**Cooper Environmental Services** 1 

# Why Do We Need a QAG?  **Multi -**  **metal CEMS would otherwise**  **depend on Method 29 for certification, validation,**  **audits and RATA.**  **PM CEMS/CPMS certifications with PS**  **11 and Method 5 are difficult,**  **costly and unreliable near detection**  **limit -**  **Requires feed and AP control modifications**  **“Generating PM concentrations**  **over the measurement**  **range is a PAIN”**  **Should be useful in new method development**  **for other species CEMS** **Cooper Environmental Services** 2 

# QAG History **and Major Milestones**
 

# 1997: Lilly Metals CEMS Development project  

# 1993 to 2004: Difficulties w **ith Method 29**   

# 2004: QAG Developed for Lilly **Xact Certification**   

# 2005: **Applied for patent**   

# 2006:EPA Approved QAG for Metals Audit  

# 2008: Lilly QAG extended to PM for **Sigrist CEMS**   

# 2008: EPRI sponsored test of BAM CEMS  

# 2009: EPRI PM QAG improvement project  

# 2011: PM QAG field tested on CFPP

# Quantitative **Aerosol Generator**  **(QAG)**

**Cooper Environmental Services** 3 **Solution Emission Rate (** 

## R **) (grams solution per minute)**  **An alyte**  **Solution Concentration (** 

## S **) (micrograms per grams solution)**  **Carrier/Drying Ai**  **r Flow**  **(** 

## F **) (cubic meters**  **per minute) Quantitativ**  **e Ae**  **rosol Conc. (**  

## C **) (micrograms per cubic meter)**  

# C = RS/F

**Tr aceable to NIST**  **Standards A**  **dev ice**  **that generates an aerosol w**  **hose concentration**  **is independently**  **traceable to NIST standards. G** **e n** **e r** **a t** **e** 

## Dilute**Cooper Environmental Services** 4 

# Key **Metals QAG Components** 

**Nebulizer Solution Control and**  **Measurement Nebulizer Carrier**  **Ai r**  **Control Droplet Size**  **Control Focused**  **Tr ansport**  **Drying Chamber**  

## Quantitative **Emissions (mg/min. and mg/dscm)** 

**Drying/Carrier Ai**  **r Drying/Carrier**  **Ai r** **Cooper Environmental Services** 5 

# Quantitative **Aerosol Generator**  **for Metals Dry**  **ing Chamber Bubblers** 

**Pump**
**Reserv oir**  **Balance Nebulizer**  **Droplet Size**  **Control Focused**  **Tr ansport** **Cooper Environmental Services** 6



# QAG EMISSIONS OVER 13 HOURS

y = -0 .1 452x

+ 1 662. 7 R 2 = 0 .9 99 1, 380 1, 400 1, 420 1, 440 1, 460 1, 480 1, 500 1, 520 1, 540

800 1, 000 1, 200 1, 400 1, 600 1, 800 2, 000 **Mi nut**  **es M** **a s** **s (** **g )** 

0 10 20 30 40 50 60 70 80 90 100**Z i** **n c** **C o** **n c** **. μ** **g /** **m 3**  

### Xact **Measur ed**  **Zinc Conc. (μg/m 3**  

### )

**Measur ed**  **NIST Solution**  **Loss Rate (R) QA**  **G Calculated**  **Emissions (C A**  **)** 

## 13 hours

# Prototype MM/PM **QAG**

**Cooper Environmental Services** 7

**Drying Chamber Frequency Generator** 

**Amplifier Hea**  **ter Contr ols**  

# EP **A -**  **Ap pr**  **ove d**  **QA G f** 

**or audits of Multi**  **- metal**  **CEMS a t a specific**  **inciner at**  **or –**  **M29 not r equir**  **ed Cooper Environmental Services**  8 

