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 for Total Mercury – Episode 6558 

Frontier Global Sciences (FGS) generated analytical data for total mercury. FGS 

analyzed the samples according to EPA Method 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 Bioreactor Effluent Day 1 6/8/2010 

1
Table 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 Bioreactor Effluent Day 2 6/9/2010 

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

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

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

71652 1006118-04 Aqueous Dissolved FGD Bioreactor 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 Field 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 that required additional qualifiers in this 

dataset. The following summarizes the findings from the data review: 

 One filter blank (lab sample number 1006085-20) exceeded the method detection 

level (MDL). The samples associated with this filter blank 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 laboratory is above the MDL requirement for EPA 

Method 1631E; however, the MDL used for 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. 

2
SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES 

As discussed in the case narrative provided by FGS, “One (1) of the 250 mL glass bottles 

submitted for grab sample 71646 FGD Bioreactor 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 dropped and broken during preservation. The 

two bottles that were broken contained the dissolved mercury aliquot (lab-filtered) and 

total mercury aliquot. Only one total mercury aliquot remained for the sample; therefore 

no dissolved mercury results were available for sample 71644 FGD Influent Day 4.” 

ONGOING PRECISION AND ACCURACY/RECOVERY 

The results for all ongoing precision and recovery (OPR) samples, in the form of blank 

spike/blank spike duplicates (BS/BSDs), fell 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 calibration verification (ICV) was 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 method-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. The samples associated with this filter 

blank, 71642, 71645, 71646 (Dissolved FGD Bioreactor Influent Day 2 only), 71649, 

71657, and 71661, do not require qualification. All of the detected values for these 

samples were at least 30 times the level found in the blank. 

3
4

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 criteria 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 matrix 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 for Total and Dissolved Metals by 200.8 –

Episode 6558 

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 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 

1
SUMMARY 

The samples were prepared for total and dissolved metals analysis according to 

TestAmerica’s “FGD ICP/MS SOP: Inductively Coupled Plasma Mass Spectrometry for 

Trace Element Analysis in Flue Gas Desulfurization Wastewaters,” dated October 6, 

2010, based on EPA Method 200.8, by ICP/MS analysis. 

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 consistently 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 than 5% for a minimum of 4 

integrations of the solution.” 

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 (RL); however, 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 continuing 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 America’s 50-150% recovery limits. 

2
3

LABORATORY CONTROL SAMPLE (LCS) 

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

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION 

Chromium in the ICSA solution was always above the RL of 4 ug/L, indicating 

interferents were not being removed effectively. Therefore, 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 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 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 MATIX 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 exceeded 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 control limits of 70-130% with the exception 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 for Total and Dissolved Metals by 200.7 – 

Episode 6558 

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 6558. 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 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 

1
Table 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 Analysis 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 dataset. 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, 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 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 (RL); however, some elements 

were found above the method detection limit (MDL) and were flagged with the “J” 

qualifier. 

2
All instrument blanks (ICB and CCB) were less than the RL; however, some elements 

were above the MDL and were flagged with the “J” qualifier. 

RL VERIFICATION STANDARD (CRI) 

All CRI samples passed TestAmerica’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 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. Sample 

71641 failed the required ±10% difference for calcium (24%), cobalt (15%), but the 

concentration was less than the RL, 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 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 MATIX SPIKE DUPLICATES (MSD) 

Matrix spike and matrix spike duplicates were performed on samples 71641, 71642, 

71643, 71648 and 71651. Many elements with high concentrations frequently failed the 

spike recovery and were flagged 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 requirements and were flagged with the “F” 

qualifier. Otherwise, the MS/MSD spike recoveries 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 than 20%, which fails TestAmerica’s RPD 

requirement; therefore, the results for these dissolved analytes for Sample 71641 were 

flagged with the “F” qualifier. 

3
4

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 analytical data for dissolved hexavalent 

chromium for Sample Episode 6558. 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 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 Influent Day 1 6/8/10 6/21/10 

71646 Aqueous FGD Bioreactor Influent Day 2 6/9/10 6/22/10 

71647 Aqueous FGD Bioreactor Influent Day 3 6/10/10 6/22/10 

71648 Aqueous FGD Bioreactor Influent Day 4 6/11/10 6/22/10 

71649 Aqueous FGD Bioreactor Effluent Day 1 6/8/10 6/22/10 

71650 Aqueous FGD Bioreactor Effluent Day 2 6/9/10 6/22/10 

71651 Aqueous FGD Bioreactor Effluent Day 3 6/10/10 6/22/10 

71652 Aqueous FGD Bioreactor Effluent Day 4 6/11/10 6/22/10 

71653 Aqueous FGD Bioreactor Influent Duplicate 6/10/10 6/22/10 

71654 Aqueous FGD Bioreactor Effluent 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 Influent FB Day 1 6/8/10 6/21/10 

71660 Aqueous FGD Bioreactor Effluent FB Day 1 6/8/10 6/22/10 

1
SUMMARY 

Samples 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, 71644, 71649, 71650, 71651, 71652, 71654, and 71660) 

were diluted prior to analysis due to the presence of high levels of nontarget chloride 

interferences. 

SAMPLE RECEIPT, HANDLING, 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 recovery (IPR) performed by FGS had recoveries within the 

method criteria. 

ONGOING PRECISION AND ACCURACY/RECOVERY 

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

correlation factor ≥0.995 as required by the analytical method. 

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

of true value required by the analytical method. 

