EPA Steam Electric Stu

SAP, Draft CRC-ICP-M

UWAG CRC Split S

Confirming Analysis 

Presentation to the U.S. EPA Eng

Analysis Division

Washington DC 3-11-2

Dr. Paul N. Boothe 

Albion Environmental 

Bryan, TX.

Dr. Tom Higgins 

CH2M-Hill 

Chantilly, VA

Ut
Understanding of G

 Goals: 

• FGD wastewater characterization• Treatment performance (removal 

effluent concentrations, pollutant 

 To help meet goals, EPA shoul

what has been learned to date
FGD Wastewater Compo

Treatment Effectiveness V

 Particulate concentrations vary ove

to batch operations 

 Hydraulic residence time varies fro Soluble concentrations vary slowly 

months

• Due to factors including coal source, a

catalyst, changes in raw water supply, efficiency of ESP, etc. 

 Treatment efficiency varies among 

similar treatment technologies
FGD Water 

Varies Over 

Time

 Significant variation 

during a year at a given plant Æ short term (daily, weekly, monthly) data may not accurately represent treatment system performance and effluent quality

0

0.5

1

1.5

2

2.5

3

3.5

NJ F 

Mercury (ug/L)

TotalSoluble
Treated FGD Wastewate

Over Time 

1

10

100

1000

10000

100000

1000000

Dec‐08

Feb‐09

Apr‐09

Jun‐09

Aug‐09

Oct‐09

Dec‐09

Mercury (ppt) 
Influent FGD Water V

Within and Among P

Metal



0

20406080

100

Soluble Fraction (%)

Soluble Fraction (%)

Fe

Al

Hg

Ba

Cu

As

Cr

Se
Soluble M

F

(Phys/Ch

0

100200300400500600700800900

1000

HG3

H

Mercury (ng/L)

Treatment Varies Amon

 FGD water varies 

Æ treatment varies

 Some factors that 

affect treatment variability

• Biological Se removal 

affected by nitrates 

• Metal precipitation 

affected by organics
Use of Influent Da

Drives Sampling App

 Characteristics of Influent

• High solids content• Variable composition among batches

 To collect representative influent to

samples: 

• Grab sample at EQ tank or• Manual flow-weighted composite of the 

overflow over a batch

 For soluble metals analyses, grab s

either point are adequate.
Summary of Recomme

 Increase:

• More plants to characterize treatability• Separate samples by more than hydraulic resi

to measure variability accurately 

• Sample over different seasons• Add selenium speciation – important to treatab• Collect WWTP operating data (PFDs, chemical 

 Decrease:

• Number of samples per week • Use of automated composite samplers 

– EQ tank and Effluent tank provide good compos

• Analytes that are consistently low in concentr

difficult to analyze (e.g., Be, Ag, Pb, Sb, Sn, an
Cyanide by EPA Metho

 Concerned about the reliability of c

accepted methods for analyzing cywastewater

• False positives resulting from cyanide 

during sample storage at high pH hav(Anita Pandit, et al.)

• False positives identified by Applied S

to presence of nitrates and nitrites in wastewater (Jan. 2009)

 Set up SAP to allow for confirmatio

positives
Hexavalent Chromium 

Method 218.6

 Concerned about the reliability 

approved methods for analyzinFGD wastewater

• Interferences with colorimetric m

 Confirm the detectable Cr+6 by 

against the dissolved chromiuthe same sample
EPA DRAFT CRC-ICP-M

 EPA-UWAG meeting 6-25-09 reco

• Develop and validate methods that 

produce acceptably accurate data waste water matrices and that can widely by the environmental testing community.

 EPA draft SOP provides a good s

address this recommendation

• Use of synthetic FGD wastewater a 

– Should be used more widely in SOP inclu

digestion with pre-digestion spike to opti
SOP Synthetic FGD Wa

versus CRC Study M

Element SOP Synthetic FGD 

Wastewater (ppm)

Boron 350 

Calcium 5000 

Chloride 15000 

Bromide 50 

Fluoride 10 

Iron 100 

Magnesium 4000 

Manganese 60 

Sodium 1000 

Sulfate 4000 
EPA DRAFT CRC-ICP-M

 Questions:

• Was draft SOP method geared for 

throughput labs with minimal efforesolving matrix interferences ide

• Was a “slug type” sample loop dis

introduction system (e.g. Agilent Idevelop the draft SOP?

• Were all split study samples analy

EPA’s contract lab (Test America, 
DRAFT CRC-ICP-MS SO

 Need more information in SOP t

method setup and implementat

• ISIS-DS specifications & setup pa• HMI specifications & setup param• Instrument setup parameters

– Plasma setup conditions– Collision cell setup parameters

• No discussion of optimizing collision ce

– Data acquisition parameters 
DRAFT CRC-ICP-MS S

 Analytical concerns raised by th

• FGD samples run undiluted regard

– Assuming “standard” ISIS-DS setup (with

loading up to twice that of analyzing FGD diluted to TDS < 2,000 ppm 

– Impact on CRC analyses interference con

• 30 second inter-sample rinse time may no

• SOP appears to quantify based on 

calibration standard

– Such extrapolation with FGD matrices no
DRAFT CRC-ICP-MS SO

 Analytical concerns raised by th

• Fixed concentration pre-digestion 

unusable MS/MSD’s for higher conelements such as selenium

– Should pre-screen and adjust spiking lev

• Failed MS/MSD’s only R-Flagged a

interference suspected

– Should require dilution and re-analysis– If MS/MSD still not pass data should be f

