1

Systems for Continuously 

Monitoring Hazardous Metals 

Emissions from Stacks and Fugitive

Sources

• Why

• How

• Performance

• Acceptance
WHY?

2

Potential for Exposure is REAL!

Well-established adverse health effects associated with exposure to 

hazardous metals such as Cr, Mn, Co, Ni, As, Se, Cd, Hg, Tl, Pb, etc.

E. St. Louis 2009 0

50

100

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200

250

300

350

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45

1:002:003:004:005:006:007:008:009:00

10:0011:0012:0013:0014:0015:0016:0017:0018:0019:0020:0021:0022:0023:00

0:00

Lead Conc (μg/m3)

Time of Day

Wind Direction

Hourly Lead (11/23/09)

Two thirds of

total lead Wind Direction

2-hr Avg. STACK FUMIGATION Conc.

 Metals represent 8 of US EPA’s top 33 urban pollutants of highest concern

 Arsenic is one of US EPA’s top three priority pollutants of concerns

 2000 - EPA determined As, Cr & Cd emissions from CFPP posed potential cancer risks

 CFPP are the largest source of As and Cr in US

 No apparent threshold for blood Pb - What is a safe level for As, Cd, etc.?

 Persistent – will not biodegrade

 Source Apportionment

1-hr Avg. FUGITIVE impact conc.
Cooper Environmental Services 3

Why Multi-Metals FLM?

Fugitive/Area/Low Level Emissions

 Infrequent/difficult measurements

 High uncertainty

 High local concentrations

 Can dominate local exposure

 Includes start up, shut down and malfunction emissions

 Environmental justice issue

 Right to know community exposure 

 Assess and protect health

 Effectively enforce compliance 

 Feedback to management to effectively reduce 

emissions before they become a problem
4

X-Ray Tube X-Ray Detector

Sample

s

s

x

x

C

I

C

I



s

s

x

x C

I

I

C 

X-ray Fluorescence Analysis of

Thin Film Metal Deposits
5

X-Ray Tube

Filter Tape

Aerosol Deposit

Chemistry Zone

Sample Flow

Analysis Area

Filter Tape

HOW DOES A MULTI-METALS CEMS WORK?
Cooper Environmental Services 6

XRF REEL-TO-REEL TAPE SYSTEM ADVANTAGES

 Proven stack monitoring reliability – 6+ years

 Demonstrated EPA acceptance for HWI

 Precise, accurate and verifiable results

 Rugged, well-established, proven technology

 Requires minimal operator interaction & training

 Non-destructive – post-test auditable samples

 No hazardous waste generated
7

XactTM Multi-Metals CEMS

EPA Method 301 

Validated for 

Multi-Metals 

AMP EPA 

Approved

EPA Site 

Certified

6+ Years OnStack Operations 

on Hazardous 

Waste Incinerator

May 2007 – EPA Clean Air 

Excellence Award

2004 2014
Cooper Environmental Services 8

Quality Assurance

1. Auto. with Every Sample

• Calibration error check

• Reactant level Check

• Leak test

2. Auto. Daily

• Calibration error check

• Flow calibration check

• Zero level check

3. Quarterly and annual audits

•Linearity

•RATA

6+ Year Maintenance History

One person day/month
Cooper Environmental Services 9

9

Xact Optimized for 

As, Se, Hg & Pb

Measurable with the Xact up to 25 selectable 
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Stable Calibration Even When Shipped 

and Installed

Xact Upscale Tests

0

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14-Mar 24-Mar 3-Apr 13-Apr 23-Apr 3-May

C

o

n

c (μ

g

/

eff

D

S

C

M)

Cr

Cd

Hg

Pb

CES Lilly

% SD: 3%

Shipped

DAILY CALIBRATION ERROR CHECK 2004
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2004 XACT DETECTION LIMITS (μg/m3)*

