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# Sour **ce Evalua tion**  **Society Mar**  **ch 28, 2013** 

**Cooper Environmental Services LLC** 

# Cooper **Environmental Services LLC** 

**Jo hn A. Cooper**  **Po rt**  **land, Or eg**  **on Cooper Environmental Services**  2



# Outline

 

# HAP Metal Emissions  

# Uncertainties **in Metal Emissions**

– 

# Actual **emissions**

– 

# Measured emissions  

# Session 9: Uncertainty Details **Applicable Sources :**  **Incinerators Coal**  **- fired Boilers**  **Smelters Mills**  **Mineral Processing Kilns**  **Plating Portland Cement**  **We lding** 

# Key HAP Metals are Different
 

# They typically **occur at trace levels**  **in feed, fuel, additives and emissions**   

# Concentrations and potency are highly variable  

# May partition betw **een vapor and particulate**  **phases to varying degrees depending on source chemistry** 

**Cooper Environmental Services** 3**Cooper Environmental Services** 4



## EP **A -**  **Designated HAP**

**Metals**
**Element Cancer**  **To xic**  **PM 2.5**  ***** **NAAQS Tr**  **ansition Metal** ** **Antimony √**  **Arsenic √**  **√ √**  **Beryllium √**  **√ Cadmium**  **√ √**  **Chr om**  **ium √**  **√ √**  **√ Cobalt**  **√ √**  **Lead √**  **√ √**  **Manganese √**  **√ Mer**  **cury √**  **Nickel √**  **√ √**  **√ Selenium**  **√ √**  

## Other **Non -**  **HAP**

**Metals of Concern**  **Thallium √**  **√ Va**  **nadium √**  **√ √**  **Ir on**  **√ √**  **√ Copper**  **√ √**  **√ Molybdenum**  **√ √**  **Zinc √**  ***Identified as a significant**  **contributor t**  **o observed PM health effects.**  Generate**  **reactive oxygen species, which cause damage to cell structur**  **es.**

# Data Quality Objectives of **Emissions Monitoring for Metals**

**Cooper Environmental Services** 5 Congress EP

A § 11 2 of CAAA (1990) Protect Public Health

with Adequate Margin of Safety MACT
Residual Risk

PM Health Ef

fects Metals are a significant contributor to PM Health Ef

fects**Cooper Environmental Services** 6



# EPA Has Said:
 **Monitoring is part of the emissions reduction and control process**  

#  **Uncertainty minimiz**  **ation is best achieved w ith**  **more measurements of emissions**  **Reducing** 

# uncertainty **in compliance measurements produces quantifiable benefits**  

# Knowing **sources of uncertainty and their**  **general magnitude is important to**  **reducing those uncertainties.**

# Examples **of Uncertainties**
 

# Typically **Small (<10%)**  

# CEMS single point sampling  

# FRM sample recovery  

# Deviations from Isokinetic sampling  

# Analytical sensor/procedure  

# Potentially **Large (~100+%)**   

# Feed/fuel composition variability  

# Process/aerosol **variability**  

# Probe loss variability  

# Surrogacy assumptions **Cooper Environmental Services** 7**Cooper Environmental Services** 8 

# Actual Metal Emissions Variability **and Measurement Uncertainty** 

Process Feed

Fuel Emissions Controls

Additives 

# Stack Emissions

Metals Emissions Measurements 

## Differences betw **een measured (PM or Metals) and**  **actual metals emissions Cooper Environmental Services**  9



# Example: HWI Compliance **Demonstration**  **Initial Tests**

**– Performance or**  “ **Trial Burn** ”

– **Determine transmission efficiency (T)**  **Metal spiking (F s**  

# )  **Method 29 measurements (C=M/U)**

– **Define plant operating parameters** 

#  **Continued compliance demonstration** 

– **Maintain plant operating parameters**

– **Monitor Feed Rate (FC i**  

# ) 

#  **Periodic** “ **Stack Tests**  ”

**- years betw**  **een tests** **Cooper Environmental Services** 10



# HWI Stack **Emissions Model** 

**Emissions Feed Rate** 

**Tr ansmission**  **Efficiency As**  **sumptions:**

**- Tr**  **ansmission efficiency is constant and independent** 

**- Metal feed rate is accurately**  **know n**  

# CVA TF E  

**Stack**

**Concentration Ve**  **locity Area** **Cooper Environmental Services** 11



# Assumed/Calculated **Concentration of i th**  

# Metal



# A V T F C o

o i o i o i 

# 

**Metal Feed Rate i**  **th** 

## Metal T **ransmission Efficiency**  **(Performance tests) Current Operating Conditions (**  ° **) Stack V**  **elocity &**  **Area Cooper Environmental Services**  12 

