Appendix B

DATA REVIEW NARRATIVES

### MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD Deb Bartram, ERG TJ Finseth, ERG From: Randy Mercurio, ERG. Donna Tedder, ERG Date: 2/11/2011 Subject: FGS Data Review Narrative for Total and Dissolved Mercury – Episode 6559

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

Table 1 summarizes the 23 samples (excluding laboratory filter blanks) FGS extracted and analyzed for total and dissolved mercury.

Table 1. EPA Episode 6559 Mercury– Sample Identification

EPA Sample # Lab Sample ID # Sample Matrix Sample Description Sampling Date

71691 1006188-01 Aqueous FGD Influent Day 1 6/21/2010

71691 1006188-02 Aqueous Dissolved FGD Influent Day 1 6/21/2010

71700 1006188-03 Aqueous FGD Influent Field Blank Day 1 6/21/2010

71701 1006188-06 Aqueous FGD Effluent Field Blank Day 1 6/21/2010

71692 1006199-01 Aqueous FGD Influent Day 2 6/22/2010

71692 1006199-02 Aqueous Dissolved FGD Influent Day 2 6/22/2010

71695 1006199-03 Aqueous FGD Effluent Day 1 6/22/2010

71695 1006199-04 Aqueous Dissolved FGD Effluent Day 1 6/22/2010

71702 1006199-05 Aqueous FGD Effluent Field Blank Day 2 6/22/2010

71703 1006205-06 Aqueous FGD Effluent Field Blank Day 3 6/23/2010

71693 1006205-07 Aqueous FGD Influent Day 3 6/23/2010

71693 1006205-08 Aqueous Dissolved FGD Influent Day 3 6/23/2010

71696 1006205-09 Aqueous FGD Effluent Day 2 6/23/2010

71696 1006205-10 Aqueous Dissolved FGD Effluent Day 2 6/23/2010

71699 1006205-11 Aqueous FGD Effluent – Duplicate Day 2 6/23/2010

71699 1006205-12 Aqueous Dissolved FGD Effl uent – Duplicate Day 2 6/23/2010

71694 1006217-01 Aqueous FGD Influent Day 4 6/24/2010

71694 1006217-02 Aqueous Dissolved FGD Influent Day 3 6/24/2010

71697 1006217-03 Aqueous FGD Effluent Day 3 6/24/2010

1Table 1. EPA Episode 6559 Mercury– Sample Identification

EPA Lab Sample Sample Sampling Sample # ID # Matrix Sample Description Date

71697 1006217-04 Aqueous Dissolved FGD Effluent Day 3 6/24/2010

71704 1006217-05 Aqueous FGD Effluent Field Blank Day 4 6/24/2010

71698 1006221-02 Aqueous FGD Effluent Day 4 6/25/2010

71698 1006221-03 Aqueous Dissolved FGD Effluent Day 4 6/25/2010

SUMMARY

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

There were no findings from the data review th at required additional qualifiers in this dataset.

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysis day. The initial calibration for the CVAFS analysis consisted of a blank and five calibration standards with a correlation factor ≥ 0.995. All method-specified criteria were met.

INITIAL AND CONTINUING CAL IBRATION VERIFICATIONS

All initial and continuing calibration verifi cations (ICVs, CCVs) met method-specified criteria.

BLANKS

All the preparation blanks or laboratory reagent blanks (LRBs) and the continuing calibration blanks (CCBs) met me thod-specified requirements.

DUPLICATES

Field duplicates, Sample 71699, were collected on the Sample 71696. The 71696/71699 total mercury RPD was 4.52% and the dissolv ed RPD was 3.34%. The method-suggest RPD criteria between field duplicates is 20%.

Laboratory duplicates were pe rformed in this episode on samples 71692 and 71698, and they all met the method-specified criteria.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

Matrix spikes (MS) and ma trix spike duplicates (MSD) were performed on samples 71692, 71695, 71696, 71694 and 71697. All recove ries were within method

23 specifications of 71-125%. The RPDs were 6.10, 0.248, 14.3, 0.935 and 0.299% respectively.

DETECTION LIMITS

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

### 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: 3/29/2011 Subject: TestAmerica Data Review Narrative fo r Total and Dissolved Metals by 200.8 – Episode 6559

TestAmerica generated analytic al data for total and dissolv ed metals (antimony, arsenic, cadmium, chromium, copper, lead, nickel, sele nium, silver, thallium, vanadium, and zinc) for Sample Episode 6559. The samples were analyzed according to EPA Method 200.8.

