Appendix B

DATA REVIEW NARRATIVES1 

### MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

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

From: Donna Tedder, ERG

Laura Aviles

- Alvarez , ERG

Date: 9 / 1 /2011 Subject: FGS Data R eview Narrative for Total and Dissolved Mercury

– Episode 65 6 3

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

Table 1 summarizes the 23 s amples ( ex cluding laboratory filter blanks) FG S extracted and analyzed for total and dissolved mercury

.

Table 1. EPA Episode 6563 Total & Dissolved Mercury

– Sample Identification

EPA Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

71891 1009100

- 03 Aqueous FGD Influent Day 1 9/13/2010

71891 1009100

- 04 Aqueous Dissolved FGD Influent, Day 1 9/13/2010

71892 1009111

- 08 Aqueous FGD Influent, Day 2 9/14/2010

71892 1009111

- 09 Aqueous Dissolved FGD Influent, Day 2 9/14/2010

71893 1009128

- 04 Aqueous FGD Influent, Day 3 9/15/2010

71893 1009128

- 05 Aqueous Dissolved FGD Influent, Day 3 9/15/2010

71894 1009134

- 03 Aqueous FGD Influent, Day 4 9/16/2010

71894 1009134

- 04 Aqueous Dissolved FGD Influent, Day 4 9/16/2010

71895 1009111

- 10 Aqueous FGD Effluent Day 1 9/14/2010

71895 1009111

- 11 Aqueous Dissolved FGD Effluent, Day 1 9/14/2010

71896 1009128

- 06 Aqueous FGD Effluent, Day 2 9/15/2010

71896 1009128

- 07 Aqueous Dissolved FGD Effluent, Day 2 9/15/2010

71897 1009134

- 05 Aqueous FGD Effluent, Day 3 9/16/2010

71897 1009134

- 06 Aqueous Dissolved FGD Effluent, Day 3 9/16/2010

71898 1009141

- 02 Aqueous FGD Effluent, Day 4 9/17/2010

71898 1009141

- 03 Aqueous Dissolved FGD Effluent, Day 4 9/17/2010

71899 1009128

- 08 Aqueous FGD Effluent Duplicate, Day 2 9/15/2010

71899 1009128

- 09 Aqueous Dissolved FGD Effluent Duplicate, Day 2 9/15/2010

71900 1009100

- 05 Aqueous FGD Influent Field Blank, Day 1 9/13/20102 Table 1. EPA Episode 6563 Total & Dissolved Mercury

– Sample Identification

EPA Sample # Lab Sample

ID # Sample

Matrix Sample Description Sampling

Date

71901 1009100

- 08 Aqueous FGD Effluent Field Blank, Day 1 9/13/2010

71902 1009111

- 12 Aqueous FGD Effluent Field Blank, Day 2 9/14/2010

71903 1009128

- 12 Aqueous FGD Effluent Field Blank, Day 3 9/15/2010

71904 1009134

- 07 Aqueous FGD Effluent Field Blank, Day 4 9/16/2010

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.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no s ample receipt issues in this data package

.

I NITIAL CAL IBRATION

FGS performed the initial calibrations on each analysis day. The i nitial calibration for

the CVAFS analysis consisted of a blank and five calibration standards with a correlation

coefficient ≥0.995

. All method

- specified criteria were met.

INITIAL AND C ONTINUING C ALIBRATION V ERIFICATION S

All initial and c ontinuing c alib ration v erifications ( ICVs, CCVs ) met method

- specified

criteria

.

BLANK S

All the preparation blanks or laboratory reagent blanks (LRBs) and the continuing calibration blanks (CCBs) met method

- specified criteria. Preparation Blanks F0 10073

- BLK 5, F0 10073

- BLK 6, F0 10122

- BLK 6, F0 10122

– BLK 7, and F0 10123

- BLK 5 had mercury level s of 0. 45, 0.29, 0.16, 0.13, and 0. 09 ng/L

, r espectively . These blank results were greater than the MDL ( 0.08 ng/L), but less than the RL ( 0.50 ng/L). Because all of the blank results were less than the RL, no samples were qualified based on these

prepara tion blank results.

DUPLICATES

A f ield duplicate , Sample 71899, was collected on the Sample 71896 . The total mercury relative percent difference ( RPD ) was 4.65% and the dissolved mercury RPD was 12.46%. The method

- suggested RPD criteria between field duplicates is 20%.3 L aboratory duplicate s w ere performed in this episode on samples 71891 and 71896 . All RPDs were less than 20% (the method

- suggested RPD criterion between field duplicates; the method does not require the analysis of laboratory duplicates )

.

LABORATORY CONTROL SAMPLES

All laboratory control samples were within Frontier’s control limits of 80

- 120% recovery and 24% RPD, except F010073

- BS3 (blank spike (BS)), which had a recovery of 121%

recovery

. Because this recovery does meet the ongoing precision and recovery ( OPR ) criteria, and because the other BS samples and all initial and continuing calibration verification samples in this batch met method criteria, there was no need to qualify any

data based on this BS failure.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on samples

71891

, 71896, and 71 897 for the total mercury analyse s . MS and MSDs were performed on sample 71897 for the dissolved mercury analyses. All aqu eous MS/MSD recoveries were within method specifications of 71

- 125%. All RPDs met method

- specified criteria

.