# Note Difference **Between Aerosol**  **Generation Transport**  **Utility Cooper Environmental Services**  9 

# Qag **, Xact, XFM Laboratory**  **Test Arrangement** **Cooper Environmental Services** 10 

# Qag **, Xact, XFM Laboratory**  **Test Arrangement** **Cooper Environmental Services** 11 

# Solution **Emission Rate Measured** 

**During Each Test**  **Solution Reservoir** 

**Balance Pump** **Cooper Environmental Services** 12 

# QAG **EMISSIONS RATE**  **OVER 13 HOURS** 

y = -0 .1 452x

+ 1 662. 7 R 2 = 0 .9 99 1, 380 1, 400 1, 420 1, 440 1, 460 1, 480 1, 500 1, 520 1, 540

800 1, 000 1, 200 1, 400 1, 600 1, 800 2, 000 **Mi nut**  **es M** **a s** **s (** **g )** 

0 10 20 30 40 50 60 70 80 90 100**Z i** **n c** **C o** **n c** **. μ** **g /** **m 3**  

### Xact Measur **ed Zinc Conc. (μg/m 3**  

### )

**Measur ed**  **NIST Solution**  **Loss Rate (R)**



## QA **G Calcula ted**  **Aer osol Conc.**  **(C A**  

## ) **13 hours Cooper Environmental Services**  13 

# Flow Diagram for Lilly’s PM & MM **CEMS Field Testing With QAG**

**~700 lpm**  **QA G Spik** 

**e**

**Sig rist**  **Photometer CES Xact MM CEMS** **Cooper Environmental Services** 14



# Spiking **Flows at Lilly Stack**

**Stack Gas**  

## QA **G Aer osol** 

**(~50 lpm**  **)**

**CEMS/XFM**

**~12 m to CEMS**

**~0.3 m Port**  **~700 lpm** **Cooper Environmental Services** 15 

# QAG 

# + **XACT VARIABILITY COMPARED**  **TO**

**METHOD 29 PRECISION** 



# Ar **seni c**  **(3 .5**  **% RS**  **D)** 0 10 20 30 40 50 60 70

4/ 9 0: 00 4/ 9 12: 00 4/ 10 0: 00 4/ 10

12: 00 4/ 11 0: 00 4/ 11

12: 00 4/ 12 0: 00 4/ 12

12: 00**C o** **n c** **. (** **μ g** **/ d** **s c** **m )** 



## N=250 **Equivalent Method 29 Expected Data Scatter**



## Thr **ee Days**



# Even with stack conc. variability **, may s**  **till pass M301 criteria with dy**  **namic spiking** **Cooper Environmental Services** 16 

# Combined QAG & XACT **PRECISION**

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

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

**As Cd**  **Cr Pb**  **Hg %** **R S** **D Cooper Environmental Services**  17



# LABORATORY: **PRECISE ,**  **ACCURATE AND**  **LINEAR**

**XFM VS. QA** 

**G CHROMIUM**

y = 0 .966x

- 1.9344 R 2 

## = 0.9903 0 20 40 60 80 100 120 140

0 50 100 150

**QA G (μg/dscm)** **X F** **M (** **μ g** **/ d** **s c** **m )**  

## Pr **ecise/Linear: R**  **2** 

## = 0.990 **Accurate: Slope = 0.966** 

# 29 XFM **Measurements Cooper Environmental Services**  18 

# XFM **Field Linearity**  **(Cr, As,**  **Hg, Pb**  **)**

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

**Mer cur**  **y**

y = 1.036x

- 1.803 R 2 = 0.991 0 20 40 60 80 100 120 140

0 20 40 60 80 100 120 140

**Re feren**  **ce Conc**  **. ( μg/ds**  **cm) X** **F M** **( μ** **g /** **d s** **c m** **) n=**  **26 Ch**  **rom iu**  **m**

y = 1.042x

- 1.605 R 2 = 0.994 0 20 40 60 80 100 120 140

0 20 40 60 80 100 120 140

**Re fe**  **ren ce**  **Conc. (μ g/ds**  **cm )** **X F** **M (** **μ g** **/ d** **s c** **m )**  **n=2 6**  **Ar se**  **nic**

y = 1.067x - 2.716 R 2 = 0.994 0 20 40 60 80 100 120 140

0 20 40 60 80 100 120 140

**Re fe**  **ren ce**  **Co nc**  **. ( μg**  **/ds cm)** **X F** **M (** **μ g** **/ d** **s c** **m )**  **n= 26** 

**Le ad** 

y = 1.068x - 2.079 R 2 = 0.991 0 20 40 60 80 100 120 140

0 20 40 60 80 100 120 140

**Re fe**  **ren ce**  **Co nc**  **. ( μg**  **/ds cm)** **X F** **M (** **μ g** **/ d** **s c** **m )**  **n= 26**  **N = 26 Slope: 1.04**  **Slope: 1.07**