Table 1 summarizes the samples TestAmerica extracted and analyzed for total and dissolved metals by EPA Method 200.8.

Table 1. EPA Episode 6559 Total & Dissolved Metals– Sample Identification

EPA Sample # EPA Sample Description Lab Sample ID # Sample Matrix Sampling Date Receipt Date

71691 FGD Influent, Day1 280-4666-1 Aqueous 6/21/2010 6/22/2010
71700 FGD Influent Field Blank, Day 1 280-4666-2 Aqueous 6/21/2010 6/22/2010
71692 FGD Influent, Day 2 280-4707-1 Aqueous 6/22/2010 6/23/2010
71695 FGD Influent, Day 1 280-4707-2 Aqueous 6/22/2010 6/23/2010
71701 FGD Effluent Field Blank, Day 1 280-4707-3 Aqueous 6/22/2010 6/23/2010
71693 FGD Influent, Day 3 280-4753-1 Aqueous 6/23/2010 6/24/2010
71696 FGD Effluent, Day 2 280-4753-2 Aqueous 6/23/2010 6/24/2010
71699 FGD Effluent-Duplicate, Day 2 280-4753-3 Aqueous 6/23/2010 6/24/2010
71694 FGD Influent, Day 4 280-4786-1 Aqueous 6/24/2010 6/25/2010
71697 FGD Effluent, Day 3 280-4786-2 Aqueous 6/24/2010 6/25/2010
71698 FGD Effluent, Day 4 280-4841-1 Aqueous 6/25/2010 6/26/2010

SUMMARY

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

1Any significant findings are summ arized below. Specific results that required additional qualifiers appear in Table 2.

 All MS/MSDs for total and dissolved silver failed the 70-130% control limits with poor recoveries. The poor re coveries are probably due to high sulfates in this episode’s samples that could form insolubl e silver sulfide and/or silver sulfate.

 The relative percent difference (RPD) for total nickel for the field duplicate samples 71696 and 71699 was 152.4%; however , the duplicate sample was less than the reporting limit; therefore, the RPD could not be cal culated accurately. The RPD for dissolved antimony was 27.3%.

INSTRUMENT TUNE CONDITIONS

The tune condition, background counts per second (Cps), were not monitored for mass 75 for calibration blanks. Based on the calibration blank, the background counts for mass 75 were always greater than 10 Cps, which is the required criteria according to Section 10.3.3 of TestAmerica’s SOP.

INTERNAL STANDARDIZATION

All internal standards used by TestAmer ica were within the method criteria.

INITIAL CALIBRATION

TestAmerica performed the initial calibra tions 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

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

BLANKS

All the method blanks were less than the reporting limit; however, some elements were found above the method detection limit (MDL) and were flagged with the “J” qualifier indicating the concentrations were an estimated value.

All instrument blanks (initial calibration blank (ICB) and conti nuing calibration blank (CCB)) were less than the reporting limit; howev er, some elements were above the MDL and were flagged with the “J” qualifier.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmer ica’s 50 – 150% recovery limits.

2LABORATORY CONTROL SAMPLES (LCS)

All LCS samples passed the QC lim its of 85-115%.

INTERFERENCE CHECK SOLUTIONS

Interference checks were perfor med using the synthetic matrix as the check solution. All recoveries met the method-specified criteria.

SERIAL DILUTION

Serial dilutions were performed for each batc h of total and dissolved samples. No QC criteria are required by EP A Method 200.8 or TestAmerica’s SOP for these samples. Most samples had concentrations less than the RL so a percent difference was not calculated; however, those samples with si gnificant concentrations did have percent differences calculated and met the typical <10% criterion, with the exception of total arsenic and dissolved selenium for Sample 71691.

FIELD/LABORATORY DUPLICATES

The RPD of the field duplicates 71696/71699 were less than 20% for all values equal to or greater than the reporting limit.

The RPD of the laboratory duplicate sample s for Sample 71697 were less than 20% for all values above the reporting limit, with the exception of dissolved arsenic, which had an RPD of 26%. Even though the RPD was greater than 20%, the dissolv ed arsenic result was not qualified because there are no speci fic control limits for laboratory duplicates specified in EPA Method 200.8.