D ETECTION LIMITS

The laboratory MDL in the synthetic matrix was 0.239 ng/L. Results below this MDL were reported as not detected (ND).1 

### MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram

, ERG

TJ Finseth

, ERG

From: Randy Mercurio, ERG

Date: 9 / 1 /2011 Subject: TestAmerica Data R eview Narrative for Total and Dissolved Metals by 200.8

– Episode 65 63

TestAmerica generated analytical data for total and dissolved metals ( a ntimony, a rsenic,

c admium, c hromium, c opper, l ead, n ickel, s elenium, s ilver, t hallium

, and v anadium ) for Sample Episode 6563

. T he 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 6563 Total & Dissolved Metals

– Sample Identification

EPA Sample

# EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71891 FGD Influent, Day 1 280

- 7312

- 1 Aqueous 9/13/2010 9/14/2010

71891 FGD Influent, Day 1

– Solid 280

- 7312

- 3 Solid 9/13/2010 9/14/2010

71891 FGD Influent, Day 1

- Filtrate 280

- 7312

- 4 Aqueous 9/13/2010 9/14/2010

71892 FGD Influent, Day 2 280

- 7362

- 1 Aqueous 9/14/2010 9/15/2010

71892 FGD Influent, Day 2

– Solid 280

- 7362

- 4 Solid 9/14/2010 9/15/2010

71892 FGD Influent, Day 2

– Filtrate 280

- 7362

- 5 Aqueous 9/14/2010 9/15/2010

71893 FGD Influent, Day 3 280

- 7401

- 1 Aqueous 9/15/2010 9/16/2010

71893 FGD Influent, Day 3

– Solid 280

- 7401

- 4 Solid 9/15/2010 9/16/2010

71893 FGD Influent, Day 3

– Filtrate 280

- 7401

- 5 Aqueous 9/15/2010 9/16/2010

71894 FGD Influent, Day 4 280

- 7482

- 1 Aqueous 9/16/2010 9/17/2010

71894 FGD Influent, Day 4

– Solid 280

- 7482

- 3 Solid 9/16/2010 9/17/2010

71894 FGD Influent, Day 4

- Filtrate 280

- 7482

- 4 Aqueous 9/16/2010 9/17/2010

71895 FGD Effluent, Day 1 280

- 7362

- 2 Aqueous 9/14/2010 9/15/2010

71896 FGD Effluent, Day 2 280

- 7401

- 2 Aqueous 9/15/2010 9/16/2010

71897 FGD Effluent, Day 3 280

- 7482

- 2 Aqueous 9/16/2010 9/17/2010

71898 FGD Effluent, Day 4 280

- 7536

- 1 Aqueous 9/17/2010 9/18/2010

71899 FGD Effluent, Day 2

- Duplicate 280

- 7401

- 3 Aqueous 9/15/2010 9/16/20102 Table 1. EPA Episode 6563 Total & Dissolved Metals

– Sample Identification

EPA Sample

# EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71900 FGD Influent Field Blank, Day 1 280

- 7312

- 2 Aqueous 9/13/2010 9/14/2010

71901 FGD Effluent Field Blank, Day 1 280

- 7362

- 3 Aqueous 9/14/2010 9/15/2010

SUMMARY

T he sample s were prepared for total and dissolved metals analysis according 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. Any significant findings are

s ummarized below. No additional data qualifiers were required

.

**•** The serial dilution analysis for thallium in the solid phase of sample 71891 did not meet TestAmerica’s requirement of ± 10% difference

.

**•** The serial dilution analysis for total nickel in the filtrate phase of sample 71891 did not meet TestAmerica’s requirement of ± 10% difference

.

**•** All matrix spike ( M S ) / matrix spike duplicates ( MSD ) for total and dissolved

s ilver failed the 70

– 130% control limits , except for dissolved silver in the MS for sample 71897

.

**•** All the MS/MSD RPDs for silver failed TestAmerica’s SOP control limits of

±20%.

**•** The MS/MSD RPD for total selenium for sample 71898 failed TestAmerica’s

SOP control limits of ±20%

.

**•** The post digestion spikes (PDS) for selenium in the solid phase for sample 71891

failed the method criteria of 85

– 115%.

**•** The PDS for silver failed the method criteria of 85

- 115% for several samples.

INTERNAL STANDARDIZA TION

All internal standards used by TestAme rica were within the method criteria.3 INITIAL CALIBRATION

Test America performed the initial calibrations on each analysis day or before each analysis if more than one analysis was performed in one day

. The initial calibration for

the ICP

- MS analysis consisted of a blank and four calibration standards

.

I NITIAL AND CONTINUING CALIBRATION VERIFICATION (ICV/CCV)

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

METHOD/INSTRUMENT BLANK S

All the method b lanks were less than the r eporting l imit ; however, some elements were above the MDL and flagged with a “J” qualifier

. No additional quali fiers were required

for method b lanks.

All i nstrument b lanks ( ICB and CCB) were less tha n the r eporting l imit ; however, some elements were above the MDL and flagged with a “J” qualifier. No additional qua lifiers were required for i nstrument b lanks.

REPORTING LIMIT VERIFICATION STANDARD ( CRI )

A ll C RI samples passed Test America’s SOP control limits of 50

– 150%.

LABORATORY CONTROL SAMPLE S (LCS)

All LCS samples passed the method limits of 85

– 115% , with the exception of s elenium in the solid sample LCS 280

- 34676/2

- A at 84% ; however, TestAmerica had a control

limit set at 78

– 108%

. No data was qualified based on this LCS.