# Calculated **Concentration Based on**  **Feed and Performance Test**  **Data**



# C i o 

#  F o 

# C

i f 

# F s t 

# C i s 

#       V t 

# V o 

#       M i t 

# U t 

#       S g 

# S f 

# R e 

## Measured **Assumed = 1.0**

**Gas Sampling Bias Feed Sampling Bias**  **Efficiency Representation Bias** 

**Method 29 Cooper Environmental Services**  13 

## Uncertainty ( **σ ) in Current**  **Calculated Gas**  **Concentration for i th**  

## Element

2 1 2 2 2 2 2 2 2 2 2 2 C 2 

## σ σ σ σ C σ σ
                                                                                                         



e R f S g S t U t i M o V t V s i C t s F f i o F o i C



## R σ S σ S σ U σ M σ V V C F F C

e f g t t i o t s i t s f i o o i 

## 

**1 to 10% ~100+%**  **1 to 10% Cooper Environmental Services**  14



# HWI Uncertainties  **Measured Parameters (<10%**  **, small)**  **Bias**

**– Sampling Stack Gas (<10%**  **, small)**
 **Bias**

**– Sampling feed, fuel, etc. (~100+%, large)**   **Bias -**  **Representation of process, controls, etc. during trial**  **burn testing (~100+%**  **, large)**  **Deviations from Assumptions (~100+% , large)** 

– **PM surrogate for metals emissions**  Small



# Large **~99% of Uncertainty in**  **Actual Metals**  **Emissions is Due to These Large Sources**

# Estimating **Magnitudes of Variability and**  **Metals Emissions Uncertainties** 

**- EXAMPLES**  ****

**Cooper Environmental Services** 15**Cooper Environmental Services LLC** 16 **N**

**E W** 

**S** 

## E. St. **Louis Monitor**  **3 AM 5 AM**  **(0.65)**
**7 AM (0.58)** 

**9 AM (0.76)**  

## 11 AM **(2,345) 1 PM**  **(173) 3 PM** 

**(11) 5 PM**  **(2.4)**



# An Example **Wi nd Dir**  **ection (Concentr**  **at ion,**  **ng /m**  **3** 

# ) 

# Ar **senic Cooper Environmental Services LLC**  17 

# E. **St. Louis Monitoring Site**

**223** ° **Inciner at**  **or Ti**  **me WD**  **WS As**  **n g/**  **m3 9**  **118 0.**  **9 0.**  **76 11**  **223 2.**  **4 2,345.00**  **13 275**  **3. 7**  **173.00** 

# Sc **hools Monitor** 

**WIND DIRECTION DURING**  **MAXIMUM ARSENIC**  **IMP**

**AC T**  

# If **y ou can see or**  **measur e it, y**  **ou can fix it.** **Cooper Environmental Services** 18 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 **ur ly**  **L ea**  **d (1**  **1/23/09) Two thir**  **ds of total lead** 

24
- hour average = 4.6 μg/m3 

### Wi **nd Dir**  **ection Cooper Environmental Services**  19 Pb Mass No. Samples 16% of samples represent 87% of Pb Mass One 1
- hour sample represents >1 1% of Pb mass

# Probe **Losses And BAM**  **- Based**  **PM**

**CEMS Correlations** 

20 **y = 1.07x -**  **2.96 R2 = 0.985** 

0.0 20.0 40.0 60.0 80.0

0.00 20.00 40.00 60.00 80.00**Q A** **G C** **o n** **c (** **m g** **/ w** **s c** **m )** 

**Beta # 1 Conc (mg/wscm) QAG**  **Corr elation**  **y = 1.05x -**  **1.35 R2 = 0.994** 

0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0

0.00 20.00 40.00 60.00 80.00**Q A** **G C** **o n** **c (** **m g** **/ w** **s c** **m )** 

**Beta # 2 Conc (mg/wscm) QAG**  **Corr elation** 

**y = 1.06x -**  **0.364 R2 = 0.993** 

0.0 20.0 40.0 60.0 80.0

0.00 20.00 40.00 60.00 80.00**Q A** **G C** **o n** **c (** **m g** **/ w** **s c** **m )** 