MATRIX SPIKE (MS) AND MATI X SPIKE DUPLICATES (MSD)

Matrix spikes and matrix spike duplicates were performed on Samples 71691, 71695, 71696, 71697 and 71698. Many spike recoveries were outside the method control limits of 70-130% when sample concentrations exceed ed the spike concentration by a factor of four or more, which have been flagged with a “4” qualifier. Otherwise, the MS/MSD spike recoveries were always within the control limits of 70-130% with th e exception of all MS/MSDs for total and dissolved silver. Th e poor recoveries for silver are probably due to high sulfates in this episode’s samples that could form insoluble silver sulfide and/or silver sulfate. The RPD for all MS/MSD passed the method-specified criteria of 20 percent.

POST DIGESITON SPIKES (PDS)

All post digestion spikes passed TestAmeri ca’s 85-115% recovery criteria with the exception of the following:

34  Total and dissolved silver for sample 71691 FGD Influent, Day 1 (280-4666-1);

 Dissolved zinc for sample 71695 FGD Effluent, Day 1 (280-4707-2);

 Total nickel and silver for sample 71696 FGD Effluent, Day 2 (280-4753-2);

 Total and dissolved silver for samp le 71697 FGD Effluent, Day 3 (280-4786-2); and

 Total silver for sample 71698 F GD Effluent, Day 4 (280-4841-1).

The poor recoveries of silver are probably due to high sulfates in this episode’s samples that could form insoluble silver sulfide and/or silver sulfate.

DETECTION LIMITS

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

Table 2. Data Review Summary

Sample Analyte Qualifier/Action Reason Level Detected

71691 Ag Matrix Interference Failed MS/MSD 1.2 μ g/L (total)

71691 Ag Matrix Interference Failed MS/MSD & RPD ND (dissolved)

71695 Ag Matrix Interference Failed MS/MSD ND (total)

71695 Ag Matrix Interference Failed MS/MSD ND (dissolved)

71696 Ag Matrix Interference Failed MS/MSD & RPD ND (total)

71696 Ag Matrix Interference Failed MS/MSD & RPD ND (dissolved)

71696 Ni Matrix Interference Failed MS/MSD 20 μ g/L (total)

71696 Zn Matrix Interference Failed MS/MSD 14 μ g/L (total)

71697 Ag Matrix Interference Failed MS/MSD & RPD ND (total)

71697 Ag Matrix Interference Failed MS/MSD & RPD ND (dissolved)

71698 Ag Matrix Interference Failed MS/MSD & RPD ND (total)

71698 Ag Matrix Interference Failed MS/MSD & RPD ND (dissolved)

### 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: 3/29/2011 Subject: TestAmerica Data Review Narrative fo r Total and Dissolved Metals by 200.7 – Episode 6559

TestAmerica generated analytical data for to tal and dissolved metals (aluminum, boron, barium, beryllium, calcium, cobalt, iron, magnesium, molybdenum, sodium, tin, titanium, manganese) for Sample Episode 6559. The sa mples were analyzed according to EPA Method 200.7.

Table 1 summarizes the samples TestAmerica extracted and analyzed for total and dissolved metals by EPA Method 200.7.

Table 1. EPA Episode 6559 Total & Dissolved Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample ID # Sample Matrix Sampling Date Receipt Date

71691 FGD Influent, Day1 280-4666-1 Aqueous 6/21/2010 6/22/2010
71700 FGD Influent Field Blank, Day 1 280-4666-2 Aqueous 6/21/2010 6/22/2010
71692 FGD Influent, Day 2 280-4707-1 Aqueous 6/22/2010 6/23/2010
71695 FGD Effluent, Day 1 280-4707-2 Aqueous 6/22/2010 6/23/2010
71701 FGD Effluent Field Blank, Day 1 280-4707-3 Aqueous 6/22/2010 6/23/2010
71693 FGD Influent, Day 3 280-4753-1 Aqueous 6/23/2010 6/24/2010
71696 FGD Effluent, Day 2 280-4753-2 Aqueous 6/23/2010 6/24/2010
71699 FGD Effluent - Duplicate, Day 2 280-4753-3 Aqueous 6/23/2010 6/24/2010
71694 FGD Influent, Day 4 280-4786-1 Aqueous 6/24/2010 6/25/2010
71697 FGD Effluent, Day 3 280-4786-2 Aqueous 6/24/2010 6/25/2010
71698 FGD Effluent, Day 4 280-4841-1 Aqueous 6/25/2010 6/26/2010

SUMMARY

The samples were prepared for total and dissolved metals analysis according to TestAmerica’s SOP for ICP Analysis for Tr ace Metals by Method 200.7. Any significant findings are summarized below. Specific results that required additional qualifiers appear in Table 2.