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION

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

ICS.

All interference check sample B (ICSAB) synthetic s pikes recovered within

TestAmerica’s SOP criteria of 70

– 130% of the true value.

SERIAL DILUTION (SRD)

The s erial dilution performed for solid sample 71 89 1 FGD Influent, Day 1

- Solid (280

- 7312

- 3) failed Test America’s requirement of ±10% difference for t hallium and was flagged “W”

. The serial dilution performed for sample 71891 FGD Influent, Day 1

-4 Filtrate (280

- 7312

- 4) failed Test America’s requirement of ±10% difference for n ickel and was flagged “W”. All other elements passed Test America’s requirement of ±10%

difference in the serial dilutions and required no further qualifiers.

FIELD DUPLICATES

The relative percent difference ( RPD ) of the field duplicates (71896/71899 ) were less

than ±20% for all values equal to or greater than the reporting limit

.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

MS and MSD were performed on Sa mple s 71897 and 71898. 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”

. All

M S/MSDs for total and dissolved s ilver failed the 70

– 130% method control limits with the exception of the dissolved silver in sample 71897 FGD Effluent, Day 3 MS

. All the

MS/MSD RPDs for s ilver failed TestAmerica’s SOP control limits of ±20 %

. Th e poor recoveries and RPD of s ilver ar e probably due to high sulfates in this episode’s samples

t hat could form insoluble silver sulfide and/or silver s ulfate. All other RPD results were less than the method required 20% with the exception of selenium for MSD sample

71898 FGD Effluent, Day 4 (280

- 7536

- 1 MSD) , which was 25%.

POST DIGESITON SPIKE S

The PDS performed on solid sample 7189 1 FGD In fluent, Day 1

- Solid (280

- 7312

- 3

PDS ) fail ed Test America’s 7 5

– 12 5% control limits for s elenium , which was flagged

“W”

. S ilver failed Test America’s 85

- 115% control limits for the following samples:

**•** T otal silver for 71891 FGD Influent, Day 1

– Filtrate (280

- 7312

- 4 PDS) ;

**•** T otal silver for 71897 FGD Effluent, Day 3 (280

- 7482

- 2 PDS);

**•** D issolved silver for 71897 FGD Effluent, Day 3 (280

- 7482

- 2 PDS); and

**•** D issolved silver for 71898 FGD Effluent, Day 4 (280

- 7536

- 1 PDS)

.

Each of these samples were flagged “W”

. The poor recoveries of s ilver ar e probably due to high sulfates in this episode’s samples that could form insolu ble s ilver s ulfide and/or

s ilver s ulfate. Sample 71897 FGD Effluent, Day 3 (280

- 7482

- 2 PDS) also failed Test

America’s 85

- 115% control limits for total s elenium, and dissolved v anadium which

w ere both flagged “W”. No additional qualifiers were required for PDS samples.

D ETECTION LIMITS

The laboratory performed an MDL study in the synthetic FGD wastewater matrix, instead of reagent water.1 

### MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram

, ERG

TJ Finseth

, ERG

From: Randy Mercurio, ERG

Date: 9 / 1 /2011 Subject: TestAmerica Data R eview Narrative for Total and Dissolved Metals by 200.7

– Episode 65 63

Test America generated analytical data for total and dissolved metals ( a l u minum, b oron, b arium, b eryllium, c alcium, c obalt, i ron, m agnesium, m anganese, m olybdenum, s odium,

t in, t itanium

, and z inc ) for Sample Episode 6563

. T he samples were analyzed according

to EPA Method 200. 7

.

Table 1 summarizes the s ample s Test America extracted and analy zed for total and dissolved metals by EPA Method 200.7

.

Table 1. EPA Episode 6563 Total & Dissolved Metals

– Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71891 FGD Influent, Day 1 280

- 7312

- 1 Aqueous 9/13 /2010 9/14 /2010

71 891 FGD Influent, Day 1

- Solids 280

- 7312

- 3 Solid 9/13 /2010 9/14 /2010

71 891 FGD Influent, Day 1

- Filtrate 280

- 7312

- 4 Aqueous 9/13 /2010 9/14 /2010

71 892 FGD In fluent , Day 2 280

- 7362

- 1 Aqueous 9/14 /2010 9/15 /2010

71 892 FGD Influent, Day 2

– Solids 280

- 7362

- 4 Solid 9/14 /2010 9/15 /2010

71 892 FGD Influent, Day 2

– Filtrate 280

- 7362

- 5 Aqueous 9/14 /2010 9/15 /2010

71 893 FGD Influent, Day 3 280

- 7401

- 1 Aqueous 9/15 /2010 9/16 /2010

71 893 FGD In fluent, Day 3

– Solids 280

- 7401

- 4 Solid 9/15 /2010 9/16 /2010

71 893 FGD In fluent, Day 3

– Filtrate 280

- 7401

- 5 Aqueous 9/15 /2010 9/16 /2010

71 894 FGD Influent, Day 4 280

- 7482

- 1 Aqueous 9/16 /2010 9/17 /2010

71 894 FGD Influent, Day 4

– Solids 280

- 7482

- 3 Solid 9/16 /2010 9/17 /2010

71894 FGD Influent, Day 4

- Filtrate 280

- 7482

- 4 Aqueous 9/16 /2010 9/17 /2010

71 895 FGD Ef fluent

, Day 1 280

- 7362

- 2 Aqueous 9/14 /2010 9/15 /2010

71 896 FGD Effluent, Day 2 280

- 7401

- 2 Aqueous 9/15 /2010 9/16 /2010

71897 FGD Effluent, Day 3 280

- 7482

- 2 Aqueous 9/16 /2010 9/17 /2010

71898 FGD Effluent, Day 4 280

- 7536

- 1 Aqueous 9/17 /2010 9/18 /2010

71899 FGD Effluent, Day 2

- Duplicate 280

- 7401

- 3 Aqueous 9/15 /2010 9/16 /20102 Table 1. EPA Episode 6563 Total & Dissolved Metals

– Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71 900 FGD Influent Field Blank, Day 1 280

- 7312

- 2 Aqueous 9/13 /2010 9/14 /2010

71 901 FGD Effluent Field Blank , Day 1 280

- 7362

- 3 Aqueous 9/14 /2010 9/15 /2010

SUMMARY

The sample s were prepared for total and dissolved metals analysis according to

Test America’s SOP for ECP Analysis for Trace Metals by Method 200.7

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

The post digestion spikes (PDS) for total barium, total calcium, and total zinc in the filtrate phase for sample 71891 failed the method criteria of 85

– 115%.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were n o s ample receipt issues i n this data package

.

INTERNAL STANDARDIZA TION

Whil e the internal standard (ISTD) y ttrium was used for these analyses, no checks for the ISTD recoveries within the ±30% criterion of the calibration blank as per Section 9.11 of

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

I NITIAL CAL IBRATION

Test America performed the initial calibrations on each analysis day. The initial

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

I NITIAL AND CONTINUING CALIBRATION VERIFICATION S

The initial c alibration v erifications (ICV) and c ontinuing c alibration v erifications (CCV) performed by Test America all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANKS

All the m ethod b lanks were less than the r eporting l imit; however, some had levels above the MDL and were flagged with the “J” qualifier.

All i nstrument b lanks (ICB and CCB) were less than the r eporting l imit; however, some elements were above the MDL and were flagged with the “J” qualifier.3 LABORATORY CONTROL SAMPLES (LCS)

All LCSs passed the method control limits of 85

– 115%.

INTERFERENCE CHECK SOLUTION S

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

REPORTING LIMIT VERIFICATION STANDARD ( CRI )

A ll CRI samples passed Test America’s SOP control limits of 50

– 150%.

FIELD DUPLICATES

The total and dissolved relative percent differences ( RPD s ) of the field duplicate (71899 ) to parent sample ( 71896 ) were less than 2 0% for values greater than the reporting limit

.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on the total and

dissolved sample s of 71897 and 71898

. Some elements with high concentrations frequently failed the EPA 200.7 Method spike recovery control limits of 70

– 130% but were flagged with a “4” qualifier indicating that the concentration in the parent sample was greater than 4 times the spike and could not be reliab ly calculated

. No MS/MSD spike reco veries failed the EPA 200.7 Method control limits of 70

– 130%

, except those already qualified with a “4” as mentioned above, and therefore no additional data qualifiers were needed

. In addition, all RPDs of the MS/MSDs were within

TestAmerica’s ± 20% requirements

.

SERIAL DILUTION (SRD)

Serial dilutions were performed for each batch of total and dissolved samples. A ll serial dilution percent differences were less than 10% as require d by Test America’s SOP

.

POST DIGESTION SPIKE

Both t otal and dissolved PDS sample s performed passed the method criteria of 85

– 115%

, with the exception of barium, calcium and z inc in the filtrate for sample 71891 FGD Influent, Day 1 (280

- 7312

- 4 PDS)

.

D ETECTION LIMITS

The laboratory performed an MDL study in the synthetic FGD wastewater matrix, instead of reagent water.1 

### MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram

, ERG

TJ Finseth

, ERG

From: Donna Tedder, ERG

Laura Aviles

- Alvarez, ERG

Date: 9 / 1 /201 1 Subject: FGS Data R eview Narrative for Dissolved Hexavalent Chromium

– Episode

65 6 3

Frontier Global Sciences (FGS) generated analytical data for dissolved hexavalent

chromium for Sample Episode 6563

. FGS analyzed t he samples according to a m odified

EPA Method 2 18. 6 for dis solved hexavalent chromium by Liquid Chromatography

– Inductively Coupled Plasma Mass Spectrometry (LC

- ICP

- MS)

.

Table 1 summarizes the s amples FG S extracted and analyzed for dissolved hexavalent

chromium

.

Table 1. EPA Episode 6563 Dissolved Hexavalent Chromium

– Sample Identification

EPA Sample

# Sample

Matrix Sample Description Sampling

Date Analysis Date

71 8 9 1 Aqueous FGD Influent Day 1 9 / 13/ 10 10/11 /10

71 8 9 2 Aqueous FGD Influent Day 2 9 / 14 /10 10/11/10

71 8 9 3 Aqueous FGD Influent Day 3 9 / 15 /10 10/12/10

71894 Aqueous FGD Influent Day 4 9/16/10 10/12/10

71895 Aqueous FGD Effluent Day 1 9/14/10 10/12/10

71896 Aqueous FGD Effluent Day 2 9/15/10 10/12/10

71897 Aqueous FGD Effluent Day 3 9/16/10 10/12/10

71898 Aqueous FGD Effluent Day 4 9/17/10 10/12/10

71899 Aqueous FGD Effluent Dup Day 2 9/15/10 10/12/10

71900 Aqueous FGD Influent F ield B lank Day 1 9/13/10 10/11/10

71 90 1 Aqueous FGD Effluent F ield B lank Day 1 9 / 14 /10 10/11/10

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

.2 Several s amples ( 718 9 1, 718 9 2, 718 9 3, 718 9 4, 718 95 , 718 9 6, 718 9 7, 718 9 8, and 718 9 9 )

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

interferences

.

