EPA 600/R-17/190 August 2017 j www.epa.gov/research
U ited States
En irorimental Protec ion
Agency
Laboratory Validation of Four Black Carbon Measurement Methods for
Determination of the Nonvolatile Particulate Matter (nvPM) Mass
Emissions from Commercial Aircraft Engines
Office of Research arid Development
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oS>A
EPA 600/R-17/190
Laboratory Validation of Four Black Carbon
Measurement Methods for Determination of the
Nonvolatile Particulate Matter (nvPM) Mass
Emissions from Commercial Aircraft Engines
Final Report
John S. Kinsey
U.S. Environmental Protection Agency
Office of Research and Development
National Risk Management Research Laboratory
Research Triangle Park, NC 27711 USA
and
Jelica Pavlovic
Oak Ridge Institute for Science and Education
Assigned to U.S. Environmental Protection Agency
Office of Research and Development
National Risk Management Research Laboratory
Research Triangle Park, NC 27711 USA
June 2017
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Notice
The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development's (ORD), conducted this investigation with contractor support through Contract
EP-C-09-027 with ARCADIS-U. S., Work Assignments 1-53, 2-53, 3-53, 4-53, 5-53, and 6-53
as well as Contract EP-C-15-008 with Jacobs Technology Inc., Work Assignments 0-019 and 1-
019. The work was supported largely by Federal Aviation Administration Interagency
Agreement No. DTFAWA-10-X-00020, with supplemental funding provided by EPA's Office of
Transportation and Air Quality and National Risk Management Research Laboratory. This report
has been peer and administratively reviewed and has been approved for publication as an EPA
document. The views expressed in this report are those of the authors and do not necessarily
reflect the views or policies of EPA. Mention of trade names or commercial products does not
constitute an endorsement or recommendation for use.
Questions concerning this document or its application should be addressed to:
John Kinsey
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency (MD-E343-02)
109. T.W. Alexander Drive
Research Triangle Park, NC 27711
Phone: (919) 541-4121
E-mail: kinsey.john@epa.gov
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Table of Contents
Notice i
List of Tables iv
List of Figures v
Acronyms and Abbreviations vi
Executive Summary x
1 Introduction 1
2 Candidate Methods 3
2.1 Carbon Burn-Off Method 3
2.2 Multi-angle Absorption Photometry 6
2.3 Laser Induced Incandescence 8
2.4 Photoacoustic Soot Sensing 10
3 Experimental Apparatus 12
3.1 General Experimental System Setup 12
3.2 Aerosol Generator System 16
3.2.1 MiniCAST 5201 and Primary Diluter 16
3.2.2 Catalytic Stripper 18
3.3 Instrumentation Suite 20
3.3.1 Thermal-Optical Carbon Analyzer 20
3.3.2 SuperMAAP 25
3.3.3 LII300 29
3.3.4 Micro Soot Sensor (MSS) 31
3.4 Reference Filter Sampler 32
3.5 Supporting Equipment 33
3.5.1 3936 Scanning Mobility Particle Sizer 33
3.5.2 PM2.5 Cyclone Preseparator 33
3.5.3 Personal Data Acquisition System 34
4 Experimental Procedures 35
4.1 Experimental Design 35
4.2 Standard Operating Procedures 36
4.3 General Operating Procedures 37
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4.4 Data Reduction 41
4.4.1 Gravimetric Method 41
4.4.2 NIOSH 5040 Method 42
4.4.3 SuperMAAP 42
4.4.4 Lll 43
4.4.5 AVLMSS 43
4.5 Data Post-Processing 44
4.5.1 Lll 44
4.5.2 SuperMAAP 44
5 Results and Discussion 46
5.1 Catalytic Stripper Results 46
5.2 Results Without Catalytic Stripper 54
5.3 Combined Experimental Results 61
5.4 Observations 64
6 Quality Assurance and Quality Control 66
6.1 Assessment of Data Quality Indicator Goals 66
6.1.1 Temperature and Pressure 66
6.1.2 Flow Rate 67
6.1.3 PM Mass 67
6.1.4 OC/EC Concentration 67
6.2 Instrument Calibrations 68
6.2.1 Sunset TOT Carbon Analyzer 68
6.2.2 SuperMAAP 68
6.2.3 AVLMSS 69
6.2.4 Lll 300 69
6.2.5 Gravimetric Method 69
6.2.6 Ancillary Equipment 69
6.3 Quality Control Procedures 69
6.3.1 Flow Tunnel 69
6.3.2 NIOSH 5040 70
6.3.3 Gravimetric Method 70
6.3.4 SuperMAAP 71
6.3.5 Lll 300 71
6.3.6 AVLMSS 71
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7 Conclusions and Recommendations 73
8 References 75
Appendix A: Operation of the Jing MiniCAST Model 5201 (Prototype) Black Carbon
Aerosol Generator (Real Soot Generator) A-1
Appendix B: Sampling and Measurement of Nonvolatile Particulate Matter Mass
Using the Thermal/Optical Transmittance Carbon Analyzer B-1
Appendix C: Development of an Improved Multi-angle Absorption Photometer
(SuperMAAP) C-1
Appendix D: Measurement of Nonvolatile Particulate Matter Mass Using the Modified
Multi-angle Absorption Photometer (MAAP)—Thermo Fisher Scientific D-1
Appendix E: Measurement of Nonvolatile Particulate Matter Mass Using the LI I 300
Laser-Induced Incandescence Instrument E-1
Appendix F: Measurement of Nonvolatile Particulate Matter Mass Using the AVL 483
Micro Soot Sensor Photoacoustic Analyzer with AVL Exhaust Conditioning Unit F-1
Appendix G: Sampling and Measurement of Nonvolatile Particulate Matter Mass
Using the Filter-Based Gravimetric Method G-1
Appendix H: Operation of the TSI Scanning Mobility Particle Sizer (SMPS) Model 3936
H-1
Appendix I: Blowers/Pump Calibration Curves 1-1
Appendix J: Experimental Verification of LI I Recalibration and SuperMAAP Flow
Adjustment and Software Changes J-1
Appendix K: APPCD Metrology Laboratory Calibration Reports K-1
List of Tables
Table 2-1. Temperature Profile for the NIOSH 5040 Method Used in this Study 4
Table 2-2. Temperature Profile for the IMPROVE Method 6
Table 3-1. Instruments and Equipment 14
Table 3-2. Software/Firmware 15
Table 3-3. DOC Properties and Dimensions Used in the Catalytic Stripper 19
Table 3-4. Filter Temperatures Measured before Calibration for NIOSH 5040 and
IMPROVE Protocol 24
Table 3-5. Filter Temperatures Measured after Calibration and Software Adjustments 25
Table 4-1. Experimental Matrix 35
Table 4-2. MiniCAST Flow Settings and Blower/Pump Operating Conditions 36
Table 4-3. List of Developed SOPs 37
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Table 5-1. Raw Experimental Data Using Catalytic Stripper 47
Table 5-2. Summary of Final Test Results Using Catalytic Stripper 49
Table 5-3. Raw Experimental Data Without Use of Catalytic Stripper 55
Table 5-4. Summary of Final Test Results Without Use of Catalytic Stripper 57
Table 6-1. DQI Assessment Summary 67
Table 6-2. Certified Weight Verifications 67
List of Figures
Figure 2-1. Thermogram for filter sample containing OC, CC, and EC 5
Figure 2-2. Arrangement of the detectors in the MAAP instrument 7
Figure 2-3. Schematic layout of the Artium LII 300 system 10
Figure 2-4. Principle of (A) photoacoustic measurement and (B) photoacoustic cell
design 11
Figure 3-1. Flow tunnel and associated measurement system 13
Figure 3-2. Sample distribution system to instruments 16
Figure 3-3. (A) Operation principle of the MiniCAST burner and (B) front view of the
MiniCAST prototype used for this study 17
Figure 3-4. MiniCAST, primary diluter, and catalytic stripper installed on the flow 17
tunnel.
Figure 3-5. Components of the catalytic stripper system 19
Figure 3-6. Sunset Laboratory thermal-optical carbon analyzer 20
Figure 3-7. The (A) sample analysis set and (B) calibration set of the Sunset Laboratory
carbon analyzer 22
Figure 3-8. Linear regression results before and after temperature calibration 24
Figure 3-9. Diagram of 5012 MAAP detection chamber 26
Figure 3-10. SuperMAAP configuration 28
Figure 3-11. MAAP software - measurement view 29
Figure 3-12. Major components of the LII 300: (1) self-contained LII 300 instrument and
(2) laser power supply 30
Figure 3-13. (A) AVL MSS model 483 and (B) AVL exhaust conditioning unit 31
Figure 5-1. PM mass concentration plots for experiments with the catalytic stripper based
on Teflon filter results 51
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Figure 5-2. PM mass concentration plots for experiments with the catalytic stripper based
on NIOSH 5040 results 52
Figure 5-3. PM mass concentration plots for target concentrations between 50 and 500
|ig/m3 with stripper based on (A) OC-corrected Teflon filter results and (B) NIOSH 5040
results 53
Figure 5-4. PM mass concentration plots for experiments without the catalytic stripper
based on the OC-corrected Teflon filter results 58
Figure 5-5. PM mass concentration plots for experiments without the catalytic stripper
based on NIOSH 5040 results 59
Figure 5-6. Mass concentration plots for target concentrations between 50 and 500 |ig/m3
without use of stripper based on (A) OC-corrected Teflon filter results and (B) NIOSH
Method 5040 60
Figure 5-7. PM mass concentration plots for all experiments based on all OC-corrected
Teflon filter results 61
Figure 5-8. PM mass concentration plots for all experiments based on all NIOSH 5040
EC results 62
Figure 5-9. Mass concentration plots for target concentrations between 50 and 500 |ig/m3
for all experiments based on (A) OC-corrected Teflon filter results and (B) NIOSH
Method 5040 63
Figure 5-10. Intercomparison of measurement methods against data from the AVL MSS 64
Acronyms and Abbreviations
AAFEX
Aviation Alternate Fuels Experiment
AIR
Aerospace Information Report
APPCD
Air Pollution Prevention and Control Division (EPA)
ARI
Aerodyne Research, Inc.
ARP
Aerospace Recommended Practice
atm
atmosphere(s)
BC
black carbon
°C
degree(s) Celsius
c
concentration, also carbon
CBC
concentration black carbon
CC
carbonate carbon
ch4
methane
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cm centimeter(s)
CNC condensation nuclei counter
CO2 carbon dioxide
CPC condensation particle counter
CS catalytic stripper
DAQ data acquisition
DAS data acquisition system
DI deionized (water)
DMA differential mobility analyzer
DOC diesel oxidation catalyst
DQI data quality indicator
DQO data quality objective
DR dilution ratio
EASA European Aviation Safety Agency
EC elemental carbon; also electrostatic classifier
EPA U.S. Environmental Protection Agency
FAA U.S. Federal Aviation Administration
FID flame ionization detector
g gram(s)
GUI graphical user interface
h hour(s)
He helium
HEPA high-efficiency particulate air
Hz hertz
IMPROVE Interagency Monitoring of Protected Visual Environments
I/O input/output
K degrees Kelvin
kPa Hg kilopascal(s) mercury
in. inch(es)
LED light-emitting diode
LII laser-induced incandescence
|ig microgram(s)
|im micrometer(s)
m meter(s)
MAAP multi-angle absorption photometer
mbar millibar(s)
MBC mass black carbon
MDL minimum detection limit
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MFC
mass flow controller
MFM
mass flow meter
mg
milligram(s)
min
minute(s)
mJ
millijoule(s)
mL
milliliter(s)
mm Hg
millimeter(s) mercury
Mn02
manganese dioxide
MOP
miscellaneous operating procedure
MSS
Micro Soot Sensor
n2
nitrogen
NASA
National Aeronautics and Space Administration
NIOSH
National Institute of Occupational Safety and Health
NIST
National Institute of Standards and Technology
nm
nanometer(s)
NRC
National Research Council-Canada
nvPM
nonvolatile particulate matter
NRMRL
National Risk Management Research Laboratory
OC
organic carbon
OD
outside diameter
PASS
photoacoustic soot sensing
PC
personal computer
PDaq
personal data acquisition (system)
PM
particulate matter
PM2.5
fine particles with a diameter of 2.5 [j,m or less
PPS
primary particle size
psi
pound(s) per square inch
Psig
pound(s) per square inch gauge
PTFE
polytetrafluoroethyl ene
PyC
pyrolytically generated carbon
QAPP
quality assurance project plan
QA
quality assurance
QC
quality control
QFF
quartz-fiber filter
R2
correlation coefficient
RMSE
root-mean-square error
RPD
relative percent difference
RSD
relative standard deviation
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s
second(s)
SD
standard deviation
sLpm
standard liter(s) per minute
SMPS
Scanning Mobility Particle Sizer
SOP
standard operating procedure
STP
standard temperature and pressure
T
temperature
AT
mean temperature difference or bias
TC
total carbon
TOA
thermal-optical analysis
TOT
thermal-optical transmittance
USB
universal serial bus
UTRC
United Technologies Research Center
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Executive Summary
Four candidate black carbon (BC) measurement techniques have been identified by the SAE
International E-31 Committee for possible use in determining nonvolatile particulate matter
(nvPM) mass emissions during commercial aircraft engine certification. These techniques are
carbon burn-off, multi-angle absorption photometry (MAAP), laser-induced incandescence (LII),
and photoacoustic soot sensing (PASS). This study compared these techniques to the filter
gravimetric method while sampling exhaust from a laboratory soot generator (Jing MiniCAST)
at five target concentrations ranging from 10 to 1,000 |ig/m3. At least six replicate tests were
conducted at each target concentration using a specially designed flow tunnel system equipped
with a single probe and series of sample splitters.
National Institute of Occupational Safety and Health (NIOSH) Method 5040 was selected as the
carbon burn-off method for determination of elemental carbon (EC) concentration. The BC
instruments evaluated included a modified Thermo Fisher Scientific 5012 MAAP (called the
SuperMAAP), Artium Technologies LII 300, and AVL Micro Soot Sensor (MSS) photoacoustic
analyzer. All instrument operation followed written procedures established before testing began.
A total of 66 test runs were performed in the program during July, August, and September 2011
at the U. S. Environmental Protection Agency's National Risk Management Research Laboratory
located in Research Triangle Park, NC, USA.
The following conclusions were reached from the study:
• The measurements made using the four BC measurement methods show a highly linear
relationship with increasing particulate matter (PM) concentration in the flow tunnel.
• The four BC measurement techniques were found to be highly correlated with the organic
carbon-corrected Teflon reference filter values and with each other for target PM
concentrations ranging from 10 to 1000 |ig/m3. Correlation coefficients (R2 values) were
generally 0.98 or greater depending on test conditions.
• When compared to either the Teflon filter results or NIOSH 5040, the linear regression
lines of the data generated by the four techniques were within a maximum of 18 % from
perfect agreement (i.e., 1:1 line) for the combined data set.
• Slightly different results were found when the range of target concentrations was limited
to 50 to 500 |ig/m3 in the combined data set. A different relationship was also observed
for the SuperMAAP and LII within this concentration range, suggesting at least some
sensitivity to measured concentration.
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Due to the high correlations observed among the various methods, there is reason to
believe that LII, MSS, and SuperMAAP can provide equivalent results if calibrated
against a common BC source.
High-quality data were generated in the program with all data quality indicator goals met
or exceeded.
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1 Introduction
The U. S. Environmental Protection Agency (EPA), U. S. Federal Aviation Administration
(FAA), and the European Aviation Safety Agency (EASA) recently requested that the SAE
International E-31 Aircraft Emissions Measurement Committee prepare an Aerospace
Recommended Practice (ARP) for the determination of nonvolatile particulate matter (nvPM)
mass and number emissions from commercial aircraft engines. The three agencies requested that
the ARP address both particulate matter (PM) mass and number to support regulatory
requirements in both the United States and Europe and to further the efforts of the International
Civil Aviation Organization to replace the outdated smoke number standard for new engine
certification. In this context, nvPM refers to those particles that exist at engine exit temperature
and pressure, consisting mainly of carbonaceous matter (black carbon) from fuel combustion
with minor amounts of PM ingested in the engine inlet and metals.
In early 2009, the E-31 Committee prepared Aerospace Information Report (AIR) 6037, which
contained extensive information on various candidate PM measurement methods to be used as
the starting point for preparation of the ARP for nvPM mass and number (SAE International,
2010). The E-31 PM Subcommittee recognized several black carbon (BC) measurement methods
as potentially useful for engine certification as a surrogate for total nvPM mass. For BC mass,
carbon burn-off, multi-angle absorption photometry (MAAP), and laser-induced incandescence
(LII) were initially identified. More recently, photoacoustic soot sensing (PASS), used in the
automotive industry, was identified as a fourth candidate method for use in the ARP. To measure
PM number, a condensation nuclei counter (CNC) was chosen as the most suitable technique.
To develop and implement a suitable ARP for nvPM mass and number, each method used for
engine certification had to have detailed operation, maintenance, and calibration procedures to
standardize the protocol and ensure the quality of the data collected. For PM number, operating
and calibration procedures have generally been developed for ground vehicles in Europe. In the
case of nvPM mass concentration, however, no such procedures were available. In addition, all
four methods identified for the measurement of BC mass are indirect techniques that determine
some parameter(s) other than the actual mass in the sample stream. Therefore, a procedure was
also needed to relate the output of each method to a National Institute of Standards and
Technology (NIST)-traceable direct mass measurement.
Under this project, initiated in spring 2010, standard operating procedures (SOP) were developed
for the four PM mass measurement techniques identified by the E-31 Committee to support
development of an ARP for nvPM mass. In addition, research was conducted to correlate the
output of each method to a NIST-traceable direct mass measurement using the filter gravimetric
method.
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Each SOP addresses all aspects of instrument operation, maintenance, and calibration, as well as
method quality assurance (QA). Experts in each analytical method were retained to provide
critical details for developing the SOPs, and a series of workshops was held to address each
instrument type. Upon completion of SOP development, a detailed method validation study was
conducted on the four measurement techniques using a system similar to that shown in AIR
6037, Section 11, Technical Annex 1 (SAE International, 2010). This work involved acquiring
the instrumentation and an aerosol generator, constructing the experimental system, and
performing all necessary calibrations and quality control (QC) checks.
Each candidate measurement method is detailed in Section 2, followed by descriptions of the
flow tunnel system and instrumentation (Section 3) and the experimental procedures (Section 4)
used in the study. Section 5 provides the experimental results, and Section 6 details the QA/QC
employed during testing. Appendices A-K contain the SOPs developed in the program, a
modified MAAP method, documentation of instrument calibration, and related information.
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2 Candidate Methods
Each of the four BC measurement techniques identified for possible use in aircraft engine
certification—carbon burn-off, MAAP, LII, and PASS—is described below. Each method was
evaluated and documented, as well as validated against a NIST-traceable filter gravimetric
technique.
2.1 Carbon Burn-Off Method
In general, the carbon burn-off method uses a laboratory carbon analyzer to determine the total
soot mass deposited on a quartz filter by measuring the carbon dioxide (CO2) produced while
increasing the temperature of the filter in the presence of excess oxygen (O2). This method is a
quantitative and comparative approach, but is a non-gravimetric technique. However, like the
gravimetric analysis of filter samples, the carbon burn-off method requires a minimum mass
loading for analysis, which limits its usefulness for "near real time" measurements as would be
required in the ARP.