**Slope: 1.04 Slope: 1.07** **Cooper Environmental Services** 19



## y **= 0.**  **999x - 0**  **.1 03**  **r = 0**  **.9 98**  **n =**  **675**

0 20 40 60 80 100 120 140

0 20 40 60 80 100 120 140

**Theor et**  **ic al**  **Concentrati on (μg/dscm)** **M e** **a s** **u r** **e d** **C o** **n c** **e n** **t r** **a t** **i o** **n (** **μ g** **/ d** **s c** **m )** **a**


## Cr As Hg Pb Cd 

# QAG **MM Linearity Demonstration**

**All data included**  

# 135 r **uns Cooper Environmental Services**  20



# XFM RELATIVE **ACCURACY**

**– QAG**  **Spiked Stack Gas**  **-**

**0 5**  **10 15**  **20**

**AS CD**  **CR PB**  **HG R** **e l** **a t** **i v** **e A** **c c** **u r** **a c** **y** 

## EP

**A Re**  **quir es**  **less than 20% Cooper Environmental Services**  21 

# Extending **QAG From Metals** 

**to PM Range**  

# Increase **droplet size and emission**  **rates**  

# Increase **PM salt solution concentration**  

# Increase **power and frequency of nebulizer**  

# Increase **carrier air flow to meet needs of**  **PM CEMS**

# Stack **and QAG Aerosol**  **Size**

**Distributions**

**Cooper Environmental Services** 22 **Stac k Aer**  **osol MMD ~ 1.5μm**  **QA G Aer**  **osol MMD ~ 0.6μm**  **Stac k**  **Sample 1**

**Stac k**  **Sample 2**  **QA G Aer**  **osol**

**MMD ~ 0.6μm** 

## 0.5 μm

**0.5 μm 0.5 μm** 

# Sigrist **, QAG & Method 5 Correlations**

**Cooper Environmental Services** 23 **Method 5 and Sigrist** 

**Sigrist (mg/**  **dscm )** **M e** **t h** **o d** **5 (** **m g** **/ d** **s c** **m )** **S i** **g r** **i s** **t (** **m g** **/ d** **s c** **m )**  **Sigrist vs**  **QA G** 

**QA G**  **(mg/ dscm**  **) Cooper Environmental Services**  24 

# Demonstrated **Performance for Prototype**  **PM QAG Criteria**  **Goal Demonstrated**   Accuracy (relative % diff.) 10% 8%  Precision (RPSD ) 10% 2%  Linearity (predicted vs measured, mg/ dscm )

– Slope 1.0 ± 0.1 0.93

– Intercept ± 1 - 0.66

– R 2 >0.85 0.99 

###  Repeatability (RPSD) 10% 5%  Traceable to NIST Stds

. Yes Yes  Max. conc. at 700 lpm (mg/ dscm ) 20 mg/ dscm 22 mg/ dscm  Max. conc. at 55 lpm (mg/ dscm ) NA 290  Transportable Yes Yes 

# All Lill **y Goals Met**

# Preliminary **PM QAG Feasibility study:**  **Interface with PM CEMS Probe**

**Cooper Environmental Services** 25 **Pr obe No**  **zzle**

**4” SS Interface “T” Cooper Environmental Services**  26 **y = 1.1981x -**  **3.0665 R2 = 0.9797** 

0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0

0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00**Q A** **G C** **o n** **c .** **( m** **g /** **m 3** **)**



