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: 2/2/2011 Subject: FGS Data Review Narrative fo r Total Mercury – Episode 6558

Frontier Global Sciences (FGS) generated an alytical data for total mercury. FGS analyzed the samples according to EPA Me thod 1631E for total mercury by Cold Vapor Atomic Fluorescence Spectrometry (CVAFS) analysis.

Table 1 summarizes the 38 samples (excluding laboratory filter blanks) FGS extracted and analyzed for total mercury.

Table 1. EPA Episode 6558 Total Mercury– Sample Identification

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

71641 1006065-01 Aqueous FGD Influent Day 1 6/7/2010

71641 1006065-02 Aqueous Dissolved FGD Influent Day 1 6/7/2010

71642 1006085-01 Aqueous FGD Influent Day 2 6/8/2010

71642 1006085-02 Aqueous Dissolved FGD Influent Day 2 6/8/2010

71643 1006092-01 Aqueous FGD Influent Day 3 6/9/2010

71643 1006092-02 Aqueous Dissolved FGD Influent Day 3 6/9/2010

71644 1006109-07 Aqueous FGD Influent Day 4 6/10/2010

71645 1006085-03 Aqueous FGD Bioreactor Influent Day 1 6/7/2010

71645 1006085-04 Aqueous Dissolved FGD Bioreactor Influent Day 1 6/7/2010

71646 1006085-14 Aqueous Dissolved FGD Bioreactor Influent Day 2 6/8/2010

71646 1006092-04 Aqueous Dissolved FGD Bioreactor Influent Day 2 6/9/2010

71646 1006092-21 Aqueous Dissolved FGD Bioreactor Influent Day 2 6/9/2010

71646 1006092-03 Aqueous FGD Bioreactor Influent Day 2 6/9/2010

71647 1006109-09 Aqueous FGD Bioreactor Influent Day 3 6/10/2010

71647 1006109-10 Aqueous Dissolved FGD Bioreactor Influent Day 3 6/10/2010

71648 1006118-01 Aqueous FGD Bioreactor Influent Day 4 6/11/2010

71648 1006118-02 Aqueous Dissolved FGD Bioreactor Influent Day 4 6/11/2010

71649 1006085-05 Aqueous FGD Bioreactor Effluent Day 1 6/8/2010

71649 1006085-06 Aqueous Dissolved FGD Bior eactor Effluent Day 1 6/8/2010

1Table 1. EPA Episode 6558 Total Mercury– Sample Identification

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

71650 1006092-05 Aqueous FGD Bioreactor Effluent Day 2 6/9/2010

71650 1006092-06 Aqueous Dissolved FGD Bior eactor Effluent Day 2 6/9/2010

71651 1006109-11 Aqueous FGD Bioreactor Effluent Day 3 6/10/2010

71651 1006109-12 Aqueous Dissolved FGD Bior eactor Effluent Day 3 6/10/2010

71652 1006118-03 Aqueous FGD Bioreactor Effluent Day 4 6/11/2010

71652 1006118-04 Aqueous Dissolved FGD Bior eactor Effluent Day 4 6/11/2010

71653 1006109-13 Aqueous FGD Bioreactor Influent Duplicate 6/10/2010

71653 1006109-14 Aqueous Dissolved FGD Bioreactor Influent Duplicate 6/10/2010

71654 1006092-07 Aqueous FGD Bioreactor Effluent Duplicate 6/9/2010

71654 1006092-08 Aqueous Dissolved FGD Bioreactor Effluent Duplicate 6/9/2010

71655 1006065-03 Aqueous FGD Influent Fi eld Blank (FB) Day 1 6/7/2010

71656 1006065-06 Aqueous FGD Bioreactor Influent FB Day 1 6/7/2010

71657 1006085-07 Aqueous FGD Bioreactor Influent FB Day 2 6/8/2010

71658 1006092-19 Aqueous FGD Bioreactor Influent FB Day 3 6/9/2010

71659 1006109-05 Aqueous FGD Bioreactor Influent FB Day 4 6/10/2010

71660 1006065-09 Aqueous FGD Bioreactor Effluent FB Day 1 6/7/2010

71661 1006085-19 Aqueous FGD Bioreactor Effluent FB Day 2 6/8/2010

71662 1006092-20 Aqueous FGD Bioreactor Effluent FB Day 3 6/9/2010

71663 1006109-06 Aqueous FGD Bioreactor Effluent FB Day 4 6/10/2010

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. The following summarizes th e findings from the data review:

 One filter blank (lab sample number 1006085-20) exceeded the method detection level (MDL). The samples associated w ith this filter bl ank do not require qualification. All of the detected values for these samples were at least 30 times the level found in the blank.

