# Appendix C

Duke Energy’s Miami Fort Station

## Section 1

CWA 308 Monitoring Letter and Instructions

### Enclosure 1

Instructions for Sample Collection, Packaging, and Shipment

EPA Sampling Program

The samples you will be collecting are very important. The samples will be used by the U.S. Environmental Protection Agency (EPA) for revising th e effluent limitations guidelines and standards for the Steam Electric Power Gen erating Industry.

These instructions are being provided to Duke Energy’s Miami F ort Station to aid in collecting, packaging, and shipping samples for this sampling pr ogram.

The plant must collect grab samples for all analytes a t the influent to the FGD wastewater treatment sampling point and 24-hour composite samples for all analytes except mercury and cyanide at the effluent from the FGD wastewater tre atment sampling point. At the FGD wastewater treatment effluent, the plant must co llect cyanide as a single grab sample and mercury must be collected as four individual grab samples over the 24-hour period (i.e., a grab sample collected every six hours).

Samples will be collected once a month for four month s. The samples should be collected and shipped to the laboratories according to the schedule provided in the cover letter of this request. If the plant has any questions re garding the timeline or the steps provided, please contact Mr. Ronald Jordan at (202) 566-1003 or j ordan.ronald@epa.gov.

Equipment Needed

The plant will need to obtain the following equipment to collect, pack, and ship the samples to the laboratories:

• Sample bottles, composite containers, and tubing sets (spe cially-cleaned according to EPA Method 1669);

• Automatic compositor;

• Powder-free gloves;

• Tyvek® coveralls or suitable alternative;

• Dust masks (for use while collecting mercury samples)

• Labels (for sample bottles and shipping samples to labora tories);

• Preservation supplies (see the “Sample Bottles and Pr eservation” Section);

• Coolers;

• Garbage bags;

• Packing material;

• Strapping tape; and

• Traffic Report (will be provided by ERG).

### Sampling Points

The plant must collect samples once per month for four months, based on the schedule specified in the letter. Samples are to be collected fr om each of the two sampling points included in the EPA’s sampling episode. Figure 1 identifies e ach of the sampling points for this sampling program. The following is a description o f the two sampling points:

• 

### FGD wastewater treatment influent (FGD scrubber purge) (SP-1) : This sampling point shall represent the FGD purge stream (e.g., hydroclone overflow) transferred to the FGD wastewater treatment system pri or to any commingling with other wastewaters or treatment system recycle s treams. This sample should be collected from the sample tap on the pipe that flow s from the secondary hydroclone overflow to the equalization tank, which is lo cated on top of the equalization tank. NOTE: the plant must collect secondar y hydroclone overflow from Unit 7 for two of the sample sets and secondary hydr oclone overflow from Unit 8 for two of the sample sets.

• 

### FGD wastewater treatment effluent (SP-2) : This sampling point shall represent the effluent from the FGD wastewater treatment syste m, prior to mixing with dilution water or other streams. This sampling point shou ld be collected from sample tap that is located on the suction side of the pum p that transfers the wastewater from the effluent tank to the ash pond.

Analytes

The analytes included in this sampling program include all ana lytes from EPA’s sampling program, except for the dissolved metals analyses (which includes hexavalent chromium). Table 1 contains the listing of all the an alytes included in the monitoring program, as well as the analytical methods that will be used to analyze the samples.

### Table 1. Analytes and Analytical Methods Included in the Moni toring Program

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 Metals Total mercury EPA 1631E Antimony, arsenic, cadmium, chromium, copper, lead, nickel, selenium, silver, thallium, vanadium, and zinc EPA 200.8 with collision

cell Aluminum, barium, beryllium, boron, calcium, cobalt, ir on, magnesium, manganese, molybdenum, sodium, tin, and titani um EPA 200.7Due to a confidentiality claim, the Miami Fort FGD Wastewater Treatment diagram cannot be released.Figure 1. Miami Fort FGD Wastewater TreatmentSystem Monitoring Program Sampling Points

### Sample Bottles and Preservation

Table 2 identifies the sample bottles that are needed fo r collecting samples. The table also identifies the on-site preservation that is requi red for the samples. Please note that the number of sample bottles listed in Table 2 refers t o the number of bottles that will need to be collected from each sampling point for each of the four sets of samples. For the Group II samples, the plant can either preserve the samples with sulfuric acid after sample collection, or the plant can order pre-preserv ed sample bottles.

For the total cyanide samples, the plant should test the wastewater from the sampling points with lead acetate paper (turns black in the presence of sulfide) and potassium iodide starch paper (turns blue/violet in the presence of chl orine). If sulfide is present, the plant will need to dilute the sample with blank water until the sulfide is not detected by the lead acetate paper. If chlorine is present, then t he plant will need to add sodium arsenite until the chlorine is not detected by the potass ium iodide starch paper. After any dilution and/or sodium arsenite is added to the sample, the plant will need to preserve the sample with sodium hydroxide until the sample reaches a pH of 10 S.U. Please see ASTM Method D 7365-09a for more details on the preservation requirements for total cyanide.

Table 2. Summary of Sample Container and Planned Preservation

Parameter Sample Container

and Volume On-Site Preservation

BOD 5 One 1-L HDPE

bottle ≤ 6 ° C

Group I a One 1-L HDPE

bottle ≤ 6 ° C

Group II b Two 1-L HDPE

bottles H 2 SO 4 to pH <2, ≤ 6 ° C

Total cyanide One 1-L HDPE

bottle Dilution until sulfide is not detected,

NaAsO 2 until total chlorine is not present, NaOH to pH >10, ≤ 6 ° C

Total metals (EPA Method 200.8 with collision cell) One 500-mL HDPE

bottle None

(acid preserve at laboratory)

Total metals (EPA Method 200.7) One 500-mL HDPE

bottle None

(acid preserve at laboratory)

Total mercury:

Laboratory composite grab samples at FGD

wastewater treatment effluent Four 125-mL glass

bottles

Influent samples and field blank samples Two 250-mL glass

bottles None

(acid preserve at laboratory)

(a) Group I includes TSS, TDS, sulfate, and chloride. (b) Group II includes ammonia as nitrogen, COD, nitrate/ni trite as nitrogen, TKN, and total phosphorus. NOTE: The number of sample bottles refers to the number of sample bottles needed for each sampling point for each of the four sets of samples.

### Sample Labeling

Label each bottle prior to collecting the sample so i t can be identified by the laboratory. Each self-adhesive label must be completed in indelible ink and must contain the following information:

• Sample number (see Table 3);

• Sampling episode number (see Table 3);

• Sampling point/description (see Table 3);

• Date of sample collection;

• Analysis to be performed;

• Sample bottle type; and

• Required on-site preservation.

If any of the information is incorrect, the plant must revise the label using indelible ink. Once applied to the sample container, the plant must co ver the labels with clear tape to prevent tampering, abrasion, smearing, or loss during trans it. For metal and mercury samples, do not place labels directly on the sample bot tles because of the potential for contamination. Instead, place the label on the outer pl astic bag of the sample bottle. To ensure that the sample label does not become separated from the bottle, the doublebagged sample bottle should be placed in an additional Zi ploc bag after collection.

Table 3 provides the sampling point descriptions, sample numbe rs, and sampling episode number for the plant for this monitoring program. The info rmation in the table should be provided on the sample bottle labels for the appropriate bottles. The “analysis to be performed” should be shown on the label as the followi ng, depending on the specific analysis:

• BOD;

• Group I;

• Group II;

• Total Cyanide;

• Total Metals – 200.8 w/ CC;

• Total Metals – 200.7;

• Total Mercury (for influent and field blank samples);

• Total Mercury – Grab 1 (for FGD wastewater treatment ef fluent laboratory composite samples. The bottles should be l abeled as Grab 1, Grab 2, Grab 3, and Grab 4 for the four respective collec tion times).

The “sample bottle type” should be shown on the label t he same as the “Sample Container and Volume” column in Table 2, except that the quantity should not be included. For example, for total mercury, the “sample bo ttle type” should be “250-mL glass bottle.” The “required on-site preservation” sh ould be shown on the label the same as the “On-Site Preservation” column in Table 2, exce pt that “(acid preserve at laboratory)” does not need to be included for the total me tals and total mercury sample

bottles.

### Table 3. Sampling Point Descriptions and Sample Numbers for Monitoring Program

Sampling Point Description Sample Number Sampling Episode Number

FGD Wastewater Treatment Influent – Set 1 72091 6567

FGD Wastewater Treatment Influent – Set 2 72092 6567

FGD Wastewater Treatment Influent – Set 3 72093 6567

FGD Wastewater Treatment Influent – Set 4 72094 6567

FGD Wastewater Treatment Effluent – Set 1 72095 6567

FGD Wastewater Treatment Effluent – Set 2 72096 6567

FGD Wastewater Treatment Effluent – Set 3 72097 6567

FGD Wastewater Treatment Effluent – Set 4 72098 6567

FGD Wastewater Treatment Influent Field Blank 72099 6567

FGD Wastewater Treatment Effluent Field Blank – Set 1 72100 6567

FGD Wastewater Treatment Effluent Field Blank – Set 2 72101 6567

FGD Wastewater Treatment Effluent Field Blank – Set 3 72102 6567

FGD Wastewater Treatment Effluent Field Blank – Set 4 72103 6567



### QC Samples

The plant is required to collect field blank samples as part of the sampling program. The field blank samples should be collected at the frequency specified in Table 4.

Table 4. Field Blank Collection Frequency

Sampling Point Total Mercury Total Metals (200.8 and 200.7) Classicals 1



### FGD Wastewater

Treatment Influent Collected during one

of the four sets Collected during one

of the four sets No field blanks

required

FGD Wastewater

Treatment Effluent Collected during all

four sets Collected during all

four sets No field blanks

required

1 Classicals includes the analyses for BOD, Group I, Group II, and total cyanide.



### The laboratory will perform MS/MSD analyses on the total metals and total mercury analyses; however, no additional sample volume is requi red.

Sample Collection

The plant must use clean sampling techniques when collecti ng the total metals and total mercury samples; therefore, the sampling team should fo llow the clean hands/dirty hands sampling techniques outlined in EPA Method 1669. Additionally, t he plant must try to avoid significant contamination during sample collection, especially from sources such as airborne particles, dirt, and corrosion particulates fr om piping, railing, etc.

### The plant must collect grab samples for all analytes a t the influent to the FGD wastewater

treatment system. The plant must collect 24-hour compo site samples for all analytes except cyanide and mercury at the FGD wastewater treatme nt effluent sampling point. The 24-hour composites must be set up to collect equal sam ple aliquots every hour over the 24-hour period. For mercury at the FGD wastewater tr eatment effluent sampling point, the plant must collect four individual grab samples over the 24-hour period (i.e., one mercury grab collected every six hours). For cyanide at th e FGD wastewater treatment effluent sampling point, the plant must collect a singl e grab sample after the one of the mercury grab samples.

If the plant collects the samples from the same taps used for the collection of samples during the EPA sampling episode, the plant can follow the instructions included in the sampling plan drafted for the EPA sampling episode to colle ct the field blank samples, set up the composite containers, and perform the composite pum p-off procedures for the FGD wastewater treatment effluent sampling point. The foll owing instructions can be used to collect the grab samples at the influent to the FGD wa stewater treatment system sampling point and for the mercury and cyanide grab samples at the FGD wastewater treatment effluent sampling point: (NOTE: If a sample tap or valv e is not available to collect these samples or if the FGD wastewater treatment effluent sampling point has intermittent flows which may interfere with the automatic composite colle ction, please contact TJ Finseth, (703) 633-1698 to discuss possible alternatives.)

1. Arrive at the sampling point location and prepare supplies and bottles for the sample collection.

2. Clean hands and dirty hands put on Tyvek® suits, masks, and powder-free gloves.

3. Dirty hands gets a clear plastic bag and opens it slightl y (touching only the outer part of the bag) so that clean hands can place h ands in the bag and open the bag completely.

4. Clean hands then uses the plastic bag to shroud the samp le tap (note that there should be no flow through the sample tap at this t ime). Clean hands will need to puncture a small hole in the bag using the ta p and dirty hands can cable tie the bag to the tap to prevent it from fall ing during sample

collection.

5. Dirty hands opens the outer bags of the field blank wat er and total mercury and total metals field blank sample bottles. Clean hand s opens the inner bag of the field blank water and unscrews the lid. Clean h ands then opens the inner bag of the total mercury and total metals field bl ank sample bottles. Clean hands pours the blank water into the fi eld blank sample bottles under the shrouding, caps the bottles, and closes the inner bags. Clean hands then places the total mercury and total met als bottles in the outer bags and dirty hands closes the outer bag.

6. Dirty hands then opens the valve to the sample tap and pur ges the tap for at least two minutes, then keeps the valve open until all sam ples have been

collected.

### 7. Dirty hands opens the outer bag for the total mercury s ample bottle. Clean hands takes the sample bottle and inner bag and holds the m under the shroud. Clean hands then opens the inner bag, opens the l id of the bottle and fills the total mercury sample bottle. Clean hands caps the sample bottle, closes the inner bag, and places the sample bo ttle in the outer bag. Dirty hands closes the outer bag. The samplers repea t this procedure for the collection of the total metals samples (both EPA 200.8 with collision cell and EPA 200.7), unless the plant is collecting the met als samples as composite samples.

8. The samplers then collect the BOD, Group I, Group II, and total cyanide samples. NOTE: the samplers can collect these samp les using the same technique as the mercury and metals samples, or they can remove the plastic bag shrouding and collect directly from the tap.

9. The Group II and total cyanide samples must be preserved prio r to shipment to the laboratories. Use the information provide d in the “Sample

Bottle and Preservation” section of these instruction f or the preservation steps. Additionally, the BOD, Group I, Group II, and tota l cyanide samples should be placed on ice immediately after sample coll ection/preservation.

Sample Packing and Shipment

The following steps should be used when packing and shipping the s amples to the

laboratories.

1. Make sure that each sample bottle has a label, and tha t the label correctly specifies the sample point.

2. Tighten the lid on each filled sample bottle, being car eful not to overtighten the lid. If bottle threads are dirty to w here the lid is impeded from closing, clean the threads on the bottle being caref ul to not introduce contamination into the sample. Clean the sample bottl e with a cloth rag or paper towel.

3. Prior to packaging, place each sample bottle requiring ≤ 6°C preservation

into an ice chest with wet ice to cool.

4. When each sample requiring ≤ 6°C preservation has reached the desired temperature, wrap each glass sample bottle with two layers of “bubble wrap” (or place bottle in two “bubble bags”). The bubble wr ap must fit snugly and completely cover the sample bottle. Enclose each “bubblewrapped” container and plastic container in an individual sealable plastic freezer bag.

5. Place two garbage bags inside each other in each of the coolers used to ship samples to the laboratories.

6. Place the classicals samples in the garbage bags in th e coolers with proper end up, close the interior garbage bag by tying, or with a tw ist-tie.

7. Add ice to the cooler to keep samples cold during shipment. Ar range blue ice or sealed plastic freezer bags filled with wet ice on top of the sample bottles (if samples require ≤ 6°C preservation). If using wet ice, place the

### ice inside two one-gallon sealable freezer bags. Put at l east 4 × 1⁄2 gallons of ice (4 × 2.5 pounds of ice) in each large cooler and 2 × 1⁄2 gallons of ice (2 × 2.5 pounds of ice) in each small cooler. Use more ice when ambient temperatures are very high. Place the ice inside the sec ond garbage bag.

8. Close the second garbage bag by tying, or with a twist-tie

. 9. Place the metals samples in the garbage bags in a diff erent cooler with proper end up, close the interior garbage bag by tying or wit h a twist-tie. Close the second garbage bag by tying, or with a twist-tie . NOTE: the metals samples are not required to be cooled; however, because the metals and classicals are being analyzed by the same laboratory, the metals can be shipped with the classicals, but the metals samples w ould need to be chilled prior to packing them in the cooler with the clas sicals and ice

would need to be added to the cooler between the interior a nd outer garbage bags to keep the samples cold.

10. Fill in any free space around the bottles in the metals and classicals coolers with additional cushioning material. Sufficient pac king material should be used so that the sample containers will not shi ft during shipment.

11. Fill out and print a traffic report form for the classi cals and metals samples (provided electronically by ERG). Seal the last two pages o f the traffic report form(s) in a plastic envelope secured to the insid e of the top of the cooler(s). NOTE: the top page of the traffic report mus t be sent to ERG at the following address:

Eastern Research Group 14555 Avion Parkway, Suite 200 Chantilly, VA 20151

Attn: TJ Finseth (703) 633-1698

12. Close the cooler(s).

13. Place a completed laboratory address label on the lid o f the cooler(s). The classicals and metals samples should be shipped to TestAme rica as

follows:

TestAmerica

4955 Yarrow Street Arvada, CO 80002 Attn: Elizabeth Eichelberger (303) 736-0100

14. Make several wraps with strapping tape around the cooler pe rpendicular to

the seal to ensure that the lid will remain closed if t he latch is accidentally released or damaged.

15. Place the mercury samples in the garbage bags in a separ ate cooler with proper end up, close the interior garbage bag by tying, or with a twist-tie.

### 16. Do not add ice to the mercury cooler, simply close the second garbage bag by tying, or with a twist-tie.

17. Fill in any free space around the bottles with additional cushioning material. Sufficient packing material should be used so that the sample containers will not shift during shipment.

18. Fill out and print a traffic report form for the mercury samples (provided electronically by ERG). Seal the last two pages of the traffic report form in a plastic envelope secured to the inside of the top o f the cooler. NOTE: the top page of the traffic report must be sent to ERG a t the same address provided in step 11:

19. Close the cooler.

20. Place a completed laboratory address label on the lid o f the cooler. The mercury samples should be shipped to Frontier as follows:

Frontier GeoSciences

414 Pontius Ave. North Seattle, WA 98109

Attn: Patrick Garcia-Strickland (206) 957-1428

21. Make several wraps with strapping tape around the cooler pe rpendicular to

the seal to ensure that the lid will remain closed if t he latch is accidentally released or damaged.

22. Fill out the necessary paperwork for FedEx or UPS to prepa re the shipment for pick up or drop off. NOTE: the samples must b e shipped priority overnight to arrive at the laboratories the following morning. Ship

the coolers to the laboratories.

23. After the coolers have been dropped off (or picked up), pleas e contact TJ Finseth at (703) 633-1698, to notify him that the samples have b een shipped to the laboratories.

Traffic Reports

An example traffic report will be provided to the plant by ERG for the first sample collection event. The plant will need to make changes t o the traffic report electronically for the other three sample collection events. Some information, such as the date and sample collection times must be entered by the plant after the sample collection and therefore, will not be included in the example provided by ERG.

After the traffic report is completed by the plant, th e plant must print the four pages in the file. The last two pages in the file must be placed in t he cooler for shipment to the laboratories and the first page must be sent to ERG. The plant can keep the second page of the traffic report.

### Engineering Data

The plant must provide engineering data regarding the operatio n of the plant and FGD systems during the sample collection period. Additionall y, the plant must make some field measurements when samples are collected, including pH , temperature, and visual observations, and provide the data to EPA after the sample collection period. The engineering data and field measurement data requirements are in an Excel® spreadsheet titled “Monitoring Program Engineering Data Tables,” which w ill be provided by ERG.

The tables are also included at the end of this enclosure. The plant must complete the engineering data sheets and field measurement sheets in th e Excel® file and e-mail the completed forms to TJ Finseth at thomas.finseth@erg.com

.

Certification Statement

The individual responsible for directing and supervising the s ample collection and the engineering data preparation must sign the certification statement (provided in Enclosure 4) and submit it upon the completion of the sampling program . The signed certification

statement should be scanned and e-mailed to TJ Finseth at thomas.finseth@erg.com , at the same time the engineering data is submitted.Complete the following tables for each sampling pointPlant NameSampleCollectionNumberDate of SampleCollectionSample CollectionTime Temperature (°C)pH(S.U.)Set 1Set 2Set 3Set 4Plant NameSampleCollectionNumberUnit OverflowSampled atInfluent(7 or 8)Influent SamplesCollected as Grabs(Yes or No)Mercury and CyanideSamples Collected asGrabs(Yes or No)Effluent SamplesCollected as 24-Hour Composites(Yes or No)Tyvek Suitsused(Yes or No)Dust MasksUsed forMercury(Yes or No)Clean Hands/DirtyHands SamplingTechniques Used(Yes or No)Description of SampleCollection Technique (ifdifferent thaninstructions)Description of AbnormalConditions in FGD Systemor FGD WastewaterTreatment System that MayImpact ConcentrationsSet 1Set 2Set 3Set 4Complete the following tables based on the plant operating characteristics during each set of samplescollectedUnits OperatingDuring SamplingDayUnits Off-lineEntireSampling DaySCRs/SNCRsOperating onUnitsSet 1Set 2Set 3Set 4Flow Rate (gpm)DurationSet 1Set 2Set 3Set 4Lime Usage(tons)Ferric ChlorideUsage(Liters/day)Organosulfide Usage(Liters/day)Polymer Usage(Liters/day)Acid Usage(Liters/day)ChemicalPrecipitationSystem EffluentFlow Rate (gpd)Set 1Set 2Set 3Set 4Plant NameSampleCollectionNumberDate of SampleCollectionPlant Operation During Sample CollectionPlant NameSampleCollectionNumberDate of SampleCollectionPlant Operation During Sample CollectionScrubber Slurry Blowdown FlowRateScrubber SlurryPercent SolidsPercent HydrocloneOverflow RecycledBack to ScrubberFGD Wastewater Treatment Operation During Sample CollectionPlant NameSampleCollectionNumberDate of SampleCollectionScrubber PurgeFlow Rate DuringInfluent SampleCollection(gpm)Unit 7 Unit 8 Daily Power Generation (MW-hrs)

Plant Name Date Provide the daily power generation for each scrubbe d unit starting two weeks prior to the first set of samples through the last set of samplesFGD Wastewater Treatment System Flow

Rates (gpd) Chemical Precipitation Effluent Plant Name Date Provide the average flow rate in the FGD wastewater treatment system for each stream included in the table starting two weeks prior to the first set of samples through the last set of samples

### Enclosure 2

Authority

This request for information is made under authority provided by Section 308 of the Federal Water Pollution Control Act, as amended, 33 USC 1318. Secti on 308 provides that, "Whenever required to carry out the objective of this Act, includi ng but not limited to . . . developing or assisting in the development of any effluent limitation . . . pretreatment standard, or standard of performance under this Act," the Administrator shall requ ire the owner or operator of any point source to "establish and maintain such records, . . make s uch reports, . . install, use, and maintain such monitoring equipment . . . sample such effluent . . . and provide such other information as he may reasonably require."

Confidentiality

A business ("you") may not withhold information from EPA on the grounds that it is confidential. You may, however, if you desire, assert a business confidentiality claim covering part or all of the information that you furnish to EPA.

EPA regulations concerning confidential business informatio n are contained in 40 CFR Part 2, Subpart B. The manner of asserting such a claim is speci fied in 40 CFR 2.203(b). Information covered by such a claim will be disclosed by EPA only to the extent, and by means of the procedures, set forth in Subpart B.

If you wish to claim as confidential any of the informat ion covered by the enclosed request, you must do so at the time you submit the information to EPA. If no such claim accompanies the information when EPA receives it, EPA may make the inf ormation available to the public without further notice to you.

EPA will notify you in the event that a request is made for release of information that you have

claimed to be confidential or EPA otherwise decides to ma ke a determination as to whether or

not such information is entitled to confidential treatm ent. At that time, EPA will request that you substantiate any claim you have made that information is c onfidential. Therefore, we encourage you to consult 40 CFR Part 2, and to claim as confidential only those items that you truly believe satisfy the criteria for confidentiality.

Note that effluent data are not eligible for confidential t reatment (see 40 CFR 2.302).

### Enclosure 3

Notice of Intent to Transfer Confidential Information to Sel ected EPA Contractors

EPA intends to grant access to confidential information collected under the sampling program to

selected EPA contractors.

In accordance with 40 CFR Sections 2.301(h)(2-3), 2.302(h)(2-3), a nd 2.305(h)(2-3), EPA may

allow those contractors identified below access to all data (including data claimed to be confidential) collected as part of the follow-on sampli ng program. Transfer of this information to these contractors is necessary in order for the cont ractors to assist EPA in performing technical, statistical, and environmental analyses to support the development of effluent limitations guidelines and standards for the Steam Electri c Power Generating industry.

The contractors and subcontractors that will be providi ng support to EPA during the development of these regulations are listed below:

EPA Office Receiving Support Contractor Name EPA Contract

No. Type of Support

Eastern Research Group, Inc. 68-C-02-095 Engineering analysi s Office of Water/

Office of

Science & Technology/ Engineering & Analysis

Division Westat EP-C-10-023 Statistical analysis

EPA has determined that it is necessary to transfer the information described above to the designated contractors and subcontractors in order that they may carry out the work required by their contracts. The contracts contain all provisions necessary to implement the confidentiality regulations (see 40 CFR 2.301(h)(2), 2.302(h)(2), and 2.305(h)(2)).