Variations of the carbon burn-off method include National Institute of Occupational Safety and
Health Method 5040 (NIOSH, 2003), the Interagency Monitoring of Protected Visual
Environments (IMPROVE) protocol (Chow at al., 2001), and the use of commercial thermal
carbon analyzers such as the LECO Model RC-412 multiphase carbon/hydrogen/moisture
determiner. Of these techniques, only NIOSH 5040 has a recognized, standardized procedure for
analysis of quartz filter samples and as such is the method routinely used for source
characterization by U.S. EPA's National Risk Management Research Laboratory (NRMRL) in
Research Triangle Park, NC, and other organizations throughout the world. This method was
originally developed for determination of organic carbon (OC) and elemental carbon (EC)
emissions from diesel-powered vehicles and has been found to be suitable for a wide variety of
source categories.
For NIOSH 5040, samples collected on prefired quartz-fiber filters are analyzed using a Sunset
Laboratory, Inc. (Tigard, OR, USA) carbon analyzer for determination of OC/EC content. This is
a two-stage thermal-optical transmittance (TOT) method with a lower detection limit of
approximately 0.2 |ig/cm2 filter area for both OC and EC. In the first stage, organic and
carbonate carbon (CC) are evolved in a helium (He) atmosphere as the temperature is stepped to
approximately 870 °C. The evolved carbon is catalytically oxidized to CO2 in a bed of granular
manganese dioxide (Mn02) and then reduced to methane (CH4) in a nitrogen/firebrick
"methanator." CH4 is subsequently quantified by a flame ionization detector (FID). In the second
stage, the oven temperature is reduced, a 02-He mix is introduced, and the temperature is stepped
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to approximately 890 °C.1 Details of the NIOSH 5040 temperature program and residence time
at each stage are given in Table 2-1.
Table 2-1. Temperature Profile for the NIOSH 5040 Method Used in this Study
Carrier Gas
Temperature
( C)
Ramp Rate
( C/s)
Residence Time
(s)
Carbon Fraction
He
310
4
70
OC1
He
475
8
60
OC2
He
615
10
60
OC3
He
870
8
105
OC4
98 % He/2 % O2
550
9
60
EC1
98 % He/2 % O2
625
10
60
EC2
98 % He/2 % O2
700
12
60
EC3
98 % He/2 % O2
775
13
60
EC4
98 % He/2 % O2
890
8
110
EC5
CalibrationOx
1
110
As O2 enters the oven, pyrolytically generated carbon (PyC)—carbon evolved between the
addition of O2 and the OC-EC split—is oxidized, causing a concurrent increase in filter
transmittance. The split between OC and EC occurs at the point at which the filter transmittance
reaches its initial value. Carbon evolved prior to the split is considered OC (including carbonate),
and carbon volatilized after the split is considered EC. If the OC-EC split occurs before the
addition of O2, PyC is zero. Figure 2-1 shows an example thermogram for a filter sample. The
split between OC and EC might be inaccurate if the sample transmittance is too low. The EC
loading at which this occurs depends on the laser intensity but, in general, is when EC loadings
are above 20 |ig/cm2 (NIOSH, 2003).
1 Note that according to Aerospace Information Report 6037 (SAE International, 2010), the temperature threshold
for nvPM is 350 °C. Since the NIOSH method heats the sample far above this temperature, the method could be
under-measuring the actual EC mass.
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OC-EC split
OC and CC
EC
2% O J He
£
He
8904C Temperature
870
Transr littance
FID
J U
PC
Time (minutes)
Figure 2-1. Thermogram for filter sample containing OC, CC, and EC. PyC is represented here
as PC. The final peak is the CH4 calibration peak. (NIOSH, 2003)
The IMPROVE, or low-temperature, protocol achieves plateaus at 120, 250, 450, and 550 °C in
an ultrahigh-purity He atmosphere, remaining at each plateau until a well-defined carbon peak
has evolved (Table 2-2). After 2 % O2 in 98 % He is added at 550 °C, additional carbon evolves,
most of which consists of EC and PyC, as indicated by the rapid increase of both the reflectance
and transmittance signals. The IMPROVE protocol continues to increase temperatures from 550
°C to 700 °C and then to 800 °C, with the residence time defined by the flattening of carbon
signals. The IMPROVE protocol separately reports the carbon evolved for four OC fractions and
three EC fractions, while the NIOSH 5040 protocol reports four OC and five EC fractions.
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Table 2-2. Temperature Profile for the IMPROVE Method
Carrier Gas
Temperature
( C)
Ramp Rate
( C/s)a
Residence Time
(s)b
Carbon Fraction
He
120
1
120
OC1
He
250
2
120
OC2
He
450
3
120
OC3
He
550
4
120
OC4
98 % He/2 % 02
550
4
120
EC1
98 % He/2 % 02
700
5
120
EC2
98 % He/2 % 02
850
6
120
EC3
CalibrationOx
1
110
a Average ramp rate for the IMPROVE protocol is calculated from a residence time of 120 s. To calculate a
residence time of 150 s, multiply by 1.25.
b Residence time at each temperature in the IMPROVE protocol depends on when the FID signal returns to
| baseline (minimum is 120 s).
In summary, the NIOSH 5040 and the IMPROVE protocols are similar except that NIOSH OC
temperature set points are higher than the temperature set points of IMPROVE. That difference
in temperature profile does not influence the total carbon (TC) sampled on the quartz filters.
However, the difference in temperatures results in a lower NIOSH EC concentration compared to
IMPROVE. The primary reason for this difference is allocation of carbon evolving at the NIOSH
870 °C temperature step in a He atmosphere to the OC rather than the EC fraction (Chow et al.,
2001). When this portion of the NIOSH OC is added to the NIOSH EC, the IMPROVE and
NIOSH analyses are in good agreement. For both methods, the pyrolysis adjustment to the EC
fraction is always higher for transmittance than for reflectance, with transmittance resulting in a
lower EC loading (Chow et al., 2001).
EPA NRMRL already had procedures in place for analysis of quartz filter samples per NIOSH
5040 (EPA, 2009a). Modifications were made to that method to provide reproducible procedures
for this investigation. However, no protocol existed for the sample collection process required
during engine certification. Therefore, a standardized sample collection protocol, similar to that
published in 40 CFR Part 86.1065 (EPA, 2012), was written as part of the carbon burn-off SOP,
which is discussed in detail in Section 3.
2.2 Multi-angle Absorption Photometry
Aerosol absorption photometry analyzes the modification of filter optical properties, such as
transmittance or reflectance, caused by the deposition of particles on the filter matrix (Petzold
and Schonlinner, 2004). Optical absorption methods are suitable for measuring BC combustion
particles because they absorb light very efficiently in the visible spectral range. In addition to its
specific sensitivity to BC, aerosol absorption photometry has the further advantage of operating
continuously so that time-resolved recording of particle emissions is possible.
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The MAAP method determines aerosol light absorption from simultaneous measurements of
radiation passing through and scattered back from a particle-loaded fiber filter. The particle-
loaded filter is treated as a two-layer system: (1) the aerosol-loaded layer of the filter and (2) the
particle-free filter matrix. Radiative processes inside both layers are taken into account
separately. Measurements are made at three detection angles to resolve the influence of light-
scattering aerosol components on the angular distribution of the back-scattered radiation (Petzold
et al., 2002, 2005). Radiation penetrating through the filter is measured at one detection angle, 9
= 0°, and radiation scattered back from the filter is measured at two detection angles, 9 = 135°
and 165° (Figure 2-2).
Light Source (LED - 670rim)
Reflectance
~ Reflectance
Photodetectors
Photodetectors
l65deg
W ¦ 135deg
Aerosol Spot —
Filter Substrate
Transmission Photo detector
Figure 2-2. Arrangement of the detectors in the MAAP instrument.
The MAAP method uses the following equation to calculate BC mass loading:
MBC = AO-SSAt) LOD/oahs. (2-1)
where MBC is the mass of BC deposited on the filter, A is the collection area (2 cm2), SSAl is
the single-scattering albedo of the aerosol-filter layer, LOD is the transmittance or optical depth
of the aerosol-loaded filter layer, and oabs is the specific absorption of BC (assumed constant as
6.6 m2/g for this instrument). The concentration of BC (CBC; mass per unit volume of air) is
then calculated using the following equation:
CBC = AMBC/V, (2-2)
where AMBC is the difference in MBC from the previous sample and V is the volume of air
sampled between time 1 (ti) and time 2 (t2).
A commercially available instrument based on the MAAP method is offered by Thermo Fisher
Scientific (Waltham, MA, USA). The Model 5012 MAAP has been shown to be both robust and
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reliable in several recent field campaigns, including one conducted at Tinker Air Force Base
(Howard et al., 2012) and the recent NASA Aviation Alternate Fuels Experiment [AAFEX]
(Anderson et al., 2011), and was selected as the method of choice for testing of the Joint Strike
Fighter. The Model 5012 has been used by many groups including EPA NRMRL, Aerodyne
Research, Inc. (ARI; Billerica, MA, USA), and the United Technologies Research Center
(UTRC; East Hartford, CT, USA).
The Model 5012 operates at 670 nm with a time resolution of 1 min. It features automatic filter
changing based on absolute transmission, constant sample flow rate (1 m3/h) controlled by a
variable speed pump, and recording of the actual sample flow, making it an ideal instrument for
unattended, long-term monitoring of BC mass loadings in the atmosphere. However, several
shortcomings of this MAAP instrument for use in source monitoring applications such as engine
certification required modifications to the instrument to allow the following:
• Reducing flow through the filter tape to extend its useful life.
• Isolating the MAAP instrument from the main sampling line during filter changes.
• Calculating BC mass on a 1-Hz basis, logging the data, and providing a graphical user
output that can be viewed in real time.
• Calculating the average BC concentrations for the selected sampling periods that will be
a function of collected BC mass on the filter and the total air volume sampled.
• Sending commands to the instrument to force a manual filter change.
• Monitoring the transmission percentage in real time so that the operator can determine
when a filter change is about to take place.
• Initiating and documenting some type of quality control check to tell the operator the
instrument is working properly and ready for use.
• Using an add-on "package" that incorporates all necessary changes for use in certification
environments.
The manufacturer (Thermo Fisher Scientific) was not interested in making these modifications
due to the low number of MAAP units sold each year. Therefore, independent research was
performed in the study to address these issues.
2.3 Laser Induced Incandescence
LII measures the thermal (incandescent light) emission from particles heated by a pulsed laser to
temperatures in the 2500 to 4500 K range (Bachalo et al., 2002). LII is a highly selective method
that responds only to the presence of BC, making it applicable for measuring the nonvolatile
particles produced as a combustion emission because the nonvolatile particles are primarily BC.
BC absorbs laser radiation over a broad spectral range and is refractory so that the nanometer-
size particles survive heating to the temperatures necessary for the incandescence to be detected.
8
-------
At these temperatures, all semivolatile organic components that might condense on the BC
particles will be evaporated promptly, and most other noncarbonaceous particles will also
evaporate or undergo sublimation.
The signals from LII are analyzed to determine mass concentration, volume concentration, active
surface area, and primary particle diameter of the particulate emissions. The LII instrument is
calibrated by the manufacturer using a known NIST-traceable spectral radiance source. The
absolute intensity calibration factors are determined for the instrument-specific optical path
(windows, lenses, mirrors, filters, photodetectors). The measurements made with LII are
produced with each laser pulse at a rate up to 20 Hz, permitting on-line, time-resolved data
collection and reporting of results in real time.
Two extractive LII instruments are currently manufactured that differ in design and operation.
Prior to this study, LII has had only limited application to the measurement of aircraft gas turbine
emissions, and no SOPs or QC checks are available for either instrument. Therefore, additional
research was conducted in this project to mature the LII technology sufficiently for use in engine
certification.
The two commercially available LII instruments are the Droplet Measurement Technologies SP2
(Boulder, CO, USA) and the Artium Technologies LII 300 (Sunnyvale, CA, USA). Of the two
instruments, the LII 300 (Figure 2-3) offers a greater dynamic range (< 0.2 to 2 x 106 |ig/m3) and
thus was selected for the present study. The LII 300's novel technique of measuring absolute
light intensity theoretically eliminates the need for calibration in a source of soot particles with a
known concentration. The absolute intensity method, or self-calibrating LII, applies two-color
pyrometry principles centered at 440 and 780 nm to determine the particle temperatures. The LII
300 system consists of a pulsed Nd: YAG laser operating with 60 mJ/pulse at 20 Hz and a
wavelength of 1064 nm. EPA NRMRL participated in a study at Wright-Patterson Air Force
Base in March 2010 where the LII 300 was shown to be a very promising technique for BC
measurement in turbine exhaust.
9
-------
Rrcdver Optica
Dcfrrlon
Aolomilk
signal
\MrunaMod
rtiJM-ti NrtiYAC Ljvrr
Anlamiltr Mttnct ( antral
/>
vl
Horner Detection
fir am
Shaping
Optlr*
Figure 2-3. Schematic layout of the Artium Lll 300 system.
(Bachalo et al.. 2002)
Although the LII 300 was the more applicable of the two instruments available, two remaining
issues with the analyzer needed to be resolved before testing:
• Incorporation of a vacuum pump to be able to control and monitor the air sampling flow
rate to the instrument.
• Development of an independent QC check to verify proper instrument operation before
starting measurement.
Each is described later in this report.
2.4 Photoacoustic Soot Sensing
In the photoacoustic measurement method (Figure 2-4A), the sample gas stream containing
"black" (i.e., strongly absorbing) soot particulates is exposed to a modulated light beam. When
turned on, this light beam heats absorbing particles, which dissipate their heat in the "off state
(Schindler et al., 2004). The resulting pressure fluctuations (expansion and contraction of the
carrier gas) are detected by a sensitive microphone. Clean air produces no signal. When the air is
loaded with soot or the exhaust gas, the signal rises proportionally to the concentration of soot in
the measurement volume. It is possible to measure BC concentrations from 1 to 5 * 104 (ig/'m3
with this method, which is appropriate to measure the emissions of both diesel and aircraft
turbine engines.
10
-------
Mia option*
D«t*ctof
Sound v/«v»
So
-------
3 Experimental Apparatus
3.1 Experimental System
A specially designed experimental system (Figure 3-1) was constructed by EPANRMRL and
used for all tests conducted during the instrument validation. The system consisted of an aerosol
generator, low-speed flow tunnel, and PM mass measurement system. Operation of the system is
generally described here with details of each major component provided below. Detailed lists of
equipment and software used are provided in Tables 3-1 and 3-2, respectively.
The aerosol generator consisted of a Jing (Bern, Switzerland) Model 5201 (prototype)
MiniCAST burner, five mass flow controllers for burner operation, a primary diluter, and a
catalytic stripper. Filtered air with a dilution ratio (DR) of 1.4:1 was provided in the primary
diluter downstream of the MiniCAST burner, which provided the additional O2 needed for
operation of the catalytic stripper. In the catalytic stripper, a portion of the OC produced by the
MiniCAST burner was destroyed by an oxidation catalyst prior to entering the flow tunnel.
At the entrance of the flow tunnel, the diluted aerosol was mixed with the main flow in a region
of high turbulence created by the tangential introduction of high-efficiency particulate air
(HEPA)-filtered laboratory air through ports located at even distances around the tunnel
circumference. This technique provided adequate mixing and low particle losses. Downstream of
the aerosol injection point, a sample was collected through a 165-cm-long straight-through
extraction probe whose entrance was located 20 tunnel diameters downstream and four diameters
upstream of any flow disturbance. The probe was connected to the instrument suite, which
consisted of a PM2.5 cyclone preseparator, short transfer line, and a series of 2 two-way flow
splitters followed by a four-way splitter that was used to provide a split aerosol sample to each of
the four candidate instruments plus the Teflon filter reference sampler (Figure 3-2). Downstream
of the four-way splitter, identical 314-cm-long transfer lines provided the split sample to the four
instruments to maintain consistent particle losses in the lines. A filtered bypass and
pneumatically operated three-way valve also were installed between the tunnel exit and splitters
to allow all analyzers to sample either filtered laboratory air or MiniCAST exhaust. The rest of
the effluent from the flow tunnel was removed from the laboratory via the building ventilation
system using either of two blowers provided with the system or, for the highest concentration
measurements, a vacuum pump.
The primary instrumentation suite consisting of the four candidate measurement methods was
supplemented by an independent "process" monitor, a TSI 3936 Scanning Mobility Particle Sizer
(SMPS), to determine PM number concentrations as well as size distribution. The SMPS was
used only to monitor MiniCAST burner operation during testing and thus was not included in the
instrument evaluation per se.