 The MDL provided by the la boratory is above the MDL requirement for EPA Method 1631E; however, the MDL used fo r this sampling program is based on analyses in the synthetic matrix and not based on blank water.

 One set of field duplicates was out of the method-suggested relative percent difference (RPD) criteria.

2SAMPLE RECEIPT, HANDLIN G, AND ST ORAGE ISSUES

As discussed in the case narrative provided by FGS, “One (1) of the 250 mL glass bottles submitted for grab sample 71646 FGD Bior eactor Influent Day 2 was dropped and broken during filtration. Per the client's request, the remaining grab aliquots for sample 71646 Dissolved FGD Bioreactor Influent Day 2 were not composited and run as discrete samples.

Also discussed in the FGS narrative, “Two (2 ) of the 250 mL glass bottles submitted for sample 71644 FGD Influent Day 4 were dropp ed and broken durin g preservation. The two bottles that were broken contained the dissolved mercury ali quot (lab-filtered) and total mercury aliquot. Only one total mercur y aliquot remained for the sample; therefore no dissolved mercury results were availabl e for sample 71644 FGD Influent Day 4.”

ONGOING PRECISION AND ACCURACY/RECOVERY

The results for all ongoing precision and recove ry (OPR) samples, in the form of blank spike/blank spike duplicates (BS/BSDs), fe ll within the method criteria of 77-123%
recovery.

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.

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

CONTINUING CALIBRATION VERIFICATION (CCV)

All CCVs met method-specified criteria.

BLANKS

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

FGS analyzed a total of five filter blanks. One filter blank, Sample 1006085-20, exceeded the MDL (0.239 ng/L) at 0.77 ng/L. Th e samples associated with this filter blank, 71642, 71645, 71646 (Dissolved FGD Bi oreactor Influent Day 2 only), 71649, 71657, and 71661, do not require qualif ication. All of the de tected values for these samples were at least 30 times the level found in the blank.

34 DETECTION LIMITS

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

DUPLICATES

Field duplicates, Samples 71654 and 71653, were collected on Samples 71650 and 71647, respectively. The 71654/71650 RPD was 185% for total mercury and 20% for dissolved mercury. The 71653/71647 RPD was 27% for total mercury and 2% for dissolved mercury. The method-suggested RPD cr iteria between field duplicates is 20%.

Laboratory duplicates were performed in this episode on Samples 71645, 71643, 71646, and they all met method-specified criteria.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

Matrix spikes (MS) and ma trix spike duplicates (MSD) were performed on Samples 71645, 71646, 71648, 71651, and 71654. All recoveries were within method specifications of 71-125%. The RPDs were 0.00, 4.24, 5.26, 2.40, and 16.7%, 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: Randy Mercurio, ERG Date: 3/29/2011 Subject: TestAmerica Data Review Narrative fo r Total and Dissolved Metals by 200.8 – Episode 6558

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 6558. 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.

EPA Sample # EPA Sample Description Lab Sample ID # Sample Matrix Sampling Date Receipt Date
71641 FGD Influent, Day 1 280-4226-1 Aqueous 6/7/2010 6/8/2010
71642 FGD Influent, Day 2 280-4279-1 Aqueous 6/8/2010 6/9/2010
71643 FGD Influent, Day 3 280-4337-1 Aqueous 6/9/2010 6/10/2010
71644 FGD Influent, Day 4 280-4376-1 Aqueous 6/10/2010 6/11/2010
71645 FGD Bioreactor Influent, Day 1 280-4279-2 Aqueous 6/8/2010 6/9/2010
71646 FGD Bioreactor Influent, Day 2 280-4337-2 Aqueous 6/9/2010 6/10/2010
71647 FGD Bioreactor Influent, Day 3 280-4376-2 Aqueous 6/10/2010 6/11/2010
71648 FGD Bioreactor Influent, Day 4 280-4415-1 Aqueous 6/11/2010 6/12/2010
71649 FGD Bioreactor Effluent, Day 1 280-4279-3 Aqueous 6/8/2010 6/9/2010
71650 FGD Bioreactor Effluent, Day 2 280-4337-3 Aqueous 6/9/2010 6/10/2010
71651 FGD Bioreactor Effluent, Day 3 280-4376-3 Aqueous 6/10/2010 6/11/2010
71652 FGD Bioreactor Effluent, Day 4 280-4415-2 Aqueous 6/11/2010 6/12/2010