In accordance with these confidentiality regulations, yo u are entitled to provide comments to EPA regarding this notice of contemplated disclosure. Any such comments must be received by EPA in writing within 10 days of your receipt of this noti ce. Please send such comments to:

Ronald Jordan USEPA Headquarters Ariel Rios Building 1200 Pennsylvania Ave., N.W.

Mail Code: 4303T Washington, DC 20460 jordan.ronald@epa.gov

### Enclosure 4

Certification Statement

The individual responsible for directing or supervising the sample collection and engineering data preparation for the sampling program must read and sig n the Certification Statement listed below. The certifying official must be a responsible co rporate official or his/her authorized representative.

Certification Statement

I certify under penalty of law that the samples collected for the sampling program were collected under my direction or supervision, that qualified personnel collected the samples following the procedures described in the instructions (including the use of clean hands/di rty hands sampling techniques described in EPA Method 1669), that qualified personnel gathered t he engineering data required, and that the sampling and engineering data provided are complete and ref lect normal operations for this plant. The engineering data submitted are, to the best of my knowledge and belief, accurate and complete. In those cases where we di d not possess direct measurement, we provided best estimates. We have to the best of our ability indicated what we believe to be company confidential business information as defined under 40 CFR Part 2, Subpart B. We understand that we may be required at a later time to jus tify our claim in detail with respect to each item claimed confidential. I am aware that there are significant penalties for submitting false information, including the possibility of fines and imprisonment as explained in Section 308 of the Clean Water Act.

Signature of Certifying Official Date



### ( ) Printed Name of Certifying Official Telephone Numbe r of Certifying Official

Title of Certifying Official

Company Name

## Section 2

On

- Site Audit Memorandum

### DATE: 4 November 2010

TO: Steam Electric Record

FROM: Jezebele Alicea

Engineering and Analysis Division

SUBJECT: Notes from Audit of Industry Self-Monitoring Sampling at Duke Energy’s

Miami Fort Station on November 1-2, 2010

EPA conducted an audit of the self-monitoring sampling con ducted at Duke Energy’s Miami Fort Station located in North Bend, Ohio. This wa s Miami Fort’s second set (“Set 2”) of self-monitoring sampling that was being conducted to comply with the requirements established in a letter from Mary Smith, Director of EPA’s Engin eering and Analysis Division, dated July 30, 2010. EPA conducted the audit on November 1-2, 2010. These notes summarize the sample collection techniques used by Miami Fort staff at each of the sampling points and EPA’s observations/findings from the on-site review. A process water diagram for the flue gas desulfurization (FGD) wastewater treatment system at Miami Fort is provided as Attachment 1. The treatment system is described in EPA’s sampling pl an for the Miami Fort plant. 1 

### The checklists that EPA completed as part of the on-site review are provided as Attachment 2.

The following sections describe the sample collection at each of the sampling points and the observations/findings from each sampling point.

Influent to FGD Wastewater Treatment System - FGD Purge ( SP-1)

Miami Fort personnel collected samples for the influen t to the FGD wastewater treatment system from the sample tap on the pipe that flows from the secondary hydroclone overflow to the equalization tank, which is located on top of the equaliza tion tank. EPA specified this location for the FGD purge sample (i.e., prior to the wastewater entering the equalization tank) because the FGD scrubber purge is commingled with other waste strea ms in the equalization tank and, therefore, the sampling point upstream of the tank provides the best representation of the FGD scrubber purge from the Miami Fort FGD system. This is th e same sampling point that EPA used during its sample collection. This sample set collected secondary hydroclone overflow from Unit

8.

Sample Collection

Set 2 samples of the FGD purge were collected on Novemb er 2, 2010. To collect the samples of the FGD purge, Miami Fort personnel followed EPA Method 1669 protocols and the EPA-provided instructions. Miami Fort samplers shrouded the tap with a clean plastic bag and let the sample flow from the tap for two minutes prior t o collecting any samples. The samplers then collected the samples underneath the shroud. All t he mercury and metals samples were

1 Eastern Research Group, Inc. (ERG). Final Sampling Plan , Duke Energy’s Miami Fort Station, North Bend, Ohio, Sampling Episode 6560. July 1, 2010.

### Memorandum

November 9, 2010 Page 2

filled while the samplers held the bottles under the shro uding. To collect the classicals samples, Miami Fort personnel did not remove the shrouding from th e sample tap.

No field blanks were collected for the influent sample po int during Set 2. Field blank samples were collected during Set 1.

Preservation

Miami Fort personnel followed all method specification s when preserving the classical samples. The Group II samples were preserved using H 2 

### SO 4 

### and the pH was confirmed to be below 2 S.U. The cyanide samples were checked for sulfide s and chlorine using lead acetate paper and potassium iodide starch paper, respectively. The s amplers did not detect sulfides or chlorine in the samples. The BOD, Group I, Group II, an d cyanide samples were all placed on ice after collection or preservation.

Field Measurements

Miami Fort personnel used a pH probe and a temperature pr obe to measure the pH and temperature of the influent field test bottle. Miami Fo rt personnel allowed the temperature and pH to stabilize and then recorded the values, which were 5.52 S.U. and 37.7°C.

Observations/Findings

EPA observed the Miami Fort personnel setting up and col lecting the Set 2 samples for the influent to wastewater treatment system. No fiel d blanks were collected at this sample point because Miami Fort personnel previously collected field bla nks during Set 1. The sampling crew followed the requirements of EPA Method 1669 (e.g., clean sa mpling protocols) while collecting samples.

Miami Fort personnel used the correct techniques to preser ve the classical samples. The Group II and cyanide samples were placed in ice immediat ely after preservation. The BOD and Group I samples were placed on ice 20 minutes after sampl e collection.

FGD Wastewater Treatment Effluent (SP-2)

Miami Fort personnel collected samples of the FGD was tewater treatment system (SP-2) from a sample tap located on the suction side of the pum p that transfers the wastewater from the effluent tank to the ash pond. This is the same sampli ng point that EPA used during its sample collection. The samples for this sampling point were c ollected as composite samples, except for the mercury and cyanide samples. For mercury samples, t he plant collected four individual grab samples over the 24-hour period. For cyanide, the plant c ollected a single grab sample after the first mercury grab sample.

### Memorandum

November 9, 2010 Page 3

Sample Collection

Miami Fort personnel collected the FGD wastewater tr eatment effluent as composite samples, except for the mercury and cyanide samples. On e ISCO automatic compositor was programmed to collect individual sample volumes into a 20 -liter container for the composite samples. The ISCO pump was calibrated and programmed to coll ect aliquots of equal volume in one-hour intervals during the 24-hour composite period. Follo wing the composite period, Miami Fort personnel pumped off the specific sample volumes in to the individual sample bottles for all analyses except mercury and cyanide. Mercury and cyanide samp les were collected as grab samples.

To collect the composite samples, Miami Fort personne l connected a carboy to the sample tap using a length of silicone tubing. Prior to compl eting the setup for the composite samples, Miami Fort personnel collected field blanks for SP-2 by threading the tubing through the ISCO 3700 peristaltic pump and attaching the end of the t ubing to a vented cap on a 10-liter carboy and pumping reagent grade water into the carboy. Aft er collecting field blank volume, the 10-L carboy was placed in ice. To collect the composit e samples, Miami Fort personnel attached the one end of the silicone tubing to one of the barbed s ample taps and the end of the tubing was attached to the vented cap, which was screwed onto a 20-lite r carboy. The samplers programmed the compositor to collect 830 mL of sample every hour for a 24-hour period.

After the 24-hour period, the samplers took both carboys to the pump-off location and pumped the sample into the individual sample bottles. M iami Fort personnel used a short piece of Teflon® tubing connected to a length of silicone tubing and the peristaltic pump on the ISCO 3700 to transfer the samples to individual sample bottles. The samplers first shook the 10-liter container to homogenize the field blank sample and then th ey attached a pump-off cap onto the carboy. The Teflon® end of the tubing was then inserted into the carboy and the tubing was purged with one liter of sample. Miami Fort personnel the n collected the field blank samples (metals only) while placing the bottles in a cleanbox to reduce the potential for atmospheric

contamination.

After the field blank samples were collected, the samp lers then filled bottles for metals and classicals using the volume collected in the 20-liter carboy. The samplers first shook the 20- liter container to homogenize the sample, and then the y transferred the pump-off cap and tubing

from the 10-liter field blank container to the 20-liter car boy. The tubing was then purged with two liters of sample. Miami Fort personnel then colle cted the metals samples with the bottles placed in the clean box. After all the metals sample s were collected, the samplers filled the classical samples outside the cleanbox.

Miami Fort personnel also collected grab samples for mercury every six hours during the sampling. The samplers collected the mercury samples a t this sampling point by shrouding the second tap on the two-way splitter with a clean plast ic bag and letting sample flow through the sample tap for two minutes prior to collecting any sample s. Samplers filled the mercury bottles directly from the tap, underneath the shroud. The cyanide samples were collected as a grab sample immediately after the first of the four mercur y grab samples at the sampling point.

### Memorandum

November 9, 2010 Page 4

Preservation

Miami Fort personnel followed all method specification s when preserving the classicals samples, which are the same as those described in the Preservation section for the FGD wastewater treatment influent stream. Additionally, t he plant kept the composite container on ice during the sample collection time period.

Field Measurements

Miami Fort personnel used a pH probe and a temperature pr obe to measure the pH and temperature of the influent field test bottle. Miami Fo rt personnel allowed the temperature and pH to stabilize and then recorded the values.

Observations/Findings

EPA observed the following activities for SP-2 during the a udit: collection of cyanide sample and mercury grab 1 (including field blank) and grab 2; fi eld blank collection and set-up for the composite samples; breakdown of the composite sampler; pump-off of composite samples; and preservation.

The sampling crew followed the requirements of EPA Met hod 1669 (e.g., clean sampling protocols) while collecting samples. Miami Fort person nel followed applicable procedures for sample collection and preservation. Samples were prese rved within 15 minutes.

No clean box was used during set-up for the composite sam ple; however, clean sampling protocols were followed. The sample tubing was provided double- bagged from the laboratory, with all tubing ends already covered by zip-tied plastic ba gs.

During field blank collection, samplers realized that vol ume collected in the 10-liter carboy may not be enough volume for purging the tubing and th e required field blank samples. Therefore, samplers opened the reagent blank water bottle again, placed the tubing inside the bottle, and pumped additional volume into the 10-L carboy . EPA noted that the reagent blank water bottle was inside an inner bag and a second bag at a ll times.

During preparation for the pump-off of composite samples, the tubing was removed from double plastics bags while outside the clean box. All tubing ends were already covered in the laboratory by zip-tied plastic bags and clean sampling protoc ols were followed while handling the tubing.

During the composite pump off, the transition of the pump -off cap from the field blank carboy to the sample carboy took less than 20 seconds, during which tim e the sample carboy was not

covered.

### Memorandum

November 9, 2010 Page 5

All bottles were pre-labeled by the laboratory. The f ield blank container was a 10-liter carboy, instead of a 20-liter carboy (a 20-liter carboy w as used to collect the 24-hour composite samples).

All observations were informed to Miami Fort personnel.

## Attachment 1

FGD Wastewater Treatment Process Flow DiagramDue to a confidentiality claim, the Miami Fort FGD Wastewater Treatment diagram cannot be released.Figure 1. Chemical Precipitation FGD Wastewater Treatment System, Miami Fort Station

## Attachment 2

Checklists

## Section 3

Signed Certification Statement

## Section 4

Engineering DataTable C4-1. Field Measurements for Sample Collection at the Influent to FGDWastewater Treatment System, Miami FortEpisode NumberSample CollectionNumberDate of SampleCollectionSample CollectionTimeTemperature(°C)pH(S.U.)6567Set 1 - Grab 1 9/28/2010083040.55.876567Set 2 - Grab 1 11/2/2010082637.75.526567Set 3 - Grab 1 12/7/2010084339.55.936567Set 4 - Grab 1 1/14/2011081843.75.34Table C4-2. Field Measurements for Sample Collection at the Effluent from FGD Wastewater Treatment System, Miami FortEpisode NumberSample CollectionNumberDate of SampleCollectionSample CollectionTimeTemperature(°C)pH(S.U.)6567Set 1 - Grab 1 9/27/2010111723.38.656567Set 1 - Grab 2 9/27/2010171327.88.796567Set 1 - Grab 3 9/27/2010231526.68.886567Set 1 - Grab 4 9/28/2010051626.58.856567Set 2 - Grab 1 11/1/2010092126.49.156567Set 2 - Grab 2 11/1/2010152325.29.216567Set 2 - Grab 3 11/1/2010212123.88.766567Set 2 - Grab 4 11/2/2010032023.08.726567Set 3 - Grab 1 12/6/2010094919.88.696567Set 3 - Grab 2 12/6/2010155417.78.856567Set 3 - Grab 3 12/6/2010214820.88.806567Set 3 - Grab 4 12/7/2010035020.88.796567Set 4 - Grab 1 1/13/2011093223.49.126567Set 4 - Grab 2 1/13/2011153321.89.236567Set 4 - Grab 3 1/13/2011213122.08.526567Set 4 - Grab 4 1/14/2011032721.38.62Table C4-3. Sample Collection Procedures Used during the Sampling EpisodeEpisodeNumberSampleCollectionNumberUnitOverflowSampledat InfluentInfluentSamplesCollected asGrabs(Yes or No)Mercuryand CyanideSamplesCollected asGrabs(Yes or No)Effluent SamplesCollected as 24-Hour Composites(Yes or No)CleanHands/DirtyHands SamplingTechniques Used(Yes or No)*Description ofSampleCollectionTechnique (ifdifferent thaninstructions)Description of AbnormalConditions in FGDSystem or FGDWastewater TreatmentSystem that May ImpactConcentrations6567 Set 1 Unit 7 Yes Yes Yes Yes NoneNone6567 Set 2 Unit 8 Yes Yes Yes Yes NoneNone6567 Set 3 Unit 7 Yes YesYesYesNoneNote 16567 Set 4 Unit 8 Yes YesYesYesNoneNote 2* Includes the use of tyveks suits during all sampling events and dust masks during the collection of mercury samples.Note 1: Electric power was lost to part of the equipment in the wastewater treatment plant from 12:10 AM to 3:20 AM on December7, 2010.Note 2: Unit 7 and 8 boilers and scrubbers were shut down just prior to the set 4 samples. Both units were operating normallyduring the 24-hour samplingcollection for set 4.Table C4-4. Generating Unit Operationat Time of Sampling, Miami FortEpisode NumberSample CollectionNumberDate of SampleCollectionPlant Operation During Sample CollectionUnits OperatingDuring SamplingDayUnits Off-line EntireSampling DaySCRs/SNCRsOperating onUnits6567Set 1 9/27/10 - 9/28/10Unit 7noneSCR6567Set 1 9/27/10 - 9/28/10Unit 8noneSCR6567Set 2 11/1/10 - 11/2/10Unit 7noneSCR6567Set 2 11/1/10 - 11/2/10 Unit 8*noneSCR6567Set 3 12/6/10 - 12/7/10Unit 7noneSCR6567Set 3 12/6/10 - 12/7/10Unit 8noneSCR6567Set 4 1/13/11 - 1/14/11Unit 7noneSCR6567Set 4 1/13/11 - 1/14/11Unit 8noneSCR* Unit 8 ran full load until 9:42 AM on November 2, 2010 and stopped generating power at 10:01 AM on November 2, 2010. All wastewatertreatment system samples were complete at 8:00 AM, prior to the Unit 8 shut down.Table C4-5. FGD Scrubber Slurry Information at Time of Sampling, Miami FortEpisodeNumberSampleCollectionNumberDate of SampleCollectionUnitsPlant Operation During Sample CollectionScrubber Slurry BlowdownFlow RateScrubberSlurryPercentSolids(%)PercentHydrocloneOverflow RecycledBack to ScrubberFlow Rate(gpm)Duration(hours)6567 Set 1 9/27/10 - 9/28/107CBI CBI CBI CBI6567 Set 1 9/27/10 - 9/28/108CBI CBI CBI CBI6567 Set 2 11/1/10 - 11/2/107CBI CBI CBI CBI6567 Set 2 11/1/10 - 11/2/108CBI CBI CBI CBI6567 Set 3 12/6/10 - 12/7/107CBI CBI CBI CBI6567 Set 3 12/6/10 - 12/7/108CBI CBI CBI CBI6567 Set 4 1/13/11 - 1/14/117CBI CBI CBI CBI6567 Set 4 1/13/11 - 1/14/118CBI CBI CBI CBI.Table C4-6. FGD Scrubber Slurry Information at Time of Sampling, Miami FortEpisodeNumberSampleCollectionNumberDate of SampleCollectionUnitsPlant Operation During Sample CollectionSecondary HydrocloneOverflow Flow RateSecondaryHydrocloneOverflowPercent Solids(%)PercentHydrocloneOverflow RecycledBack to ScrubberFlow Rate(gpm)Duration(hours)6567 Set 1 9/27/10 - 9/28/107CBI CBI CBI CBI6567 Set 1 9/27/10 - 9/28/108CBI CBI CBI CBI6567 Set 2 11/1/10 - 11/2/107CBI CBI CBI CBI6567 Set 2 11/1/10 - 11/2/108CBI CBI CBI CBI6567 Set 3 12/6/10 - 12/7/107CBI CBI CBI CBI6567 Set 3 12/6/10 - 12/7/108CBI CBI CBI CBI6567 Set 4 1/13/11 - 1/14/117CBI CBI CBI CBI6567 Set 4 1/13/11 - 1/14/118CBI CBI CBI CBITable C4-7. FGD Wastewater Treatment System Operation Information, Miami FortEpisodeNumberSampleCollectionNumberDate of SampleCollectionScrubber PurgeFlow Rate DuringInfluent SampleCollection(gpm)FGD Wastewater Treatment Operation During Sample CollectionLimeUsage(tons)FerricChlorideUsage(Liters/day)Nalmet 1689Usage(Liters/day)Polymer Usage(Liters/day)Acid Usage(Liters/day)6567 Set 1 9/28/2010 CBI CBI CBI CBI CBI CBI6567 Set 2 11/2/2010 CBI CBI CBI CBI CBI CBI6567 Set 3 12/7/2010 CBI CBI CBI CBI CBI CBI6567 Set 4 1/14/2011 CBI CBI CBI CBI CBI CBITable C4-8. Daily Power Generation During Sampling Period, Miami Fort

Episode Number Date Daily Power Generation (MW-hrs)

Unit 7 Unit 8
6567 9/13/2010 11,819 12,181
6567 9/14/2010 11,794 12,020
6567 9/15/2010 11,586 12,167
6567 9/16/2010 12,114 12,507
6567 9/17/2010 12,756 12,048
6567 9/18/2010 11,624 11,622
6567 9/19/2010 11,363 11,403
6567 9/20/2010 12,636 12,752
6567 9/21/2010 12,219 11,831
6567 9/22/2010 12,389 12,807
6567 9/23/2010 11,618 11,889
6567 9/24/2010 12,358 12,467
6567 9/25/2010 11,939 12,486
6567 9/26/2010 9,637 10,081
6567 9/27/2010 11,973 12,199
6567 9/28/2010 11,599 11,739
6567 9/29/2010 12,682 12,992
6567 9/30/2010 12,392 12,837
6567 10/1/2010 11,456 12,857
6567 10/2/2010 11,986 12,233
6567 10/3/2010 11,306 11,529
6567 10/4/2010 12,271 12,665
6567 10/5/2010 12,403 12,867
6567 10/6/2010 12,236 12,618
6567 10/7/2010 11,753 12,393
6567 10/8/2010 12,190 12,847
6567 10/9/2010 11,602 12,038
6567 10/10/2010 10,652 11,365
6567 10/11/2010 11,516 11,961
6567 10/12/2010 11,974 12,424
6567 10/13/2010 12,386 12,847
6567 10/14/2010 11,834 12,033
6567 10/15/2010 12,038 12,645
6567 10/16/2010 10,488 12,743
6567 10/17/2010 11,981 12,505
6567 10/18/2010 12,195 12,276
6567 10/19/2010 12,233 12,820
6567 10/20/2010 12,375 12,818
6567 10/21/2010 12,041 12,232
6567 10/22/2010 11,880 12,175
6567 10/23/2010 10,364 10,538Table C4-8. Daily Power Generation During Sampling Period, Miami Fort

Episode Number Date Daily Power Generation (MW-hrs)

Unit 7 Unit 8
6567 10/24/2010 10,966 11,256
6567 10/25/2010 11,546 12,194
6567 10/26/2010 11,677 11,960
6567 10/27/2010 12,221 12,532
6567 10/28/2010 12,240 12,446
6567 10/29/2010 12,876 12,988
6567 10/30/2010 12,847 12,982
6567 10/31/2010 12,410 12,769
6567 11/1/2010 12,015 13,017
6567 11/2/2010 12,821 5,442
6567 11/3/2010 11,426 0
6567 11/4/2010 12,884 0
6567 11/5/2010 13,062 0
6567 11/6/2010 13,005 0
6567 11/7/2010 12,774 2
6567 11/8/2010 12,486 8,514
6567 11/9/2010 12,557 10,533
6567 11/10/2010 11,937 12,220
6567 11/11/2010 12,176 12,235
6567 11/12/2010 12,297 12,633
6567 11/13/2010 9,427 12,843
6567 11/14/2010 12,215 12,430
6567 11/15/2010 12,841 12,867
6567 11/16/2010 12,805 13,115
6567 11/17/2010 12,941 13,109
6567 11/18/2010 13,090 13,203
6567 11/19/2010 12,799 12,904
6567 11/20/2010 12,838 12,902
6567 11/21/2010 12,131 12,377
6567 11/22/2010 12,136 6,623
6567 11/23/2010 12,100 0
6567 11/24/2010 12,965 0
6567 11/25/2010 12,586 0
6567 11/26/2010 12,014 0
6567 11/27/2010 12,998 0
6567 11/28/2010 12,711 0
6567 11/29/2010 12,623 0
6567 11/30/2010 11,955 6,020
6567 12/1/2010 12,595 12,503
6567 12/2/2010 12,659 13,162
6567 12/3/2010 13,007 13,186
6567 12/4/2010 12,969 8,873
6567 12/5/2010 12,913 11,666Table C4-8. Daily Power Generation During Sampling Period, Miami Fort

Episode Number Date Daily Power Generation (MW-hrs)

Unit 7 Unit 8
6567 12/6/2010 12,886 13,178
6567 12/7/2010 12,899 13,237
6567 12/8/2010 11,704 13,184
6567 12/9/2010 10,970 13,061
6567 12/10/2010 11,879 12,663
6567 12/11/2010 11,482 12,164
6567 12/12/2010 11,777 12,535
6567 12/13/2010 12,993 13,151
6567 12/14/2010 13,028 13,029
6567 12/15/2010 12,911 13,071
6567 12/16/2010 12,944 13,120
6567 12/17/2010 12,644 12,898
6567 12/18/2010 12,885 10,634
6567 12/19/2010 12,971 13,159
6567 12/20/2010 12,567 12,824
6567 12/21/2010 8,459 8,311
6567 12/22/2010 10,920 11,524
6567 12/23/2010 13,040 13,195
6567 12/24/2010 12,730 13,018
6567 12/25/2010 10,892 11,298
6567 12/26/2010 12,591 12,868
6567 12/27/2010 13,095 13,158
6567 12/28/2010 12,950 13,117
6567 12/29/2010 12,652 12,921
6567 12/30/2010 12,530 12,872
6567 12/31/2010 11,636 11,988
6567 1/1/2011 10,750 10,948
6567 1/2/2011 12,497 9,901
6567 1/3/2011 13,045 13,210
6567 1/4/2011 12,984 13,154
6567 1/5/2011 13,102 7,388
6567 1/6/2011 13,124 0
6567 1/7/2011 11,410 0
6567 1/8/2011 11,457 0
6567 1/9/2011 11,620 0
6567 1/10/2011 3,279 0

6567 1/11/2011 0 144
6567 1/14/2011 9,309 13,165
6567 1/15/2011 0 13,053
6567 1/16/2011 0 13,010
6567 1/17/2011 0 13,101
6567 1/18/2011 4,166 12,378
6567 1/19/2011 12,654 12,840Table C4-8. Daily Power Generation During Sampling Period, Miami Fort

Episode Number Date Daily Power Generation (MW-hrs)

Unit 7 Unit 8
6567 1/20/2011 12,917 13,119
6567 1/21/2011 13,140 13,174
6567 1/22/2011 13,110 8,540
6567 1/23/2011 12,943 12,552
6567 1/24/2011 12,301 12,228
6567 1/25/2011 13,120 13,095Table C4-9. FGD Wastewater Treatment System Flow Rate during Sampling Period, Miami

Fort

Episode Number Date FGD Wastewater Treatment System Flow Rates (gpd)