Element 15 Min.* 60 Min. Meth. 29**

Cr 0.2 0.03 0.3

As 0.1 0.02 0.4 

Cd 2.4 0.3 0.03

Hg 0.3 0.04 0.6

Pb 0.4 0.06 0.3

Mn 0.3 0.04 0.3

Co 0.3 0.04 0.3

Ni 0.3 0.04 5.4

Se 0.1 0.02 0.8

Ag 4.6 0.6 2.6

Sb 6.1 0.7 1.1

*95% confidence based on 3899 blanks

**120 minute samples
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Flow Diagram for Lilly’s PM & MM CEMS

~700 lpm

QAG Spike

Sigrist Photometer

CES Xact MM CEMS

~60 feet
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XACT PRECISION

- Spiked Stack Gas -

0

1

2

3

4

As Cd Cr Pb Hg

%

R

S

D
Xact Laboratory - Linearity

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y = 0.952x - 1.10

r = 0.995

n = 960 

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a

c

t

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o

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c

e

n

t

r

a

tio

n (μ

g/d

s

c

m) a

QAG Reference Concentration (μg/dscm) 

Cr

As

Hg

Pb

Cd

All RESULTS INCLUDED
Cooper Environmental Services 15

Phase II: Method 301 Xact/XFM Validation Summary

 Precision (RSD) <10% <3% Pass

 Bias Correction Factor

– XFM Measured (n=26) 0.8 – 1.2 0.94 – 0.97 Pass

– Xact Measured (n=192) 0.8 – 1.2 1.00 – 1.14 Pass

 Corr. Coeff. (R) >0.85 >0.99 Pass

 NIST traceable Yes Yes Pass

 Normalized Metal Ratio 0.9 – 1.1 1.00±0.01 Pass

 Slope ND 1.05±0.09 ND

 Intercept ND 1.5±0.7 ND

Goal Stack Gas

ND: Not Defined

301 Goal

All measurement results included
Cooper Environmental Services 16

Xact Mercury Upscale Results

March 2006 - March 2007

0

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400

500

Feb-06 May-06 Aug-06 Nov-06 Mar-07

Date

C

o

n

c

e

n

t

r

a

tio

n (μ

g

/

d

s

c

m)

± 5% error

Re-calibration not required 

during this 12 Month period

Passed 

RATA

Passed 

Quarterly Audit

Difference

As – 2.2%

Cd – 2.8%

Cr – 1.5%

Pb – 2.3%

Hg – 1.8%

12 Month Daily Calibration Error Check

Calibrated
17

Xact Long Term QA Data – Quarterly 

Audits

Cr As Cd Hg Pb

1 3/1/2007 3.04% 1.46% 2.18% 2.84% 1.75% 2.34%

2 5/25/2007 3.13% 3.32% 0.13% 4.23% 2.60% 2.96%

3 8/29/2007 0.68% -3.74% 2.18% -4.13% 2.36% 2.76%

4 12/26/2007 1.42% 6.50% 0.36% 7.36% 4.18% 0.40%

1 2/15/2008 NA 0.22% 0.11% 1.20% -0.99% 0.87%

2 3/17/2008 1.07% 1.93% 0.66% 1.82% 2.16% 2.34%

3 5/20/2008 0.53% 2.96% 2.61% 3.30% 2.53% 0.68%

4 10/20/2008 1.37% 1.77% 0.72% 1.48% 0.56% 1.06%

1 1/7/2009 2.10% 0.60% 2.94% 1.52% 3.45% 0.46%

2 5/6/2009 3.67% 1.49% 4.09% 1.07% 1.78% 0.30%

3 7/9/2009 0.84% 2.00% 5.43% 2.78% 0.72% 0.22%

4 NA NA NA NA NA NA NA

1 1/12/2010 NA 1.60% 5.13% 0.45% 0.71% 2.11%

2 4/25/2010 NA 1.61% 5.92% 1.12% 4.00% 0.96%

3 7/13/2010 1.68% -3.47% -0.92% -2.82% -2.42% -2.11%

4 12/10/2010 NA 2.00% 0.82% 2.70% 1.83% 2.91%

1.77% 1.35% 2.16% 1.66% 1.68% 1.22%

NA - Data Not Available

AVE

Audit Year Quarter Audit Date

2007

2008

2009

2010

XRF Audit Error

Flow Error
18

Example Long Term Xact QA – Annual RATA

XACT Annual RATA Results

Cr As Cd Hg Pb Average

2006 0.83 0.90 0.85 0.82 0.85 0.85

2006 (Quarterly) 0.91 0.77 0.95 0.92 0.93 0.89

2007 0.84 0.82 0.88 0.84 0.81 0.84

2008 0.96 0.71 0.98 0.99 0.97 0.92

2009 0.96 0.99 0.99 1.10 1.00 1.01

2010 0.97 1.06 1.11 1.02 1.04 1.04

Average 0.91 0.87 0.96 0.95 0.93 0.93

Slope

Year

2009 Cr Audit

y = 0.9644x + 3.9424

R

2

 = 0.9735

0.00

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100.00

150.00

200.00

250.00

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Reference Cr Concentration (μg/dscm)

X

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ct

C

r

C

o

n

c

e

n

t

r

a

tio

n (μg/

d

s

c

m)

The Xact Passed All Annual RATA Requirements
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Applicable Sources?

