1 

# Systems for Continuously **Monitoring Hazardous Metals Emissions from**  **Stacks and**  **Fugitive**

**Sources**

• **Wh y** 
• **Ho w** 
• **Pe rf**  **or mance** 
• **Acceptance**

# WHY?

2 

### Po **tential f**

**or Exposur e is**  

### REAL! **We ll**  **- established adv**  **er se**  **health ef fe**  **cts associa ted with e**  **xposur e to**  **hazar dous metals suc**  **h as Cr , Mn, Co, Ni, As, Se, Cd, Hg, T**  **l, Pb, etc.**

**E. St. Louis 2009** 0 50 100 150 200 250 300 350

0 5 10 15 20 25 30 35 40 451:002:003:004:005:006:007:008:009:0010:0011:0012:0013:0014:0015:0016:0017:0018:0019:0020:0021:0022:0023:000:00**L e** **a d** **C o** **n c** **( μ** **g /** **m 3** **)**

**Time of**  **D ay** **W i** **n d** **D i** **r e** **c t** **i o** **n Ho**  **urly L**  **ead (1**  **1/23/09)**
**Two thirds**  **of total lead**  **Wind Direction 2**  **- hr Avg.**  **ST**

**ACK FUMIGA**

**TION Conc.** 



###  **Metals r epr**  **esent 8 of US EP A’**  **s top 33 urban pollutants of highest concern**  **Arsenic is one of US EP A’**  **s top thr ee 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**  **A s, 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**  **Tu be**  **X -**  **Ray Detector** 

**Sample**



## s s

x x 

# C I C I  s s x x 

# C I I C  **X -**  **ra y F**  **luor escence Anal**  **ysis of Th**  **in Film Metal Deposits**5 

## X **- Ray T**  **ube**

**Filter T**  **ape Aer**  **osol Deposit Chemistry Z**  **one**

**Sample Flow Analysis**  **Ar ea** 

**Filter T**  **ape** 

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

# XRF REEL **- TO**  **- REEL**  **TAPE SYSTEM ADVANTAGES** 

 

# Proven stack monitoring **reliability –**  **6+ ye**  **ars**  

# 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



# Xact **TM** 

# Multi **- Metals**  **CEMS EP**  **A Method 301**  **Va lidated for**  **Multi -**  **Metals AMP**  **EP A**  **Approved EP**  **A Site**  **Certified 6+**  **Ye ars On**  **** **Stack Operations on Hazardous**  **Wa ste Incinerator**  **May 2**  **007 –**  **EP A**  **Clean Air**  **Excellence Aw**  **ard** 

# 2004 **2014 Cooper Environmental Services**  8



# Quality Assur **ance 1.**  **Auto. with Every S**  **ample** 

# • **Calibration error check** 

# • **Reactant level Check** 

# • **Leak test** 

# 2. **Auto. Daily**  

# • **Calibration error check** 

# • **Flow calibration**  **check** 

# • **Zero level check** 

# 3. Quarterly **a nd annual audits**  

# • **Linearity** 

# • **RA TA**  

# 6+ **Ye ar Maintenance**  **History One person day**  **/month Cooper Environmental Services**  9 9



## Xact Optimiz **ed f**

**or As, Se, Hg & Pb** 

**Measur able with the Xact up to 25 selectable** **Cooper Environmental Services** 10 

# Stable **Calibration Even**  **When Shipped**

**and Installed**
**Xa ct**  **Upscal e Tests** 

0 50 100 150 200 250

14-Mar 24-Mar 3-A pr 13-A pr 23-A pr 3-May**C o** **n c** **( μ** **g /** **e f** **f D** **S C** **M )**  Cr Cd Hg Pb


### CES **Lilly** 

## % **SD: 3% Shipped**  **DA IL**  **Y CALIBRA**

**TION ERR OR CHECK 2004** **Cooper Environmental Services** 11 

# 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**Cooper Environmental Services** 12 

# Flow Diagram **for Lilly’s PM & MM CEMS** 

**~700 lpm**  **QAG Spike** 

**Sigrist Photometer CES Xact MM CEMS**  

### ~60 **feet Cooper Environmental Services**  13



# XACT **PRECISION**

**- Spiked Stack Gas**  **-**

**0 1**  **2 3**  **4**

**As Cd**  **Cr Pb**  **Hg %** **R S** **D**

# Xact Laboratory **- Linearity** 

**Cooper Environmental Services** 14 

# y **= 0.**  **952x -**  **1. 10**  **r =**  **0. 995**  **n =**  **960**

0 20 40 60 80 100 120 140

0 20 40 60 80 100 120**X a** **c t** **C o** **n c** **e n** **t r** **a t** **i o** **n (** **μ g** **/ d** **s c** **m )** **a**