for compliance reporting purposes. 
DRAFT CRC-ICP-MS SO

 Other suggested additions to SO

• Alternate element masses and oth

monitored to assess data quality n

– Very important to facilitate this monitorin

• Expand list of internal standard ele

– Need statement that internal standards m

“naturally” in some FGD wastewaters

• For example, scandium will be present in 

– Need more recommended internal standa

and statement on when and how to subs
DRAFT CRC-ICP-MS SO

 Clean analytical procedures sim

EPA method 1638 should be incthe SOP and emphasized as neelow detection limits

 Aluminum & zinc are the poster child

contamination

 Identifying and correcting interfe

controlled by CRC guidance shoexpanded (see section 2.4)
Recommendations for F

Draft SOP 

 Need joint sharing of CRC Split Sam

without compromising blind intercaapproach

• UWAG confirming analyses data impor

validating efficacy of draft SOP CRC m

• Follow-up meeting to share data, etc.• Additional analytical validation may be 

sharing split sample data 

 SOP needs considerable expansion 

easier to implement by typical labor

• UWAG can provide a more detailed rev

writing 
UWAG CRC SPLIT SAMPL

CONFIRMING ANALYSIS 

 Lacking FGD CRM’s, confirming 

split sample data is the best way validate the accuracy of the data using the EPA draft CRC-ICP-MS 

 Sample collection

• Quasi-conventional sampling proc

• All samples collected by local pers

– Following sampling instructions develop

UWAG

• “Multi-pour” splits- EPA bottles & 
UWAG CRC SPLIT SAMP

CONFIRMING ANALYSIS 

 UWAG split sample processing

• Specific conductance pre-screeni• ‘Raw” sample “multi-pour” sub-sa

– Treat as dissolved samples

• Preservation pH < 2 under clean r• Four different total recoverable di• “Multi-pour” splits of appropriate 

participating confirming analysis 

• Blind intercalibration

– All labs diluted digestions prior to analy

< 2,000 ppm
Split Sample Study Samp

Facility Sampling Points 

A FGD Influent

Bioreactor Influent

Bioreactor Effluent

B FGD Influent

FGD Effluent

C FGD Influent

FGD Effluent

D FGD Influent

FGD Effluent

E FGD Influent

FGD Effluent

F FGD Influent

FGD Effluent

G FGD Influent

FGD Effluent

H FGD Influent

Bioreactor Influent

Bioreactor Effluent

I FGD Influent

FGD Effluent
UWAG Multi-Digestio

Dig. 

# Description

Acids 

Used Digest QA Spikes

1 Closed Vessel (EPA 1638)

+ UV photo-oxidation (AE 

only for HGAF)

2% HNO3 2 DUP

2 MS/MSD

Method Blk

Post-Diges

2 Open Vessel Minimal 

Volume Reduction (EPA 

200.2/ 200.8)

1% HNO3

0.5% HCL

1 DUP

1 MS/MSD

SRM

Blank SPK

3 M-BLKs

2 Chk SPKs

Pre-Digest 

3 Diluted Open Vessel 

Minimal Volume Reduction 

(EPA 200.2/ 200.8)

1% HNO3

0.5% HCL

Same as # 2 

except no DUP or 

MS/MSD

NA 

4 Open Vessel 80% Volume 

Reduction (EPA 200.2/ 

200.8)

1% HNO3

0.5% HCL

1 MS

SRM

Blank SPK

2 M-BLKs

2 Chk SPKs

Pre-Digest 

5 “Raw” Undigested (EPA 

200.8/1638)

1% HNO3 2 DUP

2 MS/MSD

1 M-BLK

Post-Diges
UWAG Confirming Analysis La

Laboratory Instrument (s) Used Method(s) Used Cell G

Ohio State Univ. 

(TERL)

Thermo HR ICP-MS HR-ICP-MS N

Albion Env. PE Elan DRC II

PSA Millenium (HGAF)

EPA 200.8/1638 STD

EPA 200.8/1638 (mod)

EPA 1632 (mod)

N

N

Applied Speciation PE Elan DRC II EPA 200.8/1638 STD

EPA 200.8/1638 (mod)

N

Southern Res. Inst. Agilent 7700 EPA 200.8/1638 STD

EPA 200.8/1638 (mod)

Duke Energy Agilent 7500

ICP-OES

EPA 200.8/1638 STD

EPA 200.8/1638 (mod)

EPA 200.7

N
UWAG Confirming Analys

Vessel Data High Se S

Increasing TDS ->
UWAG Confirming Analys

Vessel Data Low Se Sa

Increasing TDS ->
UWAG Confirming Analysis 

Data High Se Samp

Increasing TDS ->
UWAG Confirming Analysis 

Data Low Se Samp

Increasing TDS ->

Failed MS/MSD
UWAG Lessons Learned 

Split Sample Stu

 ICP-OES selenium data (EPA 20

agrees well with HR data excepto reporting limits 

• Robust 200.7 implementation goo

method for most metals in FGD w

 DRC Se data generally agrees w Most CRC Se data lower than b

data by 20-25%

• Still working on what this means
UWAG Lessons Learned 

Split Sample Stu

 HGAF Se data generally lower t

• ~ 10% and influenced by uv diges

 Inter-method variability increas Different digestion procedures 

result in significant metals data 

• Indication of volatile loss of Se in 

wastewater matrices in open dige

– Need to use matrix specific MS/MSD’s t– Not sure how widespread this effect ma– Closed vessel digestions safest approa