T here were no issues requiring additional data qualifiers for the hexavalent chromium data in this episode.

SAMPLE REC E IPT, HANDLING, AND STORAGE ISSUES

There were no s ample receipt issues in this data package

.

I NITIAL P RECISION AND ACCURACY/ R ECOVERY

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

method criteria.

O N

- GOING P RECISION AND ACCURACY/ R ECOVERY

The analytical method did not require the analysis of an on

- going precision and recovery ( OPR )

.

I NITIAL CAL IBRATION

FGS performed the initial calibrations on each analysis day. The i nitial 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 within the ± 10 % of true

value required by the method

.

C ONTINUING C ALIBRATION V ERIFICATION

All CCVs me t method

- specified criteria

, ± 10% of true value with recoveries ranging

from 9 4.9 to 95.5 %.

BLANK

All of the prep aration blanks /laboratory reagent blanks (LRBs) and the continuing calibration blanks (CCBs) met method

- specified requirements

.

OTHER CHECKS

The l aboratory c ontrol s ample /duplicate (LCS /LCSD ) or laboratory fortified

blank /duplicate (LFB /LFBD ) passed method criteria of ± 10% of true value with

recoveries of 101 % and 102%

. The method suggested that a second source quality3 control sample (QCS) must be analyzed by the laboratory at least once a quarter. The

second source ICV meets this recommendation

.

D ETECTION 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 ).

One field duplicate w as collected and analyzed. Sample 71899 was a du plicate of

effluent sample 71896

. 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 M S and matrix spike duplicate ( MSD ) were performed using a secondary source spike on sample s 71891 and 718 97

. All MS/MSD recoveries with within 75%

- 125%,

with RPD s of 2.63 % and 1.88 % , respectively

.1 

### MEMORANDUM

To: Ron Jordan

, Work Assignment Manager

, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD

Deb Bartram

, ERG TJ Finseth, ERG

From: Donna Tedder

, ERG

Date: 9 / 1 /201 1 Subject: TestAmerica Data Review Narrative for C lassicals Analyses

– Episode 6563

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry analyses for Sample Episode 65 63

. All samples were tested for the following analytes:

**•** Ammonia by EPA M ethod 350.1,

**•** Biochemical Oxygen Demand

– 5 day (BOD 5 ) by SM 5210B,

**•** Chloride and S ulfate 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 D issolved S olids (TDS) by SM 2540C,

**•** Total K jeldah l N itrogen (TKN) by EPA Method 351 .2

, and

**•** Total S uspended S olids (TSS) by SM 2540D

.

The TSS concentration of the influent samples was greater than one percent, so as requested, the laboratory separated the solid and liquid port ions of the samples and analyzed both portions separately for the following analytes :

**•** Ammonia,

**•** Chloride,

**•** Cyanide,

**•** Nitrate/Nitrite,

**•** Phosphorus,

**•** Sulfate, and

**•** TKN.

Table 1 summarizes the nine field samples analyzed by TestAmerica and particularly highlights how the laboratory split and analyzed the influent samples.2 Table 1. EPA Episode 65 63 Classical Analytes

– Sample Identification

EPA Sample # Sample Description Sampling

Date Sample

Matrix Portion of Sample Analytes

71 891 FGD Influent, Day 1 9/13 /10 Water Entire

Fraction BOD 5 , COD, TDS, and

TSS

Water Filtrate Ammonia, Chloride, Cyanide, Nitrate/Nitrite, Sulfate, Phosphorus, and

TKN

Solids Solids Ammonia, Chloride, Cyanide, Nitrate/Nitrite, Sulfate, Phosphorus, and

TKN

71 892 FGD Influent, Day 2 9/14 /10 Water Entire

Fraction BOD 5 , COD, TDS, and

TSS

Water Filtrate Ammonia, Chloride, Cyanide, Nitrate/Nitrite, Sulfate, Phosphorus, and

TKN

Solids Solids Ammonia, Chloride, Cyanide, Nitrate/Nitrite, Sulfate, Phosphorus, and

TKN

71 893 FGD Influent, Day 3 9/15 /10 Water Entire

Fraction BOD 5 , COD, TDS, and

TSS

Water Filtrate Ammonia, Chloride, Cyanide, Nitrate/Nitrite, Sulfate, Phosphorus, and

TKN

Solids Solids Ammonia, Chloride, Cyanide, Nitrate/Nitrite, Sulfate, Phosphorus, and

TKN

71 894 FGD Influent, Day 4 9/16 /10 Water Entire

Fraction BOD 5 , COD, TDS, and

TSS

Water Filtrate Ammonia, Chloride, Cyanide, Nitrate/Nitrite, Sulfate, Phosphorus, and

