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: Randy Mercurio , ERG Donna Tedder, ERG

Date: 9 / 1 /201 1 Subject: FGS Data R eview Narra tive for Total and Dissolved Mercury

– Episode 65 61

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 Spectrometr y (CVAFS) analysis.

Table 1 summarizes the 37 s amples ( ex cluding laboratory filter blanks) FG S extracted and analyzed for total and dissolved mercury

.

Table 1. EPA Episode 6561 Total & Dissolved Mercury

– Sample Identification

EPA Sample # Lab Sampl e ID # Sample

Matrix Sample Description Sampling

Date

71791 1008018

- 01 Aqueous FGD Influent Day 1 8/2/2010

71791 1008018

- 02 Aqueous Dissolved FGD Influent, Day 1 8/2/2010

71792 1008031

- 13 Aqueous FGD Influent, Day 2 8/3/2010

71792 1008031

- 14 Aqueous Di ssolved FGD Influent, Day 2 8/3/2010

71793 1008045

- 01 Aqueous FGD Influent, Day 3 8/4/2010

71793 1008045

- 02 Aqueous Dissolved FGD Influent, Day 3 8/4/2010

71794 1008062

- 01 Aqueous FGD Influent, Day 4 8/5/2010

71794 1008062

- 02 Aqueous Dissolved FGD Infl uent, Day 4 8/5/2010

71795 1008031

- 15 Aqueous FGD Bioreactor Influent, Day 1 8/3/2010

71795 1008031

- 16 Aqueous Dissolved FGD Bioreactor Influent, Day 2 8/3/2010

71796 1008045

- 03 Aqueous FGD Bioreactor Influent, Day 2 8/4/2010

71796 1008045

- 04 Aqueous D issolved FGD Bioreactor Influent, Day 2 8/4/2010

71797 1008062

- 03 Aqueous FGD Bioreactor Influent, Day 3 8/5/2010

71797 1008062

- 04 Aqueous Dissolved FGD Bioreactor Influent, Day 3 8/5/2010

71798 1008072

- 03 Aqueous FGD Bioreactor Influent , Day 4 8/6/201 0

71798 1008072

- 04 Aqueous Dissolved FGD Bioreactor Influent , Day 4 8/6/2010

71799 1008031

- 17 Aqueous FGD Bioreactor Effluent, Day 1 8/3/2010

71799 1008031

- 18 Aqueous Dissolved FGD Bioreactor Effluent, Day 1 8/3/2010

71800 1008045

- 05 Aqueous FGD Biore actor Effluent, Day 2 8/4/20102 Table 1. EPA Episode 6561 Total & Dissolved Mercury