12
-------
AVL MSS
(photo-
acoustic)
Four-Way
Sample
Spffittf/
HEPA
Filter
20 Oumottri
Two-Way
Sample
Splitter
Catalytic
Stripper
OHuter
Mini-
CAST n
Ittliwi)
Cyehwt# *
Two-Way
Sampto
SpM1«r
HEPA
flbn
[along
clrcumlaranca of
duel lor turbulent
rnmrig 1
~ SMPS
OriRM
To
ExKausI
Duel
To
Exhaust
Duel
Teflon ~
Quartz Filter
Blowers 7
Motor
Conlrollor
Quartz ,,
H«* He*
Filter Centres*'
••uinp
Figure 3-1. Flow tunnel and associated measurement system
13
-------
Table 3-1. Instruments and Equipment
Name
Abbreviation
Model Number
Supplier
Location in Tunnel
System
Soot generator
MiniCAST or
CAST
5201 MiniCAST
Prototype
Jing Ltd., Bern, Switzerland
Tunnel inlet
Mass flow controller
(MFC) system for soot
generator
MFC box
F-42
Jing Ltd., Bern, Switzerland
Tunnel inlet
Catalytic stripper (CS)
with temperature
controller
CS
NA
Southwest Research
Institute, San Antonio, TX,
USA
Downstream of
MiniCAST at tunnel
inlet
Multi-angle absorption
photometer
SuperMAAP
Modified 5012
MAAP
Thermo Fisher Scientific,
Waltham, MA, USA
Instrument suite
Laser-induced
incandescence
instrument with laser
power supply
Lll 300
Lll 300 + ICE 450
Artium Technology, Inc.,
Sunnyvale, CA, USA
Instrument suite
Micro Soot Sensor with
conditioning unit
MSS 483
AVL MSS 488 +
AVL conditioning
unit
AVL, Graz, Austria
Instrument suite
Scanning Mobility Particle
Sizer
SMPS
3081 differential
mobility analyzer
(DMA) + 3025A
condensation
particle counter
(CPC)
TSI, Shoreview, MN, USA
Tunnel sampling
port
Thermal-optical carbon
analyzer
OC/EC analyzer
Dual-optical carbon
analyzer
Sunset Laboratory, Tigard,
OR, USA
NA
Analytical microbalance
Microbalance
Sartorius ME5
Sartorius-North America,
Elk Grove, IL, USA
NA
Laboratory transducer -
low pressure
Orifice meter
differential
pressure (dP)
cell
PX653-10D5V
Omega Engineering,
Stamford, CT, USA
Teflon filter sampler
Air-actuated bypass valve
Air switch valve
SR63-530163
Industrial Automation
Components, London,
Canada
Three-way switching
valve upstream of
cyclone
Pressure transducer
PT - sample line
PX309-015A5V
Omega Engineering,
Stamford, CT, USA
Teflon filter sampler
Pressure transducer
PT - tunnel line
PX309-015A5V
Omega Engineering,
Stamford, CT, USA
Tunnel sampling
port
PM2.5 cyclone
Cyclone
URG-2000-30EC
URG Corporation, Chapel
Hill, NC, USA
Between switching
valve and flow
splitters
Personal Data Acquisition
System
PDaq
PDaq/56
Measurement Computing
Corporation, Norton, MA,
USA (now National
Instruments, Austin, TX,
USA)
Two pressure
transducers, tunnel
temperature,
primary diluter mass
flow meter (MFM),
dump line MFM,
quartz filter sampler
MFC, Teflon filter
sampler dP cell
pressure transducer
14
-------
Name
Abbreviation
Model Number
Supplier
Location in Tunnel
System
MFM 0-50 sLpm nitrogen
(N2)
MFM - dilution
air
FMA 1700/1800
Omega Engineering,
Stamford, CT, USA
Primary diluter
downstream of
MiniCAST
MFM 0-50 sLpm N2
MFM - dump line
FMA 1700/1800
Omega Engineering,
Stamford, CT, USA
Dump line off first
two-way flow splitter
MFC 0-50 sLpm
MFC - quartz-
fiber filter (QFF)
line
GFC-1133
Dwyer Instruments Inc,
Niagara Falls, NY, USA
Quartz filter sampler
Ring compressor
Big blower
VFC400A-7W
Fuji Electric, Japan
Main tunnel flow
Ring compressor
Small blower
VFC200A-7W
Fuji Electric, Japan
Main tunnel flow
Vacuum pump
Pump- QFF line
0523-101Q-
Q582DX
Gast MFG Corp., Benton
Harbor, Ml, USA
Quartz filter sampler
Vacuum pump
Pump- dump
line
0523-V103-G18DX
Gast MFG Corp., Benton
Harbor, Ml, USA
Dump line from first
two-way flow splitter
Vacuum pump
Pump - Teflon
filter line
2807CE72J
Rietschie Thomas,
Sheboygan, Wl, USA
Teflon filter sampler
Vacuum pump
Pump for 1000
|jg/m3
2807CE72J
Rietschie Thomas,
Sheboygan, Wl, USA
Main tunnel flow
Vacuum pump
Pump for Lll
2107CA20 C
Rietschie Thomas,
Sheboygan, Wl, USA
Lll 300
Table 3-2. Software/Firmware
Instrument/Device
Firmware Version
Software Version
Sof tware/F i rm wa re
Manufacturer
MiniCAST + MFC box
NA
Get Red-y
Vogtlin Instruments AG, Aesch,
Switzerland
Modified MAAP
V1.29
V1.3
(Custom)
Thermo Fisher Scientific,
Waltham, MA, USA and
National Instruments Corp,
Austin, TX, USA (LabView)
Lll 300
IP.192.168.1.110
AIMS 3.8
Artium Technologies,
Sunnyvale, CA, USA
AVL488
2.0
1.1.0.5
AVL, Graz, Austria
PDaq
NA
DasyLab 10.00.01
National Instruments Corp,
Austin, TX, USA
SMPS
2.11
AIM 9.0.0.0
TSI Inc., Shoreview, MN, USA
15
-------
Figure 3-2. Sample distribution system to instruments.
Except for the cyclone, all components are made of stainless steel.
3,2 Aerosol Generator System
3.2.1 MiniCAST 5201 and Primary Diluter
A Jing MiniCAST Model 5201 prototype2 (Figure 3-3), used as the soot generating device,
produces an aerosol of carbonaceous particles of adjustable and repeatable size and chemical
composition. As a soot source, the MiniCAST uses a propane diffusion flame, in which soot
particles are formed during pyrolysis of the fuel. To generate the soot particles, the oxidation air
supply was kept below stoichiometric limits. Consequently particles contained within the exhaust
gases arose out of the flame and left the combustion chamber. The particle stream was then
mixed with quenching gas (N2) to prevent further combustion and to stabilize the soot particles.
2 Note that this is a standard Model 5201 device specifically modified by the manufacturer (Jing) at EPA's request to
produce a slight positive pressure at the outlet of the unit. It was known before starting the study that the MiniCAST
does not produce a soot aerosol representative of aircraft turbines. It was, however, the best commercially available
laboratory soot generator suitable for use in the study.
16
-------
This quenching inhibits condensation when the particle stream escapes from the flame to the
ambient air. Subsequently, an axial flow of dilution air was supplied to reduce the concentration
of the particle stream prior to exiting the MiniCAST. Operation of the MiniCAST, together with
the different gas flows, is illustrated in Figure 3-3; the experimental setup is shown in Figure 3-4.
Particle
Output
Dilution
air
Quench 93s
Dilution
Flame
Air Caseous Asi
fuet
Figure 3-3. (A) Operation principle of the MiniCAST burner and (B) front view of the MiniCAST
prototype used for this study.
Figure 3-4. MiniCAST, primary diluter, and catalytic stripper installed on the flow tunnel.
17
-------
The MiniCAST flame supplies soot particles at high concentration (107— 109 particles/cm3),
which are diluted for different applications. The state of the flame and the features of the
generated soot particles primarily result from the flow settings. By varying the flow settings, the
particle size can be adjusted in a range of 20 to 200 nm (mean electrical mobility particle
diameter). In addition, the OC/EC ratio varies with operational set point. The equivalence ratio
and the flow of mixing nitrogen gas are the most important parameters responsible for formation
of particles of different sizes. The rich flames (higher propane/air ratio) result in a high
proportion of OC and small particle sizes. A lean flame (lower propane/air ratio) results in less
OC and more EC and generally larger particle sizes. Thus, for the higher EC content desired in
the current work, lean flames were more favorable and thus used in the study.
In addition to the burner itself, a Model PMF-42 MFC unit (on loan from the National Research
Council [NRC]-Canada) was used in order to control five flow settings: fuel (propane),
oxidation air, mixing gas (N2), quenching gas (N2), and dilution air. The unit consists of five gas
flow controllers (Red-y Smart series, Vogtlin Instruments, Aesch, Switzerland). The Get Red-y
software package provided by the manufacturer is used to control, change, and log the operating
parameters of these five units. All MFCs were calibrated by the EPA NRMRL Air Pollution
Prevention and Control Division (APPCD) Metrology Laboratory prior to use according to
miscellaneous operating procedure (MOP) FV-0201.1 (EPA, 2009b).3 Detailed instructions on
operating the MiniCAST and PMF-42 control unit, together with the control PC software, are
provided in SOP 2101 in Appendix A.
In the present study, the soot aerosol exiting the MiniCAST was diluted (DR = 1.4) with HEPA-
filtered compressed air before it reached the catalytic stripper (CS). The dilution flow was
measured using an Omega Engineering Model FMA 1700/1800 MFM. The total flow entering
the CS was approximately 43 L/min (-18 L/min from MiniCAST plus 25 L/min dilution air). To
test the selectivity of each candidate instrument/method, the same experiments (same
concentration conditions) were performed both with and without the CS in operation.
3.2.2 Catalytic Stripper
The purpose of the CS was to remove the semivolatile (typically OC) fraction by passing raw or
diluted exhaust over an oxidation catalyst heated to 300 °C. The CS consisted of a heated
platinum oxidation catalyst, a temperature probe at the inlet and outlet, heating elements, and a
temperature controller capable of maintaining 300 °C (Figure 3-5). The oxidation catalyst used is
a commercially available diesel oxidation catalyst (DOC; Clariant SE, Munich, Germany)
designed to remove volatile hydrocarbons from diesel exhaust by oxidizing the volatile
hydrocarbon species to CO2 and H2O. The catalyst and geometry of the substrate were
characterized and sized to minimize solid particle losses in the size range typical of diesel
3 Note that all SOPs and MOPs are either appended or can be found at the internal APPCD SharePoint site. SOPs are
generally developed for major equipment used in the study and MOPs are for ancillary equipment.
18
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exhaust and theoretically to achieve near complete removal of volatile material (Khalek, 2007).
The DOC was insulated and equipped for heating up to 400 °C, as shown in Figure 3-5.
The CS, provided to EPA by Southwest Research Institute, had a stainless steel enclosure and
conical (12.5°) inlet and outlet with 9.5-mm inlet and outlet outside diameter connections
(Khalek, 2007; Khalek and Bougher, 2011). The CS is sized for a flow rate of 0.025 sLpm
through each channel of the catalyst. Detailed properti es and dimensions of the DOC are
provided in Table 3-3.
Figure 3-5. Components of the catalytic stripper system.
Table 3-3. DOC Properties and Dimensions Used in the Catalytic Stripper
DOC Component
Property/Dimensions
Material
Ceramic monolith
Wash coat
Zeolite, alumina
Catalyst
Platinum
Geometry
Square channel
Overall length (cm)
-7.5
Overall diameter (cm)
-7.5
Cell density (number of cells per cm2)
54.2
Square channel wall thickness (cm)
0.0139
Square channel length (cm)
-7.5
Square channel open width or height (cm)
0.127
19
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3.3 Instrumentation Suite
As described in Section 2, four candidate methods were tested in the study:
• Carbon burn-off method (NIOSH 5040) with laboratory thermal-optical carbon analyzer
from Sunset Laboratory, Inc.
• Multi-angle absorption photometry with the modified 5012 MAAP instrument from
Thermo Fi sher Scientific Corporation.
• Laser-induced incandescence with the LII 300 instrument from Artium Technologies.
• Photoacoustic soot sensing with the MSS 483 from AVL.
The four candidate methods are described briefly in the following sections. SOPs for each
instrument and documentation of development of an improved MAAP method (SuperMAAP)
can be found in Appendices B through F
3.3.1 Thermal-Optical Carbon Analyzer
Samples were collected on 47-mm quartz-fiber filters (QFFs) that were prefired at 550 °C for 12
h before sampling and stored in a freezer at a nominal temperature of -20 °C. Upon completion
of each experiment, the QFF samples were analyzed using a Sunset Laboratory TOT carbon
analyzer that simultaneously measures transmission and reflectance signals. A schematic
diagram of the Sunset Laboratory analyzer is shown in Figure 3-6. Details for collection and
analysis of the quartz filter samples are provided in SOP 2104 available in Appendix B.
FD
met nanatw
thermocouple
diode
bs«r f||tCr
clamp
0
e
-------
During analysis, a 1.5 cm2 punch from the exposed filter is placed in a quartz boat and positioned
in the path of a red-light diode laser that is used to monitor transmittance of the filter and to
determine the OC/EC split time. An internal thermocouple at the end of the boat is used to
monitor the sample temperature during the analysis. All carbon species evolved from the filter
are converted to CO2 in the oxidation oven, and then the CO2 is catalytically reduced to CH4
before being measured by an FID. Before starting sample analysis for the present project, the
MFCs used to control delivery of gases to the Sunset analyzer were calibrated using a Gilibrator
system (Zefon International, Ocala, FL, USA) by the APPCD Metrology Laboratory using MOP
FV-0237.0 (EPA, 2010).
In addition to MFC calibration, studies performed by Phuah et al. (2009) and Chow et al. (2005)
showed that the sample (filter) temperature and the temperature measured by the thermocouple
can differ by 10 to 50 °C. Since temperature precision in thermal-optical analysis (TOA) is
required for accurate measurements, Sunset Laboratory developed a temperature calibration
procedure that was performed on the instrument used in this study before starting the
measurements (Pavlovic et al., 2014).
Sunset Laboratory provided the temperature calibration kit, which is designed to satisfy QA/QC
requirements, increase reliability of carbon results, and improve inter-instrument comparisons.
The calibration kit consists of a serial temperature data acquisition unit (precision ± 0.3 °C for
the -80-500 °C temperature range and ± 0.55 °C for the 500-1350 °C range [Model MDSi8,
Omega Engineering, Stamford, CT, USA]), NIST-traceable thermocouple (Inconel-shielded K-
type thermocouple certified for high temperatures [Omega Engineering Calibration Report #
OM-110802626] with 1/16-in. sheath diameter, and front oven interface hardware.
Thermocouple-produced temperature data were recorded at a frequency of 1 Hz and with 0.1 °C
resolution. For calibration, the quartz boat with quartz filter (Figure 3-7A) used during normal
TOA were replaced with the front oven interface hardware outfitted with the NIST-traceable
thermocouple (Figure 3-7B).
21
-------
Thermocouple
/
/
/
/
/-
| Loser
-Jo
2.0 cm
/
/
/
1.5 em
Quart simple oven
OuarG boat with handle
/
/
/
/
/ Heftum
/
/
/
B
Themocouple
/
/
/
/
/
_/
/
/-
/
/
/
LLaser
2Qcm
~
Quartz sample oven
Cahbrabon thermocouple
/
/
j-/ EJata logger
-y
- — Hetiuii
"v;
/
/
Figure 3-7. The (A) sample analysis set and (B) calibration set of the Sunset Laboratory carbon
analyzer.
(Note the position of the oven temperature sensor relative to the filter sample.)
The tip of the oven calibration thermocouple was positioned where the center of the quartz filter
typically resides during TOA operation, which is approximately 2 cm upstream of the
thermocouple used to monitor the oven temperature (Figure 3-7). This position also happens to
be where the laser beam (k = 632.8 nm) used to monitor pyrolysis passes through the filter. For
the sake of comparison, oven calibrations were performed using both the NIOSH 5040 and
IMPROVE temperature operating conditions. Details about residence time and temperature ramp
rate set points for the NIOSH 5040 protocol can be found in Khan et al. (2012). For calibration
using the IMPROVE protocol, the residence time at each temperature step was 120 s.
Two temperatures were recorded during the oven calibration routine: Toven as measured by the
built-in oven temperature sensor and Tfilter as measured by the calibration kit. Both
temperatures were recorded when the readings for the sample oven (Toven) were stable at each
set-point temperature (Tsetpoint) required by the NIOSH 5040 and IMPROVE protocols for each
temperature step. Before calibration, Tsetpoint = Toven. However, previous studies such as
Phuah et al. (2009) showed that Tfilter ^ Tsetpoint and therefore Tfilter ^ Toven. Differences
among Tsetpoint, Toven, and Tfilter were determined, and temperature coefficients
22
-------
(approximately equal to temperature biases measured) in the instrument control software
parameter files were adjusted so that Tfilter = Tsetpoint. In other words, coefficient values were
adjusted to force the temperature at the sample oven thermocouple (Toven) to reflect the value
required to achieve Tsetpoint at the filter because Toven ^ Tfilter either before or after the
calibration. For each TOA method (NIOSH 5040 and IMPROVE), the oven calibration
procedure was performed in triplicate with the calibration unit removed and then replaced for
each trial. This calibration was accomplished before adjustment of the temperature coefficients.
After the coefficients were adjusted in the software, the calibration/checking procedure was
performed again in triplicate to measure and record Tfilter during each temperature step
required by the NIOSH 5040 and IMPROVE methods to ensure Tfilter = Tsetpoint and full
compliance with the method.
All temperatures reported here as Tfilter (measured by the calibration thermocouple) represent
the temperatures measured in the center of the filter, while in practice there will be gradients
across the filter. In addition, the quartz boat with filter used during normal instrument operation
compared with the calibration thermocouple might experience different heating rates inside the
front oven of the instrument, given that the heat capacity of the contents inside the oven is
different. However, this study focused on the temperatures recorded only when they reached
steady state for each temperature step. The assumption for this study was that the steady-state
temperature of the quartz boat with filter inside the front oven will be the same as the steady-
state temperature recorded during calibration with the thermocouple.
Table 3-4 summarizes temperatures required (Tsetpoint) at each programmed step and the
average Tfilter measured by the calibration kit, along with the average temperature deviations
(% difference) for the dual-optics analyzer tested as part of the current study. Tfilter values were
systematically lower than Tsetpoint values prior to calibration over the entire temperature range
evaluated for both TOA protocols. This was presumably due to (1) the unique location of each
thermocouple as shown previously in Figure 3-7 and (2) a different allocation of heating coils
around the sample boat and in the sample oven. Phuah et al. (2009) attributed the lower Tfilter
temperatures to the less tightly packed heating coils around the quartz tube where the
transmittance laser passes compared to the tightly packed heating coils in the sample oven. These
existing instrument limitations most likely resulted in mean temperature difference or bias (AT)
between Tsetpoint and Tfilter measured in this study between 32 °C and 75 °C. The AT
observed is less at low temperatures (< 43 °C for temperatures < 450 °C) than at high
temperatures (< 75 °C for temperatures < 890 °C). The AT under the NIOSH and IMPROVE
protocols varied at the Tsetpoint of 550 °C. Inherent in the NIOSH temperature protocol was a
higher AT (70 °C) at the He-02 introduction step where temperature decreases from 870 °C to
550 °C. The high AT at that step is presumably due to the wide temperature gap (870 °C to 550
°C) and short residence time.
23
-------
Table 3-4. Filter Temperatures Measured before Calibration for NIOSH 5040 and IMPROVE
Protocol
Carbon
Fraction
Tsetpoint
NIOSH 5040
Tfilter AT C
Tsetpoint
IMPROVE
Tfilter
AT C
( C)
( C)
(% difference)
( C)
( C)
(% difference)
OC1
310
278
32 (10)
120
88
32 (27)
OC2
475
435
40 (8)
250
211
39 (16)
OC3
615
569
46 (7)
450
407
43 (10)
OC4
870
800
70 (8)
550
501
49 (9)
EC1
550
482
68 (12)
550
501
49 (9)
EC2
625
563
62 (10)
700
639
61 (9)
EC3
700
637
63 (9)
850
777
73(9)
EC4
775
707
68 (9)
EC5
890
813
75 (8)
Consistent with our findings, Phuah et al. (2009) observed AT values of 35-85 °C that varied
with each Sunset Laboratory instrument, while Chow et al. (2005) found that AT depended on
the temperature ramp. Chow et al. (2005) did not observe a linear correlation between Tfilter
and Tsetpoint, although Phuah et al. (2009) and the present study do indicate such a correlation.
Figure 3-8 shows that the Tfilter and Tsetpoint relationship is linear based on temperature data
obtained at nine NIOSH and six IMPROVE temperatures that precede calibration. Regression
analysis shows the slope approaching unity (0.94 ±0.01) but lower than the values measured on
four other Sunset Laboratory instruments found by Phuah et al. (2009). A regression correlation
{r = 1.000; R2 = 0.999) suggests that the Tsetpoint can be increased systematically until Tfilter =
Tsetpoint and Tfilter meets the Tsetpoint requirements of the NIOSH and IMPROVE protocols.
1000
800
= 600
AFTER TCAL
V = 0.99x + 3.34
R2 = 0.999
S
U
K
ce
400
200
*
ML
•x
,-G'
%'
BEFORE TCAL
y = 0.94x-19.58
R*= 0.999
ZOO 400 600
S ETPOI NT TEM PER ATU RE (eC)
800
1000
Figure 3-8. Linear regression results before and after temperature calibration.