**QAG Re**  **fe re**  **nce Concentration (μg/dscm)**  

## Cr As Hg Pb Cd 

# All RESUL

**TS 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



## Xa **ct M**  **er cur** 

**y Up**  **scal e**  **Re sul**  **ts Ma**  **rc h 2006 -**  **M ar**  **ch 2007**

0 100 200 300 400 500

Feb- 06 Ma y- 06 Au g- 06 No v- 06 Ma r-0 7 **Da te** **C o** **n c** **e n** **t r** **a t** **i o** **n (** **μ g** **/ d** **s c** **m )** 


### ± **5% error**  

# Re **- calibration**  **not required during**  **this 12 Month period**  **Passed RA**  **TA Passed**  **Quarterly Au**  **dit Difference**  **As –**  **2.2% Cd**  **– 2.8%**  **Cr –**  **1.5% Pb**  **– 2.3%**  **Hg –**  **1.8%** 

## 12 Month Dail **y Calibr at**  **ion Er ro**  **r Chec k** 

**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

**AV E**  **Quarter Au**  **dit Year Au**  **dit Date** 2007

2008

2009

2010 **XRF A udit Error**  **Flow Error**18 

## Example Long Term Xact QA **– Annual RATA**  **XA CT A**  **nnual RA**

**TA R**  **esults**
**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**  **Sl ope**  **Year** 

## 2009 **Cr Audi**  **t**

y = 0 .9 644x + 3. 9424 R 2 

### = 0 .9 735

0. 00 50. 00 100. 00 150. 00 200. 00 250. 00

0. 00 50. 00 100. 00 150. 00 200. 00 250. 00

**Re fe**  **ren ce**  **Cr Conc**  **en tr**  **at io**  **n (μ g/**  **ds cm**  **) X** **a c** **t C** **r C** **o n** **c e** **n t** **r a** **t i** **o n** **( μ** **g /** **d s** **c m** **)**



## The Xact Passed All Annual RA TA R equirements**Cooper Environmental Services** 19



# 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/m 3 

### n g/m 3 

### μg/m 3 

### mg/m 3



## Concentration range of interest

**Xact 620 Remote**  **Am bient** 
**Xact 640 Xact 625**  **Urban & Fence Line CEMS** 
**QA G**  **Quantitativ e**  **Ae rosol**  **Generator Certification &**  **Au dits**  

## Ty **pical EP**

**A IO 3.3 1 pg Hg vapor/m3 = 0.0001 PPTV** 

# Hg Measurement on a Coal Fired **Power Plant –**  **RATA Results** 

**Cooper Environmental Services** 21 0 1 2 3 4 5 6 7 8 9 10

0 1 2 3 4 5 6 7 8 9 10 11 12 13**M e** **r c** **u r** **y C** **o n** **c .** **(****g /** **d s** **c m** **)**

**RA TA**  **N um**  **be r**  CE S Xa ct Me th od 30B Th erm o CM M 

### Thermo QA

**P eriod**  

# 3.53% RELA

**TIVE ACCURACY** 

**F OR CES**  **XACT**

**Passed PS 12 Audit Requirements**  **for Hg CEMS** 

# Xact calibr **at ed in la**  **b, tr**  **anspor ted to and setup**  **at CFPP one w**  **eek bef or**  **e RA**  **TA t**  **est without re**  **calibr at**  **ion!**22 

## HAP Metals Measurement Accuracy on a 

# Coal **Combustion Source (EPA SBIR)** 

**y = 1**  **.0 949x**  **+ 0 .1**  **847 R**  **2 = 0**  **.9 918** 

0 50 100 150 200 250 300 350

0 50 100 150 200 250 300 **Re fe**  **re nce**  **A er**  **os**

**ol C**  **once nt**  **ra ti**  **on (μ**  **g/ds cm**  **) X** **a c** **t R** **e p** **o r** **t e** **d C** **o n** **c e** **n t** **r a** **t i** **o n** **( μ** **g /** **d s** **c m** **)**

