters. Inductively coupled plasma-mass spectrometry (ICP/MS), as described in EPA Methods 200.8 and 1638, was used with a collision cell to mitigate the effects of interferences in the samples. These procedures are intended for use by analysts experienced with applying ICP/MS to complex wastewater samples.

1.2 These procedures are applicable to the analysis of acid digested FGD wastewater, and have been evaluated for the analysis of 13 elements of interest. These are Al, As, Cd, Cr, Cu, Pb, Mn, Ni, Se, Ag, Tl, V and Zn. Additional elements may be included provided that the performance criteria presented in
Sections 9 and 12 are met.

1.3 Flue Gas Desulfurization wastewaters frequently have very high levels of calcium, sodium, magnesium, manganese, chloride and sulfate (up to thousands of ppm). The use of instrument configurations and/or accessories designed to accommodate samples with high dissolved solids levels is highly recommended.

2.0 Summary

2.1 Aqueous samples, digestates, or leachates are nebulized into a spray chamber where a stream of argon carries the sample aerosol through the quartz torch and injects it into an RF plasma. There the sample is decomposed and desolvated.

2.2 The ions produced are entrained in the plasma gas and by means of a watercooled, differentially pumped interface, introduced into a high-vacuum chamber that houses a quadrupole mass spectrometer capable of providing a resolution better than or equal to 0.9 amu peak width at 10% of the peak height. The ions are separated according to their mass-to-charge ratio and measured with a detector, such as an electron multiplier.

2.3 A collision/reaction cell utilizing He and (optionally) H 2 gases is used to remove

molecular interferences.

2.4 Interferences not eliminated by the collision/reaction cell must be assessed and valid corrections applied, or the data flagged to indicate problems. Interference correction must include compensation for interferences not removed by the collision / reaction cell. Recommended elemental equations are listed in Attachment 1. Use of the internal standard technique is required to compensate for suppressions and enhancements caused by sample matrices.

3.0 Definitions

3.1 Batch – A group of samples which behave similarly with respect to the sampling or the testing procedures being employed and which are processed as a unit. For QC purposes, if the number of samples in a group is greater than 20, then each group of 20 samples or less will all be handled as a separate batch

### 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 78 Se, which can be avoided by using argon free of krypton.

4.2 Isobaric Molecular Isobaric molecular interferences are caused by ions consisting of more than one atom. These molecular interferences are minimized by use of the collision cell utilizing He and/or H 2 gases. Common examples are potential interferences from

40 Ar 35 Cl or 40 Ca 35 Cl on 75 As, or 35 Cl 16 O on 51 V, or 40 Ar 12 C on 52 Cr. Collision cell interference removal works both by causing the interfering molecular ion to dissociate and by reducing the kinetic energy of the ion. The latter is termed Kinetic Energy Discrimination (KED), and is the primary mechanism for interference removal. Polyatomic ions are larger than elemental ions and so collide with the helium atoms in the collision cell more frequently than the smaller elemental ions. Each collision reduces the energy of the ion, so the molecular ions lose energy more quickly. At the end of the collision cell a positive voltage plate prevents passage of the now low energy molecular ions. Thus, the

interference is eliminated because the molecular ions do not reach the detector.

4.3 Doubly Charged Ion Interferences

Doubly charged elemental ions are possible in cases where the second ionization potential of the element is significantly below the fist ionization potential for argon (15.7eV). If a doubly charged ion is formed, it will cause a response at half of its elemental mass, potentially causing an interference. Fortunately, most elements have high enough second ionization potentials that formation of doubly charged ions is not an issue. For the target analytes in this procedure, a significant potential for interference is from 150 Nd and 150 Dy (potential interference on 75 As and from 156 Gd (potential interference on 78 Se). To check for these potential interferences, monitor the response for mass 150 and 156. If the cps for these masses is > 5 times the cps for the quantitation limit for arsenic (in the case of mass 150) or selenium (in the case of mass 156) an interference is possible. In this case analyze a 100ppb standard of Nd and Dy (if mass 150 is observed) or Gd (if mass 156 is observed) and measure the response at 150 and 75 (or 156 and 78). This ratio can then be used to create an interference correction equation. For example, if the response for a 100ppb Gd standard at mass 156 is 10,000 cps, and the observed response for the same standard at mass 78 is 1,000 counts, then the equation for 78 Se would be:

78 Se = 78 Se – ( 156 Gd/10)

4.4 Physical Interferences

 Physical interferences are associated with the transport and nebulization process. Internal standards are used to compensate for these types of

interferences.