– Sample Identification

EPA Sample # Lab Sampl e ID # Sample

Matrix Sample Description Sampling

Date

71800 1008045

- 06 Aqueous Dissolved FGD Bioreactor Effluent, Day 2 8/4/2010

71801 1008062

- 05 Aqueous FGD Bioreactor Effluent, Day 3 8/5/2010

71801 1008062

- 06 Aqueous Dissolved FGD Bioreactor Effluent, Day 3 8/5/2010

71802 1008072

- 05 Aqueous FGD Bioreactor Effluent , Day 4 8/6/2010

71802 1008072

- 06 Aqueous Dissolved FGD Bioreactor Effluent , Day 4 8/6/2010

71803 1008062

- 07 Aqueous FGD Bioreactor Influent Duplicate 8/5/2010

71803 1008062

- 08 Aqueous Dissolved FGD Bioreactor Influent Duplicate 8/5/2010

71804 1008045

- 07 Aqueous FGD Bioreactor Effluent Duplicate, Day 2 8/4/2010

71804 1008045

- 08 Aqueous Dissolved FGD Bioreactor Effluent Duplicate, Day 2 8/4/2010

71805 1008018

- 03 Aqueous FGD Influent Field Blank, Day 1 8/2/201 0

71806 1008018

- 06 Aqueous FGD Bioreactor Influent Field Blank, Day 1 8/2/2010

71807 1008031

- 19 Aqueous FGD Biorea ctor Influent Field Blank, Day 2 8/3/2010

71808 1008045

- 15 Aqueous FGD Bioreactor Influent Field Blank , Day 3 8/4/2010

71809 1008062

- 13 Aq ueous FGD Bioreactor Influent Field Blank , Day 4 8/5/2010

71810 1008018

- 09 Aqueous FGD Bioreactor Effluent Field Blank, Day 1 8/2/2010

71811 1008031

- 12 Aqueous FGD Bioreactor Effluent Field Blank, Day 2 8/3/2010

71812 1008045

- 16 Aqueous FGD Bioreactor E ffluent Field Blank , Day 3 8/4/2010

71813 1008062

- 14 Aqueous FGD Bioreactor Effluent Field Blank, Day 4 8/5/2010

SUMMARY

The samples were prepared according to EPA Method 1631 E 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 calibr ation 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

.3 BLANK S

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

- suggested criteria. Preparation Blanks F00900 1

- BLK2 and F009002

- BLK4 had mercury levels of 0.10 and 0.27 ng/L

, r espectively, which

are greater than the MDL

, but less than the reporting li mit . These blank results were appropriately fagged with a “J” qualifier

.

DUPLICATES

Field duplicates , Sample 71804, were collected on S ample 71800

. The 71800/71804

total mercury relative percent difference ( RPD ) was 10.4% and the dissolved mercury
RPD w as 1.8% . The method

- suggested RPD criterion between field duplicates is 20%.

L aboratory duplicates were performed in this episode on samples 71795

, 71796 and

71801

. All RPDs were less than 20% (the method

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

.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD)

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on samples 71796 and 71801 for the total mercury analyses. MS and MS Ds were performed on samples 71791, 71795, 71801 & 71798 for the dissolved mercury analyses. All MS/MSD recoveries were within method specifications of 71

- 125%. All RPDs met

method

- specified criteria.

D ETECTION LIMITS

The laboratory MDL in the syntheti c 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 Donna Tedder, ERG

Date: 9 / 1 /201 1 Subject: TestAmerica Data R eview Narrative for Total and Dissolved Metals by 200.8

– Episode 65 61

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, v anadium, and z inc ) for Sample Episode 6561

. 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 6561 Total & Dissolved Metals

– Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

7179 1 FGD Influent, Day 1 280

- 5932

- 1 Aqueous 8/2 /2010 8/3 /2010

71 792 FGD Influent, Day 2 280

- 5964

- 1 Aqueous 8/3 /2010 8/4 /2010

71 793 FGD Influent, Day 3 280

- 6008

- 1 Aqueous 8/4 /2010 8/5 /2010

71 794 FGD Influent, Day 4 280

- 6067

- 4 Aqueous 8/5 /2010 8/6 /2010

71 795 FGD Bioreactor Influent, Day 1 280

- 5964

- 2 Aqueous 8/3 /2010 8/4 /2010

71 796 FGD Bioreactor Influent, Day 2 280

- 6008

- 2 Aqueous 8/4 /2010 8/5 /2010

71797 FGD Bioreactor Influent, Day 3 280

- 6067

- 1 Aqueous 8/5 /2010 8/6 /2010

71798 FGD Bioreactor Influent, Day 4 280

- 6117

- 1 Aqueous 8/6 /2010 8/7 /2010

717 99 FGD Bioreactor Ef fluent , Day 1 280

- 5964

- 3 Aqueous 8/3 /2010 8/4 /2010

71 800 FGD Bioreactor Effluent, Day 2 280

- 6008

- 3 Aqueous 8/4 /2010 8/5 /2010

71 801 FGD Bioreactor Ef fluent, Day 3 280

- 6067

- 2 Aqueous 8/5 /2010 8/6 /2010

71 802 FGD Bioreactor Effluent, Day 4 280

- 6117

- 2 Aqueous 8/6 /2010 8/7 /2010

71 803 FGD Bioreactor In fluent

- Duplicate , Day 3 280

- 6067

- 3 Aqueous 8/5 /2010 8/6 /2010

71 804 FGD Bioreactor Effluent

- Duplicate , Day 2 280

- 6008

- 4 Aqueous 8/4 /2010 8/5 /2010

71 805 FGD Influent Field Blank, Day

1 280

- 5932

- 2 Aqueous 8/2 /2010 8/3 /2010

71 806 FGD Bioreactor In fluent Field

Blank , Day 1 280

- 5964

- 4 Aqueous 8/3 /2010 8/4 /20102 Table 1. EPA Episode 6561 Total & Dissolved Metals

– Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71 810 FGD Bioreactor Effluent Field

Blank , Day 1 280

- 5964

- 5 Aqueous 8/3 /2010 8/4 /2010

SUMMARY

T he sample s 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 / M S analysis.

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

INTERNAL STANDARDIZA TION

All internal standards used by TestAmerica were within the method criteria.

INITIAL CALIBRATION

TestAmerica 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 CONTINU ING CALIBRATION VERIFICATION (ICV/CCV)

The i nitial c alibration v erifications ( ICV ) and c ontinuing c alibration v erifications (CCV) performed by TestAmerica all had recoveries within the method criteria.

BLANK S

All the m ethod b lanks were less than the r eporting l imit (RL)

. No additional qualifiers were required for m ethod b lanks.

All i nstrument b lanks ( initial calibration blank ( ICB ) and continuing calibration blank ( CCB ) ) were less than the RL ; however, a ntimony w as above the instrument detection

limit ( I DL ) in one ICB and w as flagged with the “J” qualifier

.

REPORTING LIMIT VERIFICATION STANDARD ( CRI )

A ll CRI samples passed TestAmerica’s 50

– 150% recovery limits

.3 LABORATORY CONTROL SAMPLE S (LCS)

All LCS samples passed the method QC limits of 85

– 115%

.

SYNTHETIC FGD I NTERFERENCE 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 presen t in the stock solution used to make the

ICS.

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

TestAmerica’s SOP criteria of 70

– 130% of the true value

.

SERIAL DILUTION

The s erial dilution performed for the total and dissolved sa mple 71799 FGD Bioreactor Effluent, Day 1 (280

- 5964

- 3) met TestAmerica ’s criteria of ±10% difference

.

FIELD DUPLICATES

The relative percent difference (RPD) of the field duplicates 71800/71804 and

71797 /71803 were less than 20% for all values greater than the reporting limit. None of

the total or dissolved analytes in parent sample 71800 and field duplicate sample 71804

were above the RL so the RPD could not be accurately determined

. The RPD for all tota l

an d dissolved analytes above the r eporting l imit in parent sample 71797 and field duplicate sample 71803 were less than TestAmerica’s ±20% requirement.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

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

71799

, 71801 and 71798

. 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 indicating concentration s in the parent sample s were greater than four times the spike amount s

. Otherwise , a ll

MS/MSD spike recoveries were within the method control limits of 70

- 130%. In addition, the RPD for all MS/MSD passed the method

- specified criteria of 20 percent.

POST DIGESITON SPIKE S

The p ost d igestion s pike performed on sample 71799 FGD Bioreactor Effluent, Day 1 (280

- 5964

- 3 ) for total and dissolved analytes passed TestAmerica’s 85

– 115% control

limits

.4 DETECTION 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 Donna Tedder, ERG

Date: 9 / 1 /201 1 Subject: TestAmerica Data R eview Narrative for Total and Dissolved Metals by 200.7

– Episode 65 61

TestAmerica generated analytical data for total and dissolved metals ( a luminum, 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 6561

. T he samples were analyzed according

to EPA Method 200. 7

.

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

.