71653 FGD Bioreactor Influent - Duplicate 280-4376-4 Aqueous 6/10/2010 6/11/2010

71654 FGD Bioreactor Effluent - Duplicate 280-4337-4 Aqueous 6/9/2010 6/10/2010
71655 FGD Influent Field Blank, Day 1 280-4226-2 Aqueous 6/7/2010 6/8/2010

71656 FGD Bioreactor Influent, Field Blank Day 1 280-4279-4 Aqueous 6/8/2010 6/9/2010

71660 FGD Bioreactor Effluent, Field Blank Day 1 280-4279-5 Aqueous 6/8/2010 6/9/2010

1SUMMARY

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 Element Analysis in Flue Gas Desulfurization Wastewaters,” dated October 6, 2010, based on EPA Method 200.8, by ICP/MS analysis.

There were no findings from the data review that required additional qualifiers (excluding those identified by the laboratory) in this dataset.

INSTRUMENT TUNE CONDITIONS

The tune report for each day of analysis c onsistently failed the required <5% relative standard deviation (RSD) for beryllium. According to Section 10.3.2 of TestAmerica’s SOP, “The relative standard deviations must be less th an 5% for a minimum of 4 integrations of the solution.”

INTERNAL STANDARDIZATION

All internal standards used by TestAmeri ca 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 re porting limit (RL); how ever, some elements were found above the method detection limit (MDL) and were flagged with the “J” qualifier.

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

REPORTING LIMIT VERIFICATION STANDARD (CRI)

All CRI samples passed Test Amer ica’s 50-150% recovery limits.

23 LABORATORY CONTROL SAMPLE (LCS)

All LCS samples passed the method limits of 85-115%.

SYNTHETIC FGD INTERFERE NCE CHECK SOLUTION

Chromium in the ICSA solution was alwa ys above the RL of 4 ug/L, indicating interferents were not being removed effectively. Therefor e, all sample results for chromium, including QC samples, from this episode have been flagged with the “^” qualifier.

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 ex ception of dissolved Selenium in Sample 71649.

FIELD/LABORATORY DUPLICATES

The relative percent difference (RPD) of the field duplicates 71650/71654 and 71647/71653 were less than 20% for all values equal to or greater than the reporting limit.

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

Matrix spikes and matrix spike duplicates were performed on Samples 71641, 71648, 71649, 71650 and 71651. 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 “4”. Otherwise, the MS/MSD spike recoveries were always within the contro l limits of 70-130% with the ex ception of the dissolved zinc (MS Sample 71651). The RPD for all MS/MSD passed the method-specified criteria of 20 percent.

POST SPIKE

Post spikes passed Test America’s 85-115% recovery with the exception of total and dissolved Selenium for sample 71648.

DETECTION LIMITS

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

### 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 6558

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 6558. 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 6558 Total & Dissolved Metals – Sample Identification

EPA Sample # EPA Sample Description Lab Sample ID # Sample Matrix Sampling Date Receipt Date
71641 FGD Influent, Day1 280-4226-1 Aqueous 6/7/2010 6/8/2010
71642 FGD Influent, Day 2 280-4279-1 Aqueous 6/8/2010 6/9/2010
71643 FGD Influent, Day 3 280-4337-1 Aqueous 6/9/2010 6/10/2010
71644 FGD Influent, Day 4 280-4376-1 Aqueous 6/10/2010 6/11/2010
71645 FGD Bioreactor Influent, Day 1 280-4279-2 Aqueous 6/8/2010 6/9/2010
71646 FGD Bioreactor Influent, Day 2 280-4337-2 Aqueous 6/9/2010 6/10/2010
71647 FGD Bioreactor Influent, Day 3 280-4376-2 Aqueous 6/10/2010 6/11/2010
71648 FGD Bioreactor Influent, Day 4 280-4415-1 Aqueous 6/11/2010 6/12/2010
71649 FGD Bioreactor Effluent, Day 1 280-4279-3 Aqueous 6/8/2010 6/9/2010
71650 FGD Bioreactor Effluent, Day 2 280-4337-3 Aqueous 6/9/2010 6/10/2010
71651 FGD Bioreactor Effluent, Day 3 280-4376-3 Aqueous 6/10/2010 6/11/2010
71652 FGD Bioreactor Effluent, Day 4 280-4415-2 Aqueous 6/11/2010 6/12/2010