Chemical Precipitation Effluent

6567 9/13/2010 CBI

6567 9/14/2010 CBI

6567 9/15/2010 CBI

6567 9/16/2010 CBI

6567 9/17/2010 CBI

6567 9/18/2010 CBI

6567 9/19/2010 CBI

6567 9/20/2010 CBI

6567 9/21/2010 CBI

6567 9/22/2010 CBI

6567 9/23/2010 CBI

6567 9/24/2010 CBI

6567 9/25/2010 CBI

6567 9/26/2010 CBI

6567 9/27/2010 CBI

6567 9/28/2010 CBI

6567 9/29/2010 CBI

6567 9/30/2010 CBI

6567 10/1/2010 CBI

6567 10/2/2010 CBI

6567 10/3/2010 CBI

6567 10/4/2010 CBI

6567 10/5/2010 CBI

6567 10/6/2010 CBI

6567 10/7/2010 CBI

6567 10/8/2010 CBI

6567 10/9/2010 CBI

6567 10/10/2010 CBI

6567 10/11/2010 CBI

6567 10/12/2010 CBI

6567 10/13/2010 CBI

6567 10/14/2010 CBI

6567 10/15/2010 CBI

6567 10/16/2010 CBI

6567 10/17/2010 CBI

6567 10/18/2010 CBI

6567 10/19/2010 CBI

6567 10/20/2010 CBI

6567 10/21/2010 CBITable C4-9. FGD Wastewater Treatment System Flow Rate during Sampling Period, Miami

Fort

Episode Number Date FGD Wastewater Treatment System Flow Rates (gpd)

Chemical Precipitation Effluent

6567 10/22/2010 CBI

6567 10/23/2010 CBI

6567 10/24/2010 CBI

6567 10/25/2010 CBI

6567 10/26/2010 CBI

6567 10/27/2010 CBI

6567 10/28/2010 CBI

6567 10/29/2010 CBI

6567 10/30/2010 CBI

6567 10/31/2010 CBI

6567 11/1/2010 CBI

6567 11/2/2010 CBI

6567 11/3/2010 CBI

6567 11/4/2010 CBI

6567 11/5/2010 CBI

6567 11/6/2010 CBI

6567 11/7/2010 CBI

6567 11/8/2010 CBI

6567 11/9/2010 CBI

6567 11/10/2010 CBI

6567 11/11/2010 CBI

6567 11/12/2010 CBI

6567 11/13/2010 CBI

6567 11/14/2010 CBI

6567 11/15/2010 CBI

6567 11/16/2010 CBI

6567 11/17/2010 CBI

6567 11/18/2010 CBI

6567 11/19/2010 CBI

6567 11/20/2010 CBI

6567 11/21/2010 CBI

6567 11/22/2010 CBI

6567 11/23/2010 CBI

6567 11/24/2010 CBI

6567 11/25/2010 CBI

6567 11/26/2010 CBI

6567 11/27/2010 CBI

6567 11/28/2010 CBI

6567 11/29/2010 CBI

6567 11/30/2010 CBI

6567 12/1/2010 CBITable C4-9. FGD Wastewater Treatment System Flow Rate during Sampling Period, Miami

Fort

Episode Number Date FGD Wastewater Treatment System Flow Rates (gpd)

Chemical Precipitation Effluent

6567 12/2/2010 CBI

6567 12/3/2010 CBI

6567 12/4/2010 CBI

6567 12/5/2010 CBI

6567 12/6/2010 CBI

6567 12/7/2010 CBI

6567 12/8/2010 CBI

6567 12/9/2010 CBI

6567 12/10/2010 CBI

6567 12/11/2010 CBI

6567 12/12/2010 CBI

6567 12/13/2010 CBI

6567 12/14/2010 CBI

6567 12/15/2010 CBI

6567 12/16/2010 CBI

6567 12/17/2010 CBI

6567 12/18/2010 CBI

6567 12/19/2010 CBI

6567 12/20/2010 CBI

6567 12/21/2010 CBI

6567 12/22/2010 CBI

6567 12/23/2010 CBI

6567 12/24/2010 CBI

6567 12/25/2010 CBI

6567 12/26/2010 CBI

6567 12/27/2010 CBI

6567 12/28/2010 CBI

6567 12/29/2010 CBI

6567 12/30/2010 CBI

6567 12/31/2010 CBI

6567 1/1/2011 CBI

6567 1/2/2011 CBI

6567 1/3/2011 CBI

6567 1/4/2011 CBI

6567 1/5/2011 CBI

6567 1/6/2011 CBI

6567 1/7/2011 CBI

6567 1/8/2011 CBI

6567 1/9/2011 CBI

6567 1/10/2011 CBI

6567 1/11/2011 CBITable C4-9. FGD Wastewater Treatment System Flow Rate during Sampling Period, Miami

Fort

Episode Number Date FGD Wastewater Treatment System Flow Rates (gpd)

Chemical Precipitation Effluent

6567 1/12/2011 CBI

6567 1/13/2011 CBI

6567 1/14/2011 CBI

6567 1/15/2011 CBI

6567 1/16/2011 CBI

6567 1/17/2011 CBI

6567 1/18/2011 CBI

6567 1/19/2011 CBI

6567 1/20/2011 CBI

6567 1/21/2011 CBI

6567 1/22/2011 CBI

6567 1/23/2011 CBI

6567 1/24/2011 CBI

6567 1/25/2011 CBI

## Section 5

Analytical Data< - 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 Tables C5-5 through C5-17 with a J flag designation. A “NQ” for the 4-set average result indicates that all results were below the quantitation limit, but at least oneresult is a J-value.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.E – MS and/or MSD exceeded the calibration range.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table C5-1. Influent to FGD Wastewater Treatment System, Miami FortAnalyteUnitsMethodInfluent to FGD Wastewater Treatment System (SP-1)Set 1Set 2Set 3Set 44-SetAverageClassicalsAmmonia mg/L 350.1 7.30 11.0 17.0 B 8.80 E,F 11.0Nitrate Nitrite as N mg/L 353.2 75.0 82.0 * 74.0 56.0 71.8Nitrogen, TotalKjeldahl mg/L 351.2 59.0 B, Min 67.0 97.0 48.0 67.8BiochemicalOxygen Demand mg/L 5210B ND (2.00)ND (2.00) NQ (5.00) 110 < 28.6Chemical OxygenDemand mg/L 410.4 730 650 B 430 850 665Chloride mg/L 300.0 8,300 12,000 11,000 8,100 9,850Sulfate mg/L 300.0 35,000 36,000 27,000 21,000 B 29,800Cyanide, Total mg/L 4500 CN E 1.10 1.20 0.790 19.0 5.52Total DissolvedSolids mg/L 2540C 54,000 Est 53,000 55,000 41,000 50,800Total SuspendedSolids mg/L 2540D 21,000 32,000 27,000 30,000 27,500Phosphorus, Total mg/L 365.1 17.0 0.0680 B NQ (0.0500) B 28.0 B < 11.3Total MetalsAluminum ug/L 200.7 570,000 830,000 B 370,000 360,000 B 533,000< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Tables C5-5 through C5-17 with a J flag designation. A “NQ” for the 4-set average result indicates that all results were below the quantitation limit, but at least oneresult is a J-value.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.E – MS and/or MSD exceeded the calibration range.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table C5-1. Influent to FGD Wastewater Treatment System, Miami FortAnalyteUnitsMethodInfluent to FGD Wastewater Treatment System (SP-1)Set 1Set 2Set 3Set 44-SetAverageAntimony ug/L 200.8 34.0 50.0 45.0 43.0 43.0Arsenic ug/L 200.8 320 670 430 560 495Barium ug/L 200.7 590 1,000 B 400 500 623Beryllium ug/L 200.7 26.0 33.0 17.0 24.0 25.0Boron ug/L 200.7 1,200,000 B 1,000,000 B 1,000,000 B 870,000 B 1,020,000Cadmium ug/L 200.8 610 840 580 570 650Calcium ug/L 200.7 1,200,000 1,300,000 B 1,500,000 1,900,000 B 1,480,000Chromium ug/L 200.8 2,700 2,900 ^ 1,600 2,000 2,300Cobalt ug/L 200.7 640 660 540 530 593Copper ug/L 200.8 890 1,100 540 880 853Iron ug/L 200.7 1,300,000 1,200,000 B 600,000 560,000 915,000Lead ug/L 200.8 400 480 270 460 403Magnesium ug/L 200.7 13,000,000 B 14,000,000 B 9,700,000 B 7,800,000 B 11,100,000Manganese ug/L 200.7 200,000 B 200,000 B 200,000 170,000 B 193,000Mercury ng/L 1631E 384,000 319,000 224,000 367,000 324,000Molybdenum ug/L 200.7 340 610 670 600 555Nickel ug/L 200.8 3,600 3,700 4,200 3,900 3,850Selenium ug/L 200.8 930 1,700 1,600 2,100 1,580Silver ug/L 200.8 NQ (2.00) 3.00 2.60 2.40 < 2.25< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).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 Tables C5-5 through C5-17 with a J flag designation. A “NQ” for the 4-set average result indicates that all results were below the quantitation limit, but at least oneresult is a J-value.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.E – MS and/or MSD exceeded the calibration range.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table C5-1. Influent to FGD Wastewater Treatment System, Miami FortAnalyteUnitsMethodInfluent to FGD Wastewater Treatment System (SP-1)Set 1Set 2Set 3Set 44-SetAverageSodium ug/L 200.7 830,000 B 950,000 B 750,000 430,000 B 740,000Thallium ug/L 200.8 14.0 65.0 34.0 70.0 45.8Tin ug/L 200.7 NQ (200) NQ (200)NQ (200) NQ (200) NQ (200)Titanium ug/L 200.7 2,800 4,500 B 2,000 3,600 3,230Vanadium ug/L 200.8 2,500 2,800 1,600 2,400 2,330Zinc ug/L 200.7 16,000 19,000 ^ 16,000 13,000 16,000< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Tables C5-5 through C5-17 with a J flag designation. A “NQ” for the 4-set average result indicates that all results were below the quantitation limit, but at least oneresult is a J-value.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.E – MS and/or MSD exceeded the calibration range.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table C5-2. Effluent from FGD Wastewater Treatment System, Miami FortAnalyteUnitsMethodEffluent from FGD Wastewater Treatment System (SP-2)Set 1Set 2Set 3Set 44-SetAverageClassicalsAmmonia mg/L 350.1 5.20 5.20 F 45.0 B 5.40 15.2Nitrate Nitrite as N mg/L 353.2 73.0 44.0 F,* 51.0 38.0 51.5Nitrogen, TotalKjeldahl mg/L 351.2 22.0 B, Min 22.0 4 74.0 24.0 35.5BiochemicalOxygen Demand mg/L 5210B 3.30 2.50 3.90 ND (2.00) < 2.68Chemical OxygenDemand mg/L 410.4 530 470 B,F 500 820 F 580Chloride mg/L 300.0 5,800 8,200 7,200 5,700 6,730Sulfate mg/L 300.0 14,000 11,000 14,000 9,600 B 12,200Cyanide, Total mg/L 4500 CN E NQ (0.100) 0.230 F 0.480 15.0 < 3.94Total DissolvedSolids mg/L 2540C 31,000 28,000 Est 32,000 26,000 29,300Total SuspendedSolids mg/L 2540D 8.40 4.80 Est 8.80 8.80 7.70Phosphorus, Total mg/L 365.1 0.360 NQ (0.0500) B 0.0950 B 0.500 B < 0.245< - 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 Tables C5-5 through C5-17 with a J flag designation. A “NQ” for the 4-set average result indicates that all results were below the quantitation limit, but at least oneresult is a J-value.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.E – MS and/or MSD exceeded the calibration range.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table C5-2. Effluent from FGD Wastewater Treatment System, Miami FortAnalyteUnitsMethodEffluent from FGD Wastewater Treatment System (SP-2)Set 1Set 2Set 3Set 44-SetAverageTotal MetalsAluminum ug/L 200.7 ND (200) ND (200)ND (200) ND (200) ND (200)Antimony ug/L 200.8 6.20 4.00 5.80 5.10 5.28Arsenic ug/L 200.8 4.40 NQ (4.00) 5.00 NQ (4.00) < 3.35Barium ug/L 200.7 130 F 130 B 100 97.0 114Beryllium ug/L 200.7 ND (2.00) ND (2.00)ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 300,000 B,4 210,000 B,4 520,000 B 590,000 B 405,000Cadmium ug/L 200.8 ND (4.00) ND (4.00)ND (4.00) ND (4.00) ND (4.00)Calcium ug/L 200.7 750,000 4 1,000,000 B,4 950,000 1,100,000 B 950,000Chromium ug/L 200.8 16.0 14.0 ^ 8.60 NQ (8.00) < 10.7Cobalt ug/L 200.7 ND (20.0) ND (20.0)ND (20.0) ND (20.0) ND (20.0)Copper ug/L 200.8 ND (4.00) ND (4.00)NQ (4.00) NQ (4.00) NQ (4.00)Iron ug/L 200.7 NQ (200) NQ (200) BNQ (200) NQ (200) NQ (200)Lead ug/L 200.8 ND (2.00) ND (2.00)ND (2.00) ND (2.00) ND (2.00)Magnesium ug/L 200.7 6,000,000 B,4 5,200,000 B,4 6,000,000 B 4,400,000 B 5,400,000Manganese ug/L 200.7 130 B 140 B 1,000 1,100 B 593Mercury ng/L 1631E 256 295 144 127 206Molybdenum ug/L 200.7 170 140 310 320 235Nickel ug/L 200.8 NQ (4.00) NQ (4.00) 4.20 4.00 < 3.05< - 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 Tables C5-5 through C5-17 with a J flag designation. A “NQ” for the 4-set average result indicates that all results were below the quantitation limit, but at least oneresult is a J-value.* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.E – MS and/or MSD exceeded the calibration range.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Min – Minimum value.Table C5-2. Effluent from FGD Wastewater Treatment System, Miami FortAnalyteUnitsMethodEffluent from FGD Wastewater Treatment System (SP-2)Set 1Set 2Set 3Set 44-SetAverageSelenium ug/L 200.8 360 4 290 4 660 830 535Silver ug/L 200.8 ND (2.00) F ND (2.00)F ND (2.00) ND (2.00) ND (2.00)Sodium ug/L 200.7 580,000 B,4 670,000 B,4 660,000 380,000 B 573,000Thallium ug/L 200.8 6.30 4.50 6.40 10.0 6.80Tin 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 14.0 10.0 21.0 23.0 17.0Zinc ug/L 200.7 NQ (40.0) NQ (40.0)^ ND (40.0) ND (40.0) NQ (40.0)< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).Table C5-3. Classical Pollutants 4-Set Average Data Summary for FGD Wastewater TreatmentSystem, Miami FortAnalyteUnitsMethodInfluent to FGDWastewater TreatmentSystem (SP-1)4-Set AverageEffluent from FGDWastewater TreatmentSystem (SP-2)4-Set AverageClassicalsAmmonia mg/L 350.1 11.0 15.2Nitrate Nitrite as N mg/L 353.2 71.8 51.5Nitrogen, Total Kjeldahl mg/L 351.2 67.8 35.5Biochemical Oxygen Demand mg/L 5210B < 28.6 < 2.68Chemical Oxygen Demand mg/L 410.4 665 580Chloride mg/L 300.0 9,850 6,730Sulfate mg/L 300.0 29,800 12,200Cyanide, Total mg/L 4500 CN E 5.52 < 3.94Total Dissolved Solids mg/L 2540C 50,800 29,300Total Suspended Solids mg/L 2540D 27,500 7.70Phosphorus, Total mg/L 365.1 < 11.3 < 0.245< - 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 Tables C5-5 through C5-17 with a J flag designation. A “NQ” for the 4-set average result indicates that all results were below the quantitation limit, but at least oneresult is a J-value.Table C5-4. Metals Pollutants 4-Set AverageData Summary for FGD Wastewater TreatmentSystem, Miami FortAnalyteUnitsMethodInfluent to FGDWastewater TreatmentSystem (SP-1)4-Set AverageEffluent from FGDWastewater TreatmentSystem (SP-2)4-Set AverageTotal MetalsAluminum ug/L 200.7 533,000 ND (200)Antimony ug/L 200.8 43.0 5.28Arsenic ug/L 200.8 495 < 3.35Barium ug/L 200.7 623 114Beryllium ug/L 200.7 25.0 ND (2.00)Boron ug/L 200.7 1,020,000 405,000Cadmium ug/L 200.8 650 ND (4.00)Calcium ug/L 200.7 1,480,000 950,000Chromium ug/L 200.8 2,300 < 10.7Cobalt ug/L 200.7 593 ND (20.0)Copper ug/L 200.8 853 NQ (4.00)Iron ug/L 200.7 915,000 NQ (200)Lead ug/L 200.8 403 ND (2.00)Magnesium ug/L 200.7 11,100,000 5,400,000Manganese ug/L 200.7 193,000 593Mercury ng/L 1631E 324,000 206Molybdenum ug/L 200.7 555 235Nickel ug/L 200.8 3,850 < 3.05Selenium ug/L 200.8 1,580 535Silver ug/L 200.8 < 2.25 ND (2.00)< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).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 Tables C5-5 through C5-17 with a J flag designation. A “NQ” for the 4-set average result indicates that all results were below the quantitation limit, but at least oneresult is a J-value.Table C5-4. Metals Pollutants 4-Set AverageData Summary for FGD Wastewater TreatmentSystem, Miami FortAnalyteUnitsMethodInfluent to FGDWastewater TreatmentSystem (SP-1)4-Set AverageEffluent from FGDWastewater TreatmentSystem (SP-2)4-Set AverageSodium ug/L 200.7 740,000 573,000Thallium ug/L 200.8 45.8 6.80Tin ug/L 200.7 NQ (200) ND (200)Titanium ug/L 200.7 3,230 ND (20.0)Vanadium ug/L 200.8 2,330 17.0Zinc ug/L 200.7 16,000 NQ (40.0)ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-5. Influent to FGD Wastewater TreatmentSystem, Set 1 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 7.3Nitrate Nitrite as N 353.2 mg/L 10 0.19 1 75Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.77 10 59 B, MinBiochemical OxygenDemand 5210B mg/L 1 0.24 2 ND (2) UChemical Oxygen Demand 410.4 mg/L 5 20 100 730Chloride 300.0 mg/L 500 130 1,500 8,300Sulfate 300.0 mg/L 1,000 230 5,000 35,000Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 1.1Total Dissolved Solids 2540C mg/L 1 160 330 54,000 EstTotal Suspended Solids 2540D mg/L 1 110 400 21,000Phosphorus, Total 365.1 mg/L 20 0.1 1 17Total MetalsAluminum 200.7 ug/L 2 9.4 200 570,000Antimony 200.8 ug/L 2 0.72 2 34Arsenic 200.8 ug/L 10 6.1 20 320Barium 200.7 ug/L 2 2.5 20 590Beryllium 200.7 ug/L 2 0.71 2 26Boron 200.7 ug/L 250 830 25,000 1,200,000 BCadmium 200.8 ug/L 2 1.2 4 610Calcium 200.7 ug/L 50 1,700 10,000 1,200,000ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-5. Influent to FGD Wastewater TreatmentSystem, Set 1 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationChromium 200.8 ug/L 2 3.3 8 2,700Cobalt 200.7 ug/L 2 1.1 20 640Copper 200.8 ug/L 2 0.96 4 890Iron 200.7 ug/L 50 800 5,000 1,300,000Lead 200.8 ug/L 2 0.73 2 400Magnesium 200.7 ug/L 50 540 10,000 13,000,000 BManganese 200.7 ug/L 50 13 500 200,000 BMercury 1631E ng/L 100,000 24,800 52,000 384,000Molybdenum 200.7 ug/L 2 1.6 40 340Nickel 200.8 ug/L 2 0.89 4 3,600Selenium 200.8 ug/L 10 3.1 20 930Silver 200.8 ug/L 2 0.59 2 0.76 JSodium 200.7 ug/L 2 180 10,000 830,000 BThallium 200.8 ug/L 2 0.47 2 14Tin 200.7 ug/L 2 4.8 200 34 JTitanium 200.7 ug/L 2 1.6 20 2,800Vanadium 200.8 ug/L 2 1.7 10 2,500Zinc 200.7 ug/L 2 9.1 40 16,000ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-6. Influent to FGD Wastewater TreatmentSystem, Set 2 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia 350.1 mg/L 2 0.11 2 11Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 82 *Nitrogen, Total Kjeldahl 351.2 mg/L 20 1.5 20 67Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 ND (2) UChemical Oxygen Demand 410.4 mg/L 5 20 100 650 BChloride 300.0 mg/L 1,000 250 3,000 12,000Sulfate 300.0 mg/L 1,000 230 5,000 36,000Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 1.2Total Dissolved Solids 2540C mg/L 1 94 200 53,000Total Suspended Solids 2540D mg/L 1 55 200 32,000Phosphorus, Total 365.1 mg/L 1 0.005 0.05 0.068 BTotal MetalsAluminum 200.7 ug/L 2 9.4 200 830,000 BAntimony 200.8 ug/L 2 0.72 2 50Arsenic 200.8 ug/L 5 3.1 10 670Barium 200.7 ug/L 2 2.5 20 1,000 BBeryllium 200.7 ug/L 2 0.71 2 33Boron 200.7 ug/L 50 170 5,000 1,000,000 BCadmium 200.8 ug/L 2 1.2 4 840Calcium 200.7 ug/L 50 1,700 10,000 1,300,000 BChromium 200.8 ug/L 2 3.3 8 2,900 ^ND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.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 C5-6. Influent to FGD Wastewater TreatmentSystem, Set 2 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationCobalt 200.7 ug/L 2 1.1 20 660Copper 200.8 ug/L 2 0.96 4 1,100Iron 200.7 ug/L 50 800 5,000 1,200,000 BLead 200.8 ug/L 2 0.73 2 480Magnesium 200.7 ug/L 50 540 10,000 14,000,000 BManganese 200.7 ug/L 50 13 500 200,000 BMercury 1631E ng/L 50,000 12,400 26,000 319,000Molybdenum 200.7 ug/L 2 1.6 40 610Nickel 200.8 ug/L 2 0.89 4 3,700Selenium 200.8 ug/L 50 16 100 1,700Silver 200.8 ug/L 2 0.59 2 3Sodium 200.7 ug/L 2 180 10,000 950,000 BThallium 200.8 ug/L 2 0.47 2 65Tin 200.7 ug/L 2 4.8 200 56 JTitanium 200.7 ug/L 2 1.6 20 4,500 BVanadium 200.8 ug/L 2 1.7 10 2,800Zinc 200.7 ug/L 2 9.1 40 19,000 ^B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.Table C5-7. Influent to FGD Wastewater TreatmentSystem, Set 3 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia 350.1 mg/L 4 0.22 4 17 BNitrate Nitrite as N 353.2 mg/L 10 0.19 1 74Nitrogen, Total Kjeldahl 351.2 mg/L 5 1.9 25 97Biochemical Oxygen Demand 5210B mg/L 1 0.59 5 4.3 JChemical Oxygen Demand 410.4 mg/L 5 20 100 430Chloride 300.0 mg/L 500 130 1,500 11,000Sulfate 300.0 mg/L 1,000 230 5,000 27,000Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.79Total Dissolved Solids 2540C mg/L 1 470 1,000 55,000Total Suspended Solids 2540D mg/L 1 140 500 27,000Phosphorus, Total 365.1 mg/L 1 0.005 0.05 0.017 J,BTotal MetalsAluminum 200.7 ug/L 50 240 5,000 370,000Antimony 200.8 ug/L 2 0.72 2 45Arsenic 200.8 ug/L 2 1.2 4 430Barium 200.7 ug/L 2 2.5 20 400Beryllium 200.7 ug/L 2 0.71 2 17Boron 200.7 ug/L 500 1,700 50,000 1,000,000 BCadmium 200.8 ug/L 2 1.2 4 580Calcium 200.7 ug/L 50 1,700 10,000 1,500,000Chromium 200.8 ug/L 2 3.3 8 1,600Cobalt 200.7 ug/L 2 1.1 20 540Copper 200.8 ug/L 2 0.96 4 540Iron 200.7 ug/L 2 32 200 600,000B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.Table C5-7. Influent to FGD Wastewater TreatmentSystem, Set 3 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationLead 200.8 ug/L 2 0.73 2 270Magnesium 200.7 ug/L 500 5,400 100,000 9,700,000 BManganese 200.7 ug/L 50 13 500 200,000Mercury 1631E ng/L 40,000 9,650 20,200 224,000Molybdenum 200.7 ug/L 2 1.6 40 670Nickel 200.8 ug/L 5 2.2 10 4,200Selenium 200.8 ug/L 10 3.1 20 1,600Silver 200.8 ug/L 2 0.59 2 2.6Sodium 200.7 ug/L 2 180 10,000 750,000Thallium 200.8 ug/L 2 0.47 2 34Tin 200.7 ug/L 2 4.8 200 19 JTitanium 200.7 ug/L 2 1.6 20 2,000Vanadium 200.8 ug/L 2 1.7 10 1,600Zinc 200.7 ug/L 50 230 1,000 16,000B – Analyte was found in the blank and sample.E – MS and/or MSD exceeded the calibration range.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.Table C5-8. Influent to FGD Wastewater TreatmentSystem, Set 4 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 8.8 E,FNitrate Nitrite as N 353.2 mg/L 10 0.19 1 56Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 48Biochemical Oxygen Demand 5210B mg/L 1 7.1 60 110Chemical Oxygen Demand 410.4 mg/L 10 41 200 850Chloride 300.0 mg/L 200 51 600 8,100Sulfate 300.0 mg/L 500 120 2,500 21,000 BCyanide, Total 4500 CN E mg/L 10 0.2 1 19Total Dissolved Solids 2540C mg/L 1 240 500 41,000Total Suspended Solids 2540D mg/L 1 140 500 30,000Phosphorus, Total 365.1 mg/L 40 0.2 2 28 BTotal MetalsAluminum 200.7 ug/L 2 9.4 200 360,000 BAntimony 200.8 ug/L 2 0.72 2 43Arsenic 200.8 ug/L 2 1.2 4 560Barium 200.7 ug/L 2 2.5 20 500Beryllium 200.7 ug/L 2 0.71 2 24Boron 200.7 ug/L 200 670 20,000 870,000 BCadmium 200.8 ug/L 2 1.2 4 570Calcium 200.7 ug/L 50 1,700 10,000 1,900,000 BChromium 200.8 ug/L 2 3.3 8 2,000Cobalt 200.7 ug/L 2 1.1 20 530Copper 200.8 ug/L 2 0.96 4 880B – Analyte was found in the blank and sample.E – MS and/or MSD exceeded the calibration range.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.Table C5-8. Influent to FGD Wastewater TreatmentSystem, Set 4 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationIron 200.7 ug/L 2 32 200 560,000Lead 200.8 ug/L 2 0.73 2 460Magnesium 200.7 ug/L 50 540 10,000 7,800,000 BManganese 200.7 ug/L 50 13 500 170,000 BMercury 1631E ng/L 10,000 2,480 5,200 367,000Molybdenum 200.7 ug/L 2 1.6 40 600Nickel 200.8 ug/L 2 0.89 4 3,900Selenium 200.8 ug/L 10 3.1 20 2,100Silver 200.8 ug/L 2 0.59 2 2.4Sodium 200.7 ug/L 2 180 10,000 430,000 BThallium 200.8 ug/L 2 0.47 2 70Tin 200.7 ug/L 2 4.8 200 28 JTitanium 200.7 ug/L 2 1.6 20 3,600Vanadium 200.8 ug/L 2 1.7 10 2,400Zinc 200.7 ug/L 2 9.1 40 13,000ND – 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.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-9. Effluent from FGD Wastewater Treatment System, Set 1 AnalyticalResults, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 5.2Nitrate Nitrite as N 353.2 mg/L 10 0.19 1 73Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 22 B, MinBiochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 3.3Chemical Oxygen Demand 410.4 mg/L 5 20 100 530Chloride 300.0 mg/L 500 130 1,500 5,800Sulfate 300.0 mg/L 500 120 2,500 14,000Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.068 JTotal Dissolved Solids 2540C mg/L 1 47 100 31,000Total Suspended Solids 2540D mg/L 1 1.1 4 8.4Phosphorus, Total 365.1 mg/L 1 0.005 0.05 0.36Total MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 6.2Arsenic 200.8 ug/L 2 1.2 4 4.4Barium 200.7 ug/L 2 2.5 20 130 FBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 250 830 25,000 300,000 B,4Cadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 750,000 4Chromium 200.8 ug/L 2 3.3 8 16ND – 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.Min – Minimum value.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-9. Effluent from FGD Wastewater Treatment System, Set 1 AnalyticalResults, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationCobalt 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 32 200 160 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 6,000,000 B,4Manganese 200.7 ug/L 2 0.51 20 130 BMercury 1631E ng/L 20 4.87 10.2 256Molybdenum 200.7 ug/L 2 1.6 40 170Nickel 200.8 ug/L 2 0.89 4 2.8 JSelenium 200.8 ug/L 5 1.6 10 360 4Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 580,000 B,4Thallium 200.8 ug/L 2 0.47 2 6.3Tin 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 14Zinc 200.7 ug/L 2 9.1 40 9.6 JND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-10. Effluent from FGDWastewater Treatment System, Set 2Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 5.2 FNitrate Nitrite as N 353.2 mg/L 5 0.095 0.5 44 F,*Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 22 4Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 2.5Chemical Oxygen Demand 410.4 mg/L 5 20 100 470 B,FChloride 300.0 mg/L 500 130 1,500 8,200Sulfate 300.0 mg/L 500 120 2,500 11,000Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.23 FTotal Dissolved Solids 2540C mg/L 1 94 200 28,000 EstTotal Suspended Solids 2540D mg/L 1 1.1 4 4.8 EstPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.049 J,BTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 4Arsenic 200.8 ug/L 2 1.2 4 3.7 JBarium 200.7 ug/L 2 2.5 20 130 BBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 50 170 5,000 210,000 B,4Cadmium 200.8 ug/L 2 1.2 4 ND (4) UND – Not detected (number in parentheses is the quantitation limit).* - LCS or LCSD is outside the laboratory control limits.^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.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.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-10. Effluent from FGDWastewater Treatment System, Set 2Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationCalcium 200.7 ug/L 50 1,700 10,000 1,000,000 B,4Chromium 200.8 ug/L 2 3.3 8 14 ^Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 140 J,BLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 5,200,000 B,4Manganese 200.7 ug/L 2 0.51 20 140 BMercury 1631E ng/L 100 24.1 50.5 295Molybdenum 200.7 ug/L 2 1.6 40 140Nickel 200.8 ug/L 2 0.89 4 3.3 JSelenium 200.8 ug/L 5 1.6 10 290 4Silver 200.8 ug/L 2 0.59 2 ND (2) U,FSodium 200.7 ug/L 2 180 10,000 670,000 B,4Thallium 200.8 ug/L 2 0.47 2 4.5Tin 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 10Zinc 200.7 ug/L 2 9.1 40 24 J,^ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-11. Effluent from FGDWastewater Treatment System, Set 3Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia 350.1 mg/L 10 0.55 10 45 BNitrate Nitrite as N 353.2 mg/L 10 0.19 1 51Nitrogen, Total Kjeldahl 351.2 mg/L 10 0.77 10 74Biochemical Oxygen Demand 5210B mg/L 1 0.3 2.5 3.9Chemical Oxygen Demand 410.4 mg/L 5 20 100 500Chloride 300.0 mg/L 500 130 1,500 7,200Sulfate 300.0 mg/L 500 120 2,500 14,000Cyanide, Total 4500 CN E mg/L 1 0.02 0.1 0.48Total Dissolved Solids 2540C mg/L 1 94 200 32,000Total Suspended Solids 2540D mg/L 1 1.1 4 8.8Phosphorus, Total 365.1 mg/L 1 0.005 0.05 0.095 BTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 5.8Arsenic 200.8 ug/L 2 1.2 4 5Barium 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 5,000 520,000 BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 50 1,700 10,000 950,000Chromium 200.8 ug/L 2 3.3 8 8.6Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 1 JND – 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 C5-11. Effluent from FGDWastewater Treatment System, Set 3Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationIron 200.7 ug/L 2 32 200 160 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 6,000,000 BManganese 200.7 ug/L 2 0.51 20 1,000Mercury 1631E ng/L 20 4.97 10.4 144Molybdenum 200.7 ug/L 2 1.6 40 310Nickel 200.8 ug/L 2 0.89 4 4.2Selenium 200.8 ug/L 5 1.6 10 660Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 660,000Thallium 200.8 ug/L 2 0.47 2 6.4Tin 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 21Zinc 200.7 ug/L 2 9.1 40 ND (40) UND – 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 C5-12. Effluent from FGDWastewater Treatment System, Set 4Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationClassicalsAmmonia 350.1 mg/L 1 0.055 1 5.4Nitrate Nitrite as N 353.2 mg/L 10 0.19 1 38Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 24Biochemical Oxygen Demand 5210B mg/L 1 0.24 2 ND (2) UChemical Oxygen Demand 410.4 mg/L 10 41 200 820 FChloride 300.0 mg/L 200 51 600 5,700Sulfate 300.0 mg/L 200 46 1,000 9,600 BCyanide, Total 4500 CN E mg/L 10 0.2 1 15Total Dissolved Solids 2540C mg/L 1 94 200 26,000Total Suspended Solids 2540D mg/L 1 1.1 4 8.8Phosphorus, Total 365.1 mg/L 1 0.005 0.05 0.5 BTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 5.1Arsenic 200.8 ug/L 2 1.2 4 3.2 JBarium 200.7 ug/L 2 2.5 20 97Beryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 200 670 20,000 590,000 BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 50 1,700 10,000 1,100,000 BChromium 200.8 ug/L 2 3.3 8 6.8 JCobalt 200.7 ug/L 2 1.1 20 ND (20) UND – 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 C5-12. Effluent from FGDWastewater Treatment System, Set 4Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecificQLConcentrationCopper 200.8 ug/L 2 0.96 4 0.99 JIron 200.7 ug/L 2 32 200 99 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 50 540 10,000 4,400,000 BManganese 200.7 ug/L 2 0.51 20 1,100 BMercury 1631E ng/L 100 24.8 52 127Molybdenum 200.7 ug/L 2 1.6 40 320Nickel 200.8 ug/L 2 0.89 4 4Selenium 200.8 ug/L 2 0.62 4 830Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 380,000 BThallium 200.8 ug/L 2 0.47 2 10Tin 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 23Zinc 200.7 ug/L 2 9.1 40 ND (40) UND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-13. Influent to FGD Wastewater Treatment System Field Blank, Set 1 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 13 J,^Antimony 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 30 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 89 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 21 J,BManganese 200.7 ug/L 2 0.51 20 ND (20) UMercury 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 10,000 250 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-13. Influent to FGD Wastewater Treatment System Field Blank, Set 1 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTitanium 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) UND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-14. Effluent fromFGD Wastewater Treatment SystemField Blank, Set 1 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) U,^Antimony 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 44 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 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 84 J,BManganese 200.7 ug/L 2 0.51 20 0.6 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 10,000 480 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-14. Effluent fromFGD Wastewater Treatment SystemField Blank, Set 1 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTitanium 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) UND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-15. Effluent fromFGD Wastewater Treatment SystemField Blank, Set 2 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 14 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 34 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) U,^Cobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 55 J,BManganese 200.7 ug/L 2 0.51 20 0.7 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 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) UND – Not detected (number in parentheses is the quantitation limit).^ - ICV, CCV, ICB, CCB, ISA, ISB, CRI, or MRL standard: Instrument related QC exceeds the control limits.B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-15. Effluent fromFGD Wastewater Treatment SystemField Blank, Set 2 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 2.2 JZinc 200.7 ug/L 2 9.1 40 ND (40) U,^ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table C5-16. Effluent from FGD Wastewater TreatmentSystem Field Blank, Set 3 Analytical Results,Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 95 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 76 JChromium 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 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 170 J,BManganese 200.7 ug/L 2 0.51 20 0.8 JMercury 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 1.1 JSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 610 JThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UND – 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 C5-16. Effluent from FGD Wastewater TreatmentSystem Field Blank, Set 3 Analytical Results,Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 2.1 JZinc 200.7 ug/L 2 9.1 40 ND (40) UND – 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 C5-17. Effluent fromFGD Wastewater Treatment SystemField Blank, Set 4 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 9.9 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 62 J,BCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 71 J,BChromium 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 58 JLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 27 J,BManganese 200.7 ug/L 2 0.51 20 0.8 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 2.9 JSilver 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) UND – 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 C5-17. Effluent fromFGD Wastewater Treatment SystemField Blank, Set 4 Analytical Results, Miami FortAnalyteMethodUnitDilutionFactorSample-SpecificMDLSample-SpecificQLConcentrationVanadium 200.8 ug/L 2 1.7 10 2.6 JZinc 200.7 ug/L 2 9.1 40 16 J