Table 1. EPA Episode 6561 Total & Dissolved Metals

– Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

7179 1 FGD Influent, Day 1 280

- 5932

- 1 Aqueous 8/2 /2010 8/3 /2010

71 792 FGD Influent, Day 2 280

- 5964

- 1 Aqueous 8/3 /2010 8/4 /2010

71 793 FGD Influent, Day 3 280

- 6008

- 1 Aqueous 8/4 /2010 8/5 /2010

71 794 FGD Influent, Day 4 280

- 6067

- 4 Aqueous 8/5 /2010 8/6 /2010

71 795 FGD Bioreactor Influent, Day 1 280

- 5964

- 2 Aqueous 8/3 /2010 8/4 /2010

71 796 FGD Bioreactor Influent, Day 2 280

- 6008

- 2 Aqueous 8/4 /2010 8/5 /2010

71797 FGD Bioreactor Influent, Day 3 280

- 6067

- 1 Aqueous 8/5 /2010 8/6 /2010

71798 FGD Bioreactor Influent, Day 4 280

- 6117

- 1 Aqueous 8/6 /2010 8/7 /2010

717 99 FGD Bioreactor Ef fluent , Day 1 280

- 5964

- 3 Aqueous 8/3 /2010 8/4 /2010

71 800 FGD Bioreactor Effluent, Day 2 280

- 6008

- 3 Aqueous 8/4 /2010 8/5 /2010

71 801 FGD Bioreactor Ef fluent, Day 3 280

- 6067

- 2 Aqueous 8/5 /2010 8/6 /2010

71 802 FGD Bioreactor Effluent, Day 4 280

- 6117

- 2 Aqueous 8/6 /2010 8/7 /2010

71 803 FGD Bioreactor In fluent

- Duplicate , Day 3 280

- 6067

- 3 Aqueous 8/5 /2010 8/6 /2010

71 804 FGD Bioreactor Effluent

- Duplicate , Day 2 280

- 6008

- 4 Aqueous 8/4 /2010 8/5 /2010

71 805 FGD Influent Field Blank, Day 1 280

- 5932

- 2 Aqueous 8/2 /2010 8/3 /20102 Table 1. EPA Episode 6561 Total & Dissolved Metals

– Sample Identification

EPA Sample # EPA Sample Description Lab Sample

ID # Sample

Matrix Sampling

Date Receipt

Date

71 806 FGD Bioreactor In fluent Field

Blank , Day 1 280

- 5964

- 4 Aqueous 8/3 /2010 8/4 /2010

71 810 FGD Bioreactor Effluent Field

Blank , Day 1 280

- 5964

- 5 Aqueous 8/3 /2010 8/4 /2010

SUMMARY

The sample s 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.

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES

There were no s ample receipt issues in this data package

.

INTERNAL STANDARDIZA TION

While the internal standard (ISTD) Yttrium 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 IBR ATION

TestAmerica 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 i nitial c alibration v erifications ( ICV ) and c ontinuing c alibration v erifications (CCV) performed by TestAmerica all had recoveries within the method criteria.

METHOD/INSTRUMENT BLANK S

All the m ethod b lanks were less than the r eporting l imit (RL) ; however, some elements

had l evels greater than the method detection limit ( MDL ) and were flagged with the “J” qualifier.

All i nstrument b lanks ( initial calibration blank ( ICB ) and continuing calibration blank ( CCB ) ) were less than the RL; however, some elements had levels greater than 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

recoveries met the method

- specified criteria.

SERIAL DILUTION

Serial dilutions were performed for each batch of total and dissolved samples. All serial dilution percent differences were less than 10% as required by TestAmerica’s SOP

.

REPORTING LIMIT VERIFICATION STANDARD ( CRI )

A ll CRI samples passed TestAmerica ’s control limits of 50

– 150%.

FIELD DUPLICATES

The relative percent difference (RPD) of the field duplicates 71800/71804 and

71797 /71803 were less than 20% for all total and dissolved values greater than the RL.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

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

dissolved sample s of 71798 , 71799 and 71801

. Many spike recoveries were outside the

method control limits of 70

- 130% when sample concentrations exceeded the spike concentrations by a factor of four or more, which have been flagged with a “4” qualifier indicating concentrations in the parent samples were greater than four times the spike amounts. Otherwise, all MS/MSD spike recoveries were within the 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, a ll RPDs of the MS/MSDs were within TestAmerica’s ± 20% requirement

.

