Multi-Metals CEMS: A Review o

Metals CEMS: A Review o

Currently g

 Available Technolog

Krag A. PettersonJh AC o n.ooper

Cooper 

Environmental Services, LLCS mposi m on Air Symposium on Air

Quality Measurement Methods and 

TechnologyNovember 3, 2010

Cooper Environmental Services 

November 3, 2010
Why Measure Metals?

z Significant adverse human health effects (cardiac 

arrhythmia neurotoxic elevated cancer risks) arrhythmia, neurotoxic, elevated cancer risks)

z Developing fetus & children especially susceptiblez Metals represent 8 of US EPA Metals represent 8 of US EPA s’ top 33 pollutants 

top 33 pollutants 

highest concern

z Arsenic is one of US EPA’s top three priority poll

of concern

z Global concern for metals – As, Cd, Cr, Pb and H

RoHS, WEEE and ELV RoHS, WEEE and ELV

•US EPA. Framework for Inorganic Metals Risk Assessment. EPA 120/R-07/001. March 2007.•US EPA. Health Effects Notebook for Hazardous Air Pollutants. EPA Technology Transfer Network AAccessed November 2007. •Agency for Toxic Substances and Disease Registry. Toxic Substances Portal. Accessed November 2

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g y gy
Examples of Contemporary Rese

y 1997, Costa and Dreher: “The lung dose of bioavailable transition 

instilled PM mass, was the primary determinant of the acute inflamfor both the combustion source and ambient PM samples. for both the combustion source and ambient PM samples.

”

y 2002, Magari et al.: “...Results of this study suggest an association 

exposure to airborne metals (vanadium, nickel, chromium, lead, copmanganese) and significant alterations in cardiac autonomic functiomanganese) and significant alterations in cardiac autonomic functio

y 2009, Chen and Lippmann: “...Concentrations of nickel and vana

air PM were associated with significant differences in mortality ratemeasured PM components were not measured PM components were not.”

y 2010, Maciejczyk et al.: “Three metals (nickel, barium, and manga

to be much more influential on lung cell responses than black carboi

o s a a e p ese a uc g e ass co ce a o s n

s th

at 

a

r

e

p

resent 

at much hi

g

h

er mass co

ncentr

ati

o

n

s.”

y Metals Are A Significant Contributor to the Health 

Associated With PM

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Multi-Metals CEMS Metals CEMS – A Brief Hist

A Brief Hist

z 1995 to 1997 EPA/DOE conducts testing of Multi-

CEMS

z 1996 – EPA Proposes Hazardous Waste Combusto

MACT – Multi-metals CEMS would be preferred mfor Monitoring Metals for Monitoring Metals

z 1997 Lilly Begins Funding of Xactz 1997 – EPA Proposes Performance Specification 1z 1997 – Third in series of EPA Tests Concludes that 

currently available multi-metals CEMS can meet performance specification 10 performance specification 10

z 1997 -2004 – Continued interest in MM CEMS fro

and Army because of potential HWC MACT requir

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Multi-Metals CEMS Metals CEMS – A Brief Hist

A Brief Hist

z 2001 and 2002 CES’ XCEM is Tested at Army Dem

Furnaces

z 2004 – Army and Lilly Purchase Xactz 2005 CES X t i M th d 301 V lid t d 2005 CES Xact is Method 301 Validatedz 2006 – Lilly’s Alternative Monitoring Petition Incl

Xact for Metals Compliance

z 2004 to Present - Lilly Xact Operates Passing all A

RATAs

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Overview of Measurement Approa

1997 Evaluation Included Eight different MM-CEMS 

stages of development

z Inductively Coupled Plasma Atomic Emission Spectrom

AES) – 2 participants (Thermo Jerrell Ash)

z Laser Induced Breakdown Spectroscopy (LIBS) Laser Induced Breakdown Spectroscopy (LIBS)

– 2 part

2 part

z Spark Induced Breakdown Spectroscopy - 1 vendorz Microwave Induced Breakdown S

p py ectroscopy

– 1 

p 

artici

z High Resolution Interferometric Spectrometer – Vendorz Hazardous Element Sampling Train (HEST) + XRF a