 Internal standards should be added at a level to give approximately 50,000 - 800,000 counts of raw signal intensity. The mass of the internal standard should ideally be within 50 amu of the mass of the measured

### 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 thathave 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 hazardou s; it is corrosive, reactive, an oxidizer, and a poison. I nhalation of vapors can cause breathing difficulties and lead to pneumonia and pulmonary edema, which may be fatal. Other symptoms may include coughing, choking, and irritation of the nose, throat, and respiratory tract. Can cause redness, pain, and severe skin burns. Concentrated solutions cause deep ulcers and stain skin a yellow or yellow-brown color. Vapors are irritating and may cause damage to the eyes. Contact may cause severe burns and permanent eye damage.

Material (1)

Hazards Exposure Limit (2) Signs and Symptoms of Exposure

Hydrochloric

Acid Corrosive

Poison 5 ppmCeiling Inhalation of vapors can cause coughing, choking, inflammation of the nose, thr oat, and upper respiratory tract, and in severe cases, pulmonary edema, circulatory failure, and death. Can cause redness, pain, and severe skin burns. Vapors are irritating and may cause damage to the eyes. Contact may cause severe burns and permanent eye damage.

1 – Always add acid to water to prevent violent reactions. 2 – Exposure limit refers to the OSHA regulatory exposure limit.

6.0 Equipment and Supplies

6.1 Instrumentation

 Inductively Coupled Plasma Mass Spectrometer (ICP/MS) capable of providing resolution, less than or equal to 0.9 amu at 10% peak height from 6-253 amu and 1.0 amu at 5% peak height from 6-253 amu with a data system that allows corrections for isobaric interferences and the application of the internal standard technique. The ICP/MS must be equipped with a collisio n cell for the removal of molecular interferences. This procedure was developed using an Agilent 7500 or 7700 instrument equipped with a high matrix interface. The interface extends the amounts of total dissolved solids that may be measured into the percent concentration range. Any collision cell instrumentation that meets the specifications in this procedure may be used.

 A discrete sample introduction system enables the use of only the exact amount of sample volume required for data acquisition.

 Accessories and configuration that are designed to accommodate samples with high levels of dissolved solids should be used.

 This sampling system results in less matrix being deposited in the system during analysis and minimizes the rinse times normally needed for difficult

matrices.

 Autosampler with autosampler tubes.

 Appropriate water cooling device.

 Block digester with tubes.

### 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. HNO 3 and 0.5
mL of conc. HCl in the flask.

 Swirl to mix.

 Pipet 0.1mL of the Tuning Solution Stock into the flask.

 Dilute to volume with reagent water. Stopper and mix.

7.2.2 PA Tuning Solution

The dual detector solution may be commercially purchased as a custom

multi-element mix.

Prepare the PA Tuning Solution as detailed below.

 Add approximately 50 mL of the 2% HNO 3 / 0.5% HCl to a 100

mL volumetric flask.

 Prepare at a concentration recommended by the instrument
manufacturer.

### 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% HNO 3 and 0.5 % HCl acid to the concentrations shown

in Attachment 8.

7.2.7 Continuing Calibration Verification (CCV) Standard

The CCV is prepared from the same source as the calibration standards. The CCV standards are prepared fresh each day of analysis
in 2% HNO 3 /0.5% HCl. The concentrations are shown in Attachment 8.

Prepare the Working CCV as detailed below.

 Dilute by 2X a known volume of the Working Calibration
Standard in the 2% HNO 3 / 0.5% HCl acid matrix.

7.2.8 Spiking Stock Solution

The spike stock solution is prepared from the same stocks as the calibration standards using the 2% HNO 3 / 0.5% HCl acid matrix. Spike

concentrations are listed in Attachment 8.