POST DIGESTION SPIKE

The post digestion spike performed on sample 71799 FGD Biorea ctor Effluent, Day1 passed TestAmerica’s control limits of 85

- 115% recovery for all total and dissolved analytes except total sodium and dissolved manganese. The post digestion spike performed on sample 71798 FGD Bioreactor Influent, Day 4 passed TestAmerica’s

control limits of 85

- 115% recovery for all total and dissolved analytes except total

sodium.4 DETECTION 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

Date: 9 / 1 /201 1

S ubject: FGS Data R eview Narrative for Dissolved Hex avalent Chromium

– Episode

65 6 1

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

chromium for Sample Episode 6561

. FGS analyzed t he samples according to a m odified

EPA Method 2 18. 6 for dissolved hexavalent chromium by Liqu id Chromatography

– Inductively Coupled Plasma Mass Spectrometry (LC

- ICP

- MS)

.

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

chromium

.

Table 1. EPA Episode 6561 Dissolved Hexavalent Chromium

– Sample Identification

EPA Sample

# Sample

Matrix Sample Description Sampling

Date Analysis Date

71 7 9 1 Aqueous FGD Influent Day 1 8 /2 /10 8/9 /10

717 9 2 Aqueous FGD Influent Day 2 8 / 3 /10 8/9/10

717 9 3 Aqueous FGD Influent Day 3 8/4/10 8/9/10

717 9 4 Aqueous FGD Influent Day 4 8/5/ 10 8/ 30 /10

717 9 5 Aqueous FGD Bioreactor Influent Day 1 8/3/10 8/9/10

717 9 6 Aqueous FGD Bioreactor Influent Day 2 8/4/10 8/9/10

717 9 7 Aqueous FGD Bioreactor Influent Day 3 8/5/10 8/ 30 /10

717 9 8 Aqueous FGD Bioreactor In fluent Day 4 8/6/10 8/ 30 /10

717 9 9 Aqueous FGD Bioreactor Effluent Day 1 8/3/10 8/9/10

71 80 0 Aqueous FGD Bioreactor Effluent Day 2 8/4/10 8/ 30 /10

71 80 1 Aqueous FGD Bioreactor Effluent Day 3 8/5/10 8/ 30 /10

71802 Aqueous FGD Bioreactor Effluent Day 4 8/6/10 8/ 30 /10

71803 Aqueous FGD Biore actor Influent Dup Day 3 8/5/10 8/ 30 /10

71804 Aqueous FGD Bioreactor Effluent Dup Day 2 8/4/10 8/ 30 /10

71805 Aqueous FGD Influent F ield B lank Day 1 8/2 /10 8/9/10

71806 Aqueous FGD Bioreactor Influent F ield B lank Day 1 8/3/10 8/9/10

71810 Aqueous FGD Bi oreactor Effluent F ield B lank Day 1 8/3/10 8/9/102 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

. Several s amples ( 717 9 1, 717 9 2, 717 9 3, 71794, 71795, 71796, 71797, 71798, and 71803 )

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 epis ode.

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 FGS 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 analyzed and passed ± 10 %

of true value required by the method

.

C ONTINUING C ALIBRATION V ERIFICATION

All CCVs met method

- specified criteria

, ± 10% of true value with recoveries ranging

from 95 to 109%.

BLANK

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

- specified requirements

.3 OTHER CHECKS

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

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

recoveries of 102% and 102%

. A second set of LFB /LFBD, for the later analysis date,

had recoveries of 100% and 99.3%. The method suggested that a second source quality 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 synth etic 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 duplicate s w ere collected and analyzed. Sample 71 803 was a duplicate of sample 71 7 97

. These samples were nondetects ( NDs ) , indicating the analyte was not

detected at or above the method detection limit. Sample 7180 4 was a duplicate of sample

71 800

. These samples we re also NDs.

