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 Effluent – 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 

1
Table 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 that 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 CALIBRATION VERIFICATIONS 

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

criteria. 

BLANKS 

All the preparation blanks or laboratory reagent blanks (LRBs) and the continuing 

calibration blanks (CCBs) met method-specified requirements. 

DUPLICATES 

Field duplicates, Sample 71699, were collected on the Sample 71696. The 71696/71699 

total mercury RPD was 4.52% and the dissolved RPD was 3.34%. The method-suggest 

RPD criteria between field duplicates is 20%. 

Laboratory duplicates were performed 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 matrix spike duplicates (MSD) were performed on samples 

71692, 71695, 71696, 71694 and 71697. All recoveries were within method 

2
3

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 for Total and Dissolved Metals by 200.8 – 

Episode 6559

TestAmerica generated analytical data for total and dissolved metals (antimony, arsenic, 

cadmium, chromium, copper, lead, nickel, selenium, 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: 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. 

1
Any significant findings are summarized 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 recoveries are probably due to high sulfates in this 

episode’s samples that could form insoluble 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 calculated 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 TestAmerica were within the method criteria. 

INITIAL CALIBRATION 

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

calibration for the ICP-MS analysis consisted of a blank and four calibration standards. 

INITIAL AND CONTINUING CALIBRATION VERIFICATION 

The initial calibration verifications (ICV) and continuing calibration 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 continuing calibration blank 

(CCB)) were less than the reporting limit; however, some elements were above the MDL 

and were flagged with the “J” qualifier. 

REPORTING LIMIT VERIFICATION STANDARD (CRI) 

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

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LABORATORY CONTROL SAMPLES (LCS) 

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

INTERFERENCE CHECK SOLUTIONS 

Interference checks were performed using the synthetic matrix as the check solution. All 

recoveries met the method-specified criteria. 

SERIAL DILUTION 

Serial dilutions were performed for each batch of total and dissolved samples. No QC 

criteria are required by EPA 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 significant 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 samples 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 dissolved arsenic result 

was not qualified because there are no specific control limits for laboratory duplicates 

specified in EPA Method 200.8. 

MATRIX SPIKE (MS) AND MATIX 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 exceeded 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 the exception of 

all MS/MSDs for total and dissolved silver. The 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 TestAmerica’s 85-115% recovery criteria with the 

exception of the following: 

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4

 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 sample 71697 FGD Effluent, Day 3 (280-4786-2); 

and 

 Total silver for sample 71698 FGD 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 μg/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 μg/L (total) 

71696 Zn Matrix 

Interference 

Failed MS/MSD 14 μg/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 for Total and Dissolved Metals by 200.7 – 

Episode 6559

TestAmerica generated analytical data for total and dissolved metals (aluminum, boron, 

barium, beryllium, calcium, cobalt, iron, magnesium, molybdenum, sodium, tin, titanium, 

manganese) for Sample Episode 6559. The samples were analyzed according to EPA 

Method 200.7. 

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

dissolved metals by EPA Method 200.7. 

Table 1. EPA Episode 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 Trace 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 concentration of iron (115 ug/L) was greater 

than the reporting limit (100 ug/L) and it was not flagged. 

 The continuing calibration verification 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 failed the EPA Method 200.7 control limits of 

70–130% are as follows: total and dissolved barium (71691 MS); total barium 

(71691 MSD); total aluminum (71695 MS/MSD); and total iron (71698 

MS/MSD). 

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 on the 

ISTD recoveries in the ±30% criterion of the calibration blank as per Section 9.11 of the 

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

INITIAL CALIBRATION 

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

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

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS 

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

All continuing calibration verifications (CCV) performed by TestAmerica passed with 

the exception of CCV 280-22121/107, which failed the method criteria for aluminum. All 

associated samples were either flagged or reanalyzed for aluminum; therefore, no 

additional qualifications were required. 

BLANKS 

All the method blanks were less than the reporting 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 measured at over 1,000 times the blank level; therefore, 

2
the sample required no further qualification. The iron result for Sample 71700 was 

flagged with a “J” qualifier; therefore, the sample required no further qualification. 

All instrument blanks (initial calibration blank (ICB) and continuing calibration blank 

(CCB)) were less than the reporting limit; however, 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 performed using the synthetic matrix as the check solution. All 

recoveries met TestAmerica’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 batch of total and dissolved samples. Sample 

71691 failed the method required ±10% difference 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. These elements were all flagged “V” as 

failing the QC criteria. These dilution tests indicate 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 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 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 matrix 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 calculated. In addition, some elements were 

flagged with the “4” qualifier when the parent sample was greater than four times the 

3
4

spike concentration, even if the MS/MSD recoveries did not fail the 70-130% recovery 

criteria. In these instances, the “4” qualifiers were removed from the sample result. 

Otherwise, the MS/MSD spike recoveries were 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 μg/L (total) 

71691 Barium Matrix 

Interference 

Failed MS 90 μg/L (dissolved) 

71695 Aluminum Matrix 

Interference 

Failed MS/MSD, 

Serial Dilution 

680 μg/L (total) 

71696 Aluminum Matrix 

Interference 

Failed MS/MSD, 

Serial Dilution 

720 μg/L (total) 

71698 Iron Matrix 

Interference 

Failed MS/MSD 390 μg/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 analytical data for dissolved hexavalent 

chromium for Sample Episode 6559. FGS analyzed the samples according to a modified 

EPA Method 218.6 for dissolved hexavalent chromium by Liquid Chromatography – 

Inductively Coupled Plasma Mass Spectrometry (LC-ICP-MS). 