71653 FGD Bioreactor Influent - Duplicate 280-4376-4 Aqueous 6/10/2010 6/11/2010

71654 FGD Bioreactor Effluent - Duplicate 280-4337-4 Aqueous 6/9/2010 6/10/2010
71655 FGD Influent Field Blank, Day 1 280-4226-2 Aqueous 6/7/2010 6/8/2010

71656 FGD Bioreactor Influent, Field Blank Day 1 280-4279-4 Aqueous 6/8/2010 6/9/2010

1Table 1. EPA Episode 6558 Total & Dissolved Metals – Sample Identification

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

71660 FGD Bioreactor Effluent, Field Blank Day 1 280-4279-5 Aqueous 6/8/2010 6/9/2010

SUMMARY

The samples were prepared for total and dissolved metals analysis according to TestAmerica’s SOP for ICP Analys is for Trace Metals by Method 200.7.

There were no findings from the data review that required additional qualifiers (excluding those identified by the laboratory) in this da taset. The following summarizes the findings from the data review:

The serial dilution of sample 71641 failed the required ±10% difference for calcium (24%), cobalt (15%) and magnesium (12 %) and sample 71643 failed for aluminum (12%); these elements were flagged “V” as failing the QC criteria. These dilution tests indicate there may be a chemical or physical interference.

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 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 re porting limit (RL); how ever, some elements were found above the method detection limit (MDL) and were flagged with the “J” qualifier.

2All instrument blanks (ICB a nd CCB) were less than the RL; however, som e elements were above the MDL and were fl agged with the “J” qualifier.

RL VERIFICATION STANDARD (CRI)

All CRI samples passed TestAmeri ca’s control limits of 50 – 150%.

LABORATORY CONTROL SAMPLE (LCS)

All LCS passed the method limits 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. Sample 71641 failed the required ±10% difference for calcium (24%), cobalt (15%), but the concentration was less than the RL, and ma gnesium (12%), and Sample 71643 failed for aluminum (12%); these elements were fla gged “V” as failing the QC criteria. These dilution tests indicate there may be a chemi cal or physical interference according to Section 9.5.2 of the 200.7 Method.

FIELD/LABORATORY DUPLICATES

The RPD of the field duplicates were less than 20% for all concentrations greater than the reporting limit, with the exception of iron for the dissolved samples 71650 and 71654.

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

Matrix spike and matrix spike duplicat es were performed on samples 71641, 71642, 71643, 71648 and 71651. Many elements with high c oncentrations frequently failed the spike recovery and were flagge d with a “4” qualifier indicating that concentrations in the parent sample was greater than four times the spike. In many cases, the MS/MSD spike recoveries failed TestAmerica’s SOP requi rements and were flagged with the “F” qualifier. Otherwise, the MS/MSD spike recoveri es were always within the control limits of 70–130% with the exception of dissolved aluminum (MS Sample 71641), which was recovered at 68%. The RPD between the MS and MSD for dissolved beryllium, iron, tin & titanium for Sample 71641 was greater th an 20%, which fails TestAmerica’s RPD requirement; therefore, the results for these dissolved analytes for Sample 71641 were flagged with the “F” qualifier.

34 DETECTION LIMITS

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

### 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: 2/2/2011 Subject: FGS Data Review Narrative for Dissolved Hexavalent Chromium – Episode 6558

Frontier Global Sciences (FGS) generated an alytical data for dissolved hexavalent chromium for Sample Episode 6558. 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 17 samples FGS extracted and analyzed for dissolved hexavalent chromium.

Table 1. EPA Episode 6558 Dissolved Hexavalent Chromium– Sample Identification

EPA Sample # Sample Matrix Sample Description Sampling Date Analysis Date
71641 Aqueous FGD Influent Day 1 6/7/10 6/21/10
71642 Aqueous FGD Influent Day 2 6/8/10 6/21/10
71643 Aqueous FGD Influent Day 3 6/9/10 6/22/10
71644 Aqueous FGD Influent Day 4 6/10/10 6/22/10
71645 Aqueous FGD Bioreactor In fluent Day 1 6/8/10 6/21/10
71646 Aqueous FGD Bioreactor Infl uent Day 2 6/9/10 6/22/10
71647 Aqueous FGD Bioreactor In fluent Day 3 6/10/10 6/22/10
71648 Aqueous FGD Bioreactor In fluent Day 4 6/11/10 6/22/10
71649 Aqueous FGD Bioreactor E ffluent Day 1 6/8/10 6/22/10
71650 Aqueous FGD Bioreactor E ffluent Day 2 6/9/10 6/22/10
71651 Aqueous FGD Bioreactor E ffluent Day 3 6/10/10 6/22/10
71652 Aqueous FGD Bioreactor E ffluent Day 4 6/11/10 6/22/10
71653 Aqueous FGD Bioreactor Infl uent Duplicate 6/10/10 6/22/10
71654 Aqueous FGD Bioreactor Effl uent Duplicate 6/9/10 6/22/10
71655 Aqueous FGD Influent Field Blank (FB) Day 1 6/7/10 6/21/10
71656 Aqueous FGD Bioreactor Infl uent FB Day 1 6/8/10 6/21/10
71660 Aqueous FGD Bioreactor Effl uent FB Day 1 6/8/10 6/22/10

