FTIR CEM Performance Specification

Modification Considerations

EPA/ICAC Emissions Measurements

Roundtable Meeting

September 17, 2013

Peter G. Zemek
MKS Instruments

Marty Spartz MKS Instruments

Prism Analytical On-Line Product Group

Technologies 2 Tech Drive, Suite 201

MultiGas FT-IR Andover, MA 01810
Automated HCl CEM Systems Tel: 978-482-5364
 Performance Specifications for
FTIR CEMS

PERFORMANCE SPECIFICATIONS:

PERFORMANCE SPECIFICATION 15 - FOR EXTRACTIVE FTIR

CONTINUOUS EMISSIONS MONITOR SYSTEMS IN STATIONARY
SOURCES
RM RATA RUN COMPARISONS FOLLOW PERFORMANCE
SPECIFICATION 2SPECIFICATIONS AND TEST PROCEDURES FOR
SO2 AND NOX CONTINUOUS EMISSION MONITORING SYSTEMS IN
STATIONARY SOURCES
DRAFT PERFORMANCE SPECIFICATION 18 AND TEST PROCEDURES
FOR HCL CONTINUOUS EMISSION MONITORING SYSTEMS IN
STATIONARY SOURCES
 FTIR Reference Methods for
CEMS
REFERENCE METHODS: TO VALIDATE UPON INSTALLATION OR RATA

METHOD 301FIELD VALIDATION OF POLLUTANT MEASUREMENT

METHODS FROM VARIOUS WASTE MEDIA
METHOD 320* - MEASUREMENT OF VAPOR PHASE ORGANIC AND
INORGANIC EMISSIONS BY EXTRACTIVE FOURIER TRANSFORM
INFRARED (FTIR) SPECTROSCOPY (INCLUDES FTIR PROTOCOL)
METHOD 321** - MEASUREMENT OF GASEOUS HYDROGEN CHLORIDE
EMISSIONS AT PORTLAND CEMENT KILNS BY FOURIER TRANSFORM
INFRARED (FTIR) SPECTROSCOPY
METHOD 318 - EXTRACTIVE FTIR METHOD FOR THE MEASUREMENT
OF EMISSIONS FROM THE MINERAL WOOL AND WOOL FIBERGLASS
INDUSTRIES
ASTM D6348-12 STANDARD TEST METHOD FOR DETERMINATION OF
GASEOUS COMPOUNDS BY EXTRACTIVE DIRECT INTERFACE
FOURIER TRANSFORM INFRARED (FTIR) SPECTROSCOPY.

*1 of 2 RM for EGU
**Only acceptable RM for Portland Cement MACT
 Confusion and Errors
Between Methods/Specifications

?TEST METHOD 320 - MEASUREMENT OF VAPOR PHASE ORGANIC AND

INORGANIC EMISSIONS BY EXTRACTIVE FOURIER TRANSFORM INFRARED
(FTIR) SPECTROSCOPY - (This is already a self-Validating Compliance
(Reference) Method with its own QA/QC)

PS-15 states- For System Validation, Since FTIR CEMS have

multicomponent capability, it is possible to perform more than one RM
simultaneously, one for each target analyte.

Interpretation, If use EPA M320, 321, 301, etc, ASTM D6348 you can RATA
w/FTIR
 Comparison PS/RM for FTIR
Parameter PS-15 PS-18 Draft EPA M320 ASTM D6348-03,12 M301

Dates Promulgated Feb 2000 Feb 2014? Feb 2000, Protocol 1995 Feb 2003, '10,'12 June 1991, '04, '11
Cal Gas Direct Accuracy 5%, 7% w/bias NA 2% or 5% 5% NA
Dynamic Spike Recovery +-30% +-15% +-30% +-30% +-30% to 50%
# of Spike Runs 24 (M301), 3 (M320) 6? 3 1 24