24
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Following oven calibration, Tfilter was within 1 % and 1.7 % of Tsetpoint for the NIOSH and
IMPROVE protocols, respectively (Table 3-5). The AT at temperatures below 450 °C was < 5 °C
as compared with AT < 43 °C before calibration (TCAL). At temperatures of 550 °C - 890 °C, AT
was < 9 °C compared with AT < 75 °C before TCAL. The Tfilter and Tsetpoint linear
relationship after calibration is also shown in Figure 3-8. A higher regression slope (0.99 ± 0.01)
and a significantly lower intercept (3.34 ± 3.05) confirm the effectiveness of the temperature
calibration.
Table 3-5. Filter Temperatures Measured after Calibration and Software Adjustments
Carbon
Fraction
Tsetpoint
( C); r*
NIOSH 5040
Tfilter AT C
( C) (% difference)
Tsetpoint
( C); r*
IMPROVE
Tfilter
( C)
AT C
(% difference)
OC1
310; 24
307
3(1.0)
120; 48
122
2(1.7)
OC2
475; 28
472
3 (0.6)
250; 39
254
4(1.6)
OC3
615; 40
609
6(1.0)
450; 42
455
5(1.1)
OC4
870; 65
866
4 (0.5)
550; 50
555
5 (0.9)
EC1
550; 61
546
4(0.7)
550; 50
555
5 (0.9)
EC2
625; 54
622
3 (0.5)
700; 61
703
3 (0.4)
EC3
700; 56
697
3(0.4)
850; 74
854
4 (0.5)
EC4
775; 61
772
3(0.4)
EC5
890; 71
881
9 (1.0)
"Temperature correction coefficients implemented in the software parameter files.
3.3.2 SuperMAAP
As described in Section 2, the Thermo Fisher Scientific 5012 MAAP measures ambient BC
concentrations and aerosol light absorption properties. The design of the MAAP detection
chamber is illustrated in Figure 3-9. The aerosol sample is drawn into the instrument through the
inlet. The sample flows through the down tube and deposits onto the glass-fiber filter tape. The
filter tape accumulates an aerosol sample up to a threshold transmission value (nominally 20 %
transmission), whereupon the filter tape automatically advances before reaching saturation.
Within the detection chamber, a 670-nm visible light source is aimed toward the deposited
aerosol and filter tape matrix. The light transmitted into the forward hemisphere is reflected into
the back hemisphere and measured by a series of photodetectors. During sample accumulation,
the light beam is attenuated from an initial reflectance reading from a clean filter spot. The
reduction of light transmission, multiple reflectance intensities, and air sample volume are
continuously integrated over the sample run to provide 1-min data output of BC concentration
measurements.
25
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Foiwdid
Sample
Inlet
Filter tape
/
Heinispheie
(transmission)
Photodetector
Exhaust
Liijlit Source (670 iidi|
B.itk Hemisphere 0efleclionf
Photodetectois
Figure 3-9. Diagram of 5012 MAAP detection chamber.
To fulfill the requirements of the present study, the 5012 MAAP was substantially modified to
produce the "SuperMAAP" as follows:4
• Flow was reduced through the filter tape to extend its useful life. Sample flow was
software controlled and consisted of a total aerosol flow that entered the inlet of the
instrument and a sample flow that was directed through the filter tape. The BC
concentration was calculated as the mass of BC collected on the tape during the analysis
per volume of sample passed through the tape.
• Software was available to collect and process BC concentration data on a 1-Jlz basis.
This information was stored in a "raw" data file that included all output parameters from
the instrument plus the MBC and CBC.
• Average BC concentrations were calculated at the end of a run along with the standard
deviation (SD) of the measurement using a linear regression approach. The average
values were stored in a "processed" data file.
• The SuperMAAP was automatically isolated from the main sampling line during the filter
changes, providing an unassisted zero check.
• A command could be sent to the instrument to force a manual filter change anytime
during the experiment.
4 EPA NRMRL staff involved in this work included Mr. William Mitchell and Mr. William Squire.
26
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• The new software monitored the percent transmission in real time so that the operator
could determine when a filter change was about to take place.
• A documented QC check was established to tell the operator if the instrument was
working properly and ready for use.
• An add-on "package" incorporating the necessary changes was developed by EPA
NRMRL for use in certification environments.
Figure 3-10 depicts the SuperMAAP configuration, which consists of the standard 5012 MAAP
instrument (lower box) plus the new hardware components installed in a separate enclosure on
top. Before use, both SuperMAAP MFCs were calibrated by the APPCD Metrology Laboratory
using MOP FV-0237.0 (EPA, 2010). Appendix C details the modifications made to the
instrument and includes a complete list of all hardware components and wiring schematics used
during development of the SuperMAAP.
A special Lab View program (kDy Automation Solutions, Morrisville, NC, USA) was written to
operate the SuperMAAP hardware and interface that hardware with the standard instrument to
fulfill the functions described above. The newly developed software that controls the
SuperMAAP consists of four menu bars: File I/O (input/output), Measurement, Status/Errors,
and Configure (Figure 3-11). The software is easy to use, and the user is only required to input
the file name and location and total aerosol and sample flows before starting the measurement.
At the end of each measurement, the processed file is automatically produced and average values
are calculated and displayed along with the SD and the R2 of the fitted line. Operating
instructions for the instrument, including the new software, are provided in SOP 2106 (Appendix
D).
27
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Figure 3-10. SuperMAAP configuration
-------
MAAP Interface *1.2
1237:27 FM
01/06/2011
l
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vaporization temperature (> 4000 K). Incandescence from the soot particles is detected by two
detectors using appropriate line filters, and the signals are recorded for subsequent analyses. A
novel method was developed for calibration of the LII (self-calibrating) based on an absolute
light intensity measurement that avoids the need for calibration with a known source of soot
particles. This method applies two-color pyrometry principles centered at 440 and 780 nm to
determine the particle temperatures.
The instrument consists of two main units: a self-contained LII unit and a laser power supply
(Figure 3-12). A water line runs between the two units to cool the laser during operation. The
instrument was controlled remotely using AIMS software with the AK communication protocol
modified for use in this study. The commercially available LII 300 model was slightly modified
as follows for the present work:
• An external vacuum pump with rotameter was incorporated to allow control and
monitoring of the air sampling flow rate to the instrumentd
• An independent QC check was provided to verify proper instrument operation before
starting measurements. The QC check was made using an operational check lamp that
tests the cleanliness of the instalment windows to determine if there is a variation higher
than a specified percentage deviation in the current values compared to factory-calibrated
values.
Detailed instructions for using the modified LU 300 instrument by Artium Technologies and the
AIMS software are provided in SOP 2102, which can be found in Appendix E.
/Is Liuiri
Figure 3-12. Major components of the LII 300: (1) self-contained LII 300 instrument and
(2) laser power supply.
30
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3.3.4 Micro Soot Sensor (MSS)
The AVL 483 MSS is based on the photoacoustic measurement principle described previously.
In the instrument measurement cell, soot (highly absorbent particles) is irradiated with
modulated light from an embedded Class 4 semiconductor laser (808 ± 5 nm wavelength).
Periodic heating and cooling inside the photoacoustic cell result in expansion and contraction of
the carrier gas. As a result of that interaction, a sound wave is formed and detected with sensitive
microphones. The signal from these microphones is subsequently analyzed electronically to
determine the BC concentration down to 1 |ig/m3. The entire sensor sensitivity (the intensity of
the laser beam and the sensitivi ty of the microphone) is checked by means of an absorber
window. The system automatically performs a check of the resonance frequency of the
microphone in the measuring cell at the end of the operating state "PAUSE" indicated in the
operating software.
The standard AVL MSS consists of three basic units:
• Measuring unit: AVL MSS (Figure 3-13a).
• AVL exhaust conditioning unit (Figure 3-13b).
• Pressure-reducing module with dilution cell (not shown).
leNBOtr MI. A Bum MO UK
Figure 3-13. (A) AVL MSS model 483 and (B) AVL exhaust conditioning unit.
31
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The operating software used in this study generally restricted the input pressure of the AVL MSS
measuring chamber to ambient pressure ± 50 mbar. (Note that newer versions of the software
limit the input pressure to ± 80 mbar.) The temperature of the exhaust gas passing through the
measuring chamber of the AVL MSS could not exceed 60 °C. To measure soot with the AVL
MSS at higher exhaust gas backpressures and temperatures, the pressure and/or temperature had
to be reduced. The pressure and temperature were conditioned by means of the pressure-reducing
module of the AVL exhaust conditioning unit. When the ambient temperature was low and/or the
exhaust gas had not been sufficiently diluted, there was a risk that condensate would form in the
measuring chamber of the AVL MSS. Thus, sufficient dilution of the exhaust gas was important
to prevent formation of condensate. Due to the ambient operating conditions and modest particle
loading of the air stream moving through the flow tunnel, exhaust gas conditioning was not
required for the current study.
The MSS was controlled with the AVL control software for conducting measurements and for
displaying and storing the measurement data with a frequency up to 1 Hz. The BC mass
concentrations were generated directly and expressed as concentration of soot in exhaust
(mg/m3). The maximum soot concentration that can be measured by the MSS is 50 mg/m3 with 1
|ig/m3 sensitivity and a published minimum detection limit of 5 |ig/m3.
The suction power of the pump is set with a throttling valve so that a constant sample flow of
approximately 3.8 L/min is pulled into the inlet of the pump unit at a negative pressure of 300
mbar. In the measuring unit, the sample flow is split into a bypass flow and a measuring flow that
passes through the measuring cell. Both flows should be approximately equal between 1.8 and 2
L/min. Thus, the AVL MSS was used as-is and without any further modifications. Detailed
instructions for using the AVL MSS instrument with the conditioning unit and the control
software are provided in SOP 2105, included here as Appendix F.
3.4 Reference Filter Sampler
Method validation was accomplished through the collection and analysis of concurrent Teflon
filter samples, as specified in AIR 6037, Section 11, Technical Annex 1 (SAE, 2010). Teflon
filter sampling was selected as the reference method because both the collection and analysis of
the samples could be fully quality-assured using standard weights and temperature, pressure, and
flow standards, all of which are NIST-traceable. The existing procedures described in Title 40
Code of Federal Regulations (CFR) Part 86.1065 were used as guidance for collection and
analysis of the Teflon filter samples (EPA, 2012). Detailed instructions on collection and
measurement of nvPM mass using the filter-based gravimetric method are provided in SOP 2103
(Appendix G).
A split sample was provided to the instruments) being evaluated and the reference filter.
Measurements were then conducted over a range of soot concentrations indicative of gas turbine
exhaust, and a correlation was established between the instrument readings and the
gravimetrically determined PM mass concentration. Preconditioned and preweighed
32
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polytetrafluoroethylene (PTFE) filters were used to collect the PM mass from the main sample
stream at an initial flow rate of approximately 45 L/min (Figure 3-1). However, studies have
found that the QFFs used for the determination of OC/EC content described in Section 3.3.1 are
also capable of adsorbing gas-phase semivolatile OC (Turpin et al., 1994) in addition to the PM
OC (positive sampling artifacts). Therefore, a backup prefired QFF was installed downstream of
the PTFE filter and analyzed for OC content as described in SOP 2104 (Appendix B) to correct
for the total gas-phase OC measured on the primary QFF.
Finally, in the original study design, it was assumed that use of the CS would adequately remove
most of the particle-phase OC from the MiniCAST exhaust so that the particles collected on the
Teflon filter would have very low OC content, allowing a direct comparison of the various
measurement methods with the Teflon filter values. However, the CS reduced the OC content
only by an average of approximately 10 % by mass as compared to the untreated aerosol.
Because of the relatively high OC content of the particles collected on the Teflon filter, some
type of correction to the PM mass concentrations obtained during the gravimetric analysis was
needed. Although unable to be verified experimentally, we assumed that the mass percentage of
OC found on the primary QFF (after artifact correction) was identical to the mass percentage of
OC found on the Teflon filter, and the total mass concentration was reduced accordingly. The
OC-corrected Teflon filter concentration calculations were used during the data analyses
described below.
3.5 Supporting Equipment
The main supporting instruments/devices used in the study were the Model 3936 SMPS,
the URG-2000-30EC PM2.5 cyclone, and Personal data acquisition (PDaq) system.
Each is described briefly below.
3.5.1 3936 Scanning Mobility Particle Sizer
The 3936 SMPS consists of a TSI3080 electrostatic classifier, a TSI3081 long differential
mobility analyzer (DMA), and a TSI 3025A condensation particle counter (CPC). The SMPS
was used throughout all experiments (with and without CS) to monitor PM number concentration
and size distribution independently by equivalent electrical mobility diameter. The SMPS
operating software was configured to cover the 13.8-723.4 nm range in the low-flow mode (3
L/min sheath air flow and 0.3 L/min aerosol flow). The impactor used a 0.0457-cm diameter
orifice. Data were collected using 180-s up-scan and 15-s down-scan times. Operation of the
SMPS followed MOP 1412 (EPA, 2004), which is included in this report as Appendix H.
3.5.2 PM2.5 Cyclone Preseparator
An aluminum (but not Teflon-coated) PM2.5 cyclone (URG-2000-30EC) designed for a flow rate
of 42 L/min was used upstream of the instrumentation to capture any large particles shed from
the tunnel walls (Figure 3-2). According to test data provided by the manufacturer, the cut-point
33
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diameter of the cyclone is < 1.5 |im at the approximately 90 L/min flow rate required for the
suite of aerosol instruments.5 The standard cyclone has a straight inlet arm and a 90-degree outlet
arm equipped with special fittings. To make necessary connections with other standard Swagelok
fittings and allow for leak-tight operation, the cyclone connections were refabricated in the EPA
NRMRL machine shop.
3.5.3 Personal Data Acquisition System
A National Instruments PDaq/56 system was used to monitor mass flows, temperatures, and
pressures throughout the flow tunnel system. The PDaq is a 22-bit, universal serial bus (USB)-
based multifunction data acquisition device that can be located up to 5 m from the personal
computer (PC). The PDaq can directly measure multiple channels of thermocouples, voltage,
pulse, frequency, and digital input/output (I/O). The unit's DasyLab software allows real-time
analysis of signals from the PDaq, conversion to operating units (L/min, mm Hg, °C, etc.), and
data logging. In this study, the PDaq recorded data for tunnel pressure and temperature, Mini-
CAST diluter flow, dump line flow, quartz filter sampler flow, differential pressure across the
Teflon filter sampler orifice meter, and static pressure behind the Teflon sampler orifice meter
(Figure 3-1).
5 A cut point of 1.5 (im was deemed appropriate since SMPS scans of the MiniCAST exhaust showed no large
particles being produced.
34
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4 Experimental Procedures
4.1 Experimental Design
The SAE International E-31 Committee decided that each candidate method should be capable of
measuring nvPM concentrations in the range 10 to 1000 |ig/m3. Therefore, experiments were
designed to encompass that concentration range. In addition, six replicate tests were conducted to
provide a statistically adequate basis for comparisons.
Since the aerosol generated by aircraft gas turbine engines is a combination of both volatile and
nonvolatile PM, each candidate method must be able to measure BC only without interference
from volatile particles. Thus, an aerosol containing two different volatile components was
evaluated using the identical experimental matrix. In the first test series, a CS was used
downstream of the MiniCAST to reduce the volatile content of the test aerosol. For the second
set of experiments, the CS was removed and the MiniCAST output was provided directly to the
flow tunnel with no removal of the volatile component. These experiments were intended to
determine the selectivity of each technique for measuring only nonvolatile soot. However, since
the CS only reduced the OC content of the MiniCAST particles by approximately 10 % instead
of near 100 % as expected, sensitivity of the methods to OC could not be fully assessed.
The experimental matrix used for this project is shown in Table 4-1. All four candidate methods
plus Teflon filter sampling were employed at five target concentrations with six replicate tests at
each concentration. In addition, the same concentrations (operating conditions) were evaluated
with and without the CS to explore the influence of volatile particles.
Table 4-1. Experimental Matrix
Aerosol Type
Sampling
Condition ID
Target Soot
Concentration
(jjg/m3)
No. of Runs
Run Time (min)
10WCS
10
6
420
"Low" volatile
PM WCSa
50WCS
50
6
360
100WCS
100
6
180
500WCS
500
6
40
1000WCS
1000
6
20
10WOCS
10
6
420
"High" volatile
PM WOCSb
50WOCS
50
6
360
100WOCS
100
6
180
500WOCS
500
6
40
1000WQCS
1000
6
20
a WCS = experiments with catalytic stripper:
= MiniCAST + CS.
| b WOCS = experiments without catalytic stripper = MiniCAST only.
35
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The MiniCAST operating conditions (gas settings) required for the 50-1000 |ig/m3 concentration
range (Table 4-2) were the same, with a fuel/air ratio of 60/1500 by volume (0.04:1). Under
those conditions, soot mass concentration at the outlet of the MiniCAST measured
approximately 7 mg/m3 and geometric mean particle diameter was in the 80-90 nm range. To
dilute the MiniCAST particle exhaust, the aerosol stream was mixed with the clean air that
entered the tunnel after passing through the HEPA filters (Figure 3-1). The air was provided to
the tunnel using either of two ring compressors (specifications listed in Table 3-1). The
compressors are also referred to in project documentation as "big blower" and "small blower".
The big blower was employed for concentrations of 10, 50, and 100 |ig/m3 and the small blower
for the 500 |ig/m3 concentration. For the highest target concentration, 1,000 |ig/m3, a small
vacuum pump capable of providing approximately 25 L/min of air was employed.
Table 4-2. MiniCAST Flow Settings and Blower/Pump Operating Conditions
Settings
10
Target Concentration (jjg/m3)
50 100 500
1000
MiniCAST
Propane (mL/min)
40
60
60
60
60
Oxidation air (L/min)
1
1.5
1.5
1.5
1.5
Nitrogen for fuel (mL/min)
200
280
280
280
280
Quench nitrogen (L/min)
4
6
6
6
6
Dilution air (L/min)
8
10
10
10
10
Blower/pump
Big blower
X
X
X
Small blower
X
Vacuum pump
X
Blower/pump reading
60 Hz
40 Hz
23 Hz
10 Hz
110 on
rotameter
Tunnel flow (sLpm)
2243
1495
861
161
25
Both blowers and the vacuum pump were calibrated to find the correlation between the standard
volume of air passing through the tunnel (L/min) and the blower controller readings (Hz) or the
pump adjustment (rotameter reading). The results of those calibrations are shown in Appendix I
with the MiniCAST settings and pump/blower conditions required to achieve the target
concentrations listed in Table 4-2.
As can be seen from Table 4-2, the MiniCAST settings were different for the lowest target
concentration of 10 |ig/m3, with propane and oxidation air flow rates of 40 mL/min and 1 L/min,
respectively. Although the flow rates were different and lower, the fuel/air ratio was kept
constant (0.04) to produce aerosol (soot) with the same general characteristics. The other flows
were also reduced proportionally.
4.2 Standard Operating Procedures
As discussed in Section 3, SOPs were prepared for each of the four measurement methods.