MATRIX SPIKE AND MATIX SPIKE DUPLICATES

The M S and matrix spike duplicate ( MSD ) were performed using a secondary source spike on sample s 71791 and 71 801

. All MS/MSD recoveries were within 75%

- 125%,

with RPD s of 1.47% and 4.44% , 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 /2011 Subject: TestAmerica Data Review Narrative for Classicals Analyses

– Episode 65 61

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry analyses for Sample Episode 65 61

. 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 m ethod 300.0,

**•** Chemical Oxygen Demand (COD) by EPA m ethod 410.4,

**•** Cyanide by SM 4500 CN - E,

**•** Nitrate / Nitrite by EPA m ethod 353.2

,

**•** Phosphorus by EPA m ethod 365.1,

**•** Total D issolved S olids (TDS) by SM 2540C,

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

, and

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

.

Table 1 summarizes the 1 4 samples that TestAmerica analyzed for the above analytes

.

Table 1. EPA Episode 6561 Classical Analytes

– Sample Identification

EPA Sample # Sample

Matrix Sample Description Sampling

Date

71791 Water FGD Influent, Day 1 8/2/10

71792 Water FGD Influent, Day 2 8/3/10

71793 Water FGD Influent, Day 3 8/4/10

71794 Water FGD Influent, Day 4 8/5/10

71795 Water FGD Bioreactor Influent, Day 1 8/3/10

71796 Water FGD Bioreactor Influent, Day 2 8/4/10

71797 Water FGD Bioreactor Influent, Day 3 8/5/10

71798 Water FGD Bioreactor Influent, Day 4 8/6/10

71799 Water FGD Bioreactor Effluent, Day 1 8/3/10

71800 Water FGD Bioreactor Effluent, Day 2 8/4/10

71801 Water FGD Bioreactor Effluent, Day 3 8/5/102 Table 1. EPA Episode 6561 Classical Analytes

– Sample Identification

EPA Sample # Sample

Matrix Sample Description Sampling

Date

71802 Water FGD Bioreactor Effluent, Day 4 8/6/10

71803 Water FGD Bioreactor Influent

- Duplicate 8/5/10

71804 Water FGD Bioreactor Effluent

- Duplicate 8/4/10

SUMMARY

All samples were analyzed within the holding time specified in 40 CFR 136 Table II . A ll samples were preserved appropriately

.

Two field duplicate samples were 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 highest standards

unless noted below. Additionally, u nless 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 (M S) sample was analyzed. Two MS samples

were run on sample s 71 79 8 (FGD bioreactor influent) and 71 80 1 (FGD bioreactor effluent) for ea ch analyte to check for matrix interferences in th ese 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 percent recoveries for the MS and MSD analysis for sample 71799 (FGD bioreactor

ef

fluent) were 112% and 116%, respectively, which are above the laboratory and method

control limits of 90

- 110%

. Sample 71 799 was qualified as a maximum value

. The LFB

associat ed with this sample met the method criteria.3 BOD 5

Even though TestAmerica ran five dilutions on sample 7 1801 , no dilutions had a dissolved oxygen (DO) depletion greater than 2.0 mg/L. Therefore, BOD 5 was rep orted

as not detect ed for this sample

.

All glucose

- glutamic acid standards and laboratory duplicates we re analyzed appropriately and met the criteria specified in SM 5210B

. BOD was not detected above

the RL in any method blank; h owever, for batch 25403, the results for the three

water/ unseeded blan k s w ere 0.24 mg/L, 0.21 mg/L, and 0.21 mg/L. All of these results

were greater than the method control criteria of 0.20 mg/L. Because of th ese detections in

the water/unseeded blanks

, sample s 71791, 71792, 71795, and 71799 were qualified with a “B” meaning the analyte was found in the sample and the blank

.

Chloride and Sulfate

The MS/MSD results of sample s 71798 and 71801 for sulfate were above the calibration curve. TestAmerica did not reanalyze the samples with a higher dilution factor because the pe rcent recoveries were within EPA Method 300.0 control limits. If reported, these MS/MSD results will be qualified as estimated values.