**Beta # 3 Conc (mg/wscm) QAG**  **Corr elation**  **Slope CEMS**  **QA G**  **PS -**  **11 R**  **2 1**  **1.07 1.17**  **>0.98 2**  **1.05 1.19**  **>0.98** 

## 1 **2**

**3**

**3 1.06**  **1.63 >0.98** 

# QAG **Calibration of BAM PM CEMS** 

**Cooper Environmental Services** 

# C **5** 

# = (1+K) **C c**  

# +B **K = C**  **p** 

# /C **c Proportional Bias Factor Constant Bias T**  **erm Probe Loss Conc.**

**M5 Measured Conc. CEMS Measured Conc.** 

## PS **- 11**  **CALIBRA**

**TION**

# Light Scattering **PM CEMS on HWI** 

**Cooper Environmental Services** 22 **Slope =** 

# - **0.27** 

### Method 5 vs Sigrist CEMS

**QAG vs Sigrist CEMS** 

# Comparison **of Light Scattering PM CEMS** 

**(PS -**  **11 Calib.) with Series of M5B**  **Measurements (Wet Stack) CEMS**  **Slope Inter**  **cept R**  **2** 

# 1 

# + 0.19 +2.7 0.74 2 

# + 0.24 +1.8 0.80 M5B 0.36 +6.2 0.38

**Cooper Environmental Services** 23 

# % M5B Probe Deposit = 95%**Cooper Environmental Services** 24 

# PM May Be Dominated by Sources **Independent of HAP Metal Sources**

Process Feed

Fuel Controls

Additives 

# Stack Emissions

FGD Scrubber Slurry PM can be dominated by slurry blow
- by

# Coal **- Fired**  **Boiler –**  **Wet Stack**

**Cooper Environmental Services** 25 1

0 0

# Hypothetical Variability of PM and HAP Metal

Emissions from CFPP

Ti me (months)PMorMetalConc.(μg/m3) 10 5 10 4 10 3 10 2 10 1 10 0 10 - 1 10 - 2 10 - 3 **Coal Blend**

**Changed Coal fr**  **om**

**differ ent seam**  **Additive** PM

Se Co, Cr

# 95% CONFIDENCE **INERVALS FOR**  **METALS**

**Cooper Environmental Services** 27 10 - 1 10 0 10 1 10 2 10 3 10 4 10 5



## Confidence Interval (μg/m **3** 

## ) HWI PM HWI Metals

CFB PM
CFB Metals 

### Data **Quality**

**Objectives: Process Optimization,**  **Compliance or Health?**

PM 2.5

# Estimated 

# Metals **Uncertainties for Compliance** 

**Demonstration Options** 

**Options Small** 

**Sour ces**  **Probe**

**Deposit** 

## * **Process**

**Va riability**  **Metals**

**Surr ogacy**  **To tal** 

**Uncertainty MM CEMS**  **< 5% < 20%**  **< 10% -------------**  **~30% PM CPMS**  **(w ith M29)**  **<5% <20%**  **> 100% ~300%**  **> 400%**
**Periodic M29 15%**  **------------**

**- > 300%**  **------------- > 300%**  **PM CEMS**

**-- BAM**  **< 5% < 20%**  **< 10% ~1000%**  **> 1000%** 

**-- L. Scat**  **< 5% < 20%**  **~ 50% ~1000%**  **> 1000%**  **PM CPMS (w**  **ith M5) <5%**  **<20% >50%**  **~1000% >**  **1000% Periodic M5**  **15% ------------** 

**- >300%**  **~1000% >**  **1000%** *** Due to Probe deposit variability**  **. Cooper Environmental Services**  29 

# Conclusions **and Recommendations**
 

## Focus on obtaining a more representative **sample by developing a probe with minimal**  **PM loss**

**– <5%**  **in either wet or dry stacks**   

## Uncertainty minimization **is best achieved with** 

# more, **direct measurements** 

**– Multi**  **- Metals**  **CEMS**  

## If the first two can be achieved, concern for process **variability is minimiz**  **ed Focus on largest sources of uncertainty** 

• **Process variability**

• **Probe loss variability**

• **Surrogacy a**  **ssumption Cooper Environmental Services**  30



# Clear Improvements **A century**  **o f improvements**  **– Pittsburg, P**  **A, USA 1925** 

**1957**

**1998**

**From A WM**  **A files**  

# If **y ou can**  **see or measur**  **e it, yo**  **u can fix it.** **Cooper Environmental Services** 31 

# QUESTIONS **?**