Separate SOPs were also prepared for the sampling and measurement of PM mass using a
36
-------
gravimetric, Teflon filter based method and for the operation of the MiniCAST. All SOPs
prepared for the project are listed in Table 4-3 with the full text found in the associated appendix.
EPA's "Guidance for Preparing Standard Operating Procedures (SOPs)" (QA/G-6; EPA, 2007)
was used to prepare the SOPs. Each SOP is self-contained and addresses all aspects of operation,
maintenance, calibration, and QA/QC procedures suitable for possible incorporation into the
ARP. Each SOP was peer reviewed by the SAE E-31 Committee's PM Mass Measurement Team
prior to beginning the measurements. The SOPs were also submitted to EPA NRMRL's QA staff
for review and approval.
In addition to the SOPs listed in Table 4-3, existing EPA MOP 1412 for operation of the TSI
3936 SMPS was also used during the validation experiments (EPA, 2004). This MOP is provided
in Appendix H.
Table 4-3. List of Developed SOPs
SOP Number
SOP Title
Appendix
2101
Operation of MiniCAST Black Carbon Aerosol Generator from Jing
Model 5201—Real Soot Generator
A
2102
Measurement of Nonvolatile Particulate Matter Mass Using the LII 300
Laser-Induced Incandescence Instrument
E
2103
Sampling and Measurement of Nonvolatile Particulate Matter Mass
Using the Filter-Based Gravimetric Method
G
2104
Sampling and Measurement of Nonvolatile Particulate Matter Mass
Using the Thermal/Optical Transmittance Carbon Analyzer
B
2105
Measurement of Nonvolatile Particulate Matter Mass Using the AVL 483
Micro Soot Sensor Photoacoustic Analyzer with AVL Exhaust
Conditioning Unit
F
2106
Measurement of Nonvolatile Particulate Matter Mass Using the Modified
Multi-angle Absorption Photometer (MAAP) - Thermo Fisher Scientific
D
4.3 General Operating Procedures
At the beginning of each day's testing, several activities and procedures were performed to
satisfy QA/QC requirements for each instrument and method used in the validation. These step-
by-step procedures and the general protocol used to conduct each experiment were as follows:
1. Turn on all instrument computers (MAAP, LII, MSS, SMPS, and MiniCAST).
2. Using the atomic clock, set the time on the LII computer, which serves as a master clock
for synchronization of all other computer clocks. The network time synchronization is
automatically performed every 10 min using the ClockWatch clock card installed in the
LII computer.
3. Open the main valves on the nitrogen tank and the fuel (propane) tank, and open the main
compressed air valve.
4. Turn on all instruments and allow them to warm up. These instruments include AVL
MSS 483 and conditioning unit; LII laser power supply (first), LII 300 instrument, and
37
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external vacuum pump; MAAP external pump, MAAP 5012 instrument, and
SuperMAAP module; MFC system for MiniCAST; and SMPS DMA and CPC units.
5. Turn on the tunnel blower/pump and set it according to Table 4-2. The choice of
blower/pump and setting will depend on target concentration.
6. Make sure the pneumatic two-way isolation valve control is in the "bypass" position.
7. Start the DasyLab software and initiate the logging.
8. Turn on the vacuum pump for the instrument excess flow (dump) line. The flow for that
line is measured by an MFM and should be approximately 21 L/min. Check the DasyLab
output for that line.
9. If needed, turn on the temperature controller for the CS (see Table 4-1 for details). The
temperature set point should be 315 °C to reach the actual temperature of 300 °C. The CS
takes approximately 10-15 min to heat up.
10. Start the AVL MSS software. Select REMOTE communication option and NO
DILUTION experiment, and press the PAUSE icon. The device requires approximately
25 min to heat up. Details of instrument operation are provided in SOP 2105 (Appendix
F).
11. Start the Get Red-y software for the MiniCAST MFCs. Open the main valve on the front
panel of the MiniCAST, but make sure the fuel control valve is completely closed. Set
the gas flows for ignition. Ignite the MiniCAST and open the fuel control valve. Inspect
the sight glass to ensure the flame is still present and stable. When the flame is stable, set
the gas flows per Table 4-2. Details of instrument operation are provided in SOP 2101
(Appendix A). Allow the burner to operate at least 30 min, and then start logging the
MFC flows in the Get Red-y software.
12. Open the valve that supplies dilution air upstream of the CS (~ 25 L/min). The flow for
that line is measured by an MFM. Check the flow for that line in the DasyLab software.
13. After the SMPS is warmed up, start the AIM software. Open and name the new file and
select devices. Choose 3 L/min for the sheath air flow and 0.3 L/min for the aerosol flow,
impactor type 0.0457 cm, particle density 1.000 g/cm3, and a multiple charge correction.
Start data collection.
14. Place a 47-mm filter cassette containing a clean, prebaked QFF into the quartz filter
holder. Install the holder in the sampler.
15. Perform a leak test for the QFF sampler. Remove the sampling line and install a pressure
gauge on the inlet of the filter holder. Close the three-way valve and start the pump.
Slowly open the valve and observe the pressure gauge until the maximum vacuum is
reached. Close the valve and turn off the pump. Observe the pressure gauge for 2 min. If
the pressure does not drop more than 15 kPa Hg, the system is leak-free.
38
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16. Move the three-way valve of the QFF sampler to the "bypass" (open to atmosphere)
position and start the pump. When ready to sample, move the three-way valve to the
"sample" position. Watch the QFF flow rate in the DasyLab software while opening the
needle valve. The flow should be approximately 6 L/min.
17. Place a 47-mm filter cassette containing a preweighed Teflon filter into the sampler filter
holder and another 47-mm filter cassette containing a clean, prebaked QFF into the
second filter holder. Install them in the sampler with the Teflon filter acting as the main
filter and the quartz filter as a backup filter. Perform a leak test for the Teflon filter
sampler using the same procedure described in step 15.
18. Move the three-way valve of the Teflon filter sampler to the "bypass" (open to
atmosphere) position and start the pump. When ready to sample, move the three-way
valve to the "sample" position. Watch the Teflon filter flow rate in the DasyLab software
while opening the needle valve. The flow should be approximately 45 L/min.
19. Start the SuperMAAP software. Make sure that total and SuperMAAP flows are 5 and
3.5 L/min, respectively. Start data logging for raw data collection. Initialize a filter
change. When ready, start the experiment in the software. Details on instrument operation
are provided in SOP 2106 (Appendix D).
20. Start the LII remote AIMS software. If necessary, perform a lamp check of the instrument
and record the results. Start data logging. Details of instrument operation are provided in
SOP 2102 (Appendix E).
21. By this time, the AVL MSS should be warmed up. If starting a test series, perform an
absorber window check. Place the AVL MSS in STANDBY position (~ 60 s for
stabilizing). In SERVICE VIEW (NUMERICAL), make sure the following parameters
are within the required ranges and record the results:
a. Zero signal (window pollution): 0.0-1.4 mV.
b. Resonance frequency: ~ 4100 Hz.
c. Maximum raw measurement value: 30-230 mV.
d. Measuring cell temperature at test: ~ 52 °C.
22. Once the MSS unit has completed the STANDBY process, start sampling by selecting the
MEASUREMENT option.
23. Stop the SuperMAAP pump and perform a QC check by observing the following
parameters and recording the results:
a. Transmission and two reflection diodes between 3000 and 3900.
b. Reference diode between 1500 and 3900.
When complete, turn the pump back on and force a manual filter change in the software.
Details of this procedure are provided in SOP 2106 (Appendix D).
39
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24. After the MiniCAST has been running for approximately 30 min, check the size
distribution and concentration in the flow tunnel measured by the SMPS. If the target
value has been reached within approximately ±10 %, the system is ready to start.
25. Start the experiment by moving the pneumatic three-way bypass valve control to the
"sample" position while simultaneously pressing START CONDITION (processing data)
in the SuperMAAP software. Record the START time to the nearest second. All
instruments should now be measuring tunnel concentrations near the target mass
concentration.
26. During the test, record any errors, discrepancies, and other experimental observations and
modifications in a laboratory notebook.
Once the test period is finished, the following steps are performed to shut down all instruments,
preserve filter samples, and save the collected data:
1. End the experiment by moving the pneumatic three-way bypass valve control to the
"bypass" position while simultaneously pressing STOP & CALC in the SuperMAAP
software.
2. Record the STOP time to the nearest second.
3. Stop data logging in the AVL MSS software, LII AIMS software, DasyLab, SMPS AIM
software, and Get Red-y software.
4. For the QFF and Teflon samplers, move the three-way valve to the "bypass" (open to
atmosphere) position and stop the pumps.
5. In the Get Red-y software, set all MiniCAST gas flows to 0 to shut down the burner.
6. If done for the day, turn off the main valve on the MiniCAST and completely close the
fuel control valve.
7. If done for the day, close the main valves on the propane and nitrogen gas cylinders and
close the compressed air valve. Release the pressure from the propane and nitrogen gas
lines.
8. If done for the day, close out the MSS, LII, DasyLab, SMPS, and Get Red-y operating
software.
9. If done for the day, turn off the LII 300 instrument, laser power supply, and external
pump; AVL MSS instrument and conditioning unit; SMPS DMA and CPC; MFC box for
the MiniCAST; SuperMAAP instrument and external pump; and vacuum pump for dump
line.
10. If done for the day, turn off the CS temperature controller (if used).
11. Leave the blower on until the next day (next test).
12. Remove the cassettes from both filter samplers (two quartz and one Teflon filter), place
them in clean and labeled cassette mailers, and store them in the portable freezer until
40
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ready for analysis. Details about filter handling and analysis are provided in the SOP
2104 and SOP 2103 (Appendix B and Appendix G, respectively).
13. At the end of the day, copy data files to a USB memory stick and then from the stick to
an office computer's hard drive.
14. Turn off all computers.
4.4 Data Reduction
4.4.1 Gravimetric Method
Total PM mass concentration was measured using 47-mm Teflon filters. The PM mass collected on a
Teflon filter during sampling was determined by weighing the filter before and after sampling. The
total PM mass concentration was obtained by dividing the PM mass collected on the filter by the total
air volume pulled through the filter during sampling. The flow rate of sample gas through the Teflon
filters was measured using an orifice meter, with the total volume of sample gas between two
consecutive readings calculated by:
Vt = Qavg tr (4-1)
where:
Vt = total volume over the sampling time (L).
Qavg = average flow rate reading (sLpm).
tr = total sampling time (min).
The actual volume is the standard volume corrected to the EPA standard temperature and
pressure (STP) conditions (25 °C and 760 mm Hg).
Thus, the total PM mass concentration is given by:
Cpm = Mpm 1000/Vt (4-2)
where:
Cpm = total mass concentration (|ig/m3).
Mpm = PM mass collected on the filter (|ig).
To correct the measured PM mass concentration from the Teflon filter results for the OC content
of the QFF sample, the following calculation was used:
OCCCvw = Cpm (1 - Mass Fraction of OC Determined on Concurrent QFF) (4-3)
where:
41
-------
OCCCpm = organic carbon corrected total mass concentration (|ig/m3).
Six experiments (runs) were conducted for each target concentration and condition. Before and
after each sample set, the background air from the tunnel (MiniCAST not running) was sampled
for the same sampling time as the samples from the target concentration. The mass of these
"tunnel blank" filters was measured and averaged (OCCCtb) using Equations 4-1, 4-2, and 4-3.
The total PM mass concentration measured using Equation 4-3 was then blank corrected (Cpm-bc)
as follows:
Cpm-bc = OCCCpm - OCCCtb (4-4)
where:
Cpm-bc = blank-corrected total mass concentration (|ig/m3).
OCCCtb = average of pre- and post-test series tunnel blank concentrations (|ig/m3).
4.4.2 NIOSH 5040 Method
The Sunset thermal-optical OC/EC analyzer measures the mass of EC, OC, and TC collected on
QFFs in units of |ig/cm2. The masses (in |ig C) of OC, EC, and TC on the filter were calculated
by multiplying the concentration (C) of each type of carbon (|ig C/cm2) by the deposit area (A ) of
the filter in cm2 as follows:
M = C A (4-5)
The filter deposit area was 11.76 cm2 for a 47-mm quartz-fiber filter used for sampling in a filter
cassette with a 38.7-mm inside diameter, which defined the deposit area. Mass (M, in |ig C) of
each type of carbon on a filter was divided by the STP volume of air sampled (Equation 4-1) to
calculate concentrations (Equation 4-2) of each type of carbon sampled in the aerosol.
As already described in Section 3, a backup quartz-fiber filter was placed behind the Teflon filter
to measure gas phase OC. The backup filter was analyzed using the same NIOSH 5040 method,
and the concentrations of each type of carbon (OC, EC, and TC) were subtracted from the
concentrations measured by the main QFF. The carbon concentrations measured by the main
QFF were also blank corrected using Equation 4-4 after analyzing the "tunnel blank" filters.
4.4.3 SuperMAAP
BC mass was calculated and stored in a raw data Excel file created by the newly developed
MAAP software. A processed Excel file then was automatically produced and the average
concentration of BC (CBC, in |ig/m3) calculated and displayed together with SD and R2 of the
linear regression line. The CBC was then manually blank corrected using the average CBC
measured by the MAAP in the two tunnel blank runs (see Equation 4-4). The MAAP required no
additional data reduction steps.
42
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4.4.4 Lll
The LII 300 PC software (AIMS) using the AK communication protocol automatically stores
data acquired during an analysis in individual Excel spreadsheet files. For the current project, BC
mass concentrations were generated on a 1-Hz basis and expressed as concentration of soot in
exhaust (mg/m3) at 25 °C and 1013 mbar (760 mm Hg). Thus, no additional STP correction was
necessary. The average CBC was calculated, and that value was blank corrected with the average
CBC measured by the LII in the tunnel during the two tunnel blank runs when the MiniCAST
was off.
It should be noted that the LII did not produce a numerical value when the measured
concentration dropped below detection. Therefore, for the tunnel blank runs, zeros were
manually entered into all blank cells of the spreadsheet generated by the AIMS software, and the
average concentration was calculated accordingly.
4.4.5 AVLMSS
The AVL MSS PC software automatically stores data acquired during an analysis in individual
Excel spreadsheet files. BC mass concentrations were generated on a 1-Hz basis and expressed
as concentration of soot in exhaust (mg/m3) at 0 °C and 1013 mbar (760 mm Hg). The following
equation was used to recalculate that value to EPA STP conditions (25 °C and 760 mm Hg):
Cstp = C x (P/Pstp) x (Tstp/T) (4-6)
where:
Cstp = soot concentration at EPA STP conditions (25 °C and 760 mm Hg).
C = soot concentration at 0 °C and 760 mm Hg generated by the MSS instrument.
P/Pstp = ratio of actual to standard pressures (in atm) under different conditions.
Tstp/T = ratio of standard to actual temperatures (in K) under different conditions.
Since both the pressures and the temperatures are known values, the conversion can be
simplified to:
Cstp = C x 0.92 (mg/m3) (4-7)
This equation accounts for the temperature conversion from 0 °C to 25 °C for the MSS.
The average CBC was also calculated, and that value was blank corrected with the CBC
measured by the AVL MSS in the two tunnel blank runs (see Equation 4-4).
43
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4.5 Data Post-Processing
Upon completion of the study, QC checks of the data were performed, revealing a number of
issues requiring corrective action. First, the results showed that for the soot aerosols generated by
the MiniCAST, the PM mass measurements performed by the MSS and NIOSH 5040 methods
were in good agreement with the OC-corrected Teflon gravimetric method. However, the LII
measurements of BC mass were significantly higher (-138 %) and the SuperMAAP instrument
measurements were lower (-35 %). The reasons for these variations were further investigated as
discussed below. Finally, a major issue was discovered late in the program with the SuperMAAP
prototype, also described below, that impacted the data collected by the other instruments. This
section outlines all corrective actions taken for the LII and SuperMAAP and post-processing of
the data.
4.5.1 LII
To diagnose problems with the LII, the instrument was returned to the manufacturer where it was
discovered that the wrong calibration constant (i.e., the irradiance value from the integrating
sphere was used instead of the radiance value) was applied before the instrument was shipped to
EPA. Working with representatives from Artium Technologies, Inc., and NRC-Canada, the
calibration was rerun and the existing LII calibration coefficients for conversion of the LII
incandescence signals to BC mass were replaced with corrected values. As a result of that
change, all raw LII data sets were reprocessed by Artium Technologies, Inc., and new average
BC concentrations computed. However, to independently verify the new coefficients, the LII
calibration change was experimentally verified as described in Appendix J. This evaluation
indicated sufficient agreement between the new experimental data and the data reprocessed by
Artium for the same test conditions that the reprocessed LII data could be used.
4.5.2 SuperMAAP
Working with Aerodyne Research, Inc., kDy Automation Solutions, Inc., and the APPCD
Metrology Laboratory, the SuperMAAP and its operating software were reevaluated to
determine the basis for the observed difference (-35 % under-measurement of BC
concentration). Two problems were found that were not apparent before the study began. First,
the tape head was determined to contain a leak whereby laboratory air was introduced into the
flow downstream of the filter tape. Based on a recalibration of the entire flow system, it was
determined that approximately 15 % less air was actually passing through the filter tape than was
actually measured by the downstream MFC. Further experiments with different filter loadings
showed that this leak was consistent and could easily be compensated for in the MFC calibration.
In addition, the existing data set could be corrected by a simple flow correction. It is generally
known that the standard 5012 MAAP is not leak tight, and this leak was thought to be minimal,
which was found not to be the case.
44
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Another problem involved the linear regression of the MBC values used to determine the average
CBC in the LabView version 1.2 software. The original code calculated the linear regression
over the entire sampling period by simply ignoring the time period(s) when filter changes
occurred. This method created approximately a 9 % difference in the average CBC from that
determined by the Aerodyne Research IgorPro software (see Appendix C). Therefore, the
LabView software code was revised to calculate individual linear regressions, statistics, and
average CBC for each period between filter changes and then calculate an overall average CBC
and statistics from these values. This revision provided results that were within 1 ng/m3 of the
value determined by the Aerodyne IgorPro code.
A LabView post-processor was developed whereby the existing experimental data could be
corrected for this problem and reported accordingly. New average BC concentrations were
computed using the post-processor. Independent experimental verification of the SuperMAAP
changes was also deemed necessary, which showed that the post-processed results were
acceptable, as discussed in Appendix J.
Finally, a major issue was discovered with the SuperMAAP prototype during use on another
project, as described in Appendix C. One of the main objectives of the instrument modification
was to make sure that the MAAP filter changes did not adversely affect the measurements made
by other instruments operating on the same sampling line. The MAAP experts who attended the
workshop held by EPA thought this problem had been solved during the design phase. However,
this was found not to be the case, and a special air flow and tracer gas study (described in detail
in Appendix C) was conducted to determine the impact of the SuperMAAP filter change on the
other instruments and to develop appropriate correction factors. These corrections were then
applied to the entire data set already corrected for the LII recalibration and the SuperMAAP leak
adjustment and software change as presented in Section 5.
45
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5 Results and Discussion
The study was conducted from July 22 to October 12, 2011, and consisted of 75 test runs
following the experimental matrix shown in Table 4-1. At least six runs were completed at each
target concentration in addition to a tunnel blank before and after each test series. The run times
varied from 7 h at the 10 |ig/m3 target concentration to 20 min at 1000 |ig/m3 to collect a
consistent mass loading for the filter samples. A consistent loading was also an additional QC
check during the laboratory analyses of the samples. The following sections provide the results
of the study.