COD

The percent recovery of the LFB associated with batch 25742 was 88.9%, which was less

than the method control criteria of 90

- 110% , but did meet the historical laboratory criteria

of 80

- 115%

. The LFBD percent recovery ( 96.7% ) did meet the method criteria. Because the laboratory originally had analyzed the percent recovery against the historical criteria,

this L FB f ailure 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 control limits. Samples 71792, 71795, and 71799 were alrea dy qualified by the laboratory with a “J” meaning the sample result was an estimated

value because it was less than the RL, so no further action was taken.

Sample s 71795 and 71801 w ere diluted by 10 fold because of matrix interferences determined by the c hloride prescreening. The diluted resu lt s w ere below the lowest

calibration standard ; h owever, these samples were already qualified by the laboratory with a “J” meaning the sample result was an estimated value because it was less than the RL, so no further action was taken.

The RPD between sample 71797 and its field duplicate 71803 was 26.5 % and the RPD

between sample 71800 and its field duplicate 71804 was 35.8 %. Even though these RPDs were greater than 20%, the samples were not qualified because there ar e no specific control limits for field duplicates specified in EPA m ethod 410.4.4 The percent recoveries for the MS/MSD analysis for sample 71798 (FGD bioreactor influent) and for the MS analysis for sample 71 801 ( F GD bioreactor ef fl uent) w ere below

the control limits of 90

- 110% required by EPA M ethod 410.4. The percent recoveries for the MS and MSD analyses for sample 71798 were 75% and 77%, respectively

, and t he percent recoveries for the MS and MSD analys e s for sample 71801 were 89 % and 96 %

, respectively. The LFB associated with these samples met the method criteria. Sample 71798 was qualified as a minimum value. Results for samples with a similar matrix ( i.e.,

FGD bioreactor influent) could also be biased low. S ample 71 801 was already qualified by the laboratory with a “J” meaning the sample result was an estimated value because it

was less than the RL ; therefore, this sample was not additionally qualified as a minimum

value.

Cyanide

Cyanide was detected at 0.00240 mg/L in the method blank associated with sample s 71794, 71797, 71798, 71801, 71802, and 71803

. 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 b ased on the L R B result

.

The RPD between sample 71800 and its field duplicate 71804 was 21.1% . Even though

t his RPD was greater than 20%, the samples were not qualified because there are no specific control limits for field duplicates specified in SM 4500 CN - E

.

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. T he results of the diluted sample for 71795, 71796, and 71804 were below the lowest calibration standard used by the laboratory (0.01 mg/L). However, these samples were already qualified by the laboratory with a “J” meaning the sample result was an estimate d value because it was less than the RL, so no further action was taken.

Nitrate / Nitrite

The result for sample 71799 was below the lowest c alibration standard . However, this sample was already qualified by the laboratory with a “J” meaning the sample res ult was

an estimated value because it was less than the RL, so no further action was taken.

The percent recovery for the MS analysis for sample 71798 (FGD bioreactor influent)

was below the control limits of 90

- 110% required by the method and below the laboratory control limits of 72

- 113%. T he percent recoveries of the MS and MSD samples were 70 % and 102%, respectively. TestAmerica qualified both the MS and MSD

results for sample 71798 with an “ E ” meaning that the results exceeded the calibration

ra nge

. T he MSD sample result was above the highest calibration standard and even though the MS sample result was within the cal ibration range
, it was expected to be

above the highest calibration standard

. If the MSD result is reported, it will be qualified

a s an estimated value because the result was above the highest calibration standard.5 The MS percent recovery for sample 71799 (FGD bioreactor effluent) was not within the method control limits, but was within the laboratory control limits. The percent

reco veries of the MS and MSD samples were 112 % and 107 %, respectively. Sample

71 799 was already qualified by the laboratory with a “J” meaning the sample result was

an estimated value because it was less than the RL, so there was no need to further qualify the result as a maximum value.

Phosphorus

The results for S amples 71792, 71793, and 71798 were less than the lowest cali bration standard (0.025 mg/L). However, these samples were already qualified by the laboratory with a “J” meaning the sample result was an estimated value because it was less than the RL, so no further action was taken.