## Section 6

Data Review Narratives

[A concentration noted as “XXX” indicates that the sample result applies to a different power plant and has been
removed.]

### 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: 2/9/2012 Subject: FGS Data Review Narrative for Total Mercury – Long-Term M onitoring: Month 1 (Part 1)

Frontier Global Sciences (FGS) generated analytical data for total mercury. FGS analyzed the samples according to EPA Method 1631E for merc ury by Cold Vapor Atomic Fluorescence Spectrometry (CVAFS) analysis.

Table 1 summarizes the 14 samples (excluding laboratory pre p blanks) FGS extracted and analyzed for total mercury.

Table 1. 

### Long-Term Monitoring Month 1 (Part 1) Mercury – Sample Identification

EPA Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

72041 1010010-01 Aqueous FGD Influent, Set 1 9/30/2010

72045 1010010-02 Aqueous FGD Effluent, Set 1 9/30/2010

72049 1010010-04 Aqueous FGD Influent Field Blank 9/30/2010

72050 1010010-03 Aqueous FGD Effluent Field Blank, Set 1 9/30/2010

72091 1009237-07 Aqueous FGD Influent, Set 1 9/28/2010

72095 1009237-08 Aqueous FGD Effluent, Set 1 9/28/2010

72099 1009237-10 Aqueous FGD Influent Field Blank 9/28/2010

72100 1009237-09 Aqueous FGD Effluent Field Blank, Set 1 9/27/2010

72191 1009237-01 Aqueous FGD Influent Set 1 9/29/2010

72195 1009237-02 Aqueous FGD SBR Influent, Set 1 9/29/2010

72199 1009237-03 Aqueous FGD SBR Effluent, Set 1 9/29/2010

72203 1009237-06 Aqueous FGD Influent Field Blank 9/29/2010

72204 1009237-04 Aqueous FGD SBR Influent Field Blank, Set 1 9/28/2010

72208 1009237-05 Aqueous FGD SBR Effluent Field Blank, Set 1 9/28/2010



### SUMMARY

The samples were prepared according to EPA Method 1631E to be analyzed by CVAFS.

### 2

There were no findings from the data review that required a dditional qualifiers in this

dataset.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysi s day. The initial calibration for the CVAFS analysis consisted of a blank and five calibrat ion standards with a correlation

coefficient ≥ 0.995. All method-specified criteria were met.

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

All initial and continuing calibration verifications (I CVs, CCVs) met method-specified

criteria.

BLANKS

All the preparation blanks or laboratory reagent blanks (L RBs) and the continuing calibration blanks (CCBs) met method-specified criteria. Some preparation blanks had mercury levels greater than the MDL (0.24 ng/L), but less t han the RL associated with each individual blank (different RLs based on preparation) . Because all of the blank results were less than the RL, no samples were quali fied based on these preparation blank

results.

DUPLICATES

No field duplicate samples were collected with these sa mpling episodes. Two samples were analyzed in duplicate at the laboratory, samples 72095 a nd 72195. The relative percent difference (RPD) for samples 72095 and 72195 were 2.45% an d 3.32%, respectively. The laboratory’s RPD criteria between an alytical duplicates is 24%.

LABORATORY CONTROL SAMPLES

All laboratory control samples were within FGS’s contr ol limits of 80-120% recovery

and 24% RPD.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

Matrix spikes (MS) and matrix spike duplicates (MSD) we re performed on samples 72095, 72199, and 72195 for the total mercury analyses. All aqueous MS/M SD recoveries were within method specifications of 71-125%. All RPDs met methodspecified criteria.

### 3

DETECTION LIMITS

The laboratory MDL in the synthetic matrix was 0.239 ng/ L. Results below this MDL were reported as not detected (ND).

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Randy Mercurio, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Total Metals by 200.8 – Long-Term Monitoring: Month 1 (Part 1)

TestAmerica generated analytical data for total metals (antimony, arsenic, cadmium, chromium, copper, lead, nickel, selenium, silver, thallium , and vanadium) for these longterm monitoring samples. The samples were analyzed accor ding to EPA Method 200.8.

Table 1 summarizes the samples TestAmerica extracted a nd analyzed for total metals by

EPA Method 200.8.

Table 1. 

### Long-Term Monitoring Month 1 (Part 1) Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

72041 FGD Influent, Set 1 280

- 7918

- 1 Aqueous 9/30/2010 10/1/2010

72045 FGD Effluent, Set 1 280

- 7918

- 2 Aqueous 9/30/2010 10/1/2010

72049 FGD Influent Field Blank 280

- 7918

- 4 Aqueous 9/30/2010 10/1/2010

72050 FGD Effluent Field Blank, Set 1 280

- 7918

- 3 Aqueous 9/30/2010 10/1/2010

72091 FGD Influent, Set 1 280

- 7817

- 1 Aqueous 9/28/2010 9/29/2010

72095 FGD Effluent, Set 1 280

- 7817

- 2 Aqueous 9/28/2010 9/29/2010

72099 FGD Influent Field Blank, Set 1 280

- 7817

- 4 Aqueous 9/28/2010 9/29/2010

72100 FGD Effluent Field Blank, Set 1 280

- 7817

- 3 Aqueous 9/28/2010 9/29/2010

72191 FGD Influent, Set 1 280

- 7870

- 1 Aqueous 9/29/2010 9/30/2010

72195 FGD SBR Influent, Set 1 280

- 7870

- 2 Aqueous 9/29/2010 9/30/2010

72199 FGD SBR Effluent, Set 1 280

- 7870

- 3 Aqueous 9/29/2010 9/30/2010

72203 FGD Influent Field Blank 280

- 7870

- 6 Aqueous 9/29/2010 9/30/2010

72204 FGD SBR Influent Field Blank,

Set 1 280

- 7870

- 4 Aqueous 9/29/2010 9/30/2010

72208 FGD SBR Effluent Field Blank,

Set 2 280

- 7870

- 5 Aqueous 9/29/2010 9/30/2010

### 2

SUMMARY

The samples were prepared for total metals analysis accor ding to TestAmerica’s “FGD ICP/MS SOP: Inductively Coupled Plasma Mass Spectrometry for Trace Elements Analysis in Flue Gas Desulfurization Wastewaters,” date d October 6, 2010, based on EPA Method 200.8, by ICP/MS analysis.

Any significant findings are summarized below. No addition al data qualifiers were required.

• The matrix spike (MS) and matrix spike duplicate (MSD) rec overies for total silver for samples 72045 and 72095 failed the EPA Method 200.8 contr ol limits of

70–130%.

• The MS/MSD relative percent difference (RPD) for tota l silver for sample 72095

failed the FGD ICP/MS SOP control limits of ±20%.

• The post digestion spike (PDS) recoveries for the follo wing analytes failed TestAmerica’s control limits of 85–115%: arsenic, chromium , selenium, silver,

and vanadium.

INTERNAL STANDARDIZATION

All internal standards used by TestAmerica were within th e method criteria.

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial calibration for the ICP-MS analysis consisted of a bla nk and four calibration standards.

INITIAL AND CONTINUING CALIBRATION VERIFICATION (IC V/CCV)

The initial calibration verifications (ICV) and continu ing calibration verifications (CCV) performed by TestAmerica all had recoveries within the m ethod criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit (RL); however, some elements were above the MDL and flagged with a “J” qualifier. No additional qualifiers were required for method blanks.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank (CCB)) were less than the RL; however, some element s were above the MDL and flagged with a “J” qualifier. No additional qualifiers were required for instrument blanks.

### 3

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s SOP control limi ts of 50–150% recovery.

LABORATORY CONTROL SAMPLES (LCS)

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

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION

Based on TestAmerica’s SOP, all interference check sa mple A (ICSA) results had analytes of interest with concentrations less than the RL or less than five times the RL when known inherent contaminants are present in the stock solution used to make the

ICS.

All interference check sample B (ICSAB) synthetic sp ikes recovered within

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

SERIAL DILUTION

The serial dilution performed on sample 72095 passed TestAmer ica’s criteria of ±10%

difference.

FIELD DUPLICATES

No field duplicate samples were collected with these sa mpling episodes.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

MS and MSD were performed on samples 72045 and 72095. The total se lenium results in the MS and MSD samples for sample 72045 and the MS sample for sample 72095 failed the 70-130% recovery method control limits and were flagged w ith a “4” qualifier indicating concentrations in the parent samples were grea ter than four times the spike amounts. These data were considered acceptable based on th e LCS passing the method

control limits.

The total silver results in the MS and MSD samples for b oth samples 72045 and 72095

failed the 70-130% method control limits with low recoveri es and were flagged with an “F” qualifier. Additionally, the RPD for silver betwee n the MS and MSD for sample 72095 failed the ICP/MS SOP ±20% control limits. The poor r ecoveries and RPD of silver are probably due to high sulfates in this episode’s samples capable of forming

insoluble silver sulfide and/or silver sulfate.

### 4

Otherwise, all MS/MSD spike recoveries were within th e method control limits of 70-

130% and the RPD for the MS/MSDs were within the FGD ICP /MS SOP control limits of ±20 percent. No additional data qualifiers were required.

POST DIGESTION SPIKES

The PDS performed on sample 72095 passed TestAmerica’s cont rol limits of 85–115% recovery for all analytes, except for arsenic, chromium , selenium, silver, and vanadium, which were all flagged with a “W” qualifier. No additional data qualifiers were required for PDS samples.

DETECTION LIMITS

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

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Randy Mercurio, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Total Metals by 200.7 – Long-Term Monitoring: Month 1 (Part 1)

TestAmerica generated analytical data for total metals (aluminum, boron, barium, beryllium, calcium, cobalt, iron, magnesium, manganese , molybdenum, sodium, tin, titanium, and zinc) for these long-term monitoring samples . The samples were analyzed according to EPA Method 200.7.

Table 1 summarizes the samples TestAmerica extracted a nd analyzed for total metals by

EPA Method 200.7.

Table 1. 

### Long-Term Monitoring Month 1 (Part 1) Total Metals – Sample

Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

72041 FGD Influent, Set 1 280

- 7918

- 1 Aqueous 9/30/2010 10/1/2010

72045 FGD Effluent, Set 1 280

- 7918

- 2 Aqueous 9/30/2010 10/1/2010

72049 FGD Influent Field Blank 280

- 7918

- 4 Aqueous 9/30/2010 10/1/2010

72050 FGD Effluent Field Blank,

Set 1 280

- 7918

- 3 Aqueous 9/30/2010 10/1/2010

72091 FGD Influent, Set 1 280

- 7817

- 1 Aqueous 9/28 /2010 9/29 /2010

7 2095 FGD Effluent, Set 1 280

- 7817

- 2 Aqueous 9/28 /2010 9/29 /2010

7 2099 FGD Influent Field Blank,

Set 1 280

- 7817

- 4 Aqueous 9/28 /2010 9/29 /2010

7 2100 FGD Ef

fluent Field Blank

, Set 1 280

- 7817

- 3 Aqueous 9/28 /2010 9/29 /2010

72191 FGD Influent, Set 1 280

- 7870

- 1 Aqueous 9/29/2010 9/30/2010

72195 FGD SBR Influent, Set 1 280

- 7870

- 2 Aqueous 9/29/2010 9/30/2010

72199 FGD SBR Effluent, Set 1 280

- 7870

- 3 Aqueous 9/29/2010 9/30/2010

72203 FGD Influent Field Blank 280

- 7870

- 6 Aqueous 9/29/2010 9/30/2010

72204 FGD SBR Influent Field

Blank, Set 1 280

- 7870

- 4 Aqueous 9/29/2010 9/30/2010

72208 FGD SBR Effluent Field

Blank, Set 2 280

- 7870

- 5 Aqueous 9/29/2010 9/30/2010

### 2

SUMMARY

The samples were prepared for total metals analysis acc ording to TestAmerica’s SOP for ICP Analysis for Trace Metals by Method 200.7. Any signific ant findings are summarized below. No additional data qualifiers were requir ed.

• The matrix spike (MS) and matrix spike duplicate (MSD) rec overies for total barium for sample 72095 failed the EPA Method 200.7 control li mits of 70–

130%.

• The MS/MSD relative percent difference (RPD) for total magnesium for sample

72095 failed TestAmerica’s SOP control limits of ±20%.

• The post digestion spike (PDS) for titanium for sample 72095 failed TestAmerica’s control limits of 85–115% recovery.

SAMPLE RECEIPT, HANDLING AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INTERNAL STANDARDIZATION

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

ISTD recoveries within the ±30% criterion of the calibra tion blank as per Section 9.11 of

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

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial calibration for the ICP analysis consisted of a blank an d one calibration standard.

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

The initial calibration verifications (ICV) and continu ing calibration verifications (CCV) performed by TestAmerica all had recoveries within the m ethod criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit (RL); however, some elements were above the method detection limit (MDL) and were f lagged with the “J” qualifier.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank (CCB)) were less than the RL; however, some element s were above the MDL and were flagged with the “J” qualifier.

### 3

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s SOP control limi ts of 50–150% recovery.

LABORATORY CONTROL SAMPLES (LCS)

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

INTERFERENCE CHECK SOLUTIONS

Interference checks were performed using the synthetic ma trix as the check solution. All data quality objectives met TestAmerica’s SOP criteria.

SERIAL DILUTION (SRD)

Serial dilutions were performed for each batch of total samples. All serial dilution percent differences were less than 10% as required by TestAmerica ’s SOP.