5.1 Catalytic Stripper Results
Table 5-1 shows the raw experimental data for all tests conducted with the CS. Recall that these
experiments were intended to determine the selectivity of each technique for measuring soot of
lower volatility. Also shown in the table are test date, start time, test duration, standard error of
each value, and EC/TC ratio. These data reflect all corrections described in Section 4.5 except
for the tunnel blanks (whose values are shown in the table), the SuperMAAP filter change
adjustments, and correction of the Teflon data for OC content. The latter correction was found to
be necessary due to the low OC removal efficiency of the CS as described previously.
Final results for each method are provided in Table 5-2. These data reflect all final corrections
and are plotted against the OC-corrected Teflon filter concentrations in Figure 5-1. Figure 5-1
also shows the linear regression results (slopes and correlation coefficients) with the dashed 1:1
line representing perfect agreement between each set of measurements. Deviation from that line
(i.e., slope) indicates the magnitude of experimental variability from the filter gravimetric
method. The linear fit lines were forced through zero,6 and their slopes indicate that the best
agreement (slope = 0.97) with the filter gravimetric method was observed for the LII instrument.
The values for the NIOSH 5040, MSS, and SuperMAAP were very close to each other, with the
NIOSH method being lower than the Teflon filter by approximately 14 % (slope = 0.86) and the
MSS instrument lower by approximately 16 % (slope = 0.84). The SuperMAAP had the least
agreement of the three instruments with the Teflon filter results, with a slope of 0.82 or an 18 %
deviation from the 1:1 line. The NIOSH 5040 EC concentrations should have matched very
closely with those obtained from the filter gravimetric method after correction for the OC content
on the quartz filters, but instead approximately a 14 % difference was found in the measurements
made by the two techniques with no apparent explanation. Correlation coefficients for all
regression lines were excellent with R2 values being > 0.99.
6 A linear fit through zero was based on the assumption agreed to by the SAE E-31 Committee that all instruments
theoretically read zero when particles are not present in the system.
46
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Table 5-1. Raw Experimental Data Using Catalytic Stripper*
Target
Concentration
(|jg/m3)b
Test
ID
Test
Date
Start Time
Duration
(min)
Teflon
Filter
(|jg/m3)c
LI I
(H9/m3)
MSS
(Mg/m3)
SuperMAAP
(Mg/m3)
NIOSH
5040 EC
(|jg/m3)d
EC/TC
(%)e
10
A
8/23/11
09:18:00
420
17.4
10.5 ± 3.40
6.69 ± 0.560
12.8 ± 0.0864
9.95
68.4
B
8/24/11
09:05:00
420
17.1
9.48 ± 3.04
7.03 ± 0.871
13.3 ± 0.129
10.6
70.8
C
8/25/11
09:15:00
420
17.4
10.7 ± 3.44
7.66 ± 0.689
13.5 ± 0.124
10.7
69.6
D
8/26/11
09:00:00
420
17.1
10.9 ± 3.56
8.04 ± 0.685
12.9 ±0.121
8.02
63.4
E
8/29/11
09:39:00
420
16.8
11.0± 3.68
8.07 ± 0.628
13.1 ± 0.115
10.9
76.2
F
8/30/11
09:00:00
420
16.7
10.9 ± 3.64
7.62 ± 0.652
12.8 ± 0.0956
8.62
74.6
G
8/31/11
08:30:00
420
0.325
0.0730 ± 10.4
-0.000106 ± 0.000548
0.0495 ± 0.00346
0.00
0.00
50
A
8/9/11
09:35:00
360
91.5
45.2 ± 7.05
52.3 ± 1.24
64.2 ± 0.600
55.9
68.4
B
8/10/11
09:02:00
360
96.5
51.9 ± 7.85
55.6 ± 1.46
68.1 ± 0.627
57.2
66.7
C
8/11/11
08:50:00
360
100
57.1 ± 8.35
56.4 ± 1.28
70.0 ± 0.604
62.6
67.9
D
8/12/11
08:57:00
360
104
61.5 ± 8.82
60.0 ± 1.19
72.5 ± 0.652
69.7
72.6
E
8/19/11
09:14:00
360
99.5
66.7 ± 9.69
56.0 ± 0.948
59.6 ± 0.528
64.6
70.9
F
8/20/11
09:25:00
360
106
72.8 ± 9.91
62.5 ± 0.996
63.7 ± 0.601
67.8
67.6
G
8/22/11
09:12:00
360
0.379
0.00465 ± 0.000198
-0.920 ± 0.000596
0.369 ± 0.126
0.00
0.00
100
A
7/22/11
12:47:00
180
4.33
8.25(10)"® ± 0.000142
-0.00140 ± 0.000608
0.0349
0.00
0.00
B
7/25/11
09:30:00
180
173
NA
96.6 ±4.11
115 ± 1.46
104
75.0
C
8/1/11
14:01:00
180
171
92.4 ± 10.0
96.8 ± 1.89
120 ± 1.02
119
74.9
D
8/2/11
09:17:00
180
167
95.6 ± 10.5
95.0 ± 1.69
114 ± 1.08
106
71.6
E
8/2/11
13:24:00
180
164
95.1 ± 10.5
93.8 ± 0.811
115 ± 1.10
103
78.0
F
8/3/11
09:00:00
180
159
95.7 ± 11.0
92.2 ± 1.75
110 ± 1.02
103
75.4
G
8/3/11
12:22:00
180
159
95.0 ± 10.9
92.4 ± 2.47
115 ± 1.06
90.2
76.5
I
8/4/11
13:03:00
180
161
97.8 ± 10.9
92.8 ± 1.18
116 ± 1.07
102
70.9
J
8/5/11
09:02:00
180
0.740
0.00473 ± 7.91 (10)-5
0.518 ± 0.565
0.0576 ± 0.230
0.00
0.00
500
A
9/1/11
11:30:00
40
607
468 ± 32.9
370 ± 14.4
413 ± 3.34
399
75.2
B
9/1/11
12:55:00
40
599
461 ± 32.2
370 ± 14.2
417 ± 3.58
388
74.1
C
9/1/11
14:50:00
40
591
453 ± 32.4
362 ± 13.8
411 ± 3.59
390
70.9
D
9/1/11
15:50:00
40
593
454 ± 31.6
358 ± 13.6
402 ± 3.67
363
73.6
E
9/2/11
09:47:00
40
624
505 ± 35.3
383 ± 16.5
420 ± 3.80
383
74.6
F
9/2/11
10:50:00
40
618
469 ±117
381 ± 33.3
407 ± 3.99
404
74.2
G
9/2/11
11:55:00
40
616
499 ± 35.9
380 ± 16.8
416 ± 4.00
403
74.1
47
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Target
Concentration
(|jg/m3)b
Test
ID
Test
Date
Start Time
Duration
(min)
Teflon
Filter
(Hg/m3)c
Lll
(Hg/m3)
MSS
(Hg/m3)
SuperMAAP
(Hg/m3)
NIOSH
5040 EC
(|jg/m3)d
EC/TC
(%)e
H
9/6/11
10:05:00
40
5.70
0.0318 ± 0.000947
0.332
0.0588 ± 0.00922
0.00
0.00
1000
A
9/9/11
08:55:00
20
1600
1130 ± 88.4
983 ± 83.4
948 ± 14.2
1000
72.9
B
9/9/11
09:38:00
20
1630
1130 ± 91.5
998 ± 84.0
942 ± 14.1
1020
73.7
C
9/9/11
10:15:00
20
1620
1140 ± 85.5
1000 ± 86.3
941 ± 13.9
1020
74.9
D
9/9/11
11:00:00
20
1330
924 ±106
818 ±115
773 ± 14.1
799
72.1
E
9/9/11
11:40:00
20
1310
914 ± 97.4
806 ±118
771 ± 14.0
815
74.0
F
9/9/11
12:30:00
20
1330
931 ± 82.9
813 ±113
794 ± 14.5
814
72.4
H
9/9/11
14:20:00
20
1320
914 ± 91.7
785 ±113
760 ± 13.7
796
73.7
I
9/9/11
15:00:00
20
15.7
1.83 ± 0.00778
1.40 ± 0.530
1.02 ± 0.332
0.00
0.00
Experimental data after correction for Lll calibration constants, SuperMAAP flow adjustment/software changes, and MSS temperature correction but without subtraction of the
tunnel blanks whose values are shown in the table. All data rounded to three significant figures. The ± values shown are the sample SDs.
bMiniCAST setting #7 for all tests conducted.
cNot adjusted for the percent OC determined from the quartz filter analyses.
dEC = elemental carbon determined by the NIOSH 5040 method.
eRatio of EC to TC determined from the quartz filter analyses.
48
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Table 5-2. Summary of Final Test Results Using Catalytic Stripper3
OC-Corrected PM Concentration
Target Concentration Measurement Method13 (Mg/m3)c
Test A
Test B
Teste
Test D
Test E
Test F
Test G
Test H
Test I
Test J
10 |jg/m3
TEFLON
17.0
16.8
17.0
16.7
16.4
16.3
Blk
NA
NA
NA
TEFLON 1
11.7
11.9
12.0
10.2
12.1
11.6
Blk
NA
NA
NA
MAAP
12.8
13.2
13.5
12.9
13.1
12.7
Blk
NA
NA
NA
MSS
6.69
7.03
7.64
8.04
8.07
7.62
Blk
NA
NA
NA
LI I
10.4
9.4
10.6
10.7
10.9
10.9
Blk
NA
NA
NA
EC 1
10.0
10.6
10.7
8.02
10.8
8.62
Blk
NA
NA
NA
OC 1
4.56
4.41
4.24
5.12
3.87
3.42
Blk
NA
NA
NA
TC 1
14.5
15.0
15.1
13.1
14.7
12.0
Blk
NA
NA
NA
50 |jg/m3
TEFLON
90.9
96.5
99.5
104
99.5
106
Blk
NA
NA
NA
TEFLON 1
62.2
64.3
67.6
75.3
70.6
71.7
Blk
NA
NA
NA
MAAP
64.1
68.1
69.9
72.5
59.5
63.7
Blk
NA
NA
NA
MSS
52.0
55.3
56.1
59.7
55.8
62.2
Blk
NA
NA
NA
Lll
45.0
51.9
57.0
61.5
66.7
72.7
Blk
NA
NA
NA
EC 1
55.9
57.2
62.6
69.7
64.6
67.8
Blk
NA
NA
NA
OC 1
25.9
28.6
29.5
26.4
26.4
32.5
Blk
NA
NA
NA
TC 1
81.8
85.7
92.1
96.0
91.0
100
Blk
NA
NA
NA
100 |jg/m3
TEFLON
Blk
170
168
164
161
156
157
NA
158
Blk
TEFLON 1
Blk
118
134
120
124
115
107
NA
118
Blk
MAAP
Blk
114
120
114
115
110
115
NA
116
Blk
MSS
Blk
96.2
96.4
94.7
93.4
91.9
92.1
NA
92.5
Blk
Lll
Blk
NA
92.4
95.5
95.0
95.7
95.0
NA
97.8
Blk
EC 1
Blk
104
119
106
103
103
90.2
NA
102
Blk
OC 1
Blk
45.9
30.0
38.2
30.7
36.1
42.0
NA
34.6
Blk
TC 1
Blk
150
149
144
134
139
132
NA
137
Blk
500 |jg/m3
TEFLON
602
594
586
588
619
613
611
Blk
NA
NA
TEFLON 1
453
440
416
433
462
455
453
Blk
NA
NA
MAAP
413
416
411
401
420
407
416
Blk
NA
NA
MSS
368
369
361
357
382
380
378
Blk
NA
NA
Lll
467
460
452
453
504
468
498
Blk
NA
NA
49
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OC-Corrected PM Concentration
Target Concentration
Measurement Method13
(Hg/m3)c
Test A
Test B
Teste
Test D Test E Test F Test G
Test H
Test 1
Test J
EC 1
OC 1
TC 1
399
132
530
387
136
523
390
160
549
363
130
493
382
130
512
404
140
544
402
128
542
Blk
Blk
Blk
NA
NA
NA
NA
NA
NA
1000 |jg/m3
TEFLON
1590
1610
1600
1310
1300
1320
NA
1310
Blk
NA
TEFLON 1
1160
1190
1200
945
961
956
NA
963
Blk
NA
MAAP
947
942
941
773
771
793
NA
759
Blk
NA
MSS
979
995
1000
815
803
810
NA
782
Blk
NA
LI I
1120
1120
1140
921
911
928
NA
911
Blk
NA
EC 1
1000
1020
1020
798
814
813
NA
795
Blk
NA
OC 1
373
366
340
310
286
310
NA
284
Blk
NA
TC 1
1370
1390
1360
1110
1100
1120
NA
1080
Blk
NA
aFinal experimental data after tunnel blank correction and adjustment for Teflon filter OC content and SuperMAAP filter changes.
TEFLON = Teflon filter gravimetric results with no correction for OC 1; TEFLON 1 = Teflon filter gravimetric results corrected for the percent OC determined by quartz
filter sampling and NIOSH 5040 analysis; EC 1 = elemental carbon determined by NIOSH 5040; OC 1 = organic carbon determined by NIOSH 5040; TC 1 = total
carbon determined by NIOSH 5040.
CAII values rounded to three significant figures. Blk = blank test; NA = not applicable or not available.
50
-------
1400
1400
1200
1000
¦D
a>
1—
3
f0
O
400
200 400 600 800 1000
OC-Corrected Teflon Filter Concentration (pg/m3)
1200
Lll
y = 0.9708x
R2 = 0.9961
NIOSH
y = 0.8545X
R2 = 0.9991
MSS
y = 0.8376X
R! = 0.9994
~ SuperMAAP
¦ MSS
ALII
ONI0SH 5040
SuperMAAP
y = 0.8238X
R2 = 0.9927
Figure 5-1. PM mass concentration plots for experiments with the catalytic stripper based on
Teflon filter results.
Similar data plotted against the NIOSH 5040 results are shown in Figure 5-2. The MSS and
SuperMAAP were both within 2 to 4 % of perfect agreement; the LII was approximately 14 %
higher. These results indicate that if the three instruments were calibrated against the same
NIOSH standard, all three would produce comparable results. This observation is of particular
importance because the NIOSH method is currently being proposed for use in routine calibration
of these instruments as the filter gravimetri c method is too costly and time consuming.
51
-------
~ SuperMAAP
¦ MSS
ALII
Ul
y= 1.1353*
R==0.994S
MSS
y= 0.9799*
R= = 8.»3BS
Su perM AAP
y = 0.9643*
RP = 0.9949
1400
1200
JNOOO
~ 000
-------
SD-fl
500 •-
a
3>
i4fB
g 300
o
y
E
0.
| 200
3
«
¦
100
--
~ SuperMAAP
ftMSS
LA
= 1-341
?== e 5-e
&
?S-
m
* **¦
!u
'
•ifdai
= 0.&S3-
1
X.
-- *
V
W03W
v =a.zmA
—
S? = c.
55S4
I
s
f
•j-
»31
r'-v
<¦
A
t^V
A
100 200 300 400 500
OC-Corrected Tefto n Filter C on centratio n (5)
600
~ SuperMAAP
¦ MS 5
*Ln
ui
1.1*741
R= = C SM4
¦f - 1. '364}>
R= = 0.J46S
100 200 300 400 500
NIOSH 5040 Elemental Carbon Concentration (MB 'nrf1!
Figure 5-3. PM mass concentration plots for target concentrations between 50 and 500 |jg/m3 with
stripper based on (A) OC-corrected Teflon filter results and (B) NIOSH 5040 results.
53
-------
5.2 Results Without Catalytic Stripper
Raw data from experiments performed without use of the CS are shown in Table 5-3. These
experiments were intended to determine the selectivity of each technique for measuring soot of a
higher volatile content. Again, the data shown in the table reflect all corrections except for the
tunnel blank corrections, the SuperMAAP filter change adjustments, and the OC correction to
the Teflon filter results, as described previously.
Table 5-4 shows the final results for each method. As before, these data reflect all final
corrections and are plotted against the OC-corrected Teflon filter data in Figure 5-4. Figure 5-4
shows that, unlike the data from experiments with the CS, the NIOSH 5040 data agree within
approximately 1 % of the OC-corrected Teflon filter concentrations with a slope of 0.99. The
MSS results showed the next closest agreement (slope = 0.84) followed by the LII (slope = 1.19)
and the SuperMAAP (slope = 0.81), both of which were within approximately 19 %. The relative
relationship between the instruments is, however, generally the same as with use of the CS but
with different regression slopes. All R2 values were 0.99 or greater.
Similar results were obtained when the data were plotted against the NIOSH 5040 EC
concentrations, as shown in Figure 5-5. Here the MSS had the best agreement with the NIOSH
method (slope = 0.85) and the LII had the worst agreement (slope = 1.21). The relative
relationship of the three instruments is, however, basically the same as shown previously in
Figure 5-4.
As observed for the "stripped" aerosol, a slightly different relationship between instruments was
obtained if the target PM concentration range was limited to 50 to 500 |ig/m3, as shown in Figure
5-6A and 5-6B for the data plotted against the Teflon filter and NIOSH 5040 results,
respectively. The LII, NIOSH, and MSS slopes are approximately the same, as observed
previously for the full range of target PM concentrations, with a significant difference shown for
the SuperMAAP. The SuperMAAP agrees with the Teflon filter data within approximately 8 %,
whereas before it was within approximately 19 % of the 1:1 line. A similar observation can be
made for the SuperMAAP data compared with the NIOSH 5040 data shown in Figure 5-6B. Like
the results with use of the stripper, the SuperMAAP seems to have better agreement with the
NIOSH 5040 method for this target concentration range.