TKN

Solids Solids Ammonia, Chloride, Cyanide, Nitrate/Nitrite, Sulfate, Phosphorus, and

TKN

71 895 FGD Effluent, Day 1 9/14 /10 Water Entire

Fraction All analytes3 Table 1. EPA Episode 65 63 Classical Analytes

– Sample Identification

EPA Sample # Sample Description Sampling

Date Sample

Matrix Portion of Sample Analytes

71 896 FGD Effluent, Day 2 9/15/ 10 Water Entire

Fraction All analytes

71 897 FGD Effluent, Day 3 9/16 /10 Water Entire

Fraction All analytes

71 898 FGD Effluent, Day 4 9/17 /10 Water Entire

Fraction All analytes

71 899 FGD Effluent

- Duplicate 9/15 /10 Water Entire

Fraction All analytes

SUMMARY

Unless otherwise noted below, all samples were analyzed within the holding time specified in 40 CFR 136 Table II

.

TestAmerica could not use a preserved sample volume for phase separation. Therefore, they combined two of the unpreserved 25 0 mL metal sample volumes and phase separated this volume. After phase separation, TestAmerica preserved the samples accordingly. Because of this process, ammonia, nitrate/nitrite, TKN, phosphorus, and cyanide influent samples were not preserved immediately fo llowing sample collection as required by the method.

One field duplicate sample w as collected and analyzed for each analyte. The r elative

p ercent d ifference (RPD) between the sample and its duplicate was less than 20% unless

otherwise noted below.

If applicab le, 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 t he lowest and highes t standards

unless noted below. Additionally, 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 cal ibration, 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 de tected 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 noted

below

.4 If required by the method, a matrix spike (M S) sample was a nalyzed on sample 7 1 897 (FGD effluent ) for each analyte to check for matrix interferences

. 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

As stated above, f iltrate and solid aliquots of samples 71 89 1

- 71 89 4 were not preserved immediately after sample collection. Instead

, TestAmerica preserved the sample after phase separation. Because these samples were not preserved immediately following

s ample collection, they were qualified as estimated values.

The data reviewer identified n o other issues. All QC samples met the criteria specified in

EPA Method 3 50.1.

BOD 5

All glucose

- glutamic acid standards and water blanks we re analyzed appropriately and

met the criteria specified in SM 5210B

.

The RPD between sample 71897 and its laboratory duplicate was 23%, which is above both the method and laboratory criteria of 20%. S ample 71897 was qualified as an

estimated value.

Three of the four batches had seed correction factors lower than 0.6 mg/L. The seed correction factors were 0.5373 mg/L, 0.552 mg/L, 0.6147 mg/L, and 0.576 mg/L for batches 31398, 31731, 31878, and 32012, respectively. TestAmerica did not flag these sample s with an “s” to indicat e the seed correction blank (SCB) recovery was low

. A low seed correction factor indicates that samples may be bi ased low. Thus, samples 71891, 71892, 71893, 71895, 71896, 71898, and 71899 were qualified as minimum values and

for co nsistency were also flagged with an “s

. ” Due to the short holding time, the samples could not be reanalyzed.

Chloride and Sulfate

The analyzed results for the MS and matrix spike duplicate ( MSD ) samples associated with sample 71897 for both chloride and sulfate were above the calibration range. TestAmerica did not rerun the samples with a greater dilution factor because the MS and MSD percent recoveries were within the method control criteria. If reported, the MS and MSD results will be qualified as estim ated values.5 COD

The percent recoveries for the MS and MSD analyse s for sample 71 897 ( F GD effluent )

were below the control limits of 90

- 110% required by EPA Method 410.4. The percent

recoveries for the MS and MSD analys e s were 8 9 % and 8 2 %

, respectively. The low percent recovery could indicate that results for samples with the same matrix (FGD

effluent ) could be biased low. Sample 71 897 was flagged as a minimum value. The LFBs associated with all samples met the method criteria.

The RPD between sample 71 896 and its field duplicate 71899 was 25.5 %. Even though

the RPD w as greater than 20%, the sample w as not qualified because there are no specific

control limits for field duplicates specified in EPA Method 410.4

.

Cyanide

As stated above, filtrate and solid aliquots of samples 71891

- 71894 were not preserved immediately after sample collection. Instead

, TestAmerica preserved the sample after performing the phase separation. The solid aliquot results of samples 71891

- 71894 were already qualified by Te stAmerica with a “J” meaning the results were estimated values because they were less than the RL, so no further qualification was necessary. Because the filtrate aliquots of samples 71891

- 71894 were not preserved immediately after sample collection, the y were qualified as estimated values.

Both solid and filtrate volumes of s ample s 71891

- 71894 were analyzed 10, 9, 8, and 7 days outside of the 14

- day holding time. All of these samples were qualified by the lab

with an “ H

, ” meaning the samples were anal yzed beyond the method

- specified hold time

. Because all of these samples were either qualified with a “J” meaning that the results were estimated values because they were less than the RL or they were qualified as estimated values because they were not pre served immediately after sample collection, no further qualification was necessary.

The analyzed results for s ample 71896 and s olid s ample s 71891

- 71894 were lower than

the lowest calibration standard. Since all th e samples were already qualified by

TestAmerica with a “ J ” indicating that the results were estimated values because they

were less than the RL , the se samples did not need to be further qualified.