1SUMMARY

Sa mples 71643, 71646, 71650, and 71654 arrived with temperatures above the required ≤ 4°C.

The samples were prepared for dissolved hexavalent chromium analysis according to FGS-129.01 Standard Operating Procedure (SOP), a modified EPA Method 218.6. Several samples (71641, 71642, 716 44, 71649, 71650, 71651, 71652, 71654, and 71660) were diluted prior to analysis due to the pr esence of high levels of nontarget chloride interferences.

SAMPLE RECEIPT, HANDLIN G, AND STORAGE ISSUES

Samples 71643, 71646, 71650, and 71654 arrived at the laboratory at 12.2°C, higher than the required temperature of ≤ 4°C (see Table 2 below).

INITIAL PRECISION AND ACCURACY/RECOVERY

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

ONGOING PRECISION AND ACCURACY/RECOVERY

The analytical method did not require the an alysis of an ongoing 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 analytical method.

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

CONTINUING CALIBRATION VERIFICATION (CCV)

All CCVs met method-specified criteria ex cept the following: CCV2 and CCV3 had high recoveries in the initial analysis sequen ce on 6/21/10. All samples affected by these failing CCVs were successfully rean alyzed with acceptable CCVs.

BLANK

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

23 OTHER CHECKS

The laboratory control sample/duplicate (LCS/L CSD) passed method criteria (± 10%).

DETECTION LIMITS

The laboratory method detecti on limit (MDL) in the synthe tic 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. Samples 71653 and 71654 were duplicates of Samples 71647 and 71650, resp ectively. Sample 71647 and its duplicate had an RPD of 5%. Sample 71650 and its duplic ate were nondetects (NDs), indicating the analyte was not detected at or above the reporting limit.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The MSs and matrix spike duplicates (MSDs) were performed using a secondary source spike on Samples 71650 and 71648. All MS/MSD recoveries were within 75-125%, with an RPD of 0.737 and 3.06%, respectively.

Table 2. Data Review Summary Table

Sample Analyte Qualifier Reason Level Detected

71643 Chromium (VI) Estimated value Receipt temperature of 12.2°C ND

71646 Chromium (VI) Estimated value Receipt temperature of 12.2°C 11.7 μg/L

71650 Chromium (VI) Estimated value Receipt temperature of 12.2°C ND

71654 Chromium (VI) Estimated value Receipt temperature of 12.2°C ND

ND - Not detected.

### 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: 2/2/2011 Subject: TestAmerica Data Review Narrative fo r Classicals Analyses – Episode 6558

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry analyses for Sample Episode 6558. All samples 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 14 samples that TestAmerica analyzed for the above analytes.

Table 1. EPA Episode 6558 Classical An alytes – Sample Identification

EPA Sample # Sample Matrix Sample Description Sampling Date 71641 Water FGD Influent, Day 1 06/07/10 71642 Water FGD Influent, Day 2 06/08/10 71643 Water FGD Influent, Day 3 06/09/10 71644 Water FGD Influent, Day 4 06/10/10 71645 Water FGD Bioreactor Influent, Day 1 06/08/10 71646 Water FGD Bioreactor Influent, Day 2 06/09/10 71647 Water FGD Bioreactor Influent, Day 3 06/10/10 71648 Water FGD Bioreactor Influent, Day 4 06/11/10 71649 Water FGD Bioreactor Effluent, Day 1 06/08/10 71650 Water FGD Bioreactor Effluent, Day 2 06/09/10 71651 Water FGD Bioreactor Effluent, Day 3 06/10/10

1Table 1. EPA Episode 6558 Classical An alytes – Sample Id entification

EPA Sample # Sample Matrix Sampling Sample Description Date 71652 Water FGD Bioreactor Effluent, Day 4 06/11/10 71653 Water FGD Bioreactor Influent - Duplicate 06/10/10 71654 Water FGD Bioreactor Effl uent - Duplicate 06/09/10

SUMMARY

Unless otherwise noted below, all samples were analyzed within the holding time specified in 40 CFR 136 Ta ble II. All samples were preserved appropriately.