CONTINUING CALIBRATION VERIFICATION (CCV) 

All CCVs met method-specified criteria except the following: CCV2 and CCV3 had high 

recoveries in the initial analysis sequence on 6/21/10. 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. 

2
3

OTHER CHECKS 

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

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. Samples 71653 and 71654 were 

duplicates of Samples 71647 and 71650, respectively. Sample 71647 and its duplicate 

had an RPD of 5%. Sample 71650 and its duplicate 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 for 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 (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 14 samples that TestAmerica analyzed for the above analytes. 

Table 1. EPA Episode 6558 Classical Analytes – 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 

1 
Table 1. EPA Episode 6558 Classical Analytes – Sample Identification 

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 Effluent - Duplicate 06/09/10 

SUMMARY 

Unless otherwise noted below, all samples were analyzed within the holding time 

specified in 40 CFR 136 Table 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 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. 

If required by the method, a matrix spike (MS) sample was analyzed. Unless noted 

below, two MS samples were run on samples 71648 (FGD bioreactor influent) and 71651 

(FGD bioreactor effluent) for each analyte to check for matrix interferences in these 

matrices. For some analytes, TestAmerica spiked more samples than required. All MS 

samples analyzed met the criteria specified in the method unless described below. 

DATA NOTES/ISSUES 

Ammonia 

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

Method 350.1. 

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BOD5 

Even though TestAmerica ran at least five dilutions on every sample, no dilutions had a 

dissolved oxygen (DO) depletion greater than 2.0 mg/L. Therefore, BOD5 was reported 

as nondetect for all samples. All glucose-glutamic acid standards, water blanks, and 

laboratory duplicates were analyzed appropriately and met the 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 bioreactor influent) and sample 71651 (FGD 

bioreactor effluent). However, the MS/MSD analysis for both chloride and sulfate was 

only run on sample 71648. The MS/MSD results for sample 71648 met the criteria of 80-

120% specified in EPA Method 300.0 indicating matrix interferences were 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 determine whether matrix interferences were 

disrupting results in FGD bioreactor 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 field 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 analyses were 86% and 87%, respectively. The 

low percent recovery could indicate that results 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 for 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 effluent) could be biased 

low. However, EPA Method 410.4 only requires that the result for the MS analysis be 

within 90-110%, so sample 71651 was not flagged. 

The RPD between sample 71647 and its field 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 qualified because there are no specific control 

limits for field duplicates specified in EPA Method 410.4.

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Cyanide 

Samples 71642, 71643, 71644, 71645, 71646, 71647, 71648, 71650, 71651, 71652, 

71653, and 71654 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 were diluted. 

The results of the diluted sample 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 analyze 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 shown by Table 2 below, nearly all 

of the MS/MSD percent recoveries were below the laboratory control 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 percent recoveries. The low MS/MSD percent 

recoveries for sample 71649 suggest that cyanide 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 above 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 

4 
118% for both the MS and MSD samples for 71651 and 119% for both the MS and MSD 

samples 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 for 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 analysis for sample 71648 was 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 concentration of 0.019 mg/L was below the lowest 

standard (0.05 mg/L) used to create the calibration 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 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 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 percent 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 qualified 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 qualified by the laboratory with a “J” because 

the result was below the RL, so no further qualification 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 with 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 required 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. 

5 
TDS was detected at 8.0 mg/L, which is above 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 affected by the TDS contamination in the LRB. 

All 14 samples analyzed for TDS did not achieve a constant weight after three drying 

cycles. In all cases, the weight increased from 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 concentrations 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. These 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 field 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 the 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 meet the control limits specified in the 

method. Furthermore, the MS/MSD percent recoveries for sample 71641 did not meet the 

laboratory criteria of 54-131%. Table 3 presents the percent 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/MSD 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 samples and the final sample result for 71651 

were analyzed in different batches. Samples of the same matrix did not appear to have 

correlating percent recoveries. 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 recoveries above the control limits. Sample 

71641 was qualified as a minimum value while samples 71649 and 71654 were qualified 

as maximum values. 

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Table 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 minimum value because the percent recovery 

of the MS sample was below the control limits specified in the method. However, this 

sample was also analyzed outside of the hold time. The ammonia and TKN results did not 

agree in the first analysis, so the sample had 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 being 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 criteria, these two samples were qualified as estimated 

values. 

7 
8 

Table 4. Data Review Summary Table 

Sample Analyte Qualifier/Action Reason Level Detected

71648 COD Minimum value MS % recovery 

below methodspecified criteria 

140 mg/L 

71648 Nitrate/Nitrite Maximum value MS % recovery 

above methodspecified criteria 

21 mg/L 

71651 Total 

Phosphorus 

Minimum value MS % recovery 

below methodspecified criteria 

0.11 mg/L 

71641 TDS Estimated value Lab duplicate 

RPD > methodspecified criteria 

17000 mg/L 

71641 TKN Minimum value MS % recovery 

below methodspecified criteria 

29 mg/L 

71649 TKN Maximum value MS % recovery 

above methodspecified criteria 

6.1 mg/L 

71651 TKN Estimated value Analyzed one day 

past holding time, 

MS % recovery 

below methodspecified criteria 

6.3 mg/L 

71654 TKN Maximum value MS % recovery 

above methodspecified criteria 

5.7 mg/L 

71641 TSS Estimated value Lab duplicate 

RPD > methodspecified criteria 

3,100 mg/L 

71643 TSS Estimated value Lab duplicate 

RPD > methodspecified criteria 

3,300 mg/L