Table 1 summarizes the samples FGS extracted analyzed for dissolved 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 (SOP), a modified EPA Method 218.6. All 

1
samples 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, HANDLING, AND STORAGE ISSUES 

There were no sample receipt issues in this data package. 

INITIAL PRECISION AND ACCURACY/RECOVERY 

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

method criteria. 

ON-GOING PRECISION AND ACCURACY/RECOVERY 

The analytical method did not require the analysis 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 blank and eight calibration standards with a 

correlation factor ≥0.995 as required by the method. 

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

of true value required by the method. 

CONTINUING CALIBRATION VERIFICATION 

All CCVs met method-specified criteria, ±10% of true value, except the CCV3 with a 

low recovery of 87.6%. All samples affected 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 method-specified requirements. 

OTHER CHECKS 

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

true value). 

2
3

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 duplicates performed in this episode 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 for Classicals Analyses – Episode 6559 

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry 

analyses for Sample Episode 6559. All samples were tested for the following analytes: 

 Ammonia by EPA method 350.1, 

 Biochemical Oxygen Demand – 5 day (BOD5) by SM 5210B, 

 Chloride and Sulfate by EPA Method 300.0, 

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

 Cyanide 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 TestAmerica analyzed for the above analytes. 

Table 1. EPA Episode 6559 Classical Analytes – 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 

1 
SUMMARY 

All samples 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 standard used to create the curve, the sample was 

diluted and reanalyzed. All sample results were between the lowest and highest standards 

unless noted below. Additionally, unless otherwise noted, all calibration blanks and 

calibration verification samples met the criteria specified in the method. 

If required by the method, the quality control sample (QCS), a secondary source standard 

used to verify calibration, was always within the control limits specified by the method. 

As described below, the analyte of interest was detected above the method detection limit 

(MDL) in some laboratory reagent blanks (LRB). However, the analyte of interest was 

never detected above the reporting limit (RL) in the LRBs. If required by the method, all 

laboratory fortified blanks (LFB) met the criteria specified in the method unless specified 

below. 

If required by the method, a matrix spike (MS) sample was analyzed for each analyte on 

sample 71697 (FGD effluent) to check for matrix interferences. For some analytes, 

TestAmerica spiked more than one sample. All MS samples analyzed met the criteria 

specified in the method unless described below. 

DATA NOTES/ISSUES 

Ammonia 

The laboratory diluted the MS/MSD samples for 71697 by two fold after 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 EPA Method 350.1. 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, 

this sample does not need to be qualified. 

2 
BOD5 

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, BOD5 was reported 

as non-detect for these samples. All glucose-glutamic acid standards and water blanks 

were analyzed appropriately and met the criteria specified in SM 5210B. 

TestAmerica analyzed four laboratory duplicates on samples 71694, 71696, 71697, and 

71698. Three of these laboratory duplicate samples 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 could 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 recoveries 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, this 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%). Because 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 qualified these samples with a “*” indicating that the LFB or 

LFBD was not within the method control limits. Samples 71694, 71695, and 71697 were 

additionally qualified as minimum values. 

The percent recoveries for the MS and MSD samples associated with 71697 were 74% 

and 75% respectively. These percent 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 suggested by the LFB failure. 

Therefore, these results indicate 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 MSD samples associated with 71691 were 75% 

and 80%, respectively. These percent recoveries also did not meet the method control 

limits. However, the LFB/LFBD associated with sample 71691 met the method criteria. 

3 
These low percent 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 concentration is greater 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 field 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 field duplicates specified in SM 4500 CN- E. 

SM 4500 CN-

 E does not require the laboratory to analyze MS/MSD samples, so there are 

no control limits specified in the method. The 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 laboratory 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 interferences. 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% 

4 
Nitrate/Nitrite 

TestAmerica 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. Thus, 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 the 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 control limits of 71-128%. 

The percent recoveries for the MS and MSD samples were 62% and 65%. Results for 

samples with a similar matrix (i.e., FGD effluent) may be biased low because of matrix 

interferences. Sample 71697 was already qualified 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 minimum value. The LFB associated with all 

samples met the method criteria. 

The analyzed results for the following samples 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 associated with sample 71698. This result was 

above the MDL, but below the RL, so there was no need to qualify the sample further.

5 
Three samples (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. Method 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 wastewater 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 LRB 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 analysis 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 Method 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 spike amount indicating the control limits are not 

reliable. TestAmerica did not flag the MSD 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 qualified 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 required 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 because it was less than the RL, so no further 

action was taken. 

6 
7 

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 the 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 duplicates specified in the method. 

Table 4. Data Review Summary Table 

Sample Analyte Qualifier/Action Reason Level Detected

71694 COD Minimum value LFB % recovery 

below methodspecified criteria 

400 mg/L 

71695 COD Minimum value LFB % recovery 

below methodspecified criteria 

390 mg/L 

71697 COD Minimum value LFB % recovery 

below methodspecified criteria, 

MS % recovery 

below methodspecified criteria 

410 mg/L 

71691 COD Minimum value MS % recovery 

below methodspecified criteria 

420 mg/L 

71698 (MSD 

Sample) 

TKN “4” Sample result > 4 

times spike 

amount 

60.3 mg/L