1 In Method Blank 280-21582, the concentrat ion of iron (115 ug/L) was greater than the reporting lim it (100 ug/ L) and it was not flagged.

 The continuing calibration verificati on 280-22121/107 failed the method criteria for aluminum. All associated samples were either flagged or reanalyzed for aluminum; therefore, no additional qualifications were required.

 The laboratory duplicate analysis of sample 71697 FGD Effluent, Day 3 (280- 4786-2) for dissolved iron had an RPD of 143% and was not flagged but was mentioned in the narrative.

 The MS/MSD spike recoveries that fa iled the EPA Method 200.7 control limits of 70–130% are as follows: total and dissolv ed barium (71691 MS); total barium (71691 MSD); total aluminum (71695 MS/MSD); and total iron (71698 MS/MSD).

SAMPLE RECEIPT, HANDLIN G, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INTERNAL STANDARDIZATION

While the internal standard (ISTD) Yttrium wa s used for these analyses, no checks on the ISTD recoveries in the ±30% criterion of the calibration bl ank as per Section 9.11 of the SOP were seen. All ISTD were within the control limits.

INITIAL CALIBRATION

TestAmerica performed the initial calibra tions on each analysis day. The initial calibration for the ICP analysis consisted of a blank and one calibration standard.

INITIAL AND CONTINUING CAL IBRATION VERIFICATIONS

All initial calibration verifications (ICV) ha d recoveries within the method criteria.

All continuing calibration verifications (CCV ) performed by TestAmerica passed with the exception of CCV 280-22121/10 7, which failed the method criteria for aluminum. All associated samples were either flagged or reanalyzed for aluminum; therefore, no additional qualificati ons were required.

BLANKS

All the method blanks were less than the re porting limit with the exception of iron in Method Blank 280-21582 where the concentration of iron (115 ug/L) was greater than the reporting limit (100 ug/L). The two iron results associated with this method blank were both flagged “B,” meaning that the element was found in the blank and the sample. The iron result for Sample 71691 was m easured at over 1,000 times th e blank level; therefore,

2the sam ple required no further qualifica tion. The iron result for Sample 71700 was flagged with a “J” qualifier; therefore, the sample re quired no further qualification.

All instrument blanks (initial calibration blank (ICB) and conti nuing calibration blank (CCB)) were less than the reporting limit; howev er, some elements were above the MDL and were flagged with the “J” qualifier.

LABORATORY CONTROL SAMPLES (LCS)

All LCSs passed the control limits of 85-115%.

INTERFERENCE CHECK SOLUTIONS

Interference checks were perfor med using the synthetic matrix as the check solution. All recoveries met TestAm erica’s SOP criteria.

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed the control limits of 50 – 150%.

SERIAL DILUTION

Serial dilutions were performed for each batc h of total and dissolved samples. Sample 71691 failed the method required ±10% differen ce for total boron (12%), barium (13%), calcium (15%), cobalt (12%), and iron (15%). Samples 71695 and 71696 failed for total aluminum (104% and 105%), respectively. Th ese elements were all flagged “V” as failing the QC criteria. These dilution tests i ndicate there may be a chemical or physical interference according to Section 9.5.2 of the 200.7 Method.

FIELD/LABORATORY DUPLICATES

The RPD of the field duplicate passed the QC criteria.

The laboratory duplicate anal ysis of sample 71697 FGD Effluent, Day 3 (280-4786-2) for dissolved iron had an RPD of 143% and wa s not flagged but was mentioned in the narrative. The parent sample value (36 ug/L) was less than the reporting limit, but the duplicate value (219 ug/L) was above the reporting limit; therefore, the RPD could not be accurately calculated.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

Matrix spikes (MS) and ma trix spike duplicates (MSD) were performed on samples 71691, 71695, 71696, 71697 and 71698. Many elements with high concentrations frequently failed the method spike recovery limits of 70-130% but were flagged with a “4” qualifier indicating that the concentration in the parent sample was greater than four times the spike and could not be reliably cal culated. In addition, so me elements were flagged with the “4” qualifier when the pare nt sample was greater than four times the

34 spike concentration, even if the MS/MSD r ecoveries did not fail the 70-130% recovery criteria. In these instances, the “4” qualifi ers were removed from the sample result. Otherwise, the MS/MSD spike recoveries we re always within the method control limits of 70-130% with exception of the following:

 Total and dissolved barium (71691 MS);

 Total barium (71691 MSD);

 Total aluminum (71695 MS/MSD);

 Total aluminum (71696 MS/MSD); and

 Total iron (71698 MS/MSD).