FIELD DUPLICATES

No field duplicate samples were collected with these sa mpling episodes.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

MS and MSDs were performed on the total samples of 72095 and 72045. Some elements with high concentrations failed the EPA 200.7 Method spike recovery control limits of 70–130% but were flagged with a “4” qualifier indicating that the c oncentration in the parent sample was greater than 4 times the spike and co uld not be reliably calculated. These data were considered acceptable based on the LCS pas sing the method control limits. Otherwise, all MS/MSD spike recoveries were within the method control criteria of 70-130%, except for barium for sample 72095, which had a reco very of 65% and was qualified with an “F”. The RPD for all MS/MSDs were wi thin TestAmerica’s ± 20% requirement, except for magnesium for sample 72095. No add itional data qualifiers were

needed.

POST DIGESTION SPIKE (PDS)

The PDS performed on sample 72095 passed TestAmerica’s cont rol limits of 85–115% recovery for all analytes except titanium, which was qual ified with a “W”. No additional data qualifiers were required.

DETECTION LIMITS

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

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Donna Tedder, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Classicals Ana lyses – Long-Term Monitoring: Month 1 (Part 1)

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry analyses for these long-term monitoring samples. All s amples were tested for the following analytes:

• Ammonia by EPA method 350.1,

• Biochemical Oxygen Demand – 5 day (BOD 5 

### ) by SM 5210B,

• Chloride and Sulfate by EPA method 300.0,

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

• Cyanide (total) by SM 4500 CN - 

### E,

• Nitrate/Nitrite by EPA method 353.2,

• Phosphorus (total) by EPA method 365.1,

• Total Dissolved Solids (TDS) by SM 2540C,

• Total Kjeldahl Nitrogen (TKN) by EPA method 351.2, and

• Total Suspended Solids (TSS) by SM 2540D.

Table 1 summarizes the seven samples that TestAmerica analyzed for the above analytes.

Table 1. Long-Term Monitoring Month 1 (Part 1) Classical Analytes – Sample

Identification

EPA Sample # Sample

Matrix Sample Description Sampling

Date 72041 Water FGD Influent, Set 1 9/30/10
72045 Water FGD Effluent, Set 1 9/30/10
72091 Water FGD Influent, Set 1 9/28/10 72095 Water FGD Effluent, Set 1 9/28/10
72191 Water FGD Influent, Set 1 9/29/10 72195 Water FGD SBR Influent, Set 1 9/29/10
72199 Water FGD SBR Effluent, Set 1 9/29/10

### 2

SUMMARY

All samples were analyzed within the holding time specif ied in 40 CFR 136 Table II. All samples were preserved appropriately unless otherwise speci fied below.

Field duplicate samples were not collected for these ep isodes. Depending on the method, a laboratory duplicate was analyzed, instead. The Relati ve Percent Difference (RPD) between the sample and its duplicate was less than 20% unl ess otherwise noted below.

If applicable, the appropriate number of standards was used to create a calibration curve. If sample results were above the highest standard used t o create the curve, the sample was diluted and reanalyzed. All sample results were between the lowest and highest standards unless noted below. Additionally, unless otherwise noted, a ll calibration blanks and calibration verification samples met the criteria sp ecified in the method.

If required by the method, the quality control sample (QC S), a secondary source standard used to verify calibration, was always within the cont rol limits specified by the method.

As described below, the analyte of interest was detecte d above the method detection limit (MDL) in some laboratory reagent blanks (LRB). However , the analyte of interest was never detected above the reporting limit (RL) in the LRBs . If required by the method, all laboratory fortified blanks (LFB) met the criteria spec ified in the method unless specified

below.

If required by the method, a matrix spike (MS) sample wa s analyzed on sample 72045 for each analyte to check for matrix interferences. For so me analytes, TestAmerica spiked more samples than required. All MS samples analyzed met the criteria specified in the

method unless described below.

DATA NOTES/ISSUES

Ammonia

No issues were identified by the data reviewer.

BOD 5



### TestAmerica analyzed five dilutions, but no dilutions had a dissolved oxygen (DO) depletion greater than 2.0 mg/L for sample 72041 and 72091. Theref ore, BOD 5 

### was reported as not detected for these samples. The rest of the samples had at least one dilution with a DO depletion greater than 2.0 mg/L. As requ ired in the method, the final result was calculated by taking the average of the resul ts 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. Ho wever, for one batch, the results for the three water/unseeded blanks were 0.22 mg/L , 0.14 mg/L, and 0.16 mg/L.

### 3

One of these water blanks was above the method contro l criteria of 0.20 mg/L. However, all samples contained in this batch (samples 72041 and 72045) we re either qualified with a “J” meaning that the sample result was an estimated v alue because it was below the RL or BOD was not detected in the sample, so no further qual ification was necessary.

One of the three batches had a seed correction factor lower than 0.6 mg/L. The seed correction factors were 0.6267 mg/L, 0.5776 mg/L, and 0.6384 mg/L for b atches 33523, 33769, and 33938, respectively. Unlike previous episodes, TestAmeric a did not flag samples in batch 33769 with an “s” indicating the seed corre ction blank (SCB) recovery was low. This low seed correction factor suggests that s amples 72191, 72195, and 72199 may be biased low. Therefore, these samples were also flagged with an “s”. Sample 72191 was already flagged by TestAmerica with a “J” meaning tha t the sample result was an estimated value because it was below the RL, so no fur ther qualification was necessary. However, samples 72195 and 72199 were flagged as minim um values. Due to the short holding time for the analysis, the samples could not be reanalyzed.

All glucose-glutamic acid standards and laboratory duplicat es were analyzed appropriately and met the criteria specified in SM 5210B.

Chloride and Sulfate

The MS and matrix spike duplicate (MSD) results for sam ple 72045 for sulfate and

chloride were above the calibration curve. TestAmerica did not reanalyze the samples with a higher dilution factor because the percent recov eries were within EPA method 300.0 control limits. If reported, these MS/MSD results w ill be qualified as estimated values. The LFB associated with this sample met the me thod criteria. The analyzed result for sample 72045 was within the calibration curve, so there was no need to qualify this sample.

COD

The percent recovery for the MSD analyses for sample 72045 was below the control limits of 90-110% required by EPA method 410.4. The percent recov eries for the MS and MSD analyses for this sample were 109% and 87%, respective ly. Because the MS percent recovery met the method criteria and an MSD is not required by the method, sample 72045 was not qualified. The LFB percent recoveries a ssociated with sample

72045 met the method criteria.

Cyanide

Samples 72041 and 72045 were received by the laboratory at neutra l pH. The lab added more NaOH to increase the pH to greater than 10 S.U. These samples are qualified as

estimated values.

Results for the following samples were less than the l owest calibration standard (0.01 mg/L): 72095, 72195, and 72199. Because all of these samples were a lready flagged by

### 4

TestAmerica with a “J”, meaning the sample result was an estimated value because it was below the RL, no further qualification was necessary.

The percent recoveries for the MS and MSD analyses o f sample 72045 were both 85%, which is outside of the laboratory control criteria of 90-110%. However, because there are no criteria for MS/MSD analyses specified in SM 4500 CN - 

### E, no further qualification was necessary.

Nitrate/Nitrite

No issues were identified by the data reviewer.

Phosphorus

The percent recoveries for the MS/MSD analysis of sam ple 72045 were not within the control limits of 90-110% specified in EPA Method 365.1 or within the laboratory control limits of 71-128%. The percent recoveries of the MS and MSD samples were 19% and 21%, respectively. The result for sample 72045 was only slightly above the RL. This low sample result could have caused the low percen t recovery. Nevertheless, sample 72045 was qualified as a minimum value. The LFB percent recov ery met the method

criteria.

TDS

Constant weight was not achieved after 3 drying cycles fo r all samples. It should be noted that the weight increased from the first weighing to the second weighing for all samples. Method 2540C warns that samples which contain high levels o f calcium, magnesium, chloride, and sulfate may be hygroscopic meaning they abso rb moisture from the air. FGD wastewater contains high concentrations of all o f these species. This was likely the cause for the inconsistent weight calculations. The sam ples were not qualified, but results may be biased high.

The RPDs for laboratory duplicates from samples 72045 and 72191 w ere less than 10% as required by SM 2540C. However, the RPD for sample 72091 was 14%. Because the RPD was greater than the method control limits, sampl e 72091 was qualified as an

estimated value.

TDS was detected at 6.0 mg/L in the method blank associa ted with samples 72191, 72195, and 72199. The method blank result was greater than the MDL (4.7 mg/L), but less than the RL (10 mg/L). No qualification was necessar y because the blank result was

less than the RL.

TKN

The percent recovery for the LFB associated with sampl es 72041, 72045, 72091, 72095, 72191, 72195, and 72199 was not within the method control limits of 90-11 0%, but was

### 5

within the laboratory control limits of 77-115%. The percen t recoveries for the LFB and LFBD were 84% and 86%, respectively. Because the percent r ecovery of the LFB was below the method criteria, samples 72041, 72045, 72091, 72095, 72191, 72195, and 72199 were qualified as minimum values.

TestAmerica performed MS/MSD analysis on sample 72045. The percent recoveries for the MS and MSD samples were 77% and 93%, respectively. The MS sample did not meet the method control limits of 90-110%, but did meet the labo ratory control limits of 54-

131%. The LFB associated with this batch was also not wit hin the laboratory control limits, so this may have caused the low MS percent reco very. Also, the sample concentration was greater than 4 times the spike amoun t in the MS and MSD samples, so TestAmerica stated that the percent recoveries and RP Ds could not be reliably calculated. Therefore, sample 72045 was not additionally qualified based on the MS failure because it is not possible to determine if the MS failure was a result of matrix interferences or the low spiking level.

TKN was detected at 0.133 mg/L in the LRB associated with samples 72041, 72045, 72091, 72095, 72191, 72195, and 72199. The blank result was greater than the MD L (0.077 mg/L), but less than the RL (1.0 mg/L). Because the bla nk result was less than the RL, no samples were qualified based on the LRB result.

TSS

The RPD for the laboratory duplicate of sample 72045 was 13%. This RPD was greater than the method control criteria of 10%. Sample 72045 and its duplicate were already qualified by TestAmerica with a “J” meaning that the resul t is an estimated value because the result is below the RL, so no further qualificatio n was necessary.

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Ac

tion Reason Level Detected

72191 BOD s SCB Recovery Low XXX mg/L
72195 BOD s, Minimum

Value SCB Recovery Low XXX mg/L

72199 BOD s, Minimum

Value SCB Recovery Low XXX mg/L

72041 Cyanide Estimated

Value Sample pH < 10 S.U.

at receipt XXX mg/L

72045 Cyanide Estimated

Value Sample pH < 10 S.U.

at receipt XXX mg/L

72045 Phosphorus Minimum

Value MS % recovery <

method-specified

criteria XXX mg/L

### 6 Table 2. Data Review Summary Table

Sample Analyte Qualifier/Ac

tion Reason Level Detected

72091 TDS Estimated

Value Lab duplicate RPD >

method-specified

criteria 54,000 mg/L

72041 TKN Minimum

Value LFB% recovery <

method-specified

criteria XXX mg/L

72045 TKN Minimum

Value LFB% recovery <

method-specified

criteria XXX mg/L

72091 TKN Minimum

Value LFB% recovery <

method-specified

criteria 59 mg/L

72095 TKN Minimum

Value LFB% recovery <

method-specified

criteria 22 mg/L

72191 TKN Minimum

Value LFB% recovery <

method-specified

criteria XXX mg/L

72195 TKN Minimum

Value LFB% recovery <

method-specified

criteria XXX mg/L

72199 TKN Minimum

Value LFB% recovery <

method-specified

criteria XXX mg/L

### 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: 2/9/2012 Subject: FGS Data Review Narrative for Total Mercury – Long-Term M onitoring: Month 2 (Part 1)

Frontier Global Sciences (FGS) generated analytical da ta for total mercury. FGS analyzed the samples according to EPA Method 1631E for merc ury by Cold Vapor Atomic Fluorescence Spectrometry (CVAFS) analysis.

Table 1 summarizes the 19 samples (excluding laboratory pre p blanks) FGS extracted and analyzed for total mercury.

Table 1. 

### Long-Term Monitoring Month 2 (Part 1) Mercury – Sample Identification

EPA Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

71992 1011064-01 Aqueous FGD Influent, Set 2 11/3/2010

71996 1011064-06 Aqueous FGD Bioreactor Influent, Set 2 11/3/2010

72000 1011064-11 Aqueous FGD Bioreactor Effluent, Set 2 11/3/2010

72005 1011064-12 Aqueous FGD Bioreactor Influent Field Blank, Set 2 11/ 3/2010

72009 1011064-13 Aqueous FGD Bioreactor Effluent Field Blank, Set 2 11/3 /2010

72042 1011043-01 Aqueous FGD Influent, Set 2 11/3/2010

72046 1011043-02 Aqueous FGD Effluent, Set 2 11/2/2010

72051 1011043-03 Aqueous FGD Effluent Field Blank, Set 2 11/2/2010

72092 1011031-01 Aqueous FGD Influent, Set 2 11/2/2010

72096 1011031-02 Aqueous FGD Effluent, Set 2 11/2/2010

72101 1011031-03 Aqueous FGD Effluent, Field Blank, Set 2 11/1/2010

72142 1011032-01 Aqueous FGD Influent, Set 2 11/1/2010

72146 1011032-02 Aqueous FGD Bioreactor Influent, Set 2 11/1/2010

72150 1011032-03 Aqueous FGD Bioreactor Effluent, Set 2 11/1/2010

72155 1011032-04 Aqueous FGD Bioreactor Influent Field Blank, Set 2 11/ 1/2010

72159 1011032-05 Aqueous FGD Bioreactor Effluent Field Blank, Set 2 11/1 /2010

72242 1011061-01 Aqueous FGD Influent, Set 2 11/4/2010

72246 1011061-06 Aqueous FGD Effluent, Set 2 11/4/2010

72251 1011061-07 Aqueous FGD Effluent Field Blank, Set 2 11/3/2010

### 2

SUMMARY

The samples were prepared according to EPA Method 1631E to be analyzed by CVAFS.

There were no findings from the data review that required a dditional qualifiers in this dataset. The following summarizes the findings from the data review:

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysi s day. The initial calibration for the CVAFS analysis consisted of a blank and five calibrat ion standards with a correlation

coefficient ≥ 0.995. All method-specified criteria were met.

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

All initial and continuing calibration verifications (I CVs, CCVs) met method-specified

criteria.

BLANKS

All the preparation blanks or laboratory reagent blanks (L RBs) and the continuing calibration blanks (CCBs) met the method-specified crite ria. Because all of the blank results were less than the RL, no samples were quali fied based on these preparation blank

results.

DUPLICATES

No field duplicate samples were collected with these sa mpling episodes. Two samples were analyzed in duplicate at the laboratory, samples 72046 a nd 72246. The relative percent difference (RPD) for samples 72046 and 72246 were 4.25% an d 0.84%, respectively. The laboratory’s RPD criteria between an alytical duplicates is 24%.

LABORATORY CONTROL SAMPLES

All laboratory control samples were within FGS’s contr ol limits of 80-120% recovery

and 24% RPD.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

Matrix spikes (MS) and matrix spike duplicates (MSD) we re performed on samples 71996, 72046, 72150, and 72246. All aqueous MS/MSD recoveries were within th e

### 3

method specifications of 71-125%, except for the MS samples for 72046 and 72150, which had recoveries of 20.1% and 54.5%, respectively. All RPD s met method-specified criteria of less than or equal to 24%, except for samples 72046 and 72150, which had RPDs of 72.2% and 24.5%, respectively. Because the MSDs an d the associated LCSs were within the method specifications, no data qualificati on is required for these samples.

DETECTION LIMITS

The laboratory MDL in the synthetic matrix was 0.239 ng/ L. Results below this MDL were reported as not detected (ND).

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Randy Mercurio, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Total Metals by 200.8 – Long-Term Monitoring: Month 2 (Part 1)

TestAmerica generated analytical data for total metals (antimony, arsenic, cadmium,chromium, copper, lead, nickel, selenium, silver, thallium and vanadium) for these longterm monitoring samples. The samples were analyzed according to EPA Method 200.8.

Table 1 summarizes the samples TestAmerica extracted and analyzed for total metals by

EPA Method 200.8.

Table 1. 

### Long-Term Monitoring Month 2 (Part 1) Total Metals – Sample

Identification

EPA Sample # EPA Sample

Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71992 FGD Influent, Set 2 280

- 9327

- 1 Aqueous 11/03/2010 11/04/2010

71996 FGD Bioreactor Influent,

Set 2 280

- 9389

- 1 Aqueous 11/04/2010 11/05/2010

72000 FGD Bioreactor Effluent,

Set 2 280

- 9389

- 2 Aqueous 11/04/2010 11/05/2010

72005 FGD Bioreactor Influent

Field Blank, Set 2 280

- 9389

- 3 Aqueous 11/04/2010 11/05/2010

72009 FGD Bioreactor Effluent

Field Blank, Set 2 280

- 9389

- 4 Aqueous 11/04/2010 11/05/2010

72042 FGD Influent, Set 2 280

- 9326

- 1 Aqueous 11/03/2010 11/04/2010

72046 FGD Effluent, Set 2 280

- 9326

- 2 Aqueous 11/03/2010 11/04/2010

72051 FGD Bioreactor Effluent

Field Blank, Set 2 280

- 9326

- 3 Aqueous 11/03/2010 11/04/2010

72092 FGD Influent, Set 2 280

- 9249

- 1 Aqueous 11/02/2010 11/03/2010

72096 FGD Effluent, Set 2 280

- 9249

- 2 Aqueous 11/02/2010 11/03/2010

72101 FGD Effluent Field

Blank, Set 2 280

- 9249

- 3 Aqueous 11/02/2010 11/03/2010

72142 FGD Influent, Set 2 280

- 9202

- 1 Aqueous 11/01/2010 11/02/2010

72146 FGD Bioreactor Influent,

Set 2 280

- 9250

- 1 Aqueous 11/02/2010 11/03/2010

### 2 Table 1. 

### Long-Term Monitoring Month 2 (Part 1) Total Metals – Sample

Identification

EPA Sample # EPA Sample

Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

72150 FGD Bioreactor Effluent,

Set 2 280

- 9250

- 2 Aqueous 11/02/2010 11/03/2010

72155 FGD Bioreactor Influent

Field Blank, Set 2 280

- 9250

- 3 Aqueous 11/02/2010 11/03/2010

72159 FGD Bioreactor Effluent

Field Blank, Set 2 280

- 9250

- 4 Aqueous 11/02/2010 11/03/2010

72242 FGD Influent, Set 2 280

- 9388

- 1 Aqueous 11/04/2010 11/05/2010

72246 FGD Effluent, Set 2 280

- 9388

- 2 Aqueous 11/04/2010 11/05/2010

72251 FGD Bioreactor Effluent

Field Blank, Set 2 280

- 9388

- 3 Aqueous 11/04/2010 11/05/2010



### SUMMARY

The samples were prepared for total metals analysis according to TestAmerica’s “FGD ICP/MS SOP: Inductively Coupled Plasma Mass Spectrometry for Trace Elements Analysis in Flue Gas Desulfurization Wastewaters,” dated October 6, 2010, based on EPA Method 200.8, by ICP/MS analysis.

Any significant findings are summarized below. No additional data qualifiers were required.

• The serial dilution for selenium for sample 72096 failed TestAmerica’s criteria of

±10% difference.

• The matrix spike (MS) and matrix spike duplicate (MSD) recoveries for silver for sample 72096 failed the EPA Method 200.8 control limits of 70–130%.

• The MS and MSD recoveries for selenium and silver for sample 72246 failed the

EPA Method 200.8 control limits of 70–130%.

• The MS/MSD relative percent difference (RPD) for silver for sample 72246 failed

the FGD ICP/MS SOP control limits of ±20%.

• The post digestion spike (PDS) recoveries for silver failed TestAmerica’s control

limits of 85–115%.

INTERNAL STANDARDIZATION

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

INITIAL CALIBRATION

### 3

TestAmerica performed the initial calibrations on each analysis day. The initial calibration for the ICP-MS analysis consisted of a blank and four calibration standards.

INITIAL AND CONTINUING CALIBRATION VERIFICATION (ICV/CCV)

The initial calibration verifications (ICV) and continuing calibration verifications (CCV) performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit (RL); however, some elements were above the MDL and flagged with a “J” qualifier. No additional qualifiers were required for method blanks.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank (CCB)) were less than the RL; however, some elements were above the MDL and flagged with a “J” qualifier. No additional qualifiers were required for instrument blanks.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s SOP control limits of 50–150% recovery.

LABORATORY CONTROL SAMPLES (LCS)

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

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION

Based on TestAmerica’s SOP, all interference check sample A (ICSA) results had analytes of interest with concentrations less than the RL or less than five times the RL when known inherent contaminants are present in the stock solution used to make the

ICS.

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

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

The ICSA solution for the method 200.8 analysis exceeded the acceptance limits for Chromium in analytical batch 280-40682. The lab has confirmed with the vendor that Chromium is a trace impurity in the ICSA solution. Therefore, corrective action was deemed unnecessary; the associated data have been flagged “^”.

### 4

SERIAL DILUTION

The serial dilution performed on sample 72096 passed TestAmerica’s criteria of ±10% difference for all analytes except selenium, which was flagged “V.” No further data qualifiers were needed for the serial dilution.

FIELD DUPLICATES

No field duplicate samples were collected with these sampling episodes.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

MS and MSD were performed on samples 72096 and 72246. The MS/MSD for sample 72096 failed the method control limits of 70–130% recovery for selenium and silver. Selenium was flagged for the MS/MSD with a “4” qualifier indicating that the concentration in the parent sample was greater than 4 times the spike and could not be reliably calculated. This result was considered acceptable based on the LCS passing the method control limits. Silver was flagged for the MS/MSD with an “F” qualifier and it is likely that silver failed due to matrix interference from the high concentration of sulfates,

which can form insoluble silver sulfide and/or silver sulfate. The silver recoveries in the associated LCS/LCSD were acceptable.

The MS/MSD for sample 72246 failed the method control limits of 70–130% recovery for selenium and silver, which were flagged with an “F” qualifier. The RPD failed the FGD ICP/MS SOP control limits of ±20% for silver for sample 72246. No additional data qualifiers were required for MS/MSD samples.

Otherwise, all MS/MSD spike recoveries were within the method control limits of 70-

130% and the RPD for the MS/MSDs were within the FGD ICP/MS SOP control limits of ±20 percent. No additional data qualifiers were required.

POST DIGESTION SPIKES (PDS)

The PDS performed on sample 72096 passed TestAmerica’s control limits of 85–115% recovery for all analytes, except for silver, which was flagged with a “W” qualifier. It is likely that silver failed due to matrix interference from the high concentration of sulfates,

which can form insoluble silver sulfide and/or silver sulfate. The silver recoveries in the associated LCS/LCSD were acceptable. No additional data qualifiers were required.

DETECTION LIMITS

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

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Randy Mercurio, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Total Metals by 200.7 – Long-Term Monitoring: Month 2 (Part 1)

TestAmerica generated analytical data for total metals (aluminum, boron, barium, beryllium, calcium, cobalt, iron, magnesium, manganese , molybdenum, sodium, tin, titanium and zinc). The samples were analyzed according t o EPA Method 200.7.

Table 1 summarizes the samples TestAmerica extracted a nd analyzed for total metals by

EPA Method 200.7.

Table 1. 

### Long-Term Monitoring Month 2 (Part 1) Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

7199 2 FGD Influent, Set 2 280

- 9327

- 1 Aqueous 11/03 /2010 11/04 /2010

71996 FGD Bioreactor Influent, Set 2 280

- 9389

- 1 Aqueous 11/04 /2010 11/05 /2010

72000 FGD Bioreactor Effluent, Set 2 280

- 9389

- 2 Aqueous 11/04 /2010 11/05 /2010

72005 FGD Bioreactor Influent Field

Blank, Set 2 280

- 9389

- 3 Aqueous 11/04 /2010 11/05 /2010

72009 FGD Bioreactor Effluent Field

Blank, Set 2 280

- 9389

- 4 Aqueous 11/04 /2010 11/05 /2010

7 2042 FGD Influent, Set 2 280

- 9326

- 1 Aqueous 11/03 /2010 11/04 /2010

7 2046 FGD Effluent, Set 2 280

- 9326

- 2 Aqueous 11/03 /2010 11/04 /2010

72051 FGD Bioreactor Effluent Field

Blank, Set 2 280

- 9326

- 3 Aqueous 11/03 /2010 11/04 /2010

7 2092 FGD Influent, Set 2 280

- 9249

- 1 Aqueous 11/02 /2010 11/03 /2010

72 101 FGD Ef

fluent Field Blank , Set 2 280

- 9249

- 3 Aqueous 11/02 /2010 11/03 /2010

72142 FGD Influent, Set 2 280

- 9202

- 1 Aqueous 11/01 /2010 11/02 /2010

7 2146 FGD Bioreactor Influent, Set 2 280

- 9250

- 1 Aqueous 11/02 /2010 11/03 /2010

7 2150 FGD Bioreactor Effluent, Set 2 280

- 9250

- 2 Aqueous 11/02 /2010 11/03 /2010

7 2155 FGD Bioreactor In fluent Field

Blank, Set 2 280

- 9250

- 3 Aqueous 11/02 /2010 11/03 /2010

7 2159 FGD Bioreactor Ef fluent Field Blank, Set 2 2 80

- 9250

- 4 Aqueous 11/02 /2010 11/03 /2010

72242 FGD Influent, Set 2 280

- 9388

- 1 Aqueous 11/04 /2010 11/05 /2010

### 2

Table 1. 