Two field duplicate samples were 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 seconda ry 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 criteria specified in the method.

If required by the method, a matrix spike (MS) sample was analyzed. Unless noted below, two MS samples were run on sa mples 71648 (FGD bioreactor influent) and 71651 (FGD bioreactor effluent) for each analyte to check for matrix in terferences in these matrices. For some analytes, TestAmerica sp iked more samples than required. All MS samples analyzed met the criteria specifie d in the method unless described below.

DATA NOTES/ISSUES

Ammonia

The data reviewer identified no issues. All QC samples met the criteria specified in EPA Method 350.1.

2BOD 5
Even though TestAmerica ran at least five d ilutions on every sample, no dilutions had a dissolved oxygen (DO) depletion great er than 2.0 mg/L. Therefore, BOD 5 was reported as nondetect for all samples. All glucose-gl utamic acid standards, water blanks, and laboratory duplicates were anal yzed appropriately and met th e criteria specified in SM 5210B.

Chloride and Sulfate

TestAmerica was required by the SOW to run a matrix spike and matrix spike duplicate (MS/MSD) analysis on sample 71648 (FGD bi oreactor influent) and sample 71651 (FGD bioreactor effluent). Howeve r, the MS/MSD analysis for both chloride and sulfate was only run on sample 71648. The MS/MSD result s for sample 71648 met the criteria of 80- 120% specified in EPA Method 300.0 indicating ma trix interferences we re not interfering with the results for samples with the same matrix (i.e., FGD bioreactor influent). The percent recoveries for chloride were 98% (MS) and 99% (MSD) and the percent recovery for both the MS and MSD samples for sulfate was 100%. Because an MS was not run on sample 71651, the data reviewer could not de termine whether matrix interferences were disrupting results in FGD bior eactor effluent samples. The LFBs associated with all samples met the method criteria.

The RPD between sample 71647 and its field duplicate 71653 for sulfate was 58.8%. Even though the RPD was greater than 20%, the sample was not qualified because there are no specific control limits for fiel d duplicates specified in EPA Method 300.0.

COD

The percent recoveries for the MS/MSD analysis for sample 71648 (FGD bioreactor influent) were below the control limits of 90-110% required by EPA Method 410.4. The percent recoveries for the MS and MSD an alyses were 86% and 87%, respectively. The low percent recovery could indicate that re sults for samples with the same matrix (FGD bioreactor influent) could be biased low. Sample 71648 was flagged as a minimum value. The LFBs associated with all samples met the method criteria.

The percent recoveries for the MS and MSD analyses fo r sample 71651 (FGD bioreactor effluent) were 92% and 86%, respectively. These MS/MSD percent recoveries indicate that results for samples with the same matrix (FGD bioreactor efflue nt) could be biased low. However, EPA Method 410.4 only requires th at the result for the MS analysis be within 90-110%, so sample 71651 was not flagged.

The RPD between sample 71647 and its fi eld duplicate 71653 was 43.5% and between sample 71654 and its field duplicate 71650 was 66.7%. Even though these RPDs were greater than 20%, the samples were not quali fied because there are no specific control limits for field duplicates specified in EPA Method 410.4.

3Cyanide

Sa mples 71642, 71643, 71644, 71645, 71646, 71647, 71648, 71650, 71651, 71652, 71653, and 71654 were diluted prior to distillat ion by a factor of 10 due to matrix interferences. The laboratory stated that the samples foam ed during preparation and in order to protect the instrument s, the samples were diluted.

The results of the diluted sa mple for 71642, 71643, 71644, 71650, 71651, 71652, and 71654 were below the lowest calibration standard used by the laboratory (0.01 mg/L). These samples were already qualified by the laboratory with a “J” indicating that the result was below the RL, so no further qualification was necessary.

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. The laboratory ran MS /MSD analysis on samples 71641, 71648, 71649, 71650, and 71651. As show n by Table 2 below, nearly all of the MS/MSD percent recoveries were be low the laboratory cont rol limits (90-110%). It should be noted that samples 71641, 71648, 71650, and 71651 were all either ND or qualified by the laboratory with a “J” because the result was less than the RL; these low results may have impacted the MS/MSD pe rcent recoveries. The low MS/MSD percent recoveries for sample 71649 suggest that cy anide results for sample 71649 and samples with a similar matrix (FGD bioreactor effluent ) could be biased low because of matrix interferences. Because SM 4500 CN - E does not require MS/MSD analysis, the data were not qualified.