Cr As Cd Hg Pb**Cooper Environmental Services** 23



## EPA SBIR MM Xact Test Results **QAG Spiked**  **CFTB Stack Gas –**  **July 2007**

**Hg Li**  **neari ty** 

y = 1 .1 405x + 4 .8635 R 2 = 0 .9965

0 50 100 150 200 250 300 350

0 50 100 150 200 250 300 **QAG Hg**  **Co nc.**  **(μg /m3**  **) X** **a c** **t H** **g C** **o n** **c .** **( μ** **g /** **m 3** **) Ca**  **dm iu**  **m L in**  **earity**

y = 1 .1 091x - 0 .4 478 R 2 = 0 .9 978

-50 0 50 100 150 200 250 300 350

0 50 100 150 200 250 300 **QA G**  **Cd C**  **onc . (**  **μg /m3**  **) X** **a c** **t C** **d C** **o n** **c .** **( μ** **g /** **m 3** **)** 

## Element **Slope Intercept**  **R2** Arsenic 1.14
- 1.4 1.00 Cadmium 1.1 1
- 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**

**Pl ot**  **te d**  **Li near**  **Regr essi**  **on fo**  **r Me rc**  **ur y** 

**y = 0**  **.9 911x**  **+ 0 .5**  **291 R**  **2 = 0**  **.9 91** 

0 50 100 150 200 250

0 50 100 150 200

**Re fe**  **re nce**  **C once**  **nt ra**  **ti on (**  **μg /ds**  **cm )** **X a** **c t** **C o** **n c** **e n** **t r** **a t** **i o** **n (** **μ g** **/ d** **s c** **m )**  

## Element **Slope Inter**  **cept R**  **2** 

###  

## 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**  **Abov e Results** 

• **Equal transport of Hg vapor and PM elements** 

• **Equal filter trapping efficiency**  **for Hg vapor and PM elements**

• **Pow er**  **of multi -**  **metal analy**  **sis capability and internal**  **standards Cooper En**  **vironmental Ser**

**vices** 25 

## Te **st Fur nace Lead Concentr**  **at ions**  **Re sults 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 pr ecision**  **for both**  **methods at**  **high concentrations Low bias** 

# Fence **Line of a Pb**  **Smelter -**  **Accuracy**

26

y = 1 .0 626x + 5. 0407 R2 = 0 .9 989

0 200 400 600 800 1000

0 200 400 600 800 1000**X a** **c t** **Z i** **n c** **( n** **g /** **m 3** **)**

**FRM Z**  **in c**  **(n g/**  **m 3**  **)** y = 1 .0 651x + 15. 451 R2 = 0 .9 976

0 500 1000 1500 2000 2500 3000

0 500 1000 1500 2000 2500 3000**X a** **c t** **L e** **a d** **( n** **g /** **m 3** **)**

**FRM L**  **ead (n**  **g/m 3**  **)** 

### Zinc (ng/m 3 

### )

Lead (ng/m 3 

### ) **Demonstrated Ac**  **curacy at ov**  **er 2500 ng/m**  **3**

**Cooper Environmental Services**PM 10 selenium, 24-hour integrated filter, ng/m 3

0.0 0.5 1.0 1.5 2.0PM10selenium,24-houraverageXact,ng/m3

0.0 0.5 1.0 1.5 2.0 Blair

Arnold

18-hour integrated filter with offline XRF, ng/m 3 -5 0 5 10 15 20 25 3018-houraverageXact,ng/m3

-5 0 5 10 15 20 25 30 

## Comparison W **ork –**  **Dr . Jay**  **T urner**  **– Wa**  **shington University**

Selenium Lead

**Cooper Environmental Services** 27

# Fence **- Line**  **Xact Precision –**  **Percent Difference** 

Cooper Environmental Services 28 

###  

## 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

 

# Xa ct 625 daily average compared to reference method PM 10 

# sampling followed by metals analysis by ICP
- MS

 

# Xa ct and reference sampler operated by Ohio EPA NOT the manufacturer

 

# Data above Xa ct quantitation limit compared to data above reference method detection limit

 

# Regression data indicates the Xa ct has excellent accuracy and precision

**Cooper Environmental Services** 29

# Xact **– Accuracy**  **- ETV**  **Study**

Lead (Pb)

Selenium (Se) **Demonstrated Ac**  **curacy dow**  **n to 1 ng/m**  **3 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 50 100 150 200 250 300 350 400

10/ 3/ 2012 0:00 10/ 8/ 2012 0:00 10/ 13/ 2012 0:00**S e** **(****g /** **d s** **c m** **)**

**Tim e** **Cooper Environmental Services LLC** 34



## Ar **gon P eak**  **Intensity**

**As Hit –**  **Ap ril**  **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 minimiz **ation 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 Aw **ard**