FTIR CEM Performance Specification

Modification Considerations

MKS Instruments

On-Line Product Group

2 Tech Drive, Suite 201

Andover, MA 01810

Tel: 978-482-5364

MultiGas™ FT-IR

Automated HCl CEM Systems

EPA/ICAC Emissions Measurements

Roundtable Meeting

September 17, 2013

Peter G. Zemek

MKS Instruments

Marty Spartz

Prism Analytical

Technologies

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 2—SPECIFICATIONS 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 301—FIELD 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

Method Relative Accuracy (DQO)

20% (RM in denom) 15%

(Emiss Limit in denom)

SO2 (10% Emiss Limit)

PS2 < 15% 2.5% 2%

Acc 10%

Prec 5% t-test comparison

"Bias" Correction Yes ?

">30% is not valid

method", but apply a corr

factor May Yes, above 10%

Calibration Error Test 10%

3 pt, <5%, intercept

<15% of Span No One Knows No depends on RM

Dry Cal check

YES (All Compounds)

Daily ? Yes, but select set..no HCl

Yes, but select

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

Detection Limitations depends on RM LOS, MDC#3, LOD MAU, OFU

MDC#1, MDC#2*,

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 (err…mid)

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

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.

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 A–97–35, Item II–B–16).

40 CFR Parts 72 and 75 [FRL–6007–8] RIN 2060–AG46 Acid Rain Program;

Continuous Emission Monitoring Rule Revisions

Uptime = Credits = $

Current PS-15 Requirements

not necessary today

PS-15 Required Reason Whats Changed

Detector Linearity Manufacturer performed

and Performance Based

New Boards and Algorithms

Cell leak test CTS will determine if

leaks present

Redundant

X-axis accuracy Will fail relative accuracy

and dynamic spike test

Only 1 manufacturer has a problem

Resolution Check Will fail relative accuracy

and dynamic spike test

Redundant

Audit Spike Dynamic spike with

Audit is Good if conc

correct

Used in place of Dynamic Spike

100%T Line 5% Req Current algorithms

correct for this

Faster computers/More stabile

Temperatures

Audit Spectra Silly Not possible unless all spectral

functions are provided

Submit Spectra for Analysis

to EPA

Really? Need multiple soft wares and training.

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

ALL TARGET COMPOUNDS

Does not represent

actual target compound

response (Need H2O),

Contaminates System

Need to measure HCl, NH3, CH2O, HF,

HCN and other polar species at very

low levels

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

MKS Instruments 14

1 set of data

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.

y = 0.0017x + 0.0201

0

0.005

0.01

0.015

0.02

0.025

0.03

0 0.2 0.4 0.6 0.8 1 1.2

HCl Std Dev as f(conc)

Std as f(c)

Linear (Std as f(c))

LOD = 0.02 ppm

1. Prepare 7 samples standard LOD1

2. Std Dev = S1

3. LOD0 = 3S1

4. LOD1 ≤ 2LOD0, then S0 = S1

5. LOD1 > 2LOD0, then:

6. 2 additional standards <LOD1

7. 7 samples std dev each = S2, S3

8. Plot S1, S2, S3 as f(conc)

9. Draw Regression Line

10.Extrapolate to zero

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

0102030405060708090

100

2 52 102 152 202 252 302

% R

ecov

ery

Spike Level (ppm)

Recovery vs. Spike Level (5 ppm native HCl)

(10 percent dilution)

70

81

8.1 ppm added to 5 ppm native HCl

Greater than 50% Rule (162%)

Matrix Effect - is it wrong?

High NH3

slip

25

Fail because not 10% DF? Why? Still reports 5 ppm at stack – correct

50% of Native Rule or 10% Flow Rule Wrong?

40

ASTM allows

up to150% of

Native Conc.

Recommendations

MKS Instruments 18

• 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