### Long-Term Monitoring Month 2 (Part 1) Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

72251 FGD Bioreactor Effluent Field

Blank, Set 2 280

- 9388

- 3 Aqueous 11/04 /2010 11/05 /2010



### SUMMARY

The samples were prepared for total metals analysis acc ording to TestAmerica’s SOP for ICP Analysis for Trace Metals by Method 200.7. Any signific ant findings are summarized below. No additional data qualifiers were requir ed for this data set.

• Aluminum, calcium, iron, magnesium, and manganese wer e measured above the reporting limit (RL) in a method blank; however, the conc entration of these elements in the samples associated with this method blank were at least 10 times

the blank result or below the RL.

• The matrix spike (MS)/matrix spike duplicate (MSD) rel ative percent difference (RPD) for boron, calcium, and magnesium for sample 72096 failed TestAmerica’s ± 20% requirement.

• The post digestion spike (PDS) for calcium, manganese, t itanium, and zinc for sample 72096 failed TestAmerica’s control limits of 85-115% re covery.

SAMPLE RECEIPT, HANDLING AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INTERNAL STANDARDIZATION

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

ISTD recoveries within the ±30% criterion of the calibra tion blank as per Section 9.11 of

the SOP were seen. All ISTD were within TestAmerica’ s SOP control limits.

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial calibration for the ICP analysis consisted of a blank an d one calibration standard.

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

The initial calibration verifications (ICV) and continu ing calibration verifications (CCV) performed by TestAmerica all had recoveries within the m ethod criteria.

### 3

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the RL, except for MB 280-40683/1-A. Aluminum, calcium, iron, magnesium, and manganese were measured ab ove the RL in this method blank; however, the concentration of these elements in the samples associated with this

method blank were at least 10 times the blank result or b elow the RL. Therefore, no data needed qualification regarding the method blank result. In the other method blanks, some elements were above the method detection limit (MDL), but less than the RL; therefore, these blanks and were flagged with the “J” qualifier.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank (CCB)) were less than the RL; however, some element s were above the MDL and were flagged with the “J” qualifier.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s SOP control limi ts of 50–150% recovery.

LABORATORY CONTROL SAMPLES (LCS)

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

INTERFERENCE CHECK SOLUTIONS

Interference checks were performed using the synthetic m atrix as the check solution. All data quality objectives met TestAmerica’s SOP criteria.

SERIAL DILUTION (SRD)

All serial dilution percent differences were less tha n 10% as required by TestAmerica’s

SOP.

FIELD DUPLICATES

No field duplicate samples were collected with these sa mpling episodes.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) w ere performed on the total samples of 72096 and 72246. Some elements with high concentrat ions failed the EPA 200.7 Method spike recovery control limits of 70–130% but were f lagged with a “4” qualifier indicating that the concentration in the paren t sample was greater than 4 times the spike and could not be reliably calculated. These da ta were considered acceptable based on the LCS passing the method criteria. Otherwi se, all MS/MSD spike recoveries

were within the method control criteria of 70-130%. The RPD for all MS/MSDs were

### 4

within TestAmerica’s ± 20% requirement, except for boron, calcium, and magnesium for sample 72096. These elements were flagged with an “F” qualif ier.

POST DIGESTION SPIKE (PDS)

The PDS performed on sample 72096 passed TestAmerica’s contr ol limits of 85-115% recovery for all analytes except boron, calcium, man ganese, sodium, titanium, and zinc. Calcium, manganese, titanium, and zinc were qualified wit h a “W;” however, Because the spike level in the MS/MSD analyses for these ele ments was less than 4 times the sample concentration, there is no evidence of matrix in terferences. Additionally, these elements passed TestAmerica’s requirement of percent d ifferences less than 10% for the serial dilution for sample 72096. Boron and sodium failed t he PDS; however, the percent recoveries were not calculated by the laboratory becaus e their concentrations were greater than 4 times the PDS spike level. Boron and sodiu m also passed the serial dilution for sample 72096 demonstrating no significant matrix interfe rences.

DETECTION LIMITS

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

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Ariel Atkinson, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Classicals Ana lyses – Long Term Monitoring: Month 2 (Part 1)

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry analyses for these long-term monitoring samples. All s amples were tested for the following analytes:

• Ammonia by EPA method 350.1,

• Biochemical Oxygen Demand – 5 day (BOD 5 

### ) by SM 5210B,

• Chloride and Sulfate by EPA method 300.0,

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

• Cyanide (total) by SM 4500 CN - 

### E,

• Nitrate/Nitrite by EPA method 353.2,

• Phosphorus (total) by EPA method 365.1,

• Total Dissolved Solids (TDS) by SM 2540C,

• Total Kjeldahl Nitrogen (TKN) by EPA method 351.2, and

• Total Suspended Solids (TSS) by SM 2540D.

Table 1 summarizes the 12 samples that TestAmerica anal yzed for the above analytes.

Table 1. Long-Term Monitoring Month 2 (Part 1) Classical Analytes – Sample

Identification

EPA Sample # Sample

Matrix Sample Description Sampling

Date 71992 Water FGD Influent, Set 2 11/3/10 71996 Water FGD Bioreactor Influent, Set 2 11/3/10(CN) 11/4/10(All other analytes) 72000 Water FGD Bioreactor Effluent, Set 2 11/3/10(CN) 11/4/10(All other analytes)
72042 Water FGD Influent, Set 2 11/3/2010
72046 Water FGD Effluent, Set 2 11/3/2010

### 2

Table 1. Long-Term Monitoring Month 2 (Part 1) Classical Analytes – Sample

Identification

EPA Sample # Sample

Matrix Sample Description Sampling

Date 72092 Water FGD Influent, Set 2 11/2/2010
72096 Water FGD Effluent, Set 2 11/2/2010
72142 Water FGD Influent, Set 2 11/1/2010
72146 Water FGD Bioreactor Influent, Set 2 11/2/2010 72150 Water FGD Bioreactor Effluent, Set 2 11/1/10(CN) 11/2/10(All other analytes)
72242 Water FGD Influent, Set 2 11/4/10
72246 Water FGD Effluent, Set 2 11/4/10

SUMMARY

All samples were analyzed within the holding time specif ied in 40 CFR 136 Table II. All samples were preserved appropriately unless otherwise speci fied below.

Field duplicate samples were not collected for these ep isodes. Depending on the method, a laboratory duplicate was analyzed, instead. The Relati ve Percent Difference (RPD) between the sample and its duplicate was less than 20% unl ess otherwise noted below.

If applicable, the appropriate number of standards was used to create a calibration curve. If sample results were above the highest standard used t o create the curve, the sample was diluted and reanalyzed unless otherwise specified below. Al l sample results were between the lowest and highest standards unless noted below. Additi onally, unless otherwise noted, all calibration blanks and calibration verificat ion samples met the criteria specified

in the method.

If required by the method, the quality control sample (QC S), a secondary source standard used to verify calibration, was always within the cont rol limits specified by the method

unless otherwise noted below.

As described below, the analyte of interest was detecte d above the method detection limit (MDL) in some laboratory reagent blanks (LRB). However , the analyte of interest was never detected above the reporting limit (RL) in the LRBs . If required by the method, all laboratory fortified blanks (LFB) met the criteria spec ified in the method unless specified

below.

If required by the method, a matrix spike (MS) sample wa s analyzed on samples 72042, 72096, and/or 72246 for each analyte to check for matrix interf erences. For some analytes, TestAmerica spiked more samples than require d. MS samples analyzed met the criteria specified in the method unless described below.

### 3

DATA NOTES/ISSUES

Ammonia

The MS result failed criteria at 111% recovery and was qualified with an “F” flag. The MSD and LCS recoveries demonstrate that the analysis was under control. No additional qualifiers were required.

BOD 5



### TestAmerica analyzed five dilutions, but no dilutions had a dissolved oxygen (DO) depletion greater than 2.0 mg/L for samples 72092, 72146, 72150 72042, 72046, 71992, 71996, and 72246. Therefore, BOD 5 

### was reported as not detected for these samples. 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 calculat ed by taking the average of the results for all dilutions with a DO depletion greater t han 2.0 mg/L and a final DO greater than 1.0 mg/L.

One of the three batches had a seed correction factor lower than 0.6 mg/L. The seed correction factors were 0.632 mg/L, 0.5533 mg/L, and 0.6267 mg/L for batches 38776, 39101, and 39326 respectively. The samples in batch 39101 should be flagg ed with an “s” indicating the seed correction blank (SCB) recovery was low. This low seed correction factor suggests that samples 72042, 72046, and 71992 may be biased low; however all these samples had a result of ND and ther efore do not require qualification.

All glucose-glutamic acid standards and laboratory duplicat es were analyzed appropriately and met the criteria specified in SM 5210B.

Chloride and Sulfate

The MS/MSD results of samples 72246 for sulfate and chlori de were above the calibration curve. TestAmerica did not reanalyze the s amples with a higher dilution factor because the percent recoveries were within EPA method 300. 0 control limits. If reported, these MS/MSD results will be qualified as estimated val ues. The LFB associated with this sample met the method criteria. The analyzed resu lt for sample 72246 was within the calibration curve, so there was no need to qualify this s ample.

COD

Several LRB and Calibration Blanks (CB) had results gr eater than the MDL; however, all the LRB and CB results less than the RL and were flagge d with a “J” qualifier. No further qualifications are necessary.

One LFB, LCSD from batch 41304, had a percent recovery grea ter that the 90-110% criteria. The LFB was flagged with a “*” qualifier indic ating the LCS or LCSD exceeds

### 4

the control limits. The sample 72046, which is associated with this LFB, was also flagged with “*” qualifier.

The percent recovery for the MS/MSD analyses for sam ples 72096 and 72246 were above the control limits of 90-110% required by EPA method 410.4. The percent recoveries for the MS and MSD analyses for sample 72096 were 115% and 118%, respectively and the recoveries for sample 72246 were 131% and 132%, respectively. These results were flagged with an “F” qualifier because t hey exceed control limits. The LFB percent recoveries associated with samples 72096 and 72246 m et the method

criteria.

MS/MSDs were not performed in batches 41739 and 41304. The sampl es associated with these batches include 72042 and 72046. These sample results were qualified with an “F” qualifier because there were no MS/MSD results.

Cyanide

The calibration was performed using standards ranging from 0.00 ppb to 400.0 ppb. The method states that the appropriate calibration range of s tandard concentrations for this method are between 5 ppb and 20 ppb. Samples 72142, 72092, 72096, 72046, 72242, a ll

had results ≥ 20 ug/L; but were not diluted because they were within the ca libration range performed by the laboratory.

The MS/MSD results for sample 72246 passed the recovery cr iteria; however, the MS/MSD results for sample 72096 failed recovery criteria. The MS/MSD results for 72096 were qualified with an “F” flag. The associated LCS/LC SD recoveries were

within control limits.

Nitrate/Nitrite

The RPD between the LFB and a duplicate LFB from batch 280-40320 is 10.7%. This does not meet the control limits, and therefore the LF B, LFB duplicate, and associated samples are flagged with a “*” qualifier meaning RPD of the LCS and LCSD exceeds the

control limit. The RPD for the MS/MSD in this batch was 1 percent; therefore the system appears to be in control. No further qualifiers were nee ded.

The MS/MSD results for samples 72042, 72096, and 72246 were above t he calibration curve. TestAmerica did not reanalyze these MS/MSDs with a higher dilution factor, but the MS/MSD results for samples 72246 and 72042 were flagged with an “E” qualifier because the results exceeded calibration range. The MS/MSD results for sample 72096 were not flagged with “E” qualifier because the percent re coveries for the MS/MSD analysis of sample 72096 were not within the method control limits of 90-110 percent; therefore, these MS/MSD results were flagged with an “ F” qualifier. The percent recoveries for the MS/MSD of 72096 were 118% and 121%, respectiv ely. Additionally, the MS of sample 72042, and the MSD of sample 72246 were not wi thin the method control limits of 90-110%. The percent recovery of the MS D for sample 72246 was 89%

### 5

and the percent recovery of the MS of sample 72042 was 88 pe rcent; however neither MS/MSDs were flagged with an “F’ qualifier because they d id meet the laboratory control limits. If reported, the 72042 MS should be flagged w ith an “F” qualifier, the 72096 MS/MSD should be qualified as estimated, and the 72246 MS sho uld be flagged with an “F” qualifier.

Phosphorus

The LRB was greater than the MDL at 0.0141 mg/L, however th e result was less than the RL. The LRB results were flagged with a “J” qualifier b ecause the result was less than the RL but greater than the MDL. No further qualifiers are needed. All samples that contained the analyte were also flagged with a “B” qualif ier because the compound was found in the blank and the sample. All calibration blank r esults were also above the MDL but less than the RL, and therefore are also flagged wi th a “J” qualifier.

The percent recoveries for the MS/MSD analysis of sa mples 72096 and 72246 were not within the control limits of 90-110% specified in EPA Method 365. 1. However the MS/MSD of sample 72096 were within the laboratory control limits of 71-128%. The percent recoveries of the MS and MSD for sample 72096 were 87% and 84%, respectively, and the MS and MSD recoveries for sample 72246 were 26% and 31%, respectively. Because the MS/MSD of sample 72096 met labo ratory control limits it was not flagged by the laboratory, but if the MS/MSD results for sample 72096 are reported, they should be flagged with an “F” qualifier.

Samples 72146, 72150, 72046, 72242, 71996, 72000, and the LRB had results that were

lower than the lowest calibration standard. Each of th ese results was flagged with a “J” qualifier because each result was less than the RL but greater than or equal to the MDL, and therefore the concentrations are approximate values. N o further qualifiers are needed.

TDS

Constant weight was not achieved after 3 drying cycles fo r all samples. It should be noted that the weight increased from the first weighing to th e second weighing for all samples except 72042, 72046, 71992, 72242, 72246, 71996, and 72000. Method 2540C warns that samples which contain high levels of calcium, magnesiu m, chloride, and sulfate may be hygroscopic meaning they absorb moisture from the air. FGD wastewater contains high concentrations of all of these species. This was likely the cause for the inconsistent weight calculations. Samples 72142, 72092, 72096, 72146, and 72150 were not qua lified, but results may be biased high.

The RPD for the laboratory duplicate from sample 72096 was 12%, which is not less than 10% as required by SM 2540C. The laboratory control limits a re 20%; therefore, the laboratory did not qualify the sample. The sample resu lt will be qualified as an estimated value as shown in Table 2. Laboratory duplicates were n ot performed in the other

batches.

### 6

TKN

TestAmerica performed MS/MSD analysis on samples 72096 and 72246. The percent recoveries for the MS and MSD for sample 72096 were 161% an d 147%, respectively, and 145% and 149% for the MS and MSD for sample 72246. These samp les did not meet the method control limits of 90-110%, nor the laboratory co ntrol 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 recove ries and RPDs could not be reliably calculated. The associated LCS/LCSD were also acceptable, therefore, no additional data qualifiers are required.

TKN was detected in the calibration blanks. The results were greater than the MDL (0.077 mg/L), but less than the RL (1.0 mg/L). Because the re sults were less than the RL, no samples were qualified, but the CBs were flagged with a “J” qualifier.

TSS

The RPDs for the laboratory duplicates performed on sam ples 72142, 72096, 72046, and 72246 were greater than the method control criteria of 10%, at 11%, 18%, 22%, and 18%, respectively. The laboratory control criterion is 20 perc ent; therefore, samples 72142, 72096, and 72246 were not qualified by the laboratory. Sample 72046 and its duplicate were already qualified by TestAmerica with a “J” meaning t hat the result is an estimated value because the result is below the RL, so no further qualification was necessary for this sample. Because the RPD was greater than the meth od control limits, sample 72142, 72096, and 72246 were qualified as estimated values.

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Ac

tion Reason Level Detected

72042 COD F MS/MSD not performed in batch XXX mg/L



### 72046 COD F MS/MSD not performed in batch XXX mg/L



### 72096 TDS Estimated

Value Lab duplicate RPD >

method-specified

criteria Sample: 28000

mg/L Dup: 24900 mg/L,12%RPD



### 72142 TSS Estimated

Value Lab duplicate RPD >

method-specified

criteria Sample: XXX

mg/L Dup: XXX mg/L; 11%RPD



### 72096 TSS Estimated

Value Lab duplicate RPD >

method-specified

criteria Sample: 4.8 mg/L Dup: 4 mg/L;

18% RPD

### 7 Table 2. Data Review Summary Table

Sample Analyte Qualifier/Ac

tion Reason Level Detected

72246 TSS Estimated

Value Lab duplicate RPD >

method-specified

criteria Sample: XXX mg/L Dup: XXX mg/L; 18% 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: Donna Tedder, ERG

Date: 2/9/2012 Subject: FGS Data Review Narrative for Total Mercury – Long-Term M onitoring:

Month 3

Frontier Global Sciences (FGS) generated analytical data for total mercury. FGS analyzed the samples according to EPA Method 1631E for merc ury by Cold Vapor Atomic Fluorescence Spectrometry (CVAFS) analysis.

Table 1 summarizes the 24 samples (excluding laboratory pre p blanks) FGS extracted and analyzed for total mercury.

Table 1. 

### Long-Term Monitoring Month 3 Mercury – Sample Identification

EPA Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

71993 1012119-01 Aqueous FGD Influent, Set 3 12/8/2010

71997 1012119-06 Aqueous FGD Bioreactor Influent, Set 3 12/8/2010

72001 1012119-11 Aqueous FGD Bioreactor Effluent, Set 3 12/8/2010

72006 1012119-12 Aqueous FGD Bioreactor Influent Field Blank, Set 3 12/ 8/2010

72010 1012119-13 Aqueous FGD Bioreactor Effluent Field Blank, Set 3 12/8 /2010

72043 1012094-01 Aqueous FGD Influent, Set 3 12/8/2010

72047 1012094-02 Aqueous FGD Effluent, Set 3 12/7/2010

72052 1012094-03 Aqueous FGD Effluent Field Blank, Set 3 12/7/2010

72093 1012077-01 Aqueous FGD Influent Set 3 12/7/2010

72097 1012077-02 Aqueous FGD Effluent, Set 3 12/7/2010

72102 1012077-03 Aqueous FGD Effluent Field Blank, Set 3 12/7/2010

72143 1012080-01 Aqueous FGD Influent, Set 3 12/6/2010

72147 1012080-06 Aqueous FGD Bioreactor Influent, Set 3 12/6/2010

72151 1012080-11 Aqueous FGD Bioreactor Effluent, Set 3 12/6/2010

72156 1012080-12 Aqueous FGD Bioreactor Influent Field Blank, Set 3 12/ 6/2010

72160 1012080-13 Aqueous FGD Bioreactor Effluent Field Blank, Set 3 12/6/2010

72192 1012105-01 Aqueous FGD Influent, Set 1 12/8/2010

72196 1012105-02 Aqueous FGD SBR Influent, Set 1 12/8/2010

72200 1012105-03 Aqueous FGD SBR Effluent, Set 1 12/8/2010

### 2 Table 1. 

### Long-Term Monitoring Month 3 Mercury – Sample Identification

EPA Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

72205 1012105-04 Aqueous FGD SBR Influent Field Blank, Set 1 12/8/2010

72209 1012105-05 Aqueous FGD SBR Effluent Field Blank, Set 1 12/8/2010

72243 1012117-01 Aqueous FGD Influent, Set 3 12/9/2010

72247 1012117-06 Aqueous FGD Effluent, Set 3 12/9/2010

72252 1012117-07 Aqueous FGD Effluent Field Blank, Set 3 12/8/2010



### SUMMARY

The samples were prepared according to EPA Method 1631E to be analyzed by CVAFS.

There were no findings from the data review that required a dditional qualifiers in this

dataset.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysi s day. The initial calibration for the CVAFS analysis consisted of a blank and five calibrat ion standards with a correlation

coefficient ≥ 0.995. All method-specified criteria were met.

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

All initial and continuing calibration verifications (I CVs, CCVs) met method-specified

criteria.

BLANKS

All the preparation blanks or laboratory reagent blanks (L RBs) and the continuing calibration blanks (CCBs) met method-specified criteria. Some preparation blanks had mercury levels greater than the MDL (0.24 ng/L), but less t han the RL associated with each individual blank (different RLs based on preparation) . Because all of the blank results were less than the RL, no samples were quali fied based on these preparation blank

results.

DUPLICATES

No field duplicate samples were collected with these sa mpling episodes. Three samples were analyzed in duplicate at the laboratory, Bioreacto r Influent sample 72147, SBR Influent sample 72196, and Effluent sample 72247. The relative pe rcent difference (RPD)

### 3

for samples 72147, 72196, and 72247 were 9.74%, 4.36%, and 9.10%, respectiv ely. A sample from another work order was analyzed in duplica te with these batches that resulted in an RPD of 79.7%, which is outside of the laborat ory’s criteria. The laboratory’s RPD criteria between analytical duplicates is 24%. No sample qualifications were needed based on these analytical duplicate results.

LABORATORY CONTROL SAMPLES

All laboratory control samples were within FGS’s contr ol limits of 80-120% recovery

and 24% RPD.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) we re performed on samples 72097, 72147, and 72196. Additionally, an MS/MSD was performed on samp le 72296, which was a rerun from the long-term monitoring, month 2 set of samples. All aqueous MS/MSD recoveries were within method specifications of 71-125%. All RPDs met method-specified criteria.

DETECTION LIMITS

The laboratory MDL in the synthetic matrix was 0.239 ng/ L. Results below this MDL were reported as not detected (ND).

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Randy Mercurio, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Total Metals by 200.8 – Long-Term Monitoring: Month 3

TestAmerica generated analytical data for total metals (antimony, arsenic, cadmium, chromium, copper, lead, nickel, selenium, silver, thalliumand vanadium) for these longterm monitoring samples. The samples were analyzed accor ding to EPA Method 200.8.

Table 1 summarizes the samples TestAmerica extracted a nd analyzed for total metals by

EPA method 200.8.

Table 1. 

### Long-Term Monitoring Month 3 Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71993 FGD Influent, Set 3 280

- 10586

- 1 Aqueous 12/08/2010 12/09/2010

71997 FGD Bioreactor Influent, Set 3 280

- 10586

- 2 Aqueous 12/08/2010 12/09/2010

71997 FGD Bioreactor Influent, Set 3 280

- 10654

- 1 Aqueous 12/09/2010 12/10/2010

72001 FGD Bioreactor Effluent, Set 3 280

- 10654

- 2 Aqueous 12/09/2010 12/10/2010

72006 FGD Bioreactor Influent Field

Blank, Set 3 280

- 10654

- 3 Aqueous 12/09/2010 12/10/2010

72010 FGD Bioreactor Effluent Field

Blank, Set 3 280

- 10654

- 4 Aqueous 12/09/2010 12/10/2010

72043 FGD Influent, Set 3 280

- 10584

- 1 Aqueous 12/08/2010 12/09/2010

72047 FGD Effluent, Set 3 280

- 10584

- 2 Aqueous 12/08/2010 12/09/2010

72052 FGD Bioreactor Effluent Field

Blank, Set 3 280

- 10584

- 3 Aqueous 12/08/2010 12/09/2010

72093 FGD Influent, Set 3 280

- 10515

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

72097 FGD Effluent, Set 3 280

- 10515

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

72102 FGD Effluent Field Blank, Set 3 280

- 10515

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

72143 FGD Influent, Set 3 280

- 10455

- 1 Aqueous 12/06/2010 12/07/2010

72147 FGD Bioreactor Influent, Set 3 280

- 10517

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

72151 FGD Bioreactor Effluent, Set 3 280

- 10517

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

72156 FGD Bioreactor Influent Field

Blank, Set 3 280

- 10517

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

72160 FGD Bioreactor Effluent Field 280

- 10517

- 4 Aqueous 12/07/2010 12/08/2010

### 2

Table 1. 

### Long-Term Monitoring Month 3 Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date
Blank, Set 3

72192 FGD Influent, Set 1 280

- 10585

- 1 Aqueous 12/08/2010 12/09/2010

72196 FGD SBR Influent, Set 1 280

- 10585

- 2 Aqueous 12/08/2010 12/09/2010

72200 FGD SBR Effluent, Set 1 280

- 10585

- 3 Aqueous 12/08/2010 12/09/2010

72205 FGD SBR Influent Field Blank,

Set 1 280

- 10585

- 4 Aqueous 12/08/2010 12/09/2010

72209 FGD SBR Effluent Field Blank,

Set 1 280

- 10585

- 5 Aqueous 12/08/2010 12/09/2010

72243 FGD Influent, Set 3 280

- 10655

- 1 Aqueous 12/09/2010 12/10/2010

72247 FGD Effluent, Set 3 280

- 10655

- 2 Aqueous 12/09/2010 12/10/2010

72252 FGD Effluent Field Blank, Set 3 280

- 10655

- 3 Aqueous 12/09/2010 12/10/2010



### SUMMARY

The samples were prepared for total metals analysis accor ding to TestAmerica’s “FGD ICP/MS SOP: Inductively Coupled Plasma Mass Spectrometry for Trace Elements Analysis in Flue Gas Desulfurization Wastewaters,” date d October 6, 2010, based on EPA Method 200.8, by ICP/MS analysis.