The RPD between sample 71896 and its field duplicate 71899 was 135%. The r esult for

71896 was below the RL and flagged with a “ J ” , but the result for 71899 was above the

RL. The low amount of cyanide present in these samples was likely the cause 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 SM 4500 CN - E

.

Cyanide was detected in the laboratory reagent blank associated with sample 71895 at 0.00415 mg/L , which was greater than the MDL, but less than the RL. Since the blank

result was less than the RL, no samples were qualified.6 Nitrate / Nitrite

As stated above, filtrate and solid aliquots of samples 71891

- 71894 were not preserved immediately after sample collection. Instead

, TestAmerica preserved the sample after phase separation. The solid aliquot results of samples 71891

- 71894 were already qualified by TestAmerica with a “J” meaning the results were estimated values because they were less than the RL, so no further qualification was necessary. Because the filtrate aliquots of samples 71891

- 71894 were not preserved immediately after sample collection, they were qualified as estimated values.

The percent recoveries for the MS analysis for sample 71 895 and the MS and MSD analys e s for sample 71 897 (FGD effluent) were below the control limits of 90

- 110% required by EPA Method 353.2 but within the laboratory control limits of 72

- 113%. T he

percent recover ies for the MS and MSD samples w ere 89% and 92% respectively for sample 71895 and were both 84% for sample 71897. The MS and MSD results for sample 71897 were above the calibration curve, but not reanalyzed using a higher

dilution factor. Because the MS and MSD results for sample 71897 at 12.7 mg/L were

more than ±10% greater than the highest calibration level (10.0 mg/L), the MS and MSD

recoveries were considered unreliable. Because it wa s not possible to tell whether the low percent recovery was caused by matrix interferences or the MS and MSD results being

above the calibration curve, sample 71897 was not qualified. Sample 71895 was qualified

as a minimum value. The LFBs associated with all samples met the method criteria.

Phosphorus

As stated above, filtrate and solid aliquots of samples 71891

- 71894 were not preserved

immed iately after sample collection. Instead

, TestAmerica preserved the sample after phase separation. The filtrate a liquot results of samples 71891 and 71894 were already qualified by TestAmerica with a “J” meaning the results were estimated values because

the y were less than the RL, so no further qualification was necessary. Phosphorus was not detected in the filtrate aliquots of samples 71892 and 71893, so these samples also did not need to be qualified. Because the solid aliquots of samples 71891

- 71894 wer e not preserved immediately after sample collection, they were qualified as estimated values.

Results for the filtrate volumes of s amples 71891 and 71894 were below the lowest calibration standard. These samples were al ready qualified with a “ J ” meaning the results were estimated values because they were less than the RL, so no further qualification was

necessary.7 TDS

Samples 71891

- 71894 were analyzed 14, 13, 12, and 11 days, respectively , past the 7

- day hold time due to laboratory error

. Tes tAmerica only qualified these samples with an “H”, so they were additionally qualified as estimated values.

All 14 samples analyzed for TDS did not achieve a constant weight after three drying cycles. T he weight increased from the first weighing to the se cond weighing for samples 71895, 71896, 71898, and 71899. 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 concentr ations 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.

The RPD between sample 71 897 and its laboratory duplicate w as less than 10 % as required by SM 2540C

. T he RPD between sample 71 891 and its laboratory duplicate was 1 1 %. Because the RPD was greater than the method control limits, sample 71 891 was qualified as an estimated value

.

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 the LRB associated with sample 71895

. Because the blank result was less than the RL, no samples needed to be qualified based on the LRB result

.

TKN

As stated above, filtrate and solid aliquots of samples 71891

- 71894 we re not preserved immediately after sample collection. Instead

, TestAmerica preserved the sample after phase separation. Because these samples were not preserved immediately after sample collection, they were qualified as estimated values.

TKN was detected in the LRB associated with filtrate sample s 71891

- 71894 at 0.133 mg/L and also detected in the LRB associated with samples 71895

- 71897 and 71899 at 0.219 mg/L

. The blank result s w ere greater than the MDL (0.077 mg/L ), but less than the RL (1.0 mg/L )

. Because the blank result s w ere less than the RL, no samples were qualified based on the LRB result s

.

The LFB and LFBD percent recoveries associated with filtrate samples 71891

- 71894

were not within the method criteria of 90

- 110%, but were within the lab oratory criteria of

77

- 115%. The percent recoveries of the LFB and LFBD were 84% and 86%, respectively. Filtrate samples 71891

- 71894 were already qualified as estimated values because the samples were not preserved immediately after sample collection, so there was no need to further qualify these samples as minimum values

.

The percent recoveries for the MS and MSD analys e s for sample 71 897 (FGD effluent ) did not meet the control limits (90

- 110%) specified in EPA Method 351.2 and did not

meet the laboratory criteria of 54

- 131%. The MS and MSD percent recoveries were8 137% and 175%. TestAmerica flagged the MS/MSD samples with a “ 4 ” because the sample result was more than 4 times the spike amount indicating the control limits are not

reliable. Thus, s ample 71897 was not additionally qualified because of the high MS/MSD percent recoveries. The LFB associated with sample 71897 met the method criteria.

TSS

The laboratory duplicate RPDs for samples 71 891 , 71 893 , and 71 895 were less than 10%

as required by SM 2540D. However, the RPD for sample 71 897 and its laboratory duplicate w as 1 2%

. Because this RPD w as above the method criteria, sample 71897 was qualified as an estima ted value

.