54
-------
Table 5-3. Raw Experimental Data Without Use of Catalytic Stripper*
Target
Concentration
(|jg/m3)b
Test
ID
Test Date
Start Time
Duration
(min)
Teflon
Filter
((jg/m3)c
Lll
(Mg/m3)
MSS
(M9/m3)
SuperMAAP
(M9/m3)
NIOSH
5040 EC
(Mg/m3)d
EC/TC
(%)e
10
A
9/14/11
09:17:00
420
0.569
0.0336 ±0.00101
0.763 ± 0.000649
0.108 ±0.00691
0.00
0.00
B
9/15/11
09:05:00
420
17.8
11.7 ±3.85
12.1 ±0.708
13.1 ±0.0783
10.8
75.9
C
9/16/11
10:55:00
420
18.9
13.0 ±4.01
12.9 ±0.679
14.2 ±0.0968
12.1
82.1
D
9/17/11
09:22:00
420
18.7
13.2 ±4.07
13.5 ±0.611
14.9 ±0.104
10.5
70.7
E
9/19/11
11:20:00
420
13.3
9.12 ±3.44
8.34 ± 0.621
9.80 ± 0.0772
8.12
77.0
F
9/20/11
09:00:00
420
14.8
9.44 ± 3.52
9.32 ± 0.635
10.1 ±0.0783
8.71
72.5
G
9/21/11
08:50:00
420
14.9
9.72 ± 3.63
8.49 ± 0.725
10.4 ±0.0818
8.91
78.9
H
9/22/11
08:45:00
420
0.961
0.0130 ±0.000587
1.31 ±0.000621
0.0369 ±0.00115
0.00
0.00
50
A
9/23/11
12:25:00
360
97.3
51.4 ±8.62
47.7 ± 0.661
58.4 ± 0.592
56.1
63.8
B
9/24/11
09:30:00
360
103
58.7 ± 9.38
51.4 ±1.00
63.8 ± 0.570
56.2
61.6
C
9/26/11
08:53:00
360
102
59.7 ± 9.65
49.0 ±0.916
62.1 ±0.563
63.5
64.5
D
9/27/11
09:00:00
360
95.2
57.5 ± 9.56
46.2 ± 0.921
59.1 ±0.552
63.9
71.3
E
9/28/11
09:00:00
360
100
58.5 ± 9.72
47.8 ±1.01
59.8 ± 0.578
53.0
60.9
F
9/29/11
10:55:00
360
100
57.1 ±9.73
46.3 ± 0.805
58.2 ± 0.581
54.8
59.5
G
9/30/11
10:45:00
360
0.251
0.0264 ± 0.000956
0.243 ±0.000613
0.0553 ± 0.00230
0.00
0.00
100
A
10/2/11
09:25:00
180
179
118 ± 14.6
86.6 ±1.33
108 ±0.855
106
64.3
B
10/2/11
13:10:00
180
178
114 ± 14.1
84.7 ± 0.982
110 ±0.961
108
63.8
C
10/3/11
09:55:00
180
177
87.4 ±10.9
86.1 ±1.03
107 ±0.982
109
64.6
D
10/3/11
13:30:00
180
176
92.2 ±11.4
85.9 ±1.70
100 ±2.13
105
63.0
E
10/4/11
10:00:00
180
188
106 ±12.5
92.9 ±1.08
114 ± 1.03
107
64.0
F
10/4/11
13:20:00
180
182
104 ±12.5
89.1 ±1.17
113 ± 1.06
106
63.9
G
10/5/11
09:05:00
180
0.882
0.0802 ± 0.00206
1.16 ±0.000574
0.175 ±0.00461
0.00
0.00
500
A
10/7/11
09:00:00
40
813
611 ±44.6
436 ± 22.6
476 ± 4.05
528
63.5
B
10/7/11
10:00:00
40
817
622 ±43.1
439 ± 24.9
482 ± 4.39
507
64.3
C
10/7/11
11:00:00
40
811
617 ±42.0
434 ± 22.7
476 ± 4.34
495
63.5
D
10/7/11
12:00:00
40
804
619 ±42.8
436 ± 23.8
468 ± 4.92
535
64.9
E
10/7/11
13:00:00
40
780
608 ± 39.4
429 ± 22.9
463 ± 4.76
527
65.9
F
10/7/11
14:00:00
40
793
608 ± 43.5
425 ± 23.6
470 ± 4.32
491
65.0
G
10/7/11
15:00:00
40
9.38
0.156 ±0.00238
-0.0835 ±0.00165
0.326 ± 0.00922
0.00
0.00
1,000
A
10/13/11
09:00:00
20
1810
1250 ±108
893 ±176
836 ± 19.8
1010
59.5
B
10/13/11
09:40:00
20
1820
1310 ± 213
912 ±204
840 ± 19.3
1050
59.9
C
10/13/11
10:20:00
20
1830
1270 ±220
904 ± 205
822 ± 19.3
1040
58.5
D
10/13/11
11:00:00
20
1820
1300 ±222
907 ± 203
836 ± 19.2
1100
61.1
55
-------
Target
Concentration
(|jg/m3)b
Test
ID
Test Date
Start Time
Duration
(min)
Teflon
Filter
((jg/m3)c
Lll
(Hg/m3)
MSS
(Hg/m3)
SuperMAAP
(Hg/m3)
NIOSH
5040 EC
(H9/m3)d
EC/TC
(%)e
E
10/13/11
11:40:00
20
1750
1270 ±220
883 ± 201
811 ± 19.2
1020
59.3
F
10/13/11
12:20:00
20
1830
1300 ±224
906 ±196
838 ± 19.1
1110
60.9
G
10/13/11
13:10:00
20
23.8
3.07 ± 0.00892
2.78 ± 0.00811
1.84 ± 0.444
0.00
0.00
Experimental data after HI recalibration, SuperMAAP flow adjustments/software changes, and MSS temperature adjustment but without correction for tunnel blanks. All data rounded to three
significant figures. The ± values shown are the sample SD.
bMiniCAST setting #7 for all tests conducted.
°Not adjusted for the percent OC determined from the quartz filter analyses.
dEC = elemental carbon determined by the NIOSH 5040 method.
| eRatio of EC to TC determined from the quartz filter analyses.
56
-------
Table 5-4. Summary of Final Test Results Without Use of Catalytic Stripper3
Measured PM Concentration
Target
Measurement
(Mg/m3)c
Concentration
Methodb
Test A
Test B
Test C Test D Test E Test F
Test G
Test H
10 |jg/m3
TEFLON
Blk
17.0
18.1
17.9
12.5
14.1
14.1
Blk
TEFLON 1
Blk
12.9
14.9
12.7
9.66
10.2
11.1
Blk
MAAP
Blk
13.1
14.1
14.8
9.73
10.1
10.3
Blk
MSS
Blk
11.4
12.2
12.8
7.64
8.63
7.79
Blk
Lll
Blk
11.7
13.0
13.2
9.09
9.42
9.69
Blk
EC 1
Blk
10.8
12.1
10.5
8.13
8.71
8.91
Blk
OC 1
Blk
3.42
2.64
4.37
2.42
3.31
2.40
Blk
TC 1
Blk
14.2
14.7
14.9
10.5
12.0
11.3
Blk
50 |jg/m3
TEFLON
96.7
102
102
94.5
99.7
99.7
Blk
NA
TEFLON 1
61.7
62.8
65.4
67.4
60.7
59.3
Blk
NA
MAAP
58.3
63.8
62.1
59.1
59.7
58.2
Blk
NA
MSS
46.9
50.6
48.2
45.5
47.0
45.6
Blk
NA
Lll
51.4
58.7
59.7
57.5
58.5
57.1
Blk
NA
EC 1
56.1
56.2
63.5
63.9
53.0
54.8
Blk
NA
OC 1
31.9
35.1
35.0
25.7
34.0
37.4
Blk
NA
TC 1
88.0
91.2
98.5
89.7
87.0
92.2
Blk
NA
100 |jg/m3
TEFLON
178
177
177
175
187
181
Blk
NA
TEFLON 1
115
113
114
110
120
116
Blk
NA
MAAP
107
109
107
100
114
112
Blk
NA
MSS
85.8
83.9
85.3
85.1
92.1
88.3
Blk
NA
Lll
118
114
87
92
106
104
Blk
NA
EC 1
106
108
109
105
107
105
Blk
NA
OC 1
58.6
61.0
59.9
61.9
60.1
59.6
Blk
NA
TC 1
164
169
169
167
167
165
Blk
NA
500 |jg/m3
TEFLON
805
809
803
797
773
785
Blk
NA
TEFLON 1
511
520
510
517
509
510
Blk
NA
MAAP
476
481
475
468
463
469
Blk
NA
MSS
435
437
432
434
427
424
Blk
NA
Lll
609
620
615
618
607
607
Blk
NA
EC 1
528
507
494
534
527
491
Blk
NA
OC 1
304
283
284
290
273
264
Blk
NA
TC 1
831
788
778
824
799
755
Blk
NA
1,000 |jg/m3
TEFLON
1790
1800
1800
1790
1730
1800
Blk
NA
TEFLON 1
1060
1080
1060
1100
1020
1100
Blk
NA
MAAP
835
839
821
835
810
837
Blk
NA
MSS
889
908
900
903
880
902
Blk
NA
Lll
1240
1300
1270
1290
1260
1300
Blk
NA
EC 1
1010
1050
1040
1090
1020
1100
Blk
NA
OC 1
689
703
738
697
699
709
Blk
NA
TC 1
1700
1750
1780
1790
1720
1810
Blk
NA
aFinal data after tunnel blank correction and adjustment for Teflon filter OC content and SuperMAAP filter changes.
bTEFLON = Teflon filter gravimetric results with no correction for OC 1; TEFLON 1 = Teflon filter gravimetric results corrected for the
percent OC determined by quartz filter sampling and NIOSH 5040 analysis; EC 1 = elemental carbon determined by NIOSH 5040; OC 1 =
organic carbon determined by NIOSH 5040; TC 1 = total carbon determined by NIOSH 5040.
°AII values rounded to three significant figures. Blk = blank test; NA = not applicable or not available.
57
-------
1400
1200
NI05H 5040
\ 1000
BOO
60D
200
200
400
600
1200
1400
OC-Correeted Teflon FitlerCon centration (pg/m3}
Figure 5-4. PM mass concentration plots for experiments without the catalytic stripper based on
the OC-corrected Teflon filter results.
58
-------
1400
1200
= 1000
c
0
1
£ 800
S
o
C
o
o
2
Cl
£
3
tt
CO
«
s
~ SuperMAAP
¦ MS S
aLH
GOO
400
200
t 2 -u.
R--0 r::
I
^:
MSS
y = £L84S£«
_ ff = 0.S3S-5
SupsrMAAP
y= fl.S1«s
Ff = 0.9S91
200 400 600 BOO 1000
N10SH5040 Elemental Carbon Concentration (tig/m J)
1200
1400
Figure 5-5. PM mass concentration plots for experiments without the catalytic stripper based on
NIOSH 5040 results.
59
-------
700
BOO
PS
-E
E 500
t3
fc 4CC
C
a
o
c
o
J? 200
a.
XI
a
i2®
¦
ID
100
~ SuperMAAP
¦MSS
aLH
NIGSH 5C4C
;
p = £ 9E4 li
?= = 0
lUPffttAAF
y= «u«2x
R= = e.W&5
y = fi S5-5.1
R- = .1
100 200 300 400 500 600 7W)
OC-CorrectedTeflon Filter Concentrationfijg.'m^li
700
| 500
; I 1 1
0
100
700
NIOSH 5040 Elemental CarbonConcentration {pg/mJ)
Figure 5-6. Mass concentration plots for target concentrations between 50 and 500 pg/m3 without
use of stripper based on (A) OC-corrected Teflon filter results and (B) NIOSH Method 5040.
60
-------
5.3 Combined Experimental Results
Figure 5-7 provides the combined final results of experiments conducted with and without the
CS plotted against the OC-corrected Teflon filter data. Also shown are the linear regression
results and the perfect fit line. As the figure shows, both the NIOSH 5040 results and the results
from the LII are within 8 % of the 1:1 line, followed by the MSS at 16 % (slope = 0.84) and
SuperMAAP at 18 % (slope = 0.82). The R2 values are also > 0.98, with the MSS having the
highest R2 value and the LII the lowest. The relative relationship between the four methods is
also similar to the relationships presented above, with the LII generally having the highest values
and the SuperMAAP the lowest compared to the Teflon filter results.
1.076x
1400 j
1200 -
1000 -
BOO -
600 -
400 -
200 -
0 \
0
~ SuperMAAPw.' Stripper
Su perM AA P woJStrip per
¦ MSS w,'Stripper
:: M SS wo .'Strip per
*LllwJStripper
A LII wfVStri pper
~ NIOSH 5640w/Stripper
NIO SH 5D40 woi Stri pper
200 40 0 6 00 BOO 1000 1 200 1400
OC-Corrected Teflon Fitter Concentration (pg/m1)
! . : I
Combined!Data Set
Figure 5-7. PM mass concentration plots for all experiments based on all OC-corrected Teflon
filter results.
Similar results are plotted against the NIOSH 5040 EC concentrations in Figure 5-8. As shown,
the best agreement was exhibited by the MSS, which was within 9 % (slope = 0.91) of the 1:1
line, followed by the SuperMAAP at 12 % (slope = 0.88) and the LII at 18 % (slope = 1.18). The
relative relationship between the three instruments is, however, the same as that shown in Figure
5-7.
61
-------
0.903*
MAAP
p8Z*
1400
Combined Data Set
~ SuperMAAPw Strip per
SuperMA A P wo/St ri pper
¦ MSS w/Strip per
~ MSS woJStripper
i LI I w,< Strip per
A LI I woJSt ri pper
200 40 0 600 8 00 1000
NfOSH EC Concentration (jjg/m4)
1200
1400
O
a
Figure 5-8. PM mass concentration plots for all experiments based on all NIOSH 5040 EC results.
Even though the correlation coefficients shown in the plots above are very good, a spread in the
data with and without use of the CS can be seen for all instruments/methods. The data suggest
that processing the MiniCAST aerosol through the CS changes the properties of the particles
beyond the obvious reduction of OC content, which is on average only < 10 % by mass. As the
particles move through the stripper, they might be increasing in density (as shown by a decrease
in void space), thus influencing the optical BC measurements in the LI I, MSS, and SuperMAAP.
An additional investigation would be needed, however, to verify this supposition, which was
beyond the scope of the current work.
Figure 5-9 shows the final experimental data with the target PM concentration range limited to
50-500 jig/m3. Figure 5-9A plots the data against the OC-corrected Teflon filter results and
Figure 5-9B as a function of NIOSH 5040. NIOSH 5040 data compared to the Teflon filter
concentrations (Figure 5-9A) exhibited a 6 % deviation (slope = 0.94) from the 1:1 line and thus
the best agreement, followed by the SuperMAAP (slope = 0.93), LII (slope = 1.11), and MSS
(slope = 0.833) in that order. When the LII, SuperMAAP, and MSS data are plotted against
NIOSH 5040 (Figure 5-9B), the same relative relationship between instalments was observed
with the SuperMAAP being within 2 % (slope = 0.98) of the perfect agreement line, followed by
the MSS at 12 % (slope = 0.88) and LII at 18 % (slope = 1.18).
62
-------
700
600
co 500
I 400
C
¦
o
c
o
o
s
a.
3-00
- 200
100
t
^ornb ined D
ate Set
Pl
LI
*
=a,9s
s
ir
la.
3
^4—
¦i
,4
k' " .
I-
€.'925
= flfffi
/
¦ t
*1
1
ASS
"tl
J
J
0 595
y
• SuperMAAPw^Strt pper
SupetfAAAP wo/Stripper
wMSSW Stripper
-
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Figure 5-9. Mass concentration plots for target concentrations between 50 and 500 pg/m3 for all
experiments based on (A) OC-corrected Teflon filter results and (B) NIOSH Method 5040.
Comparing the results in Figure 5-9A to those in Figure 5-7 shows the relative position of the
SuperMAAP changed from an 18 % deviation from the 1:1 line for the entire range of target
63
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concentrations to only 7 % for target concentrations of 50-500 |ig/m3. A much smaller change in
slope was observed for the LII (from 8 % to 11 %). The data in Figure 5-9B compared to the data
in Figure 5-8 show a similar result: the SuperMAAP went from a 9 % variation from the 1:1 line
to only a 2 % variation. These results again suggest that the SuperMAAP and LII instruments
were sensitive to the range of BC concentration measured during the experiments.
Finally, an intercomparison of the four methods was made for the combined data set. Figure 5-10
shows the LII, NIOSH, and SuperMAAP data plotted as a function of the PM concentrations
measured by the MSS instrument. Also shown are the regression results and the perfect
agreement line. Figure 5-10 shows the SuperMAAP (slope = 0.97) exhibited the best agreement
with the MSS, followed by NIOSH 5040 (slope = 1.1) and LII (slope = 1.28). The correlation
coefficients were all 0.98 or greater, indicating excellent correlation among the various
techniques for all test conditions. These results further support the supposition that comparable
results can be obtained by any of the methods evaluated if a common calibration source is
applied to each.
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Figure 5-10. Intercomparison of measurement methods against data from the AVL MSS.
5.4 General Observations
As the results above show, a high-quality data set was generated from this study. The correlation
coefficients of the regression lines were typically > 0.98, which is excellent for measurements of
this type. Over the entire range of target concentrations, the LII and NIOSH 5040 both had the
64
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highest overall agreement with the Teflon filter results, and the MSS had the best agreement with
NIOSH 5040. Within the 50-500 |ig/m3 concentration range, however, NIOSH 5040 agreed best
with the Teflon data and the SuperMAAP was best correlated with NIOSH 5040. In addition,
both the LII and SuperMAAP showed at least some sensitivity to the PM concentration. How
sensitive these instruments are to the measured PM concentration will, however, need to be
evaluated using real turbine exhaust.
Given the results above, all three automated BC methods (LII, MSS, and SuperMAAP) would be
expected to provide comparable results during engine certification if calibrated against a
common BC source. Due to the time and expense involved, Teflon filter sampling is not a viable
option for any type of routine calibration. For this reason, the SAE E-31 Committee
recommended that NIOSH 5040 be used for this purpose along with a diffusion flame soot
generator comparable to the one used in this study. Details of the calibration requirements have
been incorporated into recently published AIR 6241 (SAE, 2013).
Finally, the SuperMAAP was developed as part of the study to explore its potential use in source
measurements such as aircraft engines. Although the experimental data indicate that the
SuperMAAP measurements were comparable to both the LII and MSS in this program,
significant further development is needed to make it a viable alternative to the two commercially
available instruments. For now, it remains strictly a research instrument until all "bugs" can be
worked out.
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6 Quality Assurance and Quality
Control
Overall data quality objectives (DQOs) established for this project were detailed in an approved
QA Category III QAPP, "Validation of Non-Volatile Particulate Matter Mass Measurement
Methods" (October 18, 2010). DQOs to accomplish program objectives included the following:
• Agreement of all PM mass measurement techniques with the filter gravimetric method
within 5 % relative percent difference (RPD).
• Data completeness of 95 % for each test series measured as the percentage of data that
satisfies the data quality indicator (DQI) goals specified in Section 6.1.
• Recovery and analysis resulting in data from at least 95 % of the total filter samples
collected and/or 99 % of the continuous monitoring time scheduled.
The DQO for agreement of all techniques to be within 5 % RPD was very ambitious. When
establishing DQOs, it was not known how closely these techniques would compare. This goal
was not achieved for the entire data set, but agreement of techniques when compared with the
reference method (Teflon filters) was generally within ± 20 % RPD with a few exceptions. The
remaining DQOs were met as described.
6.1 Assessment of Data Quality Indicator Goals
The DQI goals that were either established originally in the QAPP or revised to reflect the
criteria actually used to assess the data set are summarized in Table 6-1. Actual values calculated
from the data set are also shown. Assessment of goals is discussed for each measurement in the
following subsections.
6.1.1 Temperature and Pressure
Thermocouples and pressure transducers were evaluated for precision and accuracy prior to use
by the APPCD Metrology Laboratory in April 2011. Verification reports summarizing results
obtained by challenging the devices with known references and the resulting estimation of
uncertainty are included in Appendix K. All measurement devices were well within the
established acceptance criteria, and these precision and accuracy measurements were 100 %
complete.