7.3 Reagents

7.3.1 Reagent Water - ASTM Type I or equivalent for the elements of interest, generated using an ion-exchange water polishing system capable of achieving 18.0 megohm-cm.

7.3.2 Blank Matrix 2% HNO 3 and 0.5% HCl.

8.0 Sample Collection, Preservation, Shipment and Storage

Sample container, preservation techniques and holding times may vary and are dependent on sample matrix, method of choice, regulatory compliance, and/or specific contract or client requests. Listed below are the holding times and the references that include preservation requirements.

Matrix Sample
Container Min. Sample
Size Preservation Holding Time Reference

Waters HDPE 50 mLs HNO 3 , pH < 2 180 Days 40 CFR Part 136.3

Soils Glass or

HDPE 4 oz Cool 4 + 2 o C 180 Days N/A

9.0 Quality Control

9.1 Quality control requirements are also summarized in Attachment 7.

9.2 Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of

### 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 Zn 64 48.6%; Zn 66 27.9%;

Zn 67 4.1%; Zn 68 18.8%; Zn 70 0.6%. The measured ratios are not expected to be exact, especially for low abundance isotopes, and some isotope may be masked by other elements in the solution, (for example Zn 70 in the above example will be masked by Ge 70 ) but it must be possible to explain the observed ratios. Because Arsenic, Manganese and Aluminum are monoisotopic, this demonstration is not possible and the level of interference observed must be less than the reporting limit

. 9.4 Synthetic FGD interference check solution The synthetic FGD matrix solution listed in section 7.2.7 is analyzed prior to initiating sample analysis, and at least once per day (immediately after calibration) while FGD wastewaters are being analyzed, and after any major changes to instrument operating conditions. Internal standard recovery must meet method criteria (Section 9.9) and concentrations of target elements observed should be less than their reporting limits. In some cases it may not be possible to obtain interference check solutions that are completely free of contamination. In this case, results up to 5X the reporting limit are acceptable if it is possible to demonstrate that the isotopic ratios correspond to natural abundances. For example, the natural abundances of zinc isotopes are Zn 64

48.6%; Zn 66 27.9%; Zn 67 4.1%; Zn 68 18.8%; Zn 70 0.6%. The measured ratios are not expected to be exact, and some isotopes may be masked by other elements in the solution, (for example Zn 70 in the above example will be masked by Ge 70 ) but it must be possible to explain the observed ratios. Because Arsenic, Manganese and Aluminum are monoisotopic, this demonstration is not possible, and the level of interference observed must be less than the reporting limit. If the Synthetic FGD solution has to be diluted in order to analyze it effectively on the ICP/MS, then all samples and QC (including the MDL replicates) must be diluted by at least the same factor.

9.4.1 Laboratory fortified Synthetic FGD solution The synthetic FGD solution is spiked with 40ppb of each of the target elements (400ppb for zinc and 4000ppb for aluminum) and analyzed once per day, immediately after the synthetic FGD check in section 9.4. All target elements must be recovered within 70-130% of the true value. If the Laboratory Fortified Synthetic FGD solution has to be diluted in order to analyze it effectively on the ICP/MS, then all samples and QC (including the MDL replicates) must be diluted by at least

the same factor.

### 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 85 o C.

10.2.8 Heat for 2 hours after 85 o C is obtained.

10.2.9 Remove from the block and allow to cool.

10.3 Calibration

10.3.1 Instrument Start Up Set up the instrument according to manufacturer’s operating instructions. Allow the instrument to become thermally stable for at least 30 minutes before tuning.

10.3.2 Instrument Tuning / Mass Calibration

Tune the instrument with a solution containing elements representing all of the mass regions of interest. The relative standard deviations must be less than 5% for a minimum of 4 integrations of the solution. Mass calibration and resolution checks using the tuning solution must be completed at the beginning of every day.

Mass Calibration Check – The mass calibration results must be within
0.1 amu from the true value. If this criterion is not met, the mass calibration must be adjusted before running samples.
Mass Resolution Check - The resolution must be verified to be less than 0.9 amu full width at 10% peak height.