CES Precursor to Xact

z Only CES’ XRF Approach is Currently Available

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Xact Review

1. How the instrument works2. M301 Validation3. QA Procedures and Instrument 

Performance

4. Compliance Performance Specifica

and Procedures

5. Results from other testing

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Xact-CEMS Connect to 

Transport 

Sampling and 

Main Flow 100 to 800 

DiluMod

p g

Analysis Module

Sub sample onto Tape ~1 LPM

CoMo

Flow Module

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XACT SAMPLING AND ANALYSIS

Aerosol Deposit

X-Ray Tu

Ray Tu

Sample Flow

Analysis Area Analysis Area

Filter Tape Filter Tape

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Determination of Stack Concentra

Mass

(XRF)

CONC (μg/m3)

=

VOLUME

(MFM)

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XACT DETECTION LIMITS (μg/m3)

Element 15 Min.

* 60 Min. Met

Cr 0.2 0.03 0As 0.1 0.02 0Cd 24 03 . . 0 Hg 0.3 0.04 0Pb 0.4 0.06 0M

n 0 3. 0 04 . 0 

Co 0.3 0.04 0Ni 0.3 0.04 5Se 0.1 0.02 0Ag 4.6 0.6 2Sb 6 1. 0 7. 1 

*95% confidence based on 3899 blanks

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**120 minute samples
Xact Method 301 Xact Method 301 - Validation Validation

Method 301 is a procedure or guidelin

determining the precision and accudetermining the precision and accu

of candidate methods

The Xact was validated using CES

Q tit ti A l G t Quantit

ative 

Aeroso

l

Genera

tor or 

as a Reference Method

Think Cal Gas for Metals Think Cal Gas for Metals

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QUANTITATIVE AEROSOL GENERATOR 

(Previous Generation Used During M301 T

ed)

NIST 

Traceable

Aero

Heated 

Drying Air

ng Air Chamber (heatTraceable e Aerosol 

-

Time

Dryin Pressure 

gauge

C RTC

V

Q

i =

(

)

/

Solution loss rate M l S l

Carrier a

volume

lizer

Flow 

Meter

Peristaltic 

Pump

Solution loss rate

Metal S

ol. conc.

Ice NIST Traceable 

M t l l ti

Nebul

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Bath

M

etals solution
M301 Arrangement 

(March 2005) Stac

X t

Ente

Xac

t

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Xact Method 301 Xact Method 301 - Precision Precision

4

M301 R i d P i i 10%

3

D

M301 Required Precision

=10%

Passed 301 for Precis

2

% RSD

10

As Cd Cr Pb 

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As Cd Cr Pb 
Xact - Linearity Linearity

y = 0.952x - 1.10 120

140

m) a

y

r = 0.995

n = 960 

80

100

on (μg/dscm

4060

oncentratio

All RESULTS INCLUDED

0

2040

Xact Co

0

0 20 40 60 80 100 120

QAG Reference Concentration (μg/dscm) 

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Method 301 Method 301 Xact Validation Summa

z Number of Runs 9 192 z P i i (RSD) 10% 3% 

Goal Test Result 

z Precision (RSD) <10% <3% 

z Bias <20% <7% 

z Corr Coeff (R) Corr. Coeff. (R) >0 85 . >0 99 . z NIST traceable Yes Yes z Slope ND 0.95 z Intercept ND 1.10 

All measurement results included

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ND: Not DefinedAll measurement results included
Automated Quality Assura

1. Every Sample

• Calibration stability 

check

2. Daily

• Upscale error c

check

• Flow calibratio

• Reactant level Check• Leak test

• Flow calibratio• Zero level chec

3. Quarterly and annual audits•Linearity •Annual RATA Annual RATA - check of the whole sy

check of the whole sy

4. Optional Optional independent analytical audit 

archived Samples archived Samples
XRF QA 

Daily Upscale R

Pd RPosever

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12 Month Daily Calibration Error 