Table 2. MS/MSD Results for Total Cyanide Analysis

Sample Number Type Result (mg/L) Spike Amount (mg/L) Spike Result (mg/L) Percent Recovery 71641 MS ND 0.100 mg/L ND 0% 71641 MSD ND 0.100 mg/L ND 0% 71649 MS 0.012 0.100 mg/L 0.0956 84% 71649 MSD 0.012 0.100 mg/L 0.0972 85% 71650 MS 0.057 1.0 mg/L 0.959 90% 71650 MSD 0.057 1.0 0.944 89% 71651 MS 0.039 1.0 0.903 86% 71651 MSD 0.039 1.0 0.916 88% 71648 MS ND 1.0 ND 0% 71648 MSD ND 1.0 ND 0% ND – Not detected.

Nitrate/Nitrite

The percent recoveries for the MS/MSD analysis for samples 71649 and 71651 (FGD bioreactor effluent) were a bove the control limits of 90-110% required by EPA Method 353.2 and above the laboratory control limits of 72-113%. The percent recovery was

4118% for both the MS and MSD samples fo r 71651 and 119% for both the MS and MSD

sam ples for 71649. Because nitrate/nitrite was not detected in sample 71649 or 71651, there was no need to qualify either sample as a maximum value.

Furthermore, the percent recoveries fo r the MS analysis for sample 71648 (FGD bioreactor influent) was above the control limits required by the method, but within the laboratory control limits. The MSD analys is for sample 71648 wa s within both the method and laboratory control limits. The MS and MSD percent recoveries were 111% and 110%, respectively. Sample 71648 was qualified as a maximum value.

The result for sample 71650 with a concentr ation of 0.019 mg/L was below the lowest standard (0.05 mg/L) used to create the calib ration curve. However, because this sample was already qualified by the laboratory with a “J” because the result was below the RL, no further qualification was necessary.

Phosphorus

Phosphorus was detected at 0.00790 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 LRB result.

The percent recoveries for the MS and MSD analyses for samples 71648 and 71651 were not within the control limits of 90-110% specified in EPA Method 365.1. The MS and MSD percent recoveries for sample 71648 (FGD bioreactor influent) were within the laboratory control limits of 71- 128%, but the MS and MSD per cent recoveries for sample 71651 were not. The percent recoveries for MS and MSD analyses on sample 71648 were both 75%. The percent recoveries for MS and MSD analyses on sample 71651 were 60% and 58%, respectively. Sample 71651 was qualifie d as a minimum value because the MS percent recovery was below the method specified criteria. The results also may be biased low for samples with a similar matrix (i.e., FGD bioreactor effluent) because of matrix interferences. Sample 71648 was already quali fied by the laboratory with a “J” because the result was below the RL, so no fu rther qualificati on was necessary.

The results for the following samples were less than the lowest calibration standard (0.025 mg/L): 71644, 71645, 71646, 71647, 71648, and 71653. However, these samples were already qualified by the laboratory w ith a “J”, so no further action was taken.

TDS

The RPDs for laboratory duplicates from samples 71642, 71643, 71644, and 71648 were less than 10% as re quired by SM 2540C. However, the RPD for sample 71641 and its laboratory duplicate was 15%. Because the RPD was greater than the method control limits, sample 71641 was qualified as an estimated value.

5TDS was detected at 8.0 m g/L, which is a bove the MDL (4.7 mg/L), but below the RL (10 mg/L), in two of the LRBs. Because the blank result was less than the RL, no samples were qualified based on LRB analyses. Furthermore, the TDS concentration in all samples was at least 1000 times greater than the concentration of TDS detected in the LRB, so sample results are unlikely to be a ffected by the TDS contamination in the LRB.

All 14 samples analyzed for TDS did not achie ve a constant weight after three drying cycles. In all cases, the weight increased fr om the first weighing to the second weighing. SM 2540C warns that samples that contain high levels of calcium, magnesium, chloride, and sulfate may be hygroscopic, meaning they absorb moisture from the air. FGD wastewater contains high con centrations of all of these species, so this was likely the cause for the inconsistent weight calculations. The samples were not qualified, but results may be biased high.