### Beta PM CEMS Conc. **(mg/m3) Linearity**  **of QAG with 90% r ecovery**  **rate and Beta PM CEMS**



# N = 18 **Y = 1.19X –**  **3.1 R squared**  **= 0.98** 

# Prototype PM QAG **2008 BAM CEMS Challenge Cooper Environmental Services**  27

# PM QAG **Linearity Determined**  **With**

**Total Capture Tests** 

**Cooper Environmental Services** 28



## Gr **av imetr**  **y Y = 1.002X**  **- .096**  **R squar ed = 0.998** 

**X -**  **Ray F luor**  **escence Y = 1.025X**  **– 0.012**  **R squar ed = 0.996** **Cooper Environmental Services** 29 

## Total Capture Aerosol Concentration Equations 

# V RTC C Q KI 

# /

) (  

# V M M C b

a G KI 

# /

) (

  

# V A D C d

I X KI 

# /

) 31
. 1 (  **QAG Predicted**

**Gravimetric Measurement** 

**XRF KI Measured**

**Solution loss rate Ti**  **me**

**Salt Sol. conc**  **. Carrier air**  **vo lume** 

**Filter mass –**  **after and before**

**Iodine aerial density Deposit area**  **KI Factor Cooper Environmental Services**  30 

# XRF KI Compared **to Gravimetric Mass** 

**y =**  **1.0342x R**  **2 =**  **0.9998**

0 100 200 300 400 500 600

0 50 100 150 200 250 300 350 400 450 500 **Gra vi**  **me try**  **(mg /s**  **am pl**  **e) X** **R F** **K I** **( m** **g /** **s a** **m p** **l e** **)**



## 4.7 cm diameter filters **20X25 cm filters** 

# N =32 **Y = 1.03X R squar**  **ed = 0.9998**

**Gravimetry (mg/**  **dscm )** **X R** **F K** **I (** **m g** **/ d** **s c** **m )** **Cooper Environmental Services** 31 

# Linearity **of QAG Emission**  **Rates**

**(mg/min.)**
**y = 0**  **.9 27x**  **R 2**  

## = 0 **.9 982** 

0. 00 2. 00 4. 00 6. 00 8. 00 10. 00 12. 00 14. 00 16. 00 18. 00

0. 00 2. 00 4. 00 6. 00 8. 00 10. 00 12. 00 14. 00 16. 00 18. 00 **QA G**  **Pr ed**  **ic te**  **d ( mg**  **/min .)** **M e** **a s** **u r** **e d** **( m** **g /** **m i** **n .** **)** 

## N = 38 **To tal**  **Capture (1.3 m U**  **- tube)**  **Salt: KI,**  **K 2**  

### SO **4** 

### Range: **0.04 to 16 mg/min. Cooper Environmental Services**  32



# Linearity **of QAG Aerosol**  **Conc. (mg/dscm)**

**y = 0.9266x -**  **0.6587 R**  **2 = 0.998** 

**0 50**  **100 150**  **200 250**  **300 350** 

**0 50**  **100 150**  **200 250**  **300 350**  **To tal Capture (1.3 m U**  **- tube,**  **4 m Lilly T ransport**  **) Salts: KI,**  **K2SO4 To**  **tal flow :**  **55 lpm Range: 0.5 to 290 mg/dscm**  **If flow w**  **ere 700 lpm**  **– Range: 0.04 to 23 mg/dscm**  **If flow w**  **ere 10 lpm**  **– Range: 3 to 1,600 mg/dscm**  **N = 40**

# Key **PM QAG Improvements** 

 

# PO **- 210 Charge neutraliz**  **er**  

# Transport system to porous tubing  

# Transport interface polished and heated  

# Custom design aerosol generation assembly  

# Change salt used for PM generation

**Cooper Environmental Services** 33**Cooper Environmental Services** 34 

# Schematic of Modified QAG

**Po 210**  **Source**

**Nebulizer Focused**  **transport/drier** 

### Aerosol **Generator Module** 

**Control Module Cooper Environmental Services**  35 

# PM QAG **With Module Doors Closed** 

**Nebulizing Module Charge Neutralizer**  **Control Module**  **Porous Metal Ae**  **rosol Focusing Guides** **Cooper Environmental Services** 36