 Incinerators (Tested and installed)

 Coal-fired Boilers (Tested and installed)

 Wet and Dry Stacks (Tested and installed)

 50 PPM Acid Gases (Tested)

 Smelters and Mills (Tested and installed)

 Cement and Lime Kilns

 Mineral Processing

 Plating and Welding
Cooper Environmental Services 20

Tools for Metals Monitoring

pg/m3 ng/m3 μg/m3 mg/m3

Concentration range of interest

Xact 620

Remote Ambient

Xact 640

Xact 625

Urban & Fence Line

CEMS

QAG Quantitative Aerosol Generator

Certification & Audits

Typical EPA IO 3.3

1 pg Hg vapor/m3 = 0.0001 PPTV
Hg Measurement on a Coal Fired 

Power Plant – RATA Results

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0

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10

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

M

e

r

c

u

r

y

C

o

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c. (

g

/

d

s

c

m)

RATA Number

CES Xact

Method 30B

Thermo CMM

Thermo QA Period

3.53% RELATIVE 

ACCURACY FOR CES 

XACT

Passed PS 12 Audit Requirements for Hg CEMS

Xact calibrated in lab, 

transported to and setup 

at CFPP one week before 

RATA test without 

recalibration!
22

HAP Metals Measurement Accuracy on a Coal 

Combustion Source (EPA SBIR)

y = 1.0949x + 0.1847

R

2

 = 0.9918

0

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350

0 50 100 150 200 250 300

Reference Aerosol Concentration (μg/dscm)

X

a

ct R

e

p

orte

d

C

o

n

c

e

ntratio

n (μ

g/d

s

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m)

Cr

As

Cd

Hg

Pb
Cooper Environmental Services 23

EPA SBIR MM Xact Test Results

QAG Spiked CFTB Stack Gas – July 2007

Hg Linearity

y = 1.1405x + 4.8635

R

2

 = 0.9965

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100

150

200

250

300

350

0 50 100 150 200 250 300

QAG Hg Conc. (μg/m3)

Xact Hg Conc. (μg/m3)

Cadmium Linearity

y = 1.1091x - 0.4478

R

2

 = 0.9978

-50

0

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100

150

200

250

300

350

0 50 100 150 200 250 300

QAG Cd Conc. (μg/m3)

Xact Cd Conc. (μg/m3)

Element Slope Intercept R2

Arsenic 1.14 -1.4 1.00

Cadmium 1.11 -0.4 1.00

Chromium 1.09 -1.0 1.00

Lead 1.00 -0.4 1.00

Mercury 1.14 4.9 1.00
Cooper Environmental Services 24

MM Xact Audit Results

QAG Spiked Stack Gas – June 2008

Plotted Linear Regression for Mercury

y = 0.9911x + 0.5291

R

2

 = 0.991

0

50

100

150

200

250

0 50 100 150 200

Reference Concentration (μg/dscm)

X

a

ct C

o

n

c

e

ntratio

n

(μ

g/d

s

c

m)

Element Slope Intercept R2

 Cadmium 0.98 2.7 0.99

 Chromium 0.96 3.7 0.99

 Lead 0.97 4.1 0.99

 Mercury 0.99 0.5 0.99

Xact calibrated with thin film standards traced to NIST Std.