TKN

TKN was detected in the LRBs associated with samples 71641, 71645, 71646, and 71651 at 0.894 mg/L, 0.645 mg/L, and 0.108 mg/L. Thes e results were greater than the MDL (0.077 mg/L), but less than the RL (1.0 mg/L). Because these blank results were all less than the RL, no samples were qualified based on the LRB analyses.

The RPD between sample 71647 and its fiel d duplicate 71653 could not be reliably determined because the result for sample 71647 was ND and the result for sample 71653 was 2.8 mg/L.

The percent recoveries for the MS/MSD analysis for samples 71641 (FGD influent) and 71654 (FGD bioreactor effluent) did not meet th e control limits (90- 110%) specified in EPA Method 351.2. The MS analysis for sample 71649 (FGD bioreactor influent) and 71651 (FGD bioreactor effluent) also did not m eet the control limits specified in the method. Furthermore, the MS/MSD percent r ecoveries for sample 71641 did not meet the laboratory criteria of 54-131% . Table 3 presents the percen t recoveries of TKN for the MS/MSD analysis.

TestAmerica appropriately analyzed sample 71641 with a 5 fold dilution, but due to analyst error analyzed the MS/M SD samples with only a 2.5 fold dilution. This was likely the reason for the very negative percent recovery for the MS/MSD samples associated with 71641. Also, sample 71651 was analyzed again in another batch because the TKN and ammonia results did not agree. However, TestAmerica did not reanalyze the MS/MSD analysis. Thus, the MS/MSD sample s and the final sample result for 71651 were analyzed in different batches. Samples of the same matrix did not appear to have correlating percent re coveries. For example, 71651 and 71654 both had similar matrices being FGD bioreactor effluent samples, but one sample had percent recoveries below the control limits and the other had percent r ecoveries above the control limits. Sample 71641 was qualified as a minimum value whil e samples 71649 and 71654 were qualified as maximum values.

6Table 3. MS/MSD Results for TKN Analysis

Sample Number Type Result (mg/L) Spike Amount (mg/L) Spike Result (mg/L) Percent Recovery 71641 MS 29 7.50 12.0 -229% 71641 MSD 29 7.50 9.74 -259% 71648 MS 2.6 3.00 5.49 96% 71648 MSD 2.6 3.00 5.86 108% 71649 MS 6.1 3.00 9.56 115% 71649 MSD 6.1 3.00 9.42 110% 71651 MS 6.3 3.00 8.49 74% 71651 MSD 6.3 3.00 9.12 95% 71654 MS 5.7 3.00 8.99 111% 71654 MSD 5.7 3.00 9.06 114%

Sample 71651 should also be qualified as a mi nimum value because the percent recovery of the MS sample was below the control lim its specified in the method. However, this sample was also analyzed outside of the hol d time. The ammonia and TKN results did not agree in the first analysis, so the sample ha d to be reanalyzed in another batch. The reanalysis of the sample was done one day outside of the 28-day hold time. The sample result was qualified by the laboratory as bei ng analyzed outside of hold time; however, it was not qualified as an estimated value. Thus, sample 71651 was reported as an estimated value.

TSS

The RPDs for laboratory duplicates for samples 71642, 71644, and 71648 were less than 10% as required by SM 2540D. However, the RPDs for samples 71641 and 71643 were 15% and 13%, respectively. Because the laboratory duplicate RPDs for samples 71641 and 71643 were above the method cr iteria, these two samples we re qualified as estimated values.

78 Table 4. Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level Detected 71648 COD Minimum value MS % recoverybelow methodspecified criteria 140 mg/L

71648 Nitrate/Nitrite Maximum value MS % recoveryabove methodspecified criteria 21 mg/L

71651 Total Phosphorus Minimum value MS % recoverybelow methodspecified criteria 0.11 mg/L

71641 TDS Estimated value Lab duplicateRPD > methodspecified criteria 17000 mg/L

71641 TKN Minimum value MS % recoverybelow methodspecified criteria 29 mg/L

71649 TKN Maximum value MS % recoveryabove methodspecified criteria 6.1 mg/L

71651 TKN Estimated value Analyzed one day past holding time,

MS % recoverybelow methodspecified criteria 6.3 mg/L

71654 TKN Maximum value MS % recoveryabove methodspecified criteria 5.7 mg/L

71641 TSS Estimated value Lab duplicateRPD > methodspecified criteria 3,100 mg/L

71643 TSS Estimated value Lab duplicateRPD > methodspecified criteria 3,300 mg/L