Xact Upscale March 2006 - March 2007

25002000

g/dscm Cd

10001500

ntration (μ Cr Hg Re-calibration was not required during this 12 month period

500

1000

ConcenPb

0

Feb-06 May-06 Aug-06 Nov-06 Ma

Date
Xact Mercury Upscale Results 

12 Month Daily Calibration Error Ch

March 2006 - March 2007

500300400

(μg/dscm ± 5% error Passed RATA Pa

Quarte

200300

entration (RATA Quarte

Diff

As 

Cd 

Conc 100e 

Cr – 

Pb 

H

g 

0

Feb-06 May-06 Aug-06 Nov-06 

Date
Micromatter Micromatter Standards Standards

z Used to calibrate thz Used to perform X

audits on the Xact (Quarterly)

z Recommended by 

Recommended by for calibration of Xinstruments

z Gravimetrically NI

traceable

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Daily Flow QA/QC Check 

- Percent Diffe

1

0.005 000 000 005.00

Difference

0.00

3000

Percent D

-5.00

±3%

-10.00

Date March 06 
Independent Verification Independent Verification of Xa

of Xa

Results

M29 vs. Xact Prototype

y = 1.09x - 9.60 2 140 160

180

cm)

72 Xact s

from ta

pe 

R

2 = 0.98

6080

100120

140

t Pb (μg/dsc 72 Xact Runs

p

analyzed i

0

2040

0 50 100 150 200

M29 Pb ( /d )

Xact

y = 0.9727x + 3.4259

140 2160180

2002

12 Method 29 Runs

M29 Pb (μg/dscm) R2 = 0.9685

6080

100120

140

c. (μg/m3) July, 2 72 Lab. Anal.

0

2040

60

Lab Con

72 Xac

Independent Verification

0 50 100 

Xact Conc. (μg/m3); M
Lilly HWI Alternative Monitoring 

z Xact Used for Compliancez Pass Performance Specification Pass Performance Specificationz On-going QA Requirements

– D il a

y

– Quarterly– Annually

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Lilly HWI Alternative Monitoring 

Performance S

pecifications

z 7 Day Stability Test – Meet Criteria Every Day for 

– Upscale Drift < 15% Drift – Checks XRF Drift– Zero Drift < 20% Drift – Checks XRF Drift in Backg– Flow Drift < 20% Drift – Checks Stability of Xact Flo

Measurement

z XRF Calibration Audit – <10% Error 

– Checks Calibration Against NIST Traceable Standard

z Flow Calibration Audit Flow Calibration Audit

- <10% Error <10% Error

– Flow Audit with NIST Traceable flow meter

z Linearit

y RATA 

– Spiking with the QAG – Three Concentration Levels– Slope between 0.80 and 1.20

Intercept less than 20% of emission limit

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– Intercept less than 20% of emission limit– Correlation Coefficient > 0.90 
Lilly HWI Alternative Monitoring 

On-Goin

g q QA Re

quirements

z Daily

– Upscale– Zero– Flow

z Quarterly

– XRF– Flow

z A ll nnua

y

– QAG Linearity

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Lilly QAG Audit Results Since 20

Cr As Cd Hg Pb 

Slope

Year

2006 0.83 0.90 0.85 0.82 0.85 

2006 (Quarterly) 0.91 0.77 0.95 0.92 0.93 

2007 0.84 0.82 0.88 0.84 0.81 2008 0.96 0.71 0.98 0.99 0.97 2009 0.96 0.99 0.99 1.10 1.00 2010 0.97 1.06 1.11 1.02 1.04 

Average 0.91 0.87 0.96 0.95 0.93 

HAS Passed All Required AnnuHAS Passed All Required Annu

and Quarterly Audits Since Sta

of AMP

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of AMP
Xact CEMS

EPA Method 301 

Validated

AM

App

EPA Site C tifi d

~6 Y

Certified St k 

Stack 

M 2007 EPA Cl AiMay 2007 – EPA Clean Air 

Excellence Award
Over View of Other Testing

z XCEM (Xact Predecessor) Comparison with M2

Army Incinerator

z Army Xact Comparison with M29 for As and H

Coal Fired Boiler

z Small Business Innovative Research Grant Small Business Innovative Research Grant