Interference test No (just mentions them) <3% span combined No bias check No

20% (RM in denom) 15%

(Emiss Limit in denom)
SO2 (10% Emiss Limit) Acc 10%
Method Relative Accuracy (DQO) PS2 < 15% 2.5% 2% Prec 5% t-test comparison
">30% is not valid
method", but apply a corr
"Bias" Correction Yes ? factor May Yes, above 10%
3 pt, <5%, intercept
Calibration Error Test 10% <15% of Span No One Knows No depends on RM
YES (All Compounds) Yes, but select
Dry Cal check Daily ? Yes, but select set..no HCl set..no HCl depends on RM
7-Day Drift No 3% of span/day No No No
Detector linearity 3 point, 2%/5% yes? 3 point, 2%/5% 3 point, 2%/5% NA
MDC#1, MDC#2*,
Detection Limitations depends on RM LOS, MDC#3, LOD MAU, OFU MDC#3 PLQ*, LOD

Cell Volumes per Data Pt. 10 spiking, 5 sample 5? 5 5 NA

Conf Intervals depends on RM 99%? 95% 95% 99% LOD, 95% t-test
* Reviewed/Revised
Manual Data Verification NA (Yes RATA RM) NA (Yes RATA RM) YES YES NO

Calibration Transfer Standard (CTS) 5% ? 5% 5% NA

*MDC #2 = PLQ (no longer used)

 FTIR is a Special Case
Most of the Methods/PS were written with traditional CEMs in mind

Traditional CEMS/GC are destruction techniques and as such change

daily due many factors, i.e. ionization plates, fuel, gas conditioning

FTIR is an optical technique where sample is not changed in any way

Therefore, it DOES not change unless it is not operating properly

If one compound does not perform 1 day, all of the compounds will be
biased, but if one compound does perform, they will all perform

EPA has stated, If EPA library reference spectra are not available,
use calibration standards to prepare reference spectra according to
Section 6 of the FTIR Protocol

EPA is stating that, if the spectra are good, the numbers will be
good Important point! Initial certification pass = very little on-
going QA/QC needed
FTIR Do not Drift or Change
Response

MKS Instruments 7
 FTIR has come far (errmid)

FTIR Requirements for CEM has been burdened to the point

that much of the daily QA/QC and initial certification is
unwarranted and will prevent its use in industry as newer
technology QA/QC becomes more efficient (FTIR Rules
Outdated)-Discriminatory
40 CFR Parts 72 and 75 [FRL60078] RIN 2060AG46 Acid Rain Program;
Continuous Emission Monitoring Rule Revisions
75.33(d) would make it a violation of the primary measurement requirement 75.10(a) to
allow the annual monitor data availability to drop below 80.0 percent for SO2, NOX, or
CO2. (Docket A9735, Item IIB16).
Consistent with current practices, the Agency would continue to expect CEMS to achieve
high data availability.., monitor downtime in excess of 5.0 percent may warrant appropriate
investigation and follow-up activities.

Uptime = Credits = $
 Current PS-15 Requirements
not necessary today
PS-15 Required Reason Whats Changed
Detector Linearity Manufacturer performed New Boards and Algorithms
and Performance Based

Cell leak test CTS will determine if Redundant

leaks present
X-axis accuracy Will fail relative accuracy Only 1 manufacturer has a problem
and dynamic spike test

Resolution Check Will fail relative accuracy Redundant

and dynamic spike test

Audit Spike Dynamic spike with Used in place of Dynamic Spike

Audit is Good if conc
correct
100%T Line 5% Req Current algorithms Faster computers/More stabile
correct for this Temperatures
Audit Spectra Silly Not possible unless all spectral
functions are provided
Submit Spectra for Analysis Really? Need multiple soft wares and training.
to EPA No one else is required to do this
Signal to Noise Calculation Meaningless Will be determined by LOD/LOS

Daily Dry Zero, Mid, Span or Does not represent Need to measure HCl, NH3, CH2O, HF,
ALL TARGET COMPOUNDS actual target compound HCN and other polar species at very
response (Need H2O), low levels
Contaminates System

If dry cal gas spans/etc are required, then certain cmpds will take hours
Cement Plant CEM Data with no
Filter Change/Back-Purge for
3 Months- End of Period Test

A steady-state is reached until the moisture changes

Once dry, HCl is liberated in very high concentrations
 Recommended On-Going PS-15
On-Going QA/QC Performance Specifications (After Initial Installation
Certification):