# Focused QAG Aerosol

# New QAG **Total Capture QA Setup** 

**Cooper Environmental Services** 37 Physical Trap Mass Flow

Meter Valve Pump QAG To Control Box Charge Neutralizer Drying Chamber

Heater Make up Air

Filter Holder 

## To **tal Capture**  **Filter**

# Example PM CEMS Interface Setup

**Cooper Environmental Services** 38

**Mass Flow M**  **eter Dilution**  **Ai r**  **PM**

**Filter**

**Exhaust PM Filter**  **Pump PM CEMS Probe**  **Ai rflow**  **Same Location as To**  **tal Capture T**

**est Filters** 

# New QAG **Laboratory Spiking**  **of**

**TSI/MC DustTrack** 

**Cooper Environmental Services** 39 **TSI/MC CEMS QA**  **G PM CEMS**  **Interface QA**  **G Nebulizer Module**  **QA G**  **Control Module**

**QA G**  **Probe Cov er** 

# Laboratory **Spiking of TSI/MC** 

**DustTrack with New QAG** 

**Cooper Environmental Services** 40 

### Y = 1.17 **– 0.80**  **R squar ed**  **= 0.999**



# Fa **ctor y Calibr**  **at ion** 

# On **- Stack Field Validation/QA**  **Setup**

**To tal captur**  **e filter holder** 

41 **Cooper Environmental Services**

# Initial QAG On **- Stack Field Linearity**  **(Total Capture vs**  **QAG) y = 0.968x**  **+ 0.186 R2 = 0.991** 

**0 2**  **4 6**  **8 10**  **12 14**  **16**

**0 2**  **4 6**  **8 10**  **12 14**  **16 T** **o t** **a l** **c a** **p t** **u r** **e C** **o n** **c .** **( m** **g /** **s c** **m )** 



## QAG Conc. (mg/scm) 

# N = 16

42 **Cooper Environmental Services**

# QAG On **- Stack Field QA**  **Total Capture Percent Recovery Recovery at Different Concentrations**   

## 3.5 mg/ **dscm 99.3%**   

## 6.5 mg/ **dscm 102%**   

## 13.0 mg/ **dscm 99.3%**  

# Recovery Over 14 Days (N = 5) **97.6 ±**  **2.8**

**Cooper Environmental Services** 43

# Summary **of QAG On**  **- Stack**  **Field Tests Key Parameters**  **Goal Actual**   

## Traceable **to NIST standards**  **Yes Yes**   

## Percent **recovery >98%**  **98.8**  

## Linearity:

– 

## Slope **1.00 ±**  **0.05 0.97** 

– 

## Intercept (mg/ **scm )**  **< 0.1 0.19** 

– 

## Correlation **coefficient ≥0.95**  **0.99**  

## PM Range (mg/ **scm ):**  **>12 >14**   

## Repeatability **(14 days) 10%**  **8.4%**

44 **Cooper Environmental Services**

# QAG **On -**  **Stack Field Evaluation**  **Setup**

45 **Cooper Environmental Services**

# On **- Stack**  **Field study setup** 

**Thermo Interface PCME Interface** 

**PM CEMS** 

46 **Cooper Environmental Services**

# QAG **Field Summary** 

#  **QAG setup**  **and QA took 2 days** 

#  **98% average PM**  **recovery over 14 days**  

#  **Recovery was**  **stable over 14 days**  

#  **Generated nominal**  **PM Concentration**  **levels at 0, 3.5, 6.5, and 14.5 mg/scm**  

#  **QAG interfaced/challenged**  **4 different PM**  **CEMS probes**  **with minimal**  **modifications**

47 **Cooper Environmental Services**

# Future Developments **& Applications**
 

## Optimiz **e QAG to better simulate**  **stack aerosol**   

## Validate QAG **- Based alternatives**  **to PS -**  **11, etc.**  

## Apply QAG to Method 301 alternative **method validation to**  **meet Non**  **- Mercury HAP Metal**  **compliance demonstration**   

## Filter spiking for method validation **– Jeff Ryan**  

# Key 2011 Method 301 Modifications
 

## No longer 

# requires **comparison to RM Methods**  

## QAG **can be used to determine precision,**  **bias and linearity with dynamic spiking and sequential sampling**   

## Method 301/QAG **~ Effort required to conduct a Performance**  **Specification** 

# Examples **of Possible QAG**  **Applications Cooper Environmental Services**  48