– Sp

Sp

with QAG on Coal Fired Test Furnace

z Hg Measurement on Coal-fired Power Plant –

Comparison with Method 30B and Thermo Hg Freedom

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XCEM Tests (2002)

z Comparison of XCEM to Method 29z Metals Spike at Army Munitions Incineratorz Spiked Concentration Measured by M29 and Xaz Sponsored by US Army Engineer Research and 

D l t C t C t ti E i i Deve

lopmen

t

Cen

ter 

Cons

truction 

Eng

ineer

ing 

Research Laboratory (EDRC/CERL)

z M29 

g y yp 

athered and anal

yzed b

y inde

pendent labo

group

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2002 XCEM Testing Results

Element % Relative 

Accuracy

Met PS-10 

Criteria

P

b

4

. %4

%

Yes

Cd 17% Yes

Cr 15% YesBa 4% Yes

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Army Xact Comparison to M29

z Later Version of Xactz Hg and As spiked into a subsample of Coal fired 

Effluent

z Hg and As Measured by M29 and Xactz R lt % R l ti A Results 

%

R

e

l

ative 

Accuracy

– Hg – 17%– As 16%

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EPA Sponsored Small Busines

Innovative Research Grant

z Coal Fired furnace - EPA’s Multi-Pollutant Con

Research Facility

Xact vs QAGfor All Elements

z Spike a subsample of effluent with the QAG at 3 

concentration levels

z Compare Xact to QAG y

= 1.1041x ‐ 1.3829 300.00

350.00

3)

Xact vs. QAGfor All Elements

z Compare Xact to QAG Linearity

y

R2

= 0.9912

150.00200.00250.00

Conc. (μg/m

Experimental Criteria Experimental 

Slope Linearity Correlation Coe

0.00

50.00

100.00

Xact C 

Criteria Result Met? Criteria Average 

Cr 1.09 yes >0.99 

As 1.14 yes >0.99 

Cd 1.11 yes

>0.99 

Element

>0.90 0.85 to 1 15 0.00 50.00 100.00 150.00 200.00 250.00 300.00

QAG Conc. (μg/m)

Cd 1.11 yes 0.99 Hg 1.14 yes >0.99 Pb 1.00 yes >0.99 

0.90 1.15

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Hg Measurement on Coal Fired Po

Plant

z 585 Mwatt Coal Fired Power Plant z Downstream of Electrostatic Precipitatorz Measurement of Stack Concentrations of Hgz Comparison with Method 30B and an on-site op

Th M F d U it Thermo 

Mercury 

Free

dom 

U

nit

z Xact was installed and operating within 2 days

Cooper Environmental Services 
Hg Measurement on a Coal Fire

Power Plant

89

10

m)

5678

c. (μg/dscm 3.53% RELATIVE 

2345

ercury Conc 

Th QA P i d ACCURACY FOR CES 

XACT

01

M

2

e Thermo QA

Perio

d

0 1 2 3 4 5 6 7 8 9 10 11 12 13

RATA Number

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Applicable Sources?

z Incinerators (Tested and installed)z Coal

-fired Boilers fired Boilers (Tested) (Tested)

z Wet and Dry Stacks (Tested)z 50 PPM Acid Gases (Tested)z Smelters and Mills Smelters and Millsz Cement and Lime Kilnsz Mineral Processingz Platin

g and Weldin

g

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g g
What Next?

z EPA Asked for Comment on the use of multi-me

CEMS as a part of CISWI MACT (August 2010

z EPA Asked for Comment on the use of multi-me

CEMS for Sewage Sludge Incinerators (Septemb2010).

z Why is EPA regulating with Surrogate (PM) ins

MM-CEMS?

z MM-CEMS as an alternative to Hg CEMS + PM 

CEMS for PC MACT, Boiler MACT, CISWI Mand Utility MACT? and Utility MACT?

Cooper Environmental Services 
QUESTIONS

Krag Pettersonkragp@cooperenvironmental.com

Cooper Environmental Services