The RPD between sample 71896 and its field duplicate 71899 was 138%. 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 2540D.

Constant weight was not achieved after three drying cycles for sample 71899. SM 2540D

warns tha t 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

inconsi stent weight calculations. The sample was not qualified, but results may be biased high.9 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detected

71891 (filtrate) Ammonia Estimate Value Sample not preserved immediately following

collection. 13 mg/L

71892 (filtrate) Ammonia Estimate Value Sample not preserved immediately following

collection. 14 mg/L

71893 (filtrate) Ammonia Estimate Value Sample not preserved immediately following

collection. 13 mg/L

71894 (filtrate) Ammonia Estimate Value Sample not preserved immediately following

collection. 12 mg/L

71891 (solids) Ammonia Estimate Value Sample not preserved immediately following

collection. 34 mg/Kg

71892 (solids) Ammonia Estimate Value Sample not preserved immediately following

collection. 29 mg/Kg

71893 (solids) Ammonia Estimate Value Sample not preserved immediately following

collection. 32 mg/Kg

71894 (solids) Ammonia Estimate Value Sample not preserved immediately following

collection. 32 mg/Kg

71891 BOD Minimum Value,

s SCB Recovery Low 10 mg/L

71892 BOD Minimum Value,

s SCB Recovery Low 9.5 mg/L

71893 BOD Minimum Value,

s SCB Recovery Low 13 mg/L

71895 BOD Minimum Value,

s SCB Recovery Low 8.5 mg/L

71896 BOD Minimum Value,

s SCB Recovery Low 7.1 mg/L

71897 BOD Estimated Value Lab duplicate RPD >

method

- specified

criteria 6.8 mg/L

71898 BOD Minimum Value,

s SCB Recovery Low 3.5 mg/L

71899 BOD Minimum Value,

s SCB Recovery Low 6.9 mg/L10 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detected

71897 COD Minimum Value MS % recovery <

method

- specified

criteria 380 mg/L

71891 (filtrate) Cyanide H, Estimated

Value Sample not preserved immediately following

collection. Analyzed 10 days past hold time 0.36 mg/L

71892 (filtrate) Cyanide H, Estimated

Value Sample not preserved immediately following

collection. Analyzed 9

days past hold time 0.20 mg/L

71893 (filtrate) Cyanide H, Estimated

Value Sample not preserved immediately following

collection. Analyzed 8

days past hold time 0.29 mg/L

71894 (filtrate) Cyanide H, Estimated

Value Sample not preserved immediately following

collection. Analyzed 7

days past hold time 0.31 mg/L

71891 (filtrate) Nitrate/Nitrite Estimated Value Sample not preserved immediately following

collection. 12 mg/L

71892 (filtrate) Nitrate/Nitrite Estimated Value Sample not preserved immediately following

collection. 14 mg/L

71893 (filtrate) Nitrate/Nitrite Estimated Value Sample not preserved immediately following

collection. 14 mg/L

71894 (filtrate) Nitrate/Nitrite Estimated Value Sample not preserved immediately following

collection. 12 mg/L

71895 Nitrate/Nitrite Minimum Value MS % recovery <

method

- specified

criteria 9.7 mg/L

71891 (solids) Phosphorus Estimated Value Sample not preserved immediately following

collection. 33 mg/Kg

71892 (solids) Phosphorus Estimated Value Sample not preserved immediately following

collection. 380 mg/Kg11 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detected

71893 (solids) Phosphorus Estimated Value Sample not preserved immediately following

collection. 34 mg/Kg

71894 (solids) Phosphorus Estimated Value Sample not preserved immediately following

collection. 6.5 mg/Kg

71891 TDS H, Estimated

Value Analyzed 14 days past hold time, Lab duplicate

RPD > method

specified criteria 35,000 mg/L

71892 TDS H, Estimated

Value Analyzed 13 days past

hold time 35,000 mg/L

71893 TDS H, Estimated

Value Analyzed 12 days past

hold time 37,000 mg/L

71894 TDS H, Estimated

Value Analyzed 11 days past

hold time 35,000 mg/L

71897 TSS Estimated Value Lab duplicate RPD >

method

- specified

criteria 7.2 mg/L

71891 (filtrate) TKN Estimated Value Sample not preserved immediately following

collection. LFB % recovery < method

specified criteria 29 mg/L

71892 (filtrate) TKN Estimated Value Sample not preserved immediately following

collection. LFB %

recovery < method

specified criteria 32 mg/L

71893 (filtrate) TKN Estimated Value Sample not preserved immediately following

collection. LFB % recovery < method

specified criteria 31 mg/L

71894 (filtrate) TKN Estimated Value Sample not preserved immediately following

collection. LFB % recovery < method

specified criteria 26 mg/L

71891 (solids) TKN Estimated Value Sample not preserved immediately following

collection. 900 mg/Kg12 Table 2 . Data Review Summary Table

Sample Analyte Qualifier/Action Reason Level

Detected

7189 2 (solids) TKN Estimated Value Sample not preserved immediately following

collection. 840 mg/Kg

7189 3 (solids) TKN Estimated Value Sample not preserved immediately following

collection. 710 mg/Kg

7189 4 (solids) TKN Estimated Value Sample not preserved immediately following

collection. 880 mg/Kg