The total barium MS/MSD, dissolved barium MS, total barium serial dilution and total barium post digestion spike failed for sample 71691 (280-4666-1). Because of the combined failure of these quality control checks, the barium results for Sample 71691 were flagged as estimated values due to matrix interferences.

All RPDs between the MS and MSD were within ± 20%, with the exception of total iron (49%) for MS/MSD sample 71698 FGD Effluent, Day 4 (280-4841-1).

DETECTION LIMITS

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

Table 2. Data Review Summary

Sample Analyte Qualifier/Action Reason Level Detected

71691 Barium Matrix Interference Failed MS/MSD, Serial Dilution & Post Spike 680 μ g/L (total)

71691 Barium Matrix Interference Failed MS 90 μ g/L (dissolved)

71695 Aluminum Matrix Interference Failed MS/MSD, Serial Dilution 680 μ g/L (total)

71696 Aluminum Matrix Interference Failed MS/MSD, Serial Dilution 720 μ g/L (total)

71698 Iron Matrix Interference Failed MS/MSD 390 μ g/L (total)

### MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD Deb Bartram, ERG TJ Finseth, ERG From: Randy Mercurio, ERG Donna Tedder, ERG Date: 2/11/2011 Subject: FGS Data Review Narrative for Dissolved Hexavalent Chromium – Episode 6559

Frontier Global Sciences (FGS) generated an alytical data for dissolved hexavalent chromium for Sample Episode 6559. FGS anal yzed the samples according to a modified EPA Method 218.6 for dissolved hexavalent chromium by Liquid Chromatography – Inductively Coupled Plasma Ma ss Spectrometry (LC-ICP-MS).

Table 1 summarizes the samples FGS extrac ted analyzed for di ssolved hexavalent chromium.

Table 1. EPA Episode 6559 Dissolved Hexavalent Chromium – Sample Identification

EPA Sample # Sample Matrix Sample Description Sampling Date Analysis Date
71691 Aqueous FGD Influent Day 1 6/21/10 6/30/10
71692 Aqueous FGD Influent Day 2 6/22/10 6/30/10
71693 Aqueous FGD Influent Day 3 6/23/10 6/30/10
71694 Aqueous FGD Influent Day 4 6/24/10 6/30/10
71695 Aqueous FGD Effluent Day 1 6/22/10 6/30/10
71696 Aqueous FGD Effluent Day 2 6/23/10 6/30/10
71697 Aqueous FGD Effluent Day 3 6/24/10 6/30/10
71698 Aqueous FGD Effluent Day 4 6/25/10 6/30/10
71699 Aqueous FGD Effluent Day 2 Duplicate 6/23/10 6/30/10
71700 Aqueous FGD Influent Field Blank Day 1 6/21/10 6/30/10
71701 Aqueous FGD Effluent Field Blank Day 1 6/22/10 6/30/10

SUMMARY

The samples were prepared for dissolved hexavalent chromium analysis according to FGS-129.01 Standard Operating Procedure (S OP), a modified EPA Method 218.6. All

1sam ples were diluted prior to analysis due to the presence of high levels of nontarget chloride interferences.

There were no issues requiring qualifiers with the hexavalent chromium data in this episode.

SAMPLE RECEIPT, HANDLIN G, AND STORAGE ISSUES

There were no sample receipt issues in this data package.

INITIAL PRECISION AND ACCURACY/RECOVERY

The initial precision and reco very (IPR) performed by FGS had recoveries within the method criteria.

ON-GOING PRECISION AND ACCURACY/RECOVERY

The analytical method did not require the an alysis of an on-going precision and recovery (OPR).

INITIAL CALIBRATION

FGS performed the initial calibrations on each analysis day. The initial calibration for the LC-ICP-MS analysis consisted of a bl ank and eight calibration standards with a correlation factor ≥ 0.995 as required by the method.

A secondary source initial calib ration verification (ICV) wa s analyzed and passed ± 10% of true value required by the method.

CONTINUING CALIBRATION VERIFICATION

All CCVs met method-specified criteria, ±10% of true va lue, except the CCV3 with a low recovery of 87.6%. All samples affect ed by these failing CCVs were successfully reanalyzed with acceptable CCVs.

BLANK

All of the preparation blanks/laboratory reagent blanks (LRBs) and the continuing calibration blanks (CCBs) met me thod-specified requirements.