Key Implications of Above Results

•Equal transport of Hg vapor and PM elements

•Equal filter trapping efficiency for Hg vapor and PM elements

•Power of multi-metal analysis capability and internal standards
Cooper Environmental Services 25

Test Furnace Lead Concentrations

Results of Blind Comparison

August 2002 

y = 0.945x - 2.233

R

2

 = 1.000

0

1,000

2,000

3,000

4,000

5,000

0 1,000 2,000 3,000 4,000 5,000

Method 29 Lead (μg/DSCM)

X

C

E

M

L

e

a

d

(

μ

g

/

D

S

C

M

)

Exceptionally high precision for both 

methods at high concentrations

Low bias
Fence Line of a Pb Smelter - Accuracy

26

y = 1.0626x + 5.0407

R2 = 0.9989

0

200

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600

800

1000

0 200 400 600 800 1000

X

act Zinc (n

g/m3

)

FRM Zinc (ng/m3)

y = 1.0651x + 15.451

R2 = 0.9976

0

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1000

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2000

2500

3000

0 500 1000 1500 2000 2500 3000

X

actLea

d (n

g/m3

)

FRM Lead (ng/m3)

Zinc (ng/m3)

Lead (ng/m3)

Demonstrated Accuracy 

at over 2500 ng/m3

Cooper Environmental Services
PM10 selenium, 24-hour integrated filter, ng/m3

0.0 0.5 1.0 1.5 2.0

P

M10

selenium, 24-hour average Xact, ng/m

3

0.0

0.5

1.0

1.5

2.0

Blair

Arnold

18-hour integrated filter with offline XRF, ng/m3

-5 0 5 10 15 20 25 30

18-hour a

v

era

g

e

X

a

ct, ng/m

3

-5

0

5

10

15

20

25

30

Comparison Work – Dr. Jay Turner –

Washington University

Selenium Lead

Cooper Environmental Services 27
Fence-Line Xact Precision – Percent 

Difference

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 Precision of hourly Xact measurement similar to that of 24 

hour FRM sampling with XRF analysis

 Precision of Xact daily average is generally better than that for 

FRM sampling with XRF analysis

 Xact Precision results include two samplers and two

analyzers

 FRM Precision results include two samplers and one analyzer
ETV Study

 Data Produced by US EPA and Batelle –

INDEPENDENT of CES or PALL

 Xact 625 daily average compared to reference 

method PM10 sampling followed by metals analysis 

by ICP-MS

 Xact and reference sampler operated by Ohio EPA 

NOT the manufacturer

 Data above Xact quantitation limit compared to data 

above reference method detection limit

 Regression data indicates the Xact has excellent 

accuracy and precision 

Cooper Environmental Services 29
Xact – Accuracy-ETV Study

Lead (Pb)

Selenium (Se)

Demonstrated Accuracy 

down to 1 ng/m3

Cooper Environmental Services 30
Xact – Accuracy-ETV Study

Zinc (Zn)

Manganese (Mn)

Xact did not sample for 

an entire 24 hours

Cooper Environmental Services 31
Linear Regression of Hg
Metals Variability

 Why measure metals with a HAP Metals CEMS instead of 

Method 29? – Variability

 Selenium variability on a Lignite/PRB Blend Source

 30-day rolling average allows metals “spikes” to average out

0

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150

200

250

300

350

400

10/3/2012 0:00 10/8/2012 0:00 10/13/2012 0:00

Se (g/dscm)

Time
Cooper Environmental Services LLC 34

Argon Peak Intensity

As Hit – April 13, 

2009
Cooper Environmental Services 35

Why Continuous Metals Monitors?

-Stationary and Mobile Platforms-

 Improved exposure estimates

 Improved source apportionment

 Plant feedback to eliminate problem

 Identification of hot spots

 Responsive to unusual events

 Define trans-boundary transport of metals

 Improved meteorological correlation

 More information at reduced monitoring costs

 Risk/insurance minimization
Cooper Environmental Services 36

Advantages of Filter-XRF Approach

 Filters can collect total Hg including particulate

 Fresh filter with each new sample – no memory

 Filters can be archived for subsequent tests

 Filters are applicable to speciated Hg sampling

 XRF does not require gas-phase Hg calibration

 XRF analysis is non-destructive

 XRF results can be independently verified

 XRF is applicable to particulate fraction

 XRF has predictable sensitivities based on fundamental 

parameters
37

EPA Acceptance of Xact CEMS 

 EPA Method 301 Validated

 Met EPA certification requirements

 EPA approved for compliance demonstration

 Six + years continuous stack monitoring 

 Passed 6 years audits and RATA

 Received EPA Clean Air Excellence Award