10.3.3 Mass 75 interference check The concentration determined for arsenic (mass 75) must be less than 0.25 x the reporting limit when the blank matrix (2% nitric acid / 0.5% hydrochloric acid) is infused (using the collision gas mode used for arsenic).

10.3.4 Initial Calibration The ICP/MS is calibrated each day of operation using a blank and at least 3 standards (see Section 7.2.3). Report the average of at least three integrations.

### 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 Value True LCS Value Found LRB

- Value Found LCS %       

 R

% 100 Value True ICV Value Found ICV %       

 R

% 100 Value True CCV Value Found CCV %       

 R

% 100 SA SR

- SSR %       

 R

### 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 g/L) ( Result V D V C  

 



### Where: C = Concentration from instrument readout, ppb

D = Instrument dilution factor V1 = Final volume in liters after sample preparation V2 = Initial volume of sample digested in liters

12.0 Method Performance

12.1 Method Detection Limit Study (MDL) An initial method detection limit study must be performed on each instrument before samples can be analyzed. MDL studies are conducted annually as

follows:

 Prepare seven samples at three to five times the estimated MDL concentration. The MDL samples are prepared in the Synthetic FGD wastewater matrix and in reagent water.

 Prepare and analyze the MDL standards as described in Section 10.

 Calculate the average concentration found in μg/L, and the standard deviation of the concentration(s) in μg/L, for each analyte.

 The MDL is calculated as Students t for the 99 th percentile times the standard deviation of the MDL replicate results, following the procedure at 40CFR Part 136, Appendix B.

NOTE1: Perform the MDL study in the synthetic FGD wastewater matrix. Spiking this matrix provides detection limits that are better matched to the complex matrix typical of FGD wastewater. These limits can be significantly higher than those obtained in a reagent water matrix. In some cases (zinc in particular), the level of contamination in the synthetic FGD solution may be high enough to result in somewhat elevated MDLs.

NOTE2: An FGD-MDL may be less than the MDL observed in method blanks. If this occurs frequently, the FGD-MDL 

##   100 2 1 2 1 / 2 1 /

  
 

 
 

 

 DU DU DU 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, Calibrati on 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 us ed as an internal standard for low mass elements.

Attachment 2: Internal Standards and Corresponding Metals

Internal Std. Associated elements 1,2

Sc Na, Mg, Al, K, Ca, V, Cr, Mn

Ge Fe, Ni, Cu, Zn, As, Se

In Ag, Cd

Ho Tl, Pb

Footnote: (1) Na, Mg, K, Ca and Fe are included in the synthetic FGD wastewater but their analytical determination is optional – the in terferences caused by these elements are more important than the determination of their exact concentration. (2) Other internal standards may be used. For example, 6 Li, Ga, Rh, Bi, Ho and Tb may be

considered for use as internal standards.

### C-20 Attachment 3: Sample Preservation and Holding Times

Measurement

Parameter Container (1) Preservative (2) Maximum Holding Time (3)

Waters:

Metals (4) P,G HNO 3 to pH < 2 6 months

Soils/Sediments/Wastes:

The preservation required for soil/sediment/waste sa mples is maintenance at 4°C ( ± 2°C) until digestion.

Footnotes : (1) Polyethylene (P) or glass (G). (2) Sample preservation is performed by the sampler immediately upon sample collection or shipped to the laboratory unpreserved for preservation at the laboratory. (3) Samples must be analyzed as soon as possible after collection. The times listed are the maximum times that sample may be held before analysis and still considered valid. Holding times are calcu lated from the date when the sample

was collected. (4) Samples are filtered immediately on-site by the sampler before adding preservative for dissolved elements.

### 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 (H 2 )

107 Silver He

23 Sodium No gas or He

205 Thallium No gas or He

51 Vanadium He

66 Zinc He

NOTE : It is strongly recommended that elements other than those of interest be monitored to indicate other potential molecular interferences which could affect the data quality.

### 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 calib ration solution at the above levels. Levels may be adjusted to meet specific requirements.

####