OTHER CHECKS

The laboratory control sample/duplicate (LCS /LCSD) passed method criteria (± 10% of true value).

23 DETECTION LIMITS

The laboratory method detection limit (MDL ) in the synthetic matrix was 0.392 ug/L. Results below this MDL were reported as not detected.

DUPLICATES

There were no laboratory duplicat es performed in this episod e other than a duplicate of the LCSD and a duplicate of the matrix spike (MS).

Two field duplicates were collected and analyzed. Sample 71699 was a duplicate of sample 71696. These samples were nondetects (NDs), indicating the analyte was not detected at or above the method detection limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The MSs and matrix spike duplicates (MSDs) were performed using a secondary source spike on samples 71697 and 71698. All MS/MSD recoveries were within 75%-125%, with an RPD of 1.20 and 4.41%, respectively.

### 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: Becky Schwantes, ERG Date: 2/11/2011 Subject: TestAmerica Data Review Narrative fo r Classicals Analyses – Episode 6559

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry analyses for Sample Episode 6559. All sample s 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 by SM 4500 CN - E,

 Nitrate/Nitrite by EPA Method 353.2

 Phosphorus 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 nine samples that Te stAmerica analyzed for the above analytes.

Table 1. EPA Episode 6559 Classical An alytes – Sample Identification

EPA Sample # Sample Matrix Sample Description Sampling Date 71691 Water FGD Influent, Day 1 06/21/10 71692 Water FGD Influent, Day 2 06/22/10 71693 Water FGD Influent, Day 3 06/23/10 71694 Water FGD Influent, Day 4 06/24/10 71695 Water FGD Effluent, Day 1 06/22/10 71696 Water FGD Effluent, Day 2 06/23/10 71697 Water FGD Effluent, Day 3 06/24/10 71698 Water FGD Effluent, Day 4 06/25/10 71699 Water FGD Effluent-Duplicate 06/23/10

1SUMMARY

All sam ples were preserved appropriately and analyzed within the holding time specified in 40 CFR 136 Table II.

One field duplicate sample was collected and analyzed for each analyte. The relative percent difference (RPD) between the sample and its duplicate was less than 20% unless otherwise noted below.

If applicable, the appropriate number of standards was used to create a calibration curve. If sample results were above the highest standa rd used to create the curve, the sample was diluted and reanalyzed. All sample results we re between the lowest and highest standards unless noted below. Additionally, unless otherwise noted, all calibration blanks and calibration verification samples met th e criteria specified in the method.

If required by the method, the quality control sample (QCS), a sec ondary source standard used to verify calibration, was always within the control limits speci fied by the method.

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

If required by the method, a matrix spike (M S) sample was analyzed for each analyte on sample 71697 (FGD effluent) to check for matr ix interferences. For some analytes, TestAmerica spiked more than one sample. All MS samples analyzed met the criteria specified in the method unl ess described below.

DATA NOTES/ISSUES

Ammonia

The laboratory diluted the MS/MSD samples for 71697 by two fold af ter distillation, but the diluted result was still above the highest calibration standard. The laboratory did not reanalyze these samples with a higher dilution factor because the MS/MSD percent recoveries were within the control limits specified by EP A Method 350.1. Therefore, if the MS/MSD results for sample 71697 are report ed, they will be qualified as estimated values. The diluted result for sample 71697 wa s within the calibrati on range; therefore, this sample does not need to be qualified.

2BOD 5
TestAmerica analyzed at least 5 dilutions, but no dilutions had a dissolved oxygen (DO) depletion greater than 2.0 mg/L for samples 71691-71695. Therefore, BOD 5 was reported as non-detect for these samples. All glucos e-glutamic acid standards and water blanks were analyzed appropriately and me t the criteria specified in SM 5210B.

TestAmerica analyzed four laborato ry duplicates on samples 71694, 71696, 71697, and 71698. Three of these laboratory duplicate samp les passed the criteria specified in SM 5210B (i.e., RPD <20%). The result for sample 71697 was 1.9 mg/L and the result for its duplicate was not detected; therefore, a RPD c ould not be determined for this sample and its duplicate.

Chloride and Sulfate

The laboratory diluted the MS/MSD samples for 71697 by 500 fold to calculate sulfate and by 50 fold to calculate chloride, but the diluted results were still above the highest calibration standard. The laboratory did not reanalyze these samples with a higher dilution factor because the MS/MSD percent r ecoveries were within the control limits specified by EPA Method 300.0. Therefore, if the MS/MSD results for sample 71697 are reported, they will be qualified as estimated values. The diluted result for sample 71697 was within the calibration range; therefore, th is sample does not need to be qualified.