QA/QC Checks that should be required on a daily basis or other basis are as
follows:

Background Times are at the Discretion of Manufacturer

Daily CEM System Zero (2% of 1st Span)
Daily - CTS indirect gas check, preferably using Ethylene or dilution of
CO2/H2O (System Check)
Daily - Dynamic spike check based on a minimum of at least 1 target
compound. (Preferably the component that is expected to be the hardest to
recover during the dynamic spiking test due to its chemical or reactive nature,
adherence to the wetted components, or has the highest spectral
interferences) (20% Recovery at 10% DF @ 50% expected or 5x MDL *
Special Cases Options should exist for HCl/NH3 streams)
Semi-Annual - RATA test with an acceptable reference method (Beware
traditional CEMs such as Chemiluminesense or CO/CO2
Calibration Transfer Standard
(CTS)
The FTIR CEM, once validated is accurate and precise if
functioning properly
Indirect CTS gas checks the instrumentation and sampling
system functionality

Used to determine:
Leaks within the sampling system
T95 Rise and Fall times
Instrument performance results for
Resolution
Signal to noise ratio (SNR)
Linearity
Frequency accuracy
Sample cell path-length
Instrument Line Shape (ILS)
Noise Equivalent Area (NEA)
Detection Limit (DL)
Spectral limits
Ensures that the correct Analytical Method is loaded
CTS Ethylene Wet or Dry
Detection Limits - Which One?
Needs Modification and
Consistent Terminology
1 set of data

MKS Instruments 14
 PS-15/PS-18 Detection Limitations
Modifications Updating (~LOS)
M301 The PLQ is a limit determined by the standard deviation of an estimate
of a concentration; if the standard deviation of the estimate exceeds a
threshold, then that estimate is unacceptable. The LOD is a limit determined
by the estimate of the concentration itself (therefore PLQ = MDC#2)

The LOD is clearly a threshold. An estimate that cannot be distinguished from

one resulting from a blank sample is unlikely to provide meaningful results.
1. Prepare 7 samples standard LOD1
HCl Std Dev as f(conc)
2. Std Dev = S1
0.03
3. LOD0 = 3S1
4. LOD1 2LOD0, then S0 = S1 0.025
5. LOD1 > 2LOD0, then: 0.02
y = 0.0017x + 0.0201
6. 2 additional standards <LOD1 0.015 Std as f(c)
Linear (Std as f(c))
7. 7 samples std dev each = S2, S3 0.01
LOD = 0.02 ppm
8. Plot S1, S2, S3 as f(conc) 0.005
9. Draw Regression Line 0
10. Extrapolate to zero 0 0.2 0.4 0.6 0.8 1 1.2
Span? Must be Defined for FTIR

Each Cal
Point is
a Span

Multi-Span
in 1 Method
Must Define
Span PS15
 For Your Consideration?
Typical dynamic spike involves diluting the CEM sample flow by 10% to get 50% addition
5 ppm native, use 25 ppm HCl cylinder diluted 10x = ~2.5 ppm added to 5 ppm native
Theoretical CEM response = ~ 7.5 ppm HCl

Recovery vs. Spike Level ASTM allows

High NH3 (5 ppm native HCl) up to150% of
slip (10 percent dilution)
Native Conc.
100
90
80
70 70
% Recovery

60
50 8.1 ppm added to 5 ppm native HCl
4040 Greater than 50% Rule (162%)
30 Matrix Effect - is it wrong?
20
10
0
2 25 52 81 102 152 202 252 302
Spike Level (ppm)

Fail because not 10% DF? Why? Still reports 5 ppm at stack correct
50% of Native Rule or 10% Flow Rule Wrong?
 Recommendations
Rewrite/Modify/Update PS15

Allow substitution of ASTM D6348-12 for M320 or

Correct/Modify/Update M320

Standardize on Terminology

Establish a sub-committee of outside interested

parties/stakeholders made up of experienced field
technicians/scientists/engineers in FTIR to provide
recommendations to EPA on changes to PS15 and M320

Make it understandable to the layman

Try to keep the Politics Out of the Science

MKS Instruments 18