The percent recoveries for the MS and MSD anal ys e s for sample s 71 79 8 and 71 80 1 were not within the control limits of 90

- 110% specified in EPA Method 365.1 , but were within the laboratory control limits of 71

- 128%

. The percent recoveries for MS and MSD analys e s on sample 71 79 8 were both 73% and t he percent recoveries for MS and MSD analys e s on sample 71 80 1 were both 74%

. The r esults may be biased low for samples

with similar matrix es (i.e., FGD bioreactor influent and FGD bioreactor effluent) because

of matrix interferences

. Sample 71801 w as qualified as a minimum value because the MS

percent recovery was below the method specified criteria. Sample 71798 was already qualified by the laboratory with a “J” meaning the sample result was an estimated value

because it was less than the RL, so there was no need to further qualify the result as a minimum value

.

The RPD between sample 7179 7 and its field duplicate 71 80 3 for phosphorus was 25.8 %.

The results for these samples 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 EPA Method 365.1.

TDS

Constant weight was not achieved after 3 drying cycles for sample s 71791, 71795, 71796, 71797, 71798, 71799, 71800, 71801, 7180 2, 71803, and 71804. For sample s 71791, 71795, 71796, 71797, 71798, 71799, 71800, 71801, and 71803 the weight increased from the first weighing to the second weighing. Method 2540C warns that samples which contain high levels of calcium, magnesium, chlorid e, and sulfate may be hygroscopic meaning they absorb moisture from the air. FGD wastewater contains high concentrations of all of these species. This was likely the cause for the inconsistent weight calculations.

The samples were not qualified , but result s may be biased high

.

At least one l aboratory duplicate was analyzed per batch

. The RPDs for all l aboratory duplicates analyzed were less than 10 % as required by SM 2540C

.6 TKN

The percent recoveries for the MS and MSD analys e s for sample 71 798 ( Bioreactor influent) did not meet the method control limits of 90 %

- 110 % or the laboratory criteria of

54 %

- 131%. The MS and MSD percent recoveries were 20 2 % and 20 6 %, respectively. The LFB associated with this sample met the method criteria. These percent r ecoveries suggest that results could be biased high for samples with a similar matrix (i.e., bioreactor influent) . Sample 71798 was qualified as a maximum value.

TSS

At least one l aboratory duplicat e w as analyzed per batch . The RPDs for laboratory duplicates for sample s 71791, 71792, 71794, and 71798 were less than 10% as required by Method SM2540D . However, the RPD for sample 71801 was 15%

. The results for sample 71801 and its laboratory duplicate were both qualified by th e laboratory with a “J” meaning the sample result was an estimated value because it was less than the RL, so sample 71801 was not additionally qualified

.

The RPD between sample 71797 and its field duplicate 71803 was 28.6%

. The RPD

between sample 71800 a nd its field duplicate 71804 was also 28.6%

. The results for these four samples were less than the reporting limit. These low concentrations could have

caused the high RPD s

. Even though t h ese RPD s w ere greater than 20%, the samples were not qualified becau se there are no specific control limits for field duplicates specified in

SM 2540D.

Table 2 . Data Review Summary Table

Sample Analyte Qualifier /Action Reason Level Detected

71799 Ammonia Maximum Value MS % recovery

above method

specified criteria 13 mg/L

71791 BOD B Unseeded water

blank > method

specified criteria 40 mg/L

71792 BOD B Unseeded water

blank > method

specified criteria 9.7 mg/L

71795 BOD B Unseeded water

blank > method

specified criteria 7.4 mg/L

71799 BOD B Unseeded water

blank > method

specified criteria 1.7 mg/L7 Table 2 . Data Review Summary Table

Sample Analyte Qualifier /Action Reason Level Detected

71798 COD Minimum Value MS % recovery

below method

specified criteria 84 mg/L

71798 Nitrate/Nitrite Minimum Value MS % recovery

below method

specified criteria 13 mg/L

71801 Total Phosphorus Minimum Value MS % recovery below method

specified criteria 0.19 mg/L

71798 TKN Maximum Value MS % recovery

above method

specified criteria 3.2 mg/L