COD

Test America analyzed both a LFB and LFBD for COD. The percent recoveries for the LFB and LFBD associated with samples 71694, 71695, and 71697 were 89% and 95% respectively. The LFB percent recovery did not meet the method control limits of 90- 110%, but did meet the historical laboratory criteria (80-115%). B ecause the laboratory originally had analyzed the percent recovery against the historical criteria, this LFB failure was not noted until after the hold time had expired, so the samples were not reanalyzed. The laboratory qua lified these samples with a “*” indicating that the LFB or LFBD was not within the method cont rol limits. Samples 71694, 71695, and 71697 were additionally qualified as minimum values.

The percent recoveries for the MS and MS D samples associated with 71697 were 74% and 75% respectively. These per cent recoveries did not meet the method control limits of 90-110%. Because the percent recoveries for both the MS and MSD samples were so much lower than the method control limits, likely the MS/MSD failure was not solely caused by the poor laboratory spiking procedures sugg ested by the LFB failure. Therefore, these results indica te that samples with the same matrix (FGD effluent) could be biased low. Sample 71697 was flagged as a minimum value.

The percent recoveries for the MS and MS D samples associated with 71691 were 75% and 80%, respectively. These percent recoveri es also did not meet the method control limits. However, the LFB/LFBD associated with sample 71691 met the method criteria.

3These low percen t recoveries indicate that samples with the same matrix (FGD influent) could be biased low. Sample 71691 was qualified as a minimum value.

Cyanide

Cyanide was detected at 0.00242 mg/L in the LRB associated with the following samples: 71691-71697, and 71699. Although this conc entration is grea ter than the MDL (0.0020 mg/L), it is lower than the RL (0.010 mg/L). Because the blank result was less than the RL, no samples were qualified based on the LRB result.

All samples were diluted prior to distillation by a factor of 10 due to matrix interferences. The laboratory stated that the samples foamed during preparation and in order to protect the instruments, the samples needed to be diluted. All sample results were within the calibration range used by the lab (0.01 mg/L – 0.4 mg/L).

The RPD between sample 71696 and its fi eld duplicate 71699 for cyanide was 27%. Even though the RPD was greater than 20%, the sample was not qualified because there are no specific control limits for fi eld duplicates speci fied in SM 4500 CN - E.

SM 4500 CN - E does not require the laboratory to an alyze MS/MSD samples, so there are no control limits specified in the method. Th e laboratory performed MS/MSD analysis on samples 71697 and 71698. As shown by Table 2, the MS/MSD percent recoveries for both these samples were below the laborator y control limits of 90-110%. These results indicate that cyanide samples with a similar matrix (FGD effluent) are likely to be biased low because of matrix inte rferences. Because SM 4500 CN - E does not require MS/MSD analysis, the samples were not qualified.

Table 2. MS/MSD Results for Total Cyanide Analysis

Sample Number Type Result Spike Amount Spike Result Percent Recovery 71697 MS 0.24 mg/L 1.00 mg/L 0.998 mg/L 76% 71697 MSD 0.24 mg/L 1.00 mg/L 0.896 mg/L 66% 71698 MS 0.18 mg/L 1.00 mg/L 0.768 mg/L 59% 71698 MSD 0.18 mg/L 1.00 mg/L 0.632 mg/L 45%

4Nitrate/Nitrite

TestAm erica performed an MS/MSD analysis on samples 71695 and 71697. All percent recoveries were within the control limits specified in the method (90-110%) except for the MSD sample for 71695, which had a percent recovery of 86%. Because EPA Method 353.2 does not require MSD samples to meet the above criteria, sample 71695 was not qualified. Furthermore, the laboratory diluted the MS/MSD samples for 71695 by 20 fold, but the diluted result was still above the highest calibration standard. The percent recovery for the MS sample was within the control limits specified in the method, so the laboratory did not dilute and rerun the MS/MSD samples. T hus, if reported, the MS/MSD results for sample 71695 will be qualified as estimated values.

Phosphorus

Phosphorus was detected at 0.0107 mg/L in the LRB associated with all samples. Although this concentration is more than th e MDL (0.005 mg/L), it is less than the RL (0.050 mg/L). Because the blank result was less than the RL, no samples were qualified based on the LRB result.

The RPD between sample 71696 and its field duplicate 71699 for phosphorus was 154%. Even though the RPD was greater than 20%, the sample was not qualified because there are no specific control limits for field duplicates specified in the EPA Method 365.1.