Any significant findings are summarized below. No addition al data qualifiers were required.

• One of the continuing calibration verifications (CCV) per formed on 12/21/2010

failed the method criteria for selenium.

• The matrix spike (MS) and matrix spike duplicate (MSD) rec overies for total silver for sample 72196 failed the EPA Method 200.8 control lim its of 70-130%. The MSD recovery for total silver for sample 72147 also fa iled the method

control limits.

• The MS/MSD relative percent difference (RPD) for tota l silver for samples 72147

and 72196 failed the FGD ICP/MS SOP control limits of ±20%.

• The post digestion spike (PDS) recoveries for copper, nic kel, and silver for sample 72147 failed TestAmerica’s control limits of 85–115%. The PDS recovery for silver for sample 71997 also failed TestAmeri ca’s control limits.

INTERNAL STANDARDIZATION

All internal standards used by TestAmerica were within th e method criteria.

### 3

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial calibration for the ICP-MS analysis consisted of a bla nk and four calibration standards.

INITIAL AND CONTINUING CALIBRATION VERIFICATION (IC V/CCV)

The initial calibration verifications (ICV) and CCV perf ormed by TestAmerica all had recoveries within the method criteria, except for seleniu m for one CCV on 12/21/2010. Samples associated with this CCV that had selenium value s less than the reporting limit were reported. Any samples with selenium values above the reporting limit were reanalyzed.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit (RL); however, some elements were above the MDL and flagged with a “J” qualifier. No additional qualifiers were required for method blanks.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank (CCB)) were less than the RL; however, some element s were above the MDL and flagged with a “J” qualifier. No additional qualifiers were required for instrument blanks.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s SOP control limi ts of 50–150% recovery.

LABORATORY CONTROL SAMPLES (LCS)

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

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION

Based on TestAmerica’s SOP, all interference check sa mple A (ICSA) results had analytes of interest with concentrations less than the RL or less than five times the RL when known inherent contaminants are present in the stock solution used to make the

ICS.

All interference check sample B (ICSAB) synthetic sp ikes recovered within

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

SERIAL DILUTION

The serial dilution performed on samples 72147 and 72196 passed Te stAmerica’s criteria

of ±10% difference.

### 4

FIELD DUPLICATES

No field duplicate samples were collected with these sa mpling episodes.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

MS and MSD were performed on samples of 72147, 72196, and 71997. The M SD of sample 72147 failed the method control limits of 70–130% recover y for silver at 69%, which was flagged with an “F” qualifier. The MS/MSD of sam ple 72196 failed the method control limits of 70–130% recovery for silver, which was flagged with an “F” qualifier. These silver failures are likely due to matrix interference from the high concentration of sulfates, which can form insoluble si lver sulfide and/or silver sulfate.

The silver recoveries in the associated LCS/LCSDs were acceptable. The RPD for the MS/MSDs for samples 72147 and 72196 failed the FGD ICP/MS SOP ± 20% control

limits for silver.

Otherwise, all MS/MSD spike recoveries were within th e method control limits of 70-

130% and the RPD for the MS/MSDs were within the FGD ICP /MS SOP control limits of ±20 percent. No additional data qualifiers were required.

POST DIGESTION SPIKES (PDS)

The PDS performed on samples 72147 and 71997 passed TestAmerica’s control limits of 85–115% recovery for all analytes, except for copper, nickel, and silver for PDS sample 72147 and silver for PDS sample 71997, which were flagged with a “W ” qualifier. No additional data qualifiers were required.

DETECTION LIMITS

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

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Randy Mercurio, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Total Metals by 200.7 – Long-Term Monitoring: Month 3

TestAmerica generated analytical data for total metals (aluminum, boron, barium, beryllium, calcium, cobalt, iron, magnesium, manganese , molybdenum, sodium, tin, titanium and zinc). The samples were analyzed according t o EPA Method 200.7.

Table 1 summarizes the samples TestAmerica extracted a nd analyzed for total metals by

EPA Method 200.7

Table 1. 

### Long-Term Monitoring Month 3 Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71993 FGD Influent , Set 3 280

- 10586

- 1 Aqueous 12/08 /2010 12/09 /2010

71997 FGD Bioreactor Influent , Set 3 280

- 10654

- 1 Aqueous 12/09 /2010 12/10 /2010

72001 FGD Bioreactor Effluent , Set 3 280

- 10654

- 2 Aqueous 12/09 /2010 12/10 /2010

72006 FGD Bioreactor Influent Field

Blank, Set 3 280

- 10654

- 3 Aqueous 12/09 /2010 12/10 /2010

72010 FGD Bioreactor Effluent Field

Blank, Set 3 280

- 10654

- 4 Aqueous 12/09 /2010 12/10 /2010

7 2043 FGD Influent, Set 3 280

- 10584

- 1 Aqueous 12/08 /2010 12/09 /2010

7 2047 FGD Effluent, Set 3 280

- 10584

- 2 Aqueous 12/08 /2010 12/09 /2010

72052 FGD Bioreactor Effluent Field

Blank, Set 3 280

- 10584

- 3 Aqueous 12/08 /2010 12/09 /2010

7 2093 FGD Influent, Set 3 280

- 10515

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

7 2097 FGD Ef fluent, Set 3 280

- 10515

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

72 102 FGD Ef

fluent Field Blank , Set 3 280

- 10515

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

72143 FGD Influent, Set 3 280

- 10455

- 1 Aqueous 12/06 /2010 12/07 /2010

7 2147 FGD Bioreactor Influent, Set 3 280

- 10517

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

7 2151 FGD Bioreactor Effluent, Set 3 280

- 10517

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

7 2156 FGD Bioreactor In fluent Field

Blank, Set 3 280

- 10517

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

7 2160 FGD Bioreactor Ef fluent Field Blank, Set 3 2 80

- 10517

- 4 Aqueous 12/07 /2010 12/08 /2010

7 2192 FGD Influent, Set 1 280

- 10585

- 1 Aqueous 12/08 /2010 12/09 /2010

### 2 Table 1. 

### Long-Term Monitoring Month 3 Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

72196 FGD SBR Influent, Set 1 280

- 10585

- 2 Aqueous 12/08 /2010 12/09 /2010

72200 FGD SBR Effluent, Set 1 280

- 10585

- 3 Aqueous 12/08 /2010 12/09 /2010

72205 FGD SBR Influent Field Blank

, Set 1 280

- 10585

- 4 Aqueous 12/08 /2010 12/09 /2010

72209 FGD SBR Effluent Field Blank

, Set 1 280

- 10585

- 5 Aqueous 12/08 /2010 12/09 /2010

72243 FGD Influent, Set 3 280

- 10655

- 1 Aqueous 12/09 /2010 12/10 /2010

72247 FGD Effluent, Set 3 280

- 10655

- 2 Aqueous 12/09 /2010 12/10 /2010

72252 FGD Effluent Field Blank, Set 3 280

- 10655

- 3 Aqueous 12/09 /2010 12/10 /2010



### SUMMARY

The samples were prepared for total metals analysis acc ording to TestAmerica’s SOP for ICP Analysis for Trace Metals by Method 200.7. Any signific ant findings are summarized below. Additional data qualifiers were require d (see Table 2).

• The serial dilution for cobalt, iron, and zinc for sa mple 72143 failed TestAmerica’s SOP control limit of percent differenc es less than 10%.

• The post digestion spike (PDS) for calcium, iron, magn esium, and zinc for sample 72143 failed TestAmerica’s control limits of 85–115% recovery.

• The PDS for manganese for sample 72147 failed TestAmerica ’s control limits of 85–115% recovery.

SAMPLE RECEIPT, HANDLING AND STORAGE ISSUES

The samples associated with Episode 6569 (72192, 72196, 72200, 72205, and 72209) did not have a sample date or time on the traffic report.

INTERNAL STANDARDIZATION

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

ISTD recoveries within the ±30% criterion of the calibra tion blank as per Section 9.11 of

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

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial calibration for the ICP analysis consisted of a blank an d one calibration standard.

### 3

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

The initial calibration verifications (ICV) and continu ing calibration verifications (CCV) performed by TestAmerica all had recoveries within the m ethod criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit (RL); however, some elements were above the method detection limit (MDL) and were f lagged with the “J” qualifier.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank (CCB)) were less than the RL; however, some element s were above the MDL and were flagged with the “J” qualifier.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s SOP control limi ts of 50–150% recovery.

LABORATORY CONTROL SAMPLES (LCS)

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

INTERFERENCE CHECK SOLUTIONS

Interference checks were performed using the synthetic m atrix as the check solution. All data quality objectives met TestAmerica’s SOP criteria.

SERIAL DILUTION (SRD)

Serial dilutions were performed for each batch of total samples. All serial dilution percent differences were less than 10% as required by TestAmeric a’s SOP, except for cobalt, iron, and zinc for sample 72143, which were flagged with a “ V” qualifier.

FIELD DUPLICATES

No field duplicate samples were collected with these sa mpling episodes.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) w ere performed on the total samples of 72143, 72147, and 72196. Some elements with high concent rations failed the EPA 200.7 Method spike recovery control limits of 70–130% but w ere flagged with a “4” qualifier indicating that the concentration in the paren t sample was greater than 4 times the spike and could not be reliably calculated. These data were considered acceptable based on the LCS passing the method control limits. Othe rwise, all MS/MSD spike

recoveries were within the method control criteria of 70-130%. The RPD for all

### 4

MS/MSDs were within TestAmerica’s ± 20% requirement. No additional data qualifiers

were needed.

POST DIGESTION SPIKE (PDS)

The PDS performed on sample 72143 passed TestAmerica’s cont rol limits of 85–115% recovery for all analytes except aluminum, boron, calc ium, iron, magnesium, titanium, and zinc. Calcium, magnesium, and zinc were qualified with a “W”. Calcium and magnesium did pass in the matrix spike for this sample. Aluminum, boron, iron and titanium failed the PDS; however, the percent recoveri es were not calculated by the laboratory because their concentrations were greater than 4 times the PDS spike level. Aluminum, boron, and titanium passed TestAmerica’s requir ement of percent differences less than 10% for the serial dilution for this sample demo nstrating that there were no significant matrix interference with these elements. Iron and zinc failed TestAmerica’s requirements for the serial dilution; therefore, based on these cumulative results, iron and zinc are being qualified as suspect due to matrix interfere nce. These additional qualifiers appear in Table 2.

The PDS performed on sample 72147 passed TestAmerica’s cont rol limits of 85–115% recovery for all analytes except boron and manganese. Manganese was qualified with a “W”. Boron failed the PDS; however, the percent recov ery was not calculated by the laboratory because its concentration was greater the 4 times the PDS spike level. Both boron and manganese passed TestAmerica’s requirement of percent differences less than 10% for the serial dilution for sample 72147 demonstrating th at there were no significant matrix interferences. No additional qualifier is requir ed due to this PDS.

The PDS performed on sample 72196 passed TestAmerica’s cont rol limits of 85–115% recovery for all analytes except boron and manganese; however, the percent recoveries were not calculated by the laboratory because their co ncentrations were greater than 4 times the PDS spike level. Both boron and manganese passed TestAmerica’s requirement of percent differences less than 10% for the serial dil ution for sample 72196 demonstrating that there were no significant matrix int erferences. No additional qualifier is required due to this PDS.

DETECTION LIMITS

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

Table 2. Data Review Summary

Sample Analyte Qualifier/Action Reason Level Detected 72143 Iron (total) Matrix

Interference PDS and SD Failed XXX μ g/L

72143 Zinc (total) Matrix

Interference PDS and SD Failed XXX ug/L

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

CC: Deb Bartram, ERG TJ Finseth, ERG

From: Jennifer Colby, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Classicals Ana lyses – Long-Term Monitoring: Month 3

TestAmerica Denver Laboratory generated analytical data f or classical wet chemistry analyses for these long-term monitoring samples. All s amples were tested for the following analytes:

• Ammonia by EPA method 350.1,

• Biochemical Oxygen Demand – 5 day (BOD 5 

### ) by SM 5210B,

• Chloride and Sulfate by EPA method 300.0,

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

• Cyanide (total) by SM 4500 CN - 

### E,

• Nitrate/Nitrite by EPA method 353.2

• Phosphorus (total) by EPA method 365.1,

• Total Dissolved Solids (TDS) by SM 2540C,

• Total Kjeldakl Nitrogen (TKN) by EPA method 351.2, and

• Total Suspended Solids (TSS) by SM 2540D.

Table 1 summarizes the 15 samples that TestAmerica anal yzed for the above analytes.

Table 1. Long-Term Monitoring Month 3 Classical Analytes – Sample

Identification

EPA Sample # Sample

Matrix Sample Description Sampling

Date 71993 Water FGD Influent, Set 3 12/08/2010
71997 Water FGD Bioreactor Influent, Set 3 12/09/2010
72001 Water FGD Bioreactor Effluent, Set 3 12/09/2010
72043 Water FGD Influent, Set 3 12/08/2010
72047 Water FGD Effluent, Set 3 12/08/2010
72093 Water FGD Influent, Set 3 12/07/2010
72097 Water FGD Effluent, Set 3 12/07/2010
72143 Water FGD Influent, Set 3 12/06/2010
72147 Water FGD Bioreactor Influent, Set 3 12/07/2010

### 2 Table 1. Long-Term Monitoring Month 3 Classical Analytes – Sample

Identification

EPA Sample # Sample

Matrix Sample Description Sampling

Date 72151 Water FGD Bioreactor Effluent, Set 3 12/07/2010
72192 Water FGD Influent, Set 1 12/08/2010
72196 Water FGD SBR Influent, Set 1 12/08/2010
72200 Water FGD SBR Effluent, Set 1 12/08/2010
72243 Water FGD Influent, Set 3 12/09/2010
72247 Water FGD Effluent, Set 3 12/09/2010

SUMMARY

All samples were analyzed within the holding time specif ied in 40 CFR 136 Table II unless otherwise noted below. All samples were preserve d appropriately unless otherwise specified below. Samples 72192, 72196, and 72200 had no colle ction dates or times listed on the traffic report, and were given the date of relinquishment. Many of the traffic reports did not have receipt temperatures.

Field duplicate samples were not collected for this epis ode. Depending on the method, a laboratory duplicate was analyzed instead. The Relative Percent Difference (RPD) between the sample and its duplicate was less than 20% unl ess otherwise noted below.

If applicable, the appropriate number of standards was used to create a calibration curve. If sample results were above the highest standard used t o create the curve, the sample was diluted and reanalyzed. All sample results were between the lowest and highest standards unless noted below. Additionally, unless otherwise noted, a ll calibration blanks and calibration verification samples met the criteria sp ecified in the method.

If required by the method, the quality control sample (QC S), a secondary source standard used to verify calibration, was always within the cont rol limits specified by the method.

As described below, the analyte of interest was detecte d above the method detection limit (MDL) in some laboratory reagent blanks (LRB). However , the analyte of interest was never detected above the reporting limit (RL) in the LRBs . If required by the method, all laboratory fortified blanks (LFB) met the criteria spec ified in the method unless specified

below.

If required by the method, a matrix spike (MS) analysis was run on sample 72147 and sample 72196 for each analyte to check for matrix interfe rences. All MS samples analyzed met the criteria specified in the method unless described below.

### 3

DATA NOTES/ISSUES

Ammonia

The result for the method blank associated with one of the batches was greater than the MDL. All associated samples were flagged with a “B” qualif ier. This affects samples 72147, 72143, 72093, 72097, and 72151. No further action is required.

The percent recoveries for the MS and matrix spike dupli cate (MSD) for sample 72147 were 93% and 102%, respectively, which is within the method co ntrol criteria; however, the results exceeded the calibration range. These MS a nd MSD and results were flagged with an “E” qualifier.

BOD 5



### TestAmerica analyzed five dilutions, but no dilutions had a dissolved oxygen (DO) depletion greater than 2.0 mg/L for samples 72143, 72151, 72043, 71993, a nd 72247. Therefore, BOD 5 

### was reported as not detected for these samples. Additiona lly, for sample 72200, the dilutions did not have a residual DO criteria of gre ater than 1.0 mg/L; therefore, BOD 5 

### was reported as not detected for this sample. The rest of the samples had at least one dilution with a DO depletion greater than 2.0 mg/L. As required in the method, the final result was calculated by taking the av erage 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.

Chloride and Sulfate

MS and MSD were performed on samples 72147 and 72196. The MS/MS D recoveries for both samples were within the method control for both chloride and sulfate; however,

the MS and MSD results for chloride exceeded the calibra tion range. Both sets of MS/MSD results were flagged with “E” qualifiers.

COD

MS and MSD were performed on samples 72147 and 72196. The MS a nd MSD recoveries for sample 72147 were 66% and 71%, respectively, w hich is outside the

method control criteria. These MS/MSD results were flagged with an “F” qualifier. The MS and MSD recoveries for sample 72196 were 72% and 70%, respec tively, which is

outside the method control criteria. These MS/MSD re sults were flagged with an “F” qualifier.

Cyanide

Because of the nature of the sample matrix, all of th e samples in this sampling episode used a lower volume, which resulted in elevated RLs being ca lculated and reported by TestAmerica with the sample results.

### 4

MS and MSD were performed on samples 72147 and 72196. The MS a nd MSD recoveries for sample 72147 were 76% and 75%, respectively. T he MS and MSD recoveries for sample 72196 were 59% and 57%, respectively. Th e LCS/LCSD recoveries associated with these batches were acceptabl e, which indicates the analytical system was operating within control. Additionally, ther e is no method requirement for the analysis of a MS/MSD and therefore, no corrective ac tion is necessary.

Nitrate/Nitrite

No MS/MSD data was reported for batch 45200 in the sample a nd QC sample report summary. The method requires that a known amount of ana lyte be added to 10% of samples per batch. The general chemistry worksheet indi cates that MS samples were performed on a sample outside of these episodes, but no spiking concentrations or percent

recoveries are indicated. The MS/MSD recoveries for the other batches were within

control limits.

Phosphorus

The results for the method blanks associated with two of the batches was greater than the MDL, but less than the RL. The blank results were flagge d with a “J” qualifier. All associated samples were qualified with a “B” flag. No additional corrective action is

necessary.

MS and MSD were performed on sample 72001, 72147 and 72196. The percen t recoveries for the MS and MSD for sample 72147 were 69% an d 70%, respectively,

which is outside the method control criteria. These MS /MSD results were flagged with an “F” qualifier. The LCS/LCSD recoveries for this ba tch were acceptable and indicate that the analytical system was operating within control . The percent recoveries for the MS and MSD for sample 72196 were 91% and 85%, respectively. The MSD recovery is outside the method control criteria, but within the labor atory criteria and therefore, was not flagged. If reported, the MSD result should be flagge d with an “F” qualifier. The LCS/LCSD recoveries for this batch were acceptable and ind icate that the analytical system was operating within control. Additionally, the MS/MSD performed on sample 72001 was in the same batch as the MS/MSD for 72196 and the pe rcent recoveries for the MS and MSD were 96% and 97%, respectively, with are within th e method control

criteria.

TDS

TA reports that constant weight was not achieved after 3 drying cycles for the following samples: 72097, 72143, 72147, 72151, 71993, 72196, 72200, 71997, 72004, and 72243. Review of the general chemistry worksheets indicates th at constant weight was achieved for all samples. No further action was necessary.

### 5

Because of the nature of the sample matrix, some of t he samples in this sampling episode used a lower volume, which resulted in elevated RLs being ca lculated and reported by TestAmerica with the sample results.

The analytical duplicate associated with sample 72143 excee ded the recovery criteria. The duplicate result was qualified with an “F” flag. Beca use an analytical duplicate was not required by the method, no further corrective action i s necessary.

TKN

MS and MSD were performed on samples 72147 and 72196. The MS a nd MSD recoveries for sample 72147 were 76% and 57%, respectively. The concentration in the original sample was greater than four times the spike a mount; therefore, the recoveries cannot be reliably calculated and the results were flagge d with a “4” qualifier. The MS and MSD recoveries for sample 72196 were 81% and 78%, respecti vely, which do not meet the method control criteria, but do meet the labo ratory control criteria and therefore, these results were not flagged by the laboratory. If r eported, the MS and MSD results should be flagged with “F” qualifiers. The LCS/LCSD reco veries associated with these batches were acceptable, which indicates the analytical system was operating within

control.

TSS

Because of the nature of the sample matrix, some of t he samples in this sampling episode used a lower volume, which resulted in elevated RLs being ca lculated and reported by TestAmerica with the sample results.

### 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: 2/9/2012 Subject: FGS Data Review Narrative for Total Mercury – Long-Term M onitoring:

Month 4 and 5

Frontier Global Sciences (FGS) generated analytical da ta for total mercury. FGS analyzed the samples according to EPA Method 1631E for merc ury by Cold Vapor Atomic Fluorescence Spectrometry (CVAFS) analysis.

Table 1 summarizes the 30 samples (excluding laboratory pre p blanks) FGS extracted and analyzed for total mercury.

Table 1. 

### Long-Term Monitoring Month 4 and 5 Mercury – Sample Identification

EPA Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

71994 1101223-48 Aqueous FGD Influent, Set 4 1/17/2011

71998 1101223-53 Aqueous FGD Bioreactor Influent, Set 4 1/17/2011

72002 1101223-58 Aqueous FGD Bioreactor Effluent, Set 4 1/17/2011

72007 1101223-59 Aqueous FGD Bioreactor Influent Field Blank, Set 4 1/17/2011

72011 1101223-60 Aqueous FGD Bioreactor Effluent Field Blank, Set 4 1/17/2011

72044 1101308-01 Aqueous FGD Influent, Set 4 1/26/2011

72048 1101308-06 Aqueous FGD Effluent, Set 4 1/25/2011

72053 1101308-07 Aqueous FGD Effluent Field Blank, Set 4 1/25/2011

72094 1101223-41 Aqueous FGD Influent, Set 4 1/14/2011

72098 1101223-46 Aqueous FGD Effluent, Set 4 1/14/2011

72103 1101223-47 Aqueous FGD Effluent Field Blank, Set 4 1/13/2011

72144 1101223-21 Aqueous FGD Influent, Set 4 1/12/2011

72148 1101223-26 Aqueous FGD Bioreactor Influent, Set 4 1/12/2011

72152 1101223-31 Aqueous FGD Bioreactor Effluent, Set 4 1/12/2011

72157 1101223-32 Aqueous FGD Bioreactor Influent Field Blank, Set 4 1/12/2011

72161 1101223-33 Aqueous FGD Bioreactor Effluent Field Blank, Set 4 1/12/2011

72193 1101223-08 Aqueous FGD Influent, Set 3 1/12/2011

72197 1101223-13 Aqueous FGD SBR Influent, Set 3 1/12/2011

72201 1101223-18 Aqueous FGD SBR Effluent, Set 3 1/12/2011

### 2

Table 1. 

### Long-Term Monitoring Month 4 and 5 Mercury – Sample Identification

EPA Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

72206 1101223-19 Aqueous FGD SBR Influent Field Blank, Set 3 1/12/2011

72210 1101223-20 Aqueous FGD SBR Effluent Field Blank, Set 3 1/12/2011

72244 1101223-34 Aqueous FGD Influent, Set 4 1/12/2011

72248 1101223-39 Aqueous FGD Effluent, Set 4 1/13/2011

72253 1101223-40 Aqueous FGD Effluent Field Blank, Set 4 1/12/2011

72293 1101223-01 Aqueous FGD Influent, Set 3 1/12/2011

72297 1101223-06 Aqueous FGD Effluent, Set 3 1/12/2011

72302 1101223-07 Aqueous FGD Effluent, Field Blank, Set 3 1/12/2011

72294 1102108-01 Aqueous FGD Influent, Set 4 2/9/2011

72298 1102108-06 Aqueous FGD Effluent, Set 4 2/9/2011

72303 1102108-07 Aqueous FGD Effluent Field Blank, Set 4 2/9/2011



### SUMMARY

The samples were prepared according to EPA Method 1631E to be analyzed by CVAFS. There were no findings from the data review that required a dditional qualifiers in this dataset. The following summarizes the findings from the data review:

• The sample number for Sample 72157 was labeled incorrectly o n the traffic
report.

• The sample description for Sample 72148 was entered incorrec tly by FGS at the time of sample receipt.

• Two laboratory duplicates were out of the method-suggested relative percent difference (RPD) criteria.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

Sample 72157 was labeled incorrectly as Sample 721557 in the tra ffic report submitted to the laboratory. The error was identified and correct ed during the data review based on the sample description. FGS incorrectly labeled Sampl e 72148 as the FGD Bioreactor Effluent, Set 4, when the correct sample description is FGD Bioreactor Influent, Set 4. This error was identified and corrected during the data review and confirmed based on the traffic report.

### 3

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysi s day. The initial calibration for the CVAFS analysis consisted of a blank and five calibrat ion standards with a correlation

coefficient ≥ 0.995. All method-specified criteria were met.