The percent recoveries for the MS and MSD analyses for sample 71697 were not within the method control limits of 90-110% or within the laboratory cont rol limits of 71-128%. The percent recoveries for the MS and MS D samples were 62% and 65%. Results for samples with a similar matrix (i.e., FGD effl uent) may be biased low because of matrix interferences. Sample 71697 was already qua lified by TestAmerica with a “J” meaning the result was an estimated value because it was less than the RL. Therefore, there was no need to further qualify the sample as a mi nimum value. The LFB associated with all samples met the method criteria.

The analyzed results for the following samp les were less than the lowest calibration standard (0.025 mg/L): 71693, 71698, and 71699. However, these samples were already qualified by the laboratory with a “J” meaning the sample result was an estimated value because it was below the RL, so no further action was taken.

TDS

The RPDs for laboratory duplicates from samples 71696 and 71697 were less than 10% as required by SM 2540C.

TDS was detected at 9.0 mg/L in the LRB a ssociated with sample 71698. This result was above the MDL, but below the RL, so there was no need to qualify the sample further.

5Three sam ples (71692, 71693, and 71698) analyzed for TDS did not achieve a constant weight after three drying cycles. In two of these samples, the weight increased from the first weighing to the second weighing. Met hod 2540C warns that samples which contain high levels of calcium, magnesium, chloride , and sulfate may be hygroscopic meaning they absorb moisture from the air. FGD wastew ater contains high concentrations of all of these species, so this was likely the cause for the inconsistent weight calculations. These samples were not qualified, but results may be biased high.

TKN

TKN was detected at 0.153 mg/L in the L RB associated with the following samples 71692-71697, and 71699. The blank result was above the MDL, but below the RL, so no samples were qualified based on the LRB result.

TestAmerica performed MS/MSD anal ysis on samples 71691, 71697, and 71698. As shown by Table 3, the percent recoveries for the MS/MSD analysis for all three samples did not meet the control limits of 90-110% specified in EPA Me thod 351.2. All MS/MSD samples analyzed, except for the MSD analysis for sample 71691, also did not meet the laboratory control limits of 54-131%.

Table 3. MS/MSD Results for TKN Analysis

Sample Number Type Result Spike Amount Spike Result Percent Recovery 71691 MS 86 mg/L 15.0 mg/L 93.6 mg/L 49% 71691 MSD 86 mg/L 15.0 mg/L 99.2 mg/L 86% 71697 MS 64 mg/L 3.00 mg/L 68.2 mg/L 147% 71697 MSD 64 mg/L 3.00 mg/L 69.3 mg/L 183% 71698 MS Not analyzed by TestAmerica. 71698 MSD 52 mg/L 3.00 mg/L 60.3 mg/L 277%

TestAmerica flagged the MS/MSD samples of 71691 and 71697 with a “4” because the sample result was more than 4 times the spik e amount indicating the control limits are not reliable. TestAmerica did not flag the MS D sample associated with 71698 even though the sample result was more than 4 times the spike amount, so this sample was flagged with a “4”. These samples were not qualif ied further because it is not possible to determine if MS/MSD failures were a result of matrix interferences or caused by the low spike level. The LFBs associated with all samples met the method criteria.

TSS

The RPDs for laboratory duplicates for samples 71691, 71692, 71693, and 71698 were less than 10%, as re quired by SM 2540D. However, the RPD for sample 71697 and its duplicate was 15%. Sample 71697 was already qualified by TestAmerica with a “J” meaning the result was an estimated value becau se it was less than the RL, so no further action was taken.

67 The RPD between sample 71696 and its field duplicate 71699 for TSS was 66.7%. The sample concentrations for 71696 and 71699 were greater than the MDL, but less than the RL. These low concentrations might be th e reason for the high RPD. Even though the RPD was greater than 20%, the sample was not qualified because there are no specific control limits for field duplicat es specified in the method.

Table 4. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level Detected 71694 COD Minimum value LFB % recoverybelow methodspecified criteria 400 mg/L

71695 COD Minimum value LFB % recoverybelow methodspecified criteria 390 mg/L

71697 COD Minimum value LFB % recoverybelow methodspecified criteria, MS % recoverybelow methodspecified criteria 410 mg/L

71691 COD Minimum value MS % recoverybelow methodspecified criteria 420 mg/L

71698 (MSD Sample) TKN “4” Sample result > 4 times spike

amount 60.3 mg/L