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

All initial and continuing calibration verifications (I CVs, CCVs) met method-specified

criteria.

BLANKS

All the preparation blanks or laboratory reagent blanks (L RBs) and the continuing calibration blanks (CCBs) met the method-specified crite ria. Because all of the blank results were less than the RL, no samples were quali fied based on these preparation blank

results.

DUPLICATES

No field duplicate samples were collected with these sa mpling episodes. Four samples were analyzed in duplicate at the laboratory, Influent s amples 72144 and 71994 and Effluent samples 72048 and 72298. The relative percent differenc e (RPD) for samples 72144, 71994, 72048, and 72298 were 30.6%, 7.66%, 19.4% and 43.9%, respectively. Two of these RPDs were outside of laboratory criteria . The samples from another sampling episode were also analyzed in duplicate with RPD s of 13.3%, 22.4%, and 3.03%. The laboratory’s RPD criteria between analytica l duplicates is 24%. Analytical duplicates are not a method requirement; therefore, no samples were qualified based on analytical duplicates.

LABORATORY CONTROL SAMPLES

All laboratory control samples were within Frontier’s control limits of 80-120% recovery

and 24% RPD.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on Influent sample 72144 and Effluent samples 72048 and 72298. MS/MSDs were also performed on samples from another sampling episode. All aqueous MS /MSD recoveries were within method specifications of 71-125%. All RPDs met metho d-specifiec criteria.

DETECTION LIMITS

The laboratory MDL in the synthetic matrix was 0.239 ng/ L. Results below this MDL were reported as not detected (ND).

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Randy Mercurio, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Total Metals by 200.8 – Long-Term Monitoring: Month 4

TestAmerica generated analytical data for total metals (antimony, arsenic, cadmium, chromium, copper, lead, nickel, selenium, silver, thalliumand vanadium) for these longterm monitoring samples. The samples were analyzed accor ding to EPA Method 200.8.

Table 1 summarizes the samples TestAmerica extracted a nd analyzed for total metals by

EPA Method 200.8.

Table 1. 

### Long-Term Monitoring Month 4 Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71994 FGD Influent, Set 4 280

- 11658

- 1 Aqueous 1/17/2011 1/18/2011

71998 FGD Bioreactor Influent, Set 4 280

- 11690

- 1 Aqueous 1/18/2011 1/19/2011

72002 FGD Bioreactor Effluent, Set 4 280

- 11690

- 2 Aqueous 1/18/2011 1/19/2011

72007 FGD Bioreactor Influent Field

Blank, Set 4 280

- 11690

- 3 Aqueous 1/18/2011 1/19/2011

72011 FGD Bioreactor Effluent Field

Blank, Set 4 280

- 11690

- 4 Aqueous 1/18/2011 1/19/2011

72094 FGD Influent, Set 4 280

- 11635

- 1 Aqueous 1/14/2011 1/15/2011

72098 FGD Effluent, Set 4 280

- 11635

- 2 Aqueous 1/14/2011 1/15/2011

72103 FGD Effluent Field Blank, Set 4 280

- 11635

- 3 Aqueous 1/14/2011 1/15/2011

72144 FGD Influent, Set 4 280

- 11555

- 1 Aqueous 1/12/2011 1/13/2011

72148 FGD Bioreactor Influent, Set 4 280

- 11597

- 1 Aqueous 1/13/2011 1/14/2011

72152 FGD Bioreactor Effluent, Set 4 280

- 11597

- 2 Aqueous 1/13/2011 1/14/2011

72157 FGD Bioreactor Influent Field

Blank, Set 4 280

- 11597

- 3 Aqueous 1/13/2011 1/14/2011

72161 FGD Bioreactor Effluent Field

Blank, Set 4 280

- 11597

- 4 Aqueous 1/13/2011 1/14/2011

72193 FGD Influent, Set 3 280

- 11552

- 1 Aqueous 1/12/2011 1/13/2011

72197 FGD SBR Influent, Set 3 280

- 11552

- 2 Aqueous 1/12/2011 1/13/2011

72201 FGD SBR Effluent, Set 3 280

- 11552

- 3 Aqueous 1/12/2011 1/13/2011

### 2

Table 1. 

### Long-Term Monitoring Month 4 Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

72206 FGD SBR Influent Field Blank,

Set 3 280

- 11552

- 4 Aqueous 1/12/2011 1/13/2011

72210 FGD SBR Effluent Field Blank,

Set 3 280

- 11552

- 5 Aqueous 1/12/2011 1/13/2011

72244 FGD Influent, Set 4 280

- 11598

- 1 Aqueous 1/13/2011 1/14/2011

72248 FGD Effluent, Set 4 280

- 11598

- 2 Aqueous 1/13/2011 1/14/2011

72253 FGD Effluent Field Blank, Set 4 280

- 11598

- 3 Aqueous 1/13/2011 1/14/2011

72293 FGD Influent, Set 3 280

- 11553

- 1 Aqueous 1/12/2011 1/13/2011

72297 FGD Effluent, Set 3 280

- 11553

- 3 Aqueous 1/12/2011 1/13/2011

72302 FGD Effluent Field Blank, Set 3 280

- 11553

- 4 Aqueous 1/12/2011 1/13/2011



### SUMMARY

The samples were prepared for total metals analysis accor ding to TestAmerica’s “FGD ICP/MS SOP: Inductively Coupled Plasma Mass Spectrometry for Trace Elements Analysis in Flue Gas Desulfurization Wastewaters,” date d October 6, 2010, based on EPA Method 200.8, by ICP/MS analysis.

Any significant findings are summarized below. No addition al data qualifiers were required.

• The sample for FGD Effluent, Set 3 associated with Epi sode 6571 was incorrectly labeled as sample 72295 on the traffic report. The correc t sample number (72297) was found on the sample bottle label and confirmed with E RG prior to analysis.

• The matrix spike (MS) and matrix spike duplicate (MSD) rec overies for total silver for sample 72248 failed the EPA Method 200.8 control lim its of 70-130%. The MSD recovery for total silver for sample 72201 also fa iled the method

control limits.

• The MS/MSD relative percent difference (RPD) for tota l silver for samples 72201

and 72248 failed the FGD ICP/MS SOP control limits of ±20%.

• The post digestion spike (PDS) recoveries for silver for samples 72201 and 72002

failed TestAmerica’s control limits of 85–115%.

INTERNAL STANDARDIZATION

All internal standards used by TestAmerica were within th e method criteria.

### 3

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial calibration for the ICP-MS analysis consisted of a bla nk and four calibration standards.

INITIAL AND CONTINUING CALIBRATION VERIFICATION (IC V/CCV)

The initial calibration verifications (ICV) and continu ing calibration verifications (CCV) performed by TestAmerica all had recoveries within the m ethod criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit (RL); however, some elements were above the MDL and flagged with a “J” qualifier. No additional qualifiers were required for method blanks.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank (CCB)) were less than the RL; however, some element s were above the MDL and flagged with a “J” qualifier. No additional qualifiers were required for instrument blanks.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s SOP control limi ts of 50–150% recovery.

LABORATORY CONTROL SAMPLES (LCS)

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

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION

Based on TestAmerica’s SOP, all interference check sa mple A (ICSA) results had analytes of interest with concentrations less than the RL or less than five times the RL when known inherent contaminants are present in the stock solution used to make the

ICS.

All interference check sample B (ICSAB) synthetic sp ikes recovered within

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

SERIAL DILUTION

The serial dilution performed on samples 72201 and 72002 passed Te stAmerica’s criteria

of ±10% difference.

FIELD DUPLICATES

No field duplicate samples were collected with these sa mpling episodes.

### 4

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

MS and MSD were performed on samples of 72201, 72248, and 72002. The MSD of sample 72201 failed the method control limits of 70–130% recover y for silver at 61%, which was flagged with an “F” qualifier. The MS/MSD of sam ple 72248 failed the method control limits of 70–130% recovery for silver at 66% a nd 45% respectively, which were flagged with an “F” qualifier. These silver fa ilures are likely due to matrix interference from the high concentration of sulfates , which can form insoluble silver

sulfide and/or silver sulfate. The silver recoveries in the associated LCS/LCSDs were acceptable. The RPD for the MS/MSDs for samples 72201 and 72248 failed the FGD

ICP/MS SOP ±20% control limits for silver.

Otherwise, all MS/MSD spike recoveries were within th e method control limits of 70-

130% and the RPD for the MS/MSDs were within the FGD ICP /MS SOP control limits of ±20 percent. No additional data qualifiers were required.

POST DIGESTION SPIKES (PDS)

The PDS performed on samples 72201 and 72002 passed TestAmerica’s control limits of 85–115% recovery for all analytes, except for silver for b oth PDS samples, which were flagged with a “W” qualifier. Additional data qualifiers wo uld be required; however silver was not detected in these samples.

DETECTION LIMITS

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

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Randy Mercurio, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Total Metals by 200.7 – Long-Term Monitoring: Month 4

TestAmerica generated analytical data for total metals (aluminum, boron, barium, beryllium, calcium, cobalt, iron, magnesium, manganese , molybdenum, sodium, tin, titanium and zinc) for these long-term monitoring samples. The samples were analyzed according to EPA Method 200.7.

Table 1 summarizes the samples TestAmerica extracted a nd analyzed for total metals by

EPA Method 200.7.

Table 1. 

### Long-Term Monitoring Month 4 Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71994 FGD Influent, Set 4 280

- 11658

- 1 Aqueous 1/17/2011 1/18/2011

71998 FGD Bioreactor Influent, Set 4 280

- 11690

- 1 Aqueous 1/18/2011 1/19/2011

72002 FGD Bioreactor Effluent, Set 4 280

- 11690

- 2 Aqueous 1/18/2011 1/19/2011

72007 FGD Bioreactor Influent Field

Blank, Set 4 280

- 11690

- 3 Aqueous 1/18/2011 1/19/2011

72011 FGD Bioreactor Effluent Field

Blank, Set 4 280

- 11690

- 4 Aqueous 1/18/2011 1/19/2011

72094 FGD Influent , Set 4 280

- 11635

- 1 Aqueous 1/14/2011 1/15 /201 1

72098 FGD Effluent , Set 4 280

- 11635

- 2 Aqueous 1/14/2011 1/15 /201 1

72103 FGD Effluent Field Blank, Set 4 280

- 11635

- 3 Aqueous 1/14/2011 1/15 /201 1

7 2144 FGD Influent, Set 4 280

- 11555

- 1 Aqueous 1/12 /201 1 1/13 /201 1

7 2148 FGD Bioreactor Influent, Set 4 280

- 11597

- 1 Aqueous 1/13/2011 1/14/2011

72152 FGD Bioreactor Effluent, Set 4 280

- 11597

- 2 Aqueous 1/13/2011 1/14/2011

72157 FGD Bioreactor Influent Field

Blank, Set 4 280

- 11597

- 3 Aqueous 1/13/2011 1/14/2011

72161 FGD Bioreactor Effluent Field

Blank, Set 4 280

- 11597

- 4 Aqueous 1/13/2011 1/14/2011

72193 FGD Influent, Set 3 280

- 11552

- 1 Aqueous 1/12 /201 1 1/13 /201 1

7 2197 FGD SBR Influent, Set 3 280

- 11552

- 2 Aqueous 1/12 /201 1 1/13 /201 1

7 2201 FGD SBR Effluent, Set 3 280

- 11552

- 3 Aqueous 1/12 /201 1 1/13 /201 1

### 2 Table 1. 

### Long-Term Monitoring Month 4 Total Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

72 206 FGD SBR Influent Field Blank,

Set 3 280

- 11552

- 4 Aqueous 1/12 /201 1 1/13 /201 1

7 2210 FGD SBR Effluent Field Blank,

Set 3 280

- 11552

- 5 Aqueous 1/12 /201 1 1/13 /201 1

72244 FGD Influent, Set 4 280

- 11598

- 1 Aqueous 1/13/2011 1/14/2011

72248 FGD Effluent , Set 4 280

- 11598

- 2 Aqueous 1/13/2011 1/14/2011

72253 FGD Effluent Field Blank, Set 4 280

- 11598

- 3 Aqueous 1/13/2011 1/14/2011

7 2293 FGD Influent, Set 3 280

- 11553

- 1 Aqueous 1/12 /201 1 1/13 /201 1

7 2297 FGD Effluent, Set 3 280

- 11553

- 3 Aqueous 1/12 /201 1 1/13 /201 1

7 2302 FGD Ef

fluent Field Blank, Set 3 2 80

- 11553

- 4 Aqueous 1/12 /201 1 1/13 /201 1



### SUMMARY

The samples were prepared for total metals analysis acc ording to TestAmerica’s SOP for ICP Analysis for Trace Metals by Method 200.7. Any signific ant findings are summarized below. No additional data qualifiers were require d for this set of data.

• Several samples did not have the date and time of sampl e collection listed on the traffic reports.

• One sample was listed with the wrong sample number on the traffic report.

• The post digestion spike (PDS) for sodium for sample 72002 fai led TestAmerica’s control limits of 85–115% recovery.

SAMPLE RECEIPT, HANDLING AND STORAGE ISSUES

Samples associated with Episode 6569 (72193, 72197, 72201, 72206, and 72210) did n ot have a sample date or time on the traffic report or s ample labels.

Samples associated with Episode 6571 (72293, 72297, and 72302) did not hav e a sample date or time on the traffic report or sample labels. Add itionally, a field sampler name was not present on the traffic report. The sample FGD Ef fluent, Set3 was listed on the traffic report as sample 72295, which is incorrect; however, the sam ple bottle was labeled correctly as sample 72297. TestAmerica used 72297 for processing the sample.

Samples of 72144 FGD Influent, Set 4 did not have a sample dat e or time listed on the sample bottles.

### 3

INTERNAL STANDARDIZATION

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

ISTD recoveries within the ±30% criterion of the calibra tion blank as per Section 9.11 of

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

INITIAL CALIBRATION

TestAmerica performed the initial calibrations on each analysis day. The initial calibration for the ICP analysis consisted of a blank an d one calibration standard.

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS

The initial calibration verifications (ICV) and continu ing calibration verifications (CCV) performed by TestAmerica all had recoveries within the m ethod criteria.

METHOD/INSTRUMENT BLANKS

All the method blanks were less than the reporting limit (RL); however, some elements were above the method detection limit (MDL) and were f lagged with the “J” qualifier.

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank (CCB)) were less than the RL; however, some element s were above the MDL and were flagged with the “J” qualifier.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmerica’s SOP control limi ts of 50–150% recovery.

LABORATORY CONTROL SAMPLES (LCS)

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

INTERFERENCE CHECK SOLUTIONS

Interference checks were performed using the synthetic m atrix as the check solution. All data quality objectives met TestAmerica’s SOP criteria.

SERIAL DILUTION (SRD)

Serial dilutions were performed for each batch of total samples. All serial dilution percent differences were less than 10% as required by TestAmerica ’s SOP.

FIELD DUPLICATES

No field duplicate samples were collected with these sa mpling episodes.

### 4

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) w ere performed on the total samples of 72201, 72248, and 72002. Some elements with high concent rations failed the EPA 200.7 Method spike recovery control limits of 70–130% but w ere flagged with a “4” qualifier indicating that the concentration in the paren t sample was greater than 4 times the spike and could not be reliably calculated. These data were considered acceptable based on the LCS passing the method control limits. Othe rwise, all MS/MSD spike

recoveries were within the method control criteria of 70-130%. The relative percent difference (RPD) for all MS/MSDs were within TestAme rica’s ± 20% requirement, except for magnesium for sample 72095. No additional data quali fiers were needed.

POST DIGESTION SPIKE (PDS)

The PDS performed on sample 72201 failed the method criteria of 85–115% recovery for boron; however, the result was not qualified with a “ W” because the sample concentration was greater than 4 times the spike amoun t.

The PDS performed on sample 72002 failed the method criteria of 85–115% recovery for boron, magnesium and manganese; however, these result s were not qualified with a “W” because their sample concentrations were greater than 4 times the spike amount. Sodium also failed the method criteria and was flagged with a “W ” qualifier. All elements passed the serial dilution for this sample demonstrating that there were no significant matrix interferences. No additional data qualifiers are required.

DETECTION LIMITS

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

### 1



## MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Jennifer Colby, ERG Donna Tedder, ERG

Date: 2/9/2012 Subject: TestAmerica Data Review Narrative for Classicals Ana lyses – Long-Term Monitoring: Month 4

TestAmerica Denver Laboratory generated analytical data f or classical wet chemistry analyses for these long-term monitoring samples. All s amples were tested for the following analytes:

• Ammonia by EPA method 350.1,

• Biochemical Oxygen Demand – 5 day (BOD 5 

### ) by SM 5210B,

• Chloride and Sulfate by EPA method 300.0,

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

• Cyanide (total) by SM 4500 CN - 

### E,

• Nitrate/Nitrite by EPA method 353.2

• Phosphorus (total) by EPA method 365.1,

• Total Dissolved Solids (TDS) by SM 2540C,

• Total Kjeldakl Nitrogen (TKN) by EPA method 351.2, and

• Total Suspended Solids (TSS) by SM 2540D.

Table 1 summarizes the 15 samples that TestAmerica anal yzed for the above analytes.

Table 1. Long-Term Monitoring Month 4 Classical Analytes – Sample

Identification

EPA Sample # Sample

Matrix Sample Description Sampling

Date 71994 Water FGD Influent, Set 4 1/21/2011
71998 Water FGD Bioreactor Influent, Set 4 1/21/2011
72002 Water FGD Bioreactor Effluent, Set 4 1/21/2011
72094 Water FGD Influent, Set 4 1/18/2011
72098 Water FGD Effluent, Set 4 1/18/2011
72144 Water FGD Influent, Set 4 1/14/2011
72148 Water FGD Bioreactor Influent, Set 4 1/17/2011

### 2 Table 1. Long-Term Monitoring Month 4 Classical Analytes – Sample

Identification

EPA Sample # Sample

Matrix Sample Description Sampling

Date 72152 Water FGD Bioreactor Effluent, Set 4 1/17/2011
72193 Water FGD Influent, Set 3 1/14/2011
72197 Water FGD SBR Influent, Set 3 1/14/2011
72201 Water FGD SBR Effluent, Set 3 1/14/2011
72244 Water FGD Influent, Set 4 1/17/2011
72248 Water FGD Effluent, Set 4 1/17/2011
72293 Water FGD Influent, Set 3 1/14/2011
72297 Water FGD Effluent, Set 3 1/14/2011

SUMMARY

All samples were analyzed within the holding time specif ied in 40 CFR 136 Table II unless otherwise noted below. All samples were preserve d appropriately unless otherwise specified. Group II samples 72293 and 72297 were receiv ed at the laboratory at a neutral pH. The laboratory preserved the volume and proceeded with the requested analyses.

Field duplicate samples were not collected for this epis ode. Depending on the method, a laboratory duplicate was analyzed instead. The Relative Percent Difference (RPD) between the sample and its duplicate was less than 20% unl ess otherwise noted below.

If applicable, the appropriate number of standards was used to create a calibration curve. If sample results were above the highest standard used t o create the curve, the sample was diluted and reanalyzed. All sample results were between the lowest and highest standards unless noted below. Additionally, unless otherwise noted, a ll calibration blanks and calibration verification samples met the criteria sp ecified in the method.

If required by the method, the quality control sample (QC S), a secondary source standard used to verify calibration, was always within the cont rol limits specified by the method.

As described below, the analyte of interest was detecte d above the method detection limit (MDL) in some laboratory reagent blanks (LRB). However , the analyte of interest was never detected above the reporting limit (RL) in the LRBs . If required by the method, all laboratory fortified blanks (LFB) met the criteria spec ified in the method unless specified

below.

If required by the method, a matrix spike (MS) analysis was run on samples 72002, 72094, 72193, 72201, 72244, and 72297 for each analyte to check for matrix interferences. All MS samples analyzed met the crite ria specified in the method unless

described below.

### 3

DATA NOTES/ISSUES

Ammonia

Samples 72293 and 72297 were received by the laboratory at a neutra l pH. Sample 72293 was qualified as an estimated, as shown in Table 2. Samp le 72297 had a result greater than the MDL, but less than the RL, so the re sult was already flagged with a ”J” qualifier, so further qualification was not necessary.

The percent recoveries for the MS and MSD performed on sample 72094 were 77% and 76%, respectively, which is outside of method control cri teria. Additionally, the MS and MSD results exceeded the calibration range. The MS/MSD results for sample 72094 were flagged with “E” and “F” qualifiers. No further qualificatio n is needed.

BOD 5



### No issues were identified by the data reviewer.

Chloride and Sulfate

MS and MSD were performed on samples 72002, 72094, and 72201. The perce nt
recoveries for the MS and MSD for all chloride and sul fate results were within the method control criteria; however, all the MS and MSD results exceeded the exceeded the calibration range, except for the MSD sulfate result f or sample 72002. All these chloride and sulfate MS and MSD results were qualified with “E” qualifiers, except for the MSD sulfate result for sample 72002.

COD

Samples 72293 and 72297 were received by the laboratory at neutral pH. These results were qualified as estimated values, as shown in Table 2.

MS and MSD were performed on samples 72002 and 72098. The percent recoveries for the MS and MSD for sample 72002 were 91% and 87%, respectively. The percent recoveries for the MS and MSD for sample 72098 were 90% an d 88%, respectively.

Both the MSD results are outside the method control c riteria. These MSD results were flagged with “F” qualifiers.

Cyanide

MS and MSD were performed on samples 72193 and 72002. The percent recoveries for the MS and MSD for sample 72193 were 74% and 78%, respectively . The percent recoveries for the MS and MSD for sample 72002 were both 88%. The LCS/LCSD recoveries were acceptable, indicating that the analyti cal system was operating within control. Additionally, there is no method requirement f or the analysis of a MS/MSD and no corrective action is necessary.

### 4

Nitrate/Nitrite

Samples 72293 and 72297 were received by the laboratory at neutral pH. These results were qualified as estimated values, as shown in Table 2.

Phosphorus

Samples 72293 and 72297 were received by the laboratory at neutral pH. These results were qualified as estimated values, as shown in Table 2.

The method blank associated with two of the batches detec ted phosphorus at levels greater than the MDL, but less than the RL. All affec ted samples were flagged with a “B” qualifier. No additional corrective action is necessary

.

MS and MSD were performed on samples 72002 and 72297. The percent recoveries for the MS and MSD for sample 72002 were 72% and 56%, respectively, which are outside

the method control criteria. The MS result was withi n the laboratory control criteria and therefore, was not flagged by the laboratory; however, the MSD result was outside the laboratory control criteria and was flagged with an “F” qualifier. The LCS/LCSD recoveries for this batch were acceptable, indicating the analytical system was operating within control. If reported, the MS result should be fl agged with an “F” qualifier.

The percent recoveries for the MS and MSD for sample 72297 were 66% and 58%, respectively, which are outside the method control crite ria. There results were flagged with “F” qualifiers. The LCS/LCSD recoveries for this batch were acceptable, indicating the analytical system was operating within control.

TDS

TA reports that constant weight was not achieved after 3 drying cycles for the following samples: 72293, 72244, 71994, 72152, and 72248. Review of the general chemist ry worksheets indicates that constant weight was achieve d for all. No further action was

necessary.

The analytical duplicate performed on sample 72002 exceeded t he recovery criteria. The duplicate result was flagged with an “F” qualifier. Becaus e an analytical duplicate was not required by the method, no further corrective action i s necessary.

TKN

Samples 72293 and 72297 were received by the laboratory at neutral pH. These results were qualified as estimated values, as shown in Table 2.

MS and MSD were performed on samples 72001 and 72002. The percent recoveries for the MS and MSD for sample 72002 were both 93%, which is withi n the method control

### 5

criteria. The percent recoveries for the MS and MSD for sample 72001 were 48% and 46%, respectively, which are outside the method control cri teria. There results were flagged with “F” qualifiers. The LCS/LCSD recoveries fo r this batch were acceptable, indicating that the analytical system was operating wit hin control.

TSS

Because of the nature of the sample matrix, some of t he samples in this sampling episode used a lower volume, which resulted in elevated RLs being c alculated and reported by TestAmerica with the sample results.

The analytical duplicate performed on sample 72248 exceeded t he recovery criteria. Because the sample result is below the RL, further qual ification was not necessary.

Table 2. Data Review Summary Table

Sample Analyte Qualifier/Ac

tion Reason Level Detected

72293 Ammonia Estimated

Value Received at neutral pH XXX mg/L

72293 COD Estimated

Value Received at neutral pH XXX mg/L

72297 COD Estimated

Value Received at neutral pH XXX mg/L

72293 Nitrate/Nitrite Estimated

Value Received at neutral pH XXX mg/L

72297 Nitrate/Nitrite Estimated

Value Received at neutral pH XXX mg/L

72293 Phosphorus Estimated

Value Received at neutral pH XXX mg/L

72297 Phosphorus Estimated

Value Received at neutral pH XXX mg/L

72293 TKN Estimated

Value Received at neutral pH XXX mg/L



### 72297 TKN Estimated

Value Received at neutral pH XXX mg/L