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Table 6-1. DQI Assessment Summary
Experimental
Parameter
Measurement
Method
Precision3
Goal
Actual
Precision
Accuracy1'
Goal
Actual
Accuracy
% Completeness
Goal/Actual
Temperature
Thermocouples0
o
LO
See 7.1.1
O
LO
+1
See 7.1.1
95/100
Differential
pressure
Transducers0
5 %
See 7.1.1
±10%
See 7.1.1
95/100
Volumetric air
flow rate
MFCs and critical
orifice0
5 %
See 7.1.2
± 10%
See 7.1.2
95/100
PM mass
Gravimetric
analysis
3 ^g
< 1.8 |jg
± 15 |jg
<2|Jg
95/100
OC/EC
concentration
Thermo-optical
analysis
10 % RSD
(concentrations
> 10 |jg/cm2)
3.3 % RSD
90-110 %
recovery
97 %
recovery
95/100
Calculated as the relative standard deviation (RSD) of the reference measurements obtained at a constant instrument set point.
bPercent bias determined as the average variation between the reference measurements and the instrument readings over the
entire operating range.
includes all on-line and time-integrated instruments.
6.1.2 Flow Rate
The MFCs and critical orifice were verified by the APPCD Metrology Laboratory in April 2011.
Verification reports summarizing results obtained by challenging the devices with known
references and the resulting estimation of uncertainty are included in Appendix K. Acceptance
criteria for accuracy and precision were met for all devices. These measurements were 100 %
complete.
6.1.3 PM Mass
QA/QC of gravimetric procedures was performed as described in SOP 2103, "Sampling and
Measurement of Nonvolatile Particulate Matter Mass Using the Filter-Based Gravimetric
Method" (Appendix G). The types of QC samples associated with this procedure are described in
Section 6.3.3. Accuracy goals were assessed by weighing 100- and 200-mg certified weights
prior to each weigh session. Bias was determined as the amount of weight (in |ig) the certified
mass was from the mean. Precision was assessed by calculating the SD from repeated weighing
of the certified weights. All acceptance criteria for accuracy and precision were met, and these
measurements were 100 % complete. Results of the certified weight checks are shown in Table
6-2.
Table 6-2. Certified Weight Verifications
Certified Mass
Actual (Mean)
Bias
Standard Deviation
100.0000 mg
99.9985 mg (n = 19)
1.5 |jg
±1.8 |jg
200.0000 mg
200.0005 mg (n = 30)
0.5 |jg
±1.7 |jg
6.1.4 OC/EC Concentration
The original DQI goals established in the QAPP were not adequately stated and were changed to
match the procedures described in SOP 2104, "Sampling and Measurement of Nonvolatile
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Particulate Matter Mass Using the Thermal/Optical-Transmittance Carbon Analyzer" (Appendix
B). For this project, a sucrose calibration check standard was run in duplicate at the beginning of
each batch of samples to assess instrument accuracy in terms of recovery and precision in terms
of RSD. The accuracy acceptance criterion for the sucrose standard was 90-110 % recovery. The
standard was run 66 times, with an average recovery of 97 %. The recovery range for all runs
was 93-106 %, so all analyses met the established acceptance criterion. The precision goal for
replicate analyses of the sucrose standard was ± 10 % RSD. The actual RSD (n = 66) was 3.3 %,
well within the DQI goal. Goals were met for all analyses for 100 % completeness.
6.2 Instrument Calibrations
Calibrations of the four candidate instruments/methods and other supporting devices are
described below and in the corresponding SOPs developed for those instruments and devices.
Appendix K contains reports for all calibrations performed by the APPCD Metrology
Laboratory.
6.2.1 Sunset TOT Carbon Analyzer
As described in Section 3, the temperature calibration of the front oven thermocouple in the
OC/EC TOT analyzer was performed by Sunset Laboratory and the APPCD Metrology
Laboratory before the measurement campaign. The acceptance criterion was ± 3 % of the set-
point temperature.
The APPCD Metrology Laboratory also performed flow sensor calibration of each of the seven
needle valves on the Sunset TOT carbon analyzer before the measurement campaign. New
calibration coefficients were calculated and replaced the existing coefficients in the software. A
flowmeter was used periodically to confirm the calibration setting. The calibration was
acceptable if the flows were within ± 5 % of actual.
In the sampling system, the MFC for the QFF sampler was calibrated by the APPCD Metrology
Laboratory according to MOP FV-0237.0 (EPA, 2010) within 1 year of use.
6.2.2 SuperMAAP
Two new MFCs installed in the SuperMAAP were calibrated by the APPCD Metrology
Laboratory according to MOP FV-0237.0 (EPA, 2010). One MFC measured the SuperMAAP
(sample) flow and the second measured the bypass flow. The APPCD Metrology Laboratory also
calibrated the total aerosol flow coming into the inlet of the instrument (sample + bypass flow)
and the actual sample flow drawn into the SuperMAAP detection chamber. That information was
important for detecting and quantifying leaks present in the system that result from the non-leak-
free design of the SuperMAAP measuring chamber. The results of these calibrations were used
to generate the SuperMAAP sample and bypass slopes and intercepts implemented in the
Lab View software. The manufacturer performed other required calibrations of the 5012
instrument.
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6.2.3 AVLMSS
The only calibration performed on the AVL MSS 483 instrument was an inlet flow check using
APPCD Metrology Laboratory MOP FV-0237.0 (EPA, 2010). As stated in the instrument
manual, the suction power of the pump is set with a throttling valve so that approximately 3.8
L/min are pulled at the inlet of the instrument. The flow rate was calibrated and found to be ± 0.1
% of the stated 3.8 L/min. That calibration report can be found in Appendix K. Other needed
calibrations were performed by the manufacturer.
6.2.4 LII300
Flow calibration was the only calibration performed on the Artium Technology LII 300. The
external pump was equipped with a rotameter that allowed control and monitoring of the air
sampling flow rate to the instrument, which was calibrated by the APPCD Metrology Laboratory
using MOP FV-0237.0 (EPA, 2010). The calibration report can be found in Appendix K. Other
required calibrations were performed by the manufacturer.
6.2.5 Gravimetric Method
Before the measurement campaign, the APPCD Metrology Laboratory calibrated the orifice flow
meter for the Teflon filter sampler according to MOP FV-0201.1 (EPA, 2009a) and the two
absolute pressure transducers (one in the Teflon filter sampler and one in the flow tunnel)
according to MOP PR-0400.0 (EPA, 2009c). The T-type thermocouple in the tunnel flow was
also calibrated by the APPCD Metrology Laboratory according to MOP TH-0301.0 (EPA, 2008)
before taking measurements.
6.2.6 Ancillary Equipment
Ancillary sensors and equipment were also calibrated prior to starting the measurements. The
five MFCs in the PMF-42 MFC box were calibrated by the APPCD Metrology Laboratory
according to MOP FV-0237.0 (EPA, 2010). The two MFMs used to regulate dilution air flow
(before the CS) and excess aerosol flow (dump line) were calibrated by the APPCD Metrology
Laboratory according to MOP FV-0237.0 (EPA, 2010). Finally, both blowers (big and small)
and the tunnel vacuum pump rotameter were calibrated by the APPCD Metrology Laboratory to
determine the correlation between the standard volume of the air passing through the tunnel
(L/min) and the blower readings (Hz) and pump adjustment (rotameter reading). The results of
those calibrations are in Appendix H.
6.3 Quality Control Procedures
6.3.1 Flow Tunnel
The flow tunnel was cleaned initially by power washing the internal surfaces using a dilute
solution of laboratory detergent in deionized (DI) water, followed by a DI water rinse. After
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power washing, the tunnel was allowed to air dry. Positive pressure (~ 0.35 bar) leak checks
were also performed on all sampling lines and connections with instruments and other supporting
equipment to ensure leak-tight operation. Finally, tunnel blank samples for all
instruments/methods were run at the beginning and end of each set of measurements for each
target concentration to measure the background PM (EC/OC) concentration from the tunnel, with
corrections applied to the data as described above.
6.3.2 NIOSH5040
Leak tests of the QFF sampler were performed prior to each test as described above. In addition,
instrument blanks, calibration checks, and duplicate punches were analyzed for QC purposes.
The instrument blank was run at the beginning of each day using a punch from a clean prefired
QFF. TC values for the blank were < 0.05 |igC/cm2. Calibration check samples (sucrose
standards) were also run at the beginning of each day. The measured TC mass for the calibration
standard was within ± 3 % of the true value. Finally, a duplicate punch for every filter sample
was run. The acceptance criterion for duplicate measurements at higher filter loadings (> 5
|ig/cm2) was based on the RPD (10-15 %) of the duplicate measurements. The acceptance
criterion for duplicate measurements at low filter loadings (< 5 |ig/cm2) was based on an absolute
error of ± 0.75 |ig/cm2. If the deposit on a filter visually appeared to be nonuniform or if a
duplicate analysis was run and the duplicate measurements did not meet the appropriate
acceptance criterion, the measurement was repeated.
6.3.3 Gravimetric Method
Leak tests of the Teflon filter sampler were performed prior to each test as described earlier.
Analytical QC was performed on the gravimetric analyses using reference filters plus reweighing
of a certain percentage of the exposed filters. Reference filters were Teflon filters that remained
in the weighing room in the same place and over the same preconditioning time as the sample
filters. The purpose of the reference filters was to verify the cleanliness of the PM stabilization
environment and to detect any unusual events that might affect PM mass on the sample filters. A
reference filter met the acceptance criterion when the weight of the filter was within ± 0.011 mg
from one weighing to the next. Also, after weighing the entire set, 20 % of the filters were
subjected to reweighing. If any reweighs did not meet the previous measurement within ± 4 |ig,
the entire set of filters was reweighed.
Gravimetric analysis results were recorded in a laboratory notebook. During this time, a total of
268 sample filters (not including reference filters) were weighed. From this batch of 268 sample
filters, the records indicate that 138 filters were weighed a second time. Four reference filters
were used over the time spanning the tests. Reference filters 1 and 2 were used simultaneously
from the time the first gravimetric weights were recorded on March 28, 2011, through September
12, 2011. In September, a different weigh room was used for filter weighing that had two new
reference filters associated with the facility. Reference filter 3 was used from September 12,
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2011, through the last record of gravimetric weights on June 25, 2012. Reference filter 4 was
only used twice, once on February 15, 2012, and again on May 5, 2012.
Calibration weights (100 and 200 mg) were used to check the balance prior to each weighing
session. These calibration checks were also used to assess the accuracy and precision of the
gravimetric analysis.
6.3.4 SuperMAAP
QC checks of the SuperMAAP consisted of observing and recording the values of the
transmission, reflection, and reference diodes on the front panel of the 5012 instrument. If any of
these readings were outside of the specified range, the instrument was turned off for subsequent
repair and recalibration.
6.3.5 LII300
The operational check lamp (details provided in Appendix E) was used as an independent QC
check for general operation of the instrument and to detect any system failures. The operational
QC check was performed before starting each concentration set or more frequently if needed.
The manufacturer had established no acceptance criterion for the lamp check. Therefore, a
variation of ±10 % in "current" values compared to "factory" calibrated values was used as a
starting point. As the study progressed, however, this criterion was determined to be too strict
and values within a 20 % maximum difference between the current and factory values were used.
Other QA procedures performed on the instrument before the measurement campaign were
sample cell temperature and pressure calibrations, which were performed by the manufacturer.
Since the LII instrument measurements are based on absolute intensity measurements of the soot
incandescence, window contamination can also systematically bias the results. Thus, the
windows were examined for contamination and cleaned with a laboratory wipe before starting
each test series and before performing the QC lamp check procedure described above.
6.3.6 AVLMSS
Of all the instruments, the MSS had the most highly developed QC procedures. The sensitivity of
the entire sensor (the intensity of the laser beam and the sensitivity of the microphone) was
checked by means of an absorber window. That QC check was carried out at the beginning of
each test series. The acceptance criterion for the deviation of the measured vs. calibration value
expressed as "deviation of calibration check" should be approximately 2-3 %, but not to exceed
10 %. Other QC procedures performed on the MSS included the following:
• Check of the resonance frequency of the microphone in the measuring cell performed
automatically during the warmup and stabilization of the instrument.
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Linearity check of the microphone performed before starting the measuring campaign.
The resulting regression coefficient had to be higher than 0.95. Smaller regression
coefficients indicated a microphone fault.
Linearity check of the laser performed before starting the measuring campaign. The
resulting regression coefficient had to be higher than 0.95. Smaller regression coefficients
indicated a laser or laser driver fault.
Calibration of the conditioning unit performed automatically during the warmup and
stabilization of the instrument.
Regular maintenance:
o Replacement of fine filters when the soot layer was visible or error 28 (flow warning)
appeared.
o Purging or replacement of sampling lines when significant pollution was visible.
o Cleaning the measuring cell and glass tube in the measuring cell when the zero signal
exceeded a value of 1.5 mV (error code 25).
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7 Conclusions and Recommendations
The following conclusions were reached from the study:
• The measurements made by the four BC measurement methods showed a highly linear
relationship with increasing PM concentration in the flow tunnel.
• The four BC measurement techniques were found to be highly correlated with the OC-
corrected Teflon reference filter values and with each other for target PM concentrations
ranging from 10 to 1,000 |ig/m3. After post-processing, R2 values were generally 0.98 or
greater depending on test conditions.
• When compared with either the Teflon filter or NIOSH 5040 results, the linear regression
lines of the data generated by the four techniques were within a maximum of 18 % from
perfect agreement (i.e., 1:1 line) for the combined data set.
• Slightly different results were found when the range of target concentrations was limited
to 50-500 |ig/m3 in the combined data set. A different relationship was also observed for
the SuperMAAP and LII within this concentration range, suggesting at least some
sensitivity to measured concentration.
• The high correlations observed among the various methods suggest that the LII, MSS,
and SuperMAAP could provide equivalent results if calibrated against a common BC
source.
• High-quality data were generated in the program with all DQI goals met or exceeded.
The following recommendations for future research are made based on the conclusions above:
• The issue of sensitivity of the three on-line instruments to volatile PM was not resolved
in the current study due to the inability of the CS to significantly reduce the OC of the
MiniCAST aerosol. Further research is needed to determine whether the response of
these instruments will change with varying levels of OC in the PM.
• A MiniCAST burner was used in the program as a surrogate for turbine exhaust. Since
major differences would be expected in the characteristics of the PM generated by a
diffusion burner and an actual aircraft engine, a field evaluation is recommended to
compare the four BC methods using real turbine exhaust.
• Additional research is needed to determine if the SuperMAAP and LII are sensitive to the
measured concentration. Again, actual turbine exhaust should be used as the test aerosol.
In response to these recommendations, a study was conducted in September 2012 using a T-63
helicopter engine owned and operated by the U.S. Air Force Research Laboratory at Wright-
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Patterson Air Force Base in Ohio. The results of this program will be reported in a subsequent
publication.
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Schindler, W.; Haisch, C.; Beck, H. A.; Niessner, R.; Jacob, E.; Rothe, D. (2004). A
photoacoustic sensor system for time resolved quantification of diesel soot emissions, SAE
Technical Paper 2004-01-0968. SAE International, Warrendale, MI, USA.
Turpin, B. J.; Huntzicker, J. J.; Hering, S. V. (1994). Investigation of organic aerosol sampling
artifacts in the Los Angeles Basin. Atmospheric Environment, 28, 3061-3071.
77
-------
Appendix A
Soot Generator SOP
August 2011
Rev. 0
Appendix A: Operation of the Jing
MiniCAST Model 5201 (Prototype) Black
Carbon Aerosol Generator (Real Soot
Generator)
STANDARD OPERATING PROCEDURE 2101
NRMRL/A PPC D
APPROVED: August 18, 2011
^tosr^
PROlt&
A-1
-------
Appendix A
Soot Generator SOP
August 2011
Rev. 0
TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION A-3
2.0 OPERATION PRINCIPLE A-3
3.0 DEFINITIONS A-4
4.0 HEALTH AND SAFETY CONSIDERATIONS A-4
5.0 EQUIPMENT AND SUPPLIES A-4
6.0 PROCEDURES A-5
7.0 ATTACHMENTS A-10
A-2
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Appendix A
Soot Generator SOP
August 2011
Rev. 0
1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) provides instructions for operation of the Model
5201 (prototype) MiniCAST (combustion aerosol standard) real soot generator from Jing
(Bern, Switzerland). The SOP gives step-by-step procedures that describe how to install
the soot generator and perform routine operations, as well as how to log the data and
export them into the working files.
2.0 OPERATION PRINCIPLE
The MiniCAST is a soot-generating device for various applications where air containing
suspended carbonaceous soot particles with adjustable and repeatable size, concentration,
and chemical composition are required. As a soot source, the MiniCAST uses a propane
diffusion flame, in which soot particles are formed during a pyrolysis process. In order to
generate the soot particles, the oxidation air supply is kept below theoretical limits. As a
consequence, particles contained within the exhaust gases arise out of the flame and leave
the combustion chamber. In the next step, the particle stream is mixed with quenching
gas (N2) in order to prevent further combustion in the particle stream and to stabilize the
soot particles. This quenching inhibits condensation in the particle stream when it escapes
from the flame unit to the ambient air. Subsequently, an axial flow of dilution air is
supplied to reduce the concentration of the particle stream prior to exiting the MiniCAST.
MiniCAST operation with different gas flows is illustrated in Figure A-l.
Dilution
air
— Quench gas
Dilution
an
Flame
Air Gaseous Air
Fuel
Figure A-l. Operating principle of MiniCAST.
Particle
Output
A-3
-------
Appendix A
Soot Generator SOP
August 2011
Rev. 0
The condition of the flame and the features of the generated soot particles, respectively,
are primarily a result of the flow settings. By means of varying the flow settings, the
particle size can be adjusted in a range of 20 to 200 nm (geometric mean electrical
mobility diameter).
3.0 DEFINITIONS
Soot: Carbonaceous particles that are by-products of the combustion of liquid or gaseous
fuels.
4.0 HEALTH AND SAFETY CONSIDERATIONS
4.1 The oxidation air and quench gas must always be present for any operation or
testing purposes in order to eliminate any danger of detonation.
4.2 Do not release the fuel gas, by depressing the flame failure device, into the burner
without oxidation air and quench gas being present.
4.3 Do not depress the igniter for testing purposes without the oxidation air and
quench gas being present.
4.4 Carefully examine the connections from the fuel gas bottle to the MiniCAST to
make sure they are safe and do not leak.
4.5 Always close the fuel gas bottle when the MiniCAST is not in use.
4.6 Never try to light the exhaust or unburned gases at the particle output.
4.7 In enclosed spaces, use a propane detector or alarm alongside the MiniCAST.
4.8 Always work with safety glasses to protect eyes and use heat protection gloves for
manipulation of MiniCAST parts when in continuous operation.
4.9 Ensure that all soot escaping from the MiniCAST is removed by a ventilation
system.
5.0 EQUIPMENT AND SUPPLIES
• MiniCAST soot generator from Jing.
• Propane (C3H8, purity 99.95 %) in compressed gas bottle with pressure regulator
adjusted to the proper pressure required by flow controllers (0-0.150 L/min).
• Compressed air cylinder with a pressure regulator adjusted to the proper pressures
required by flow controllers (0-3 L/min and 0-20 L/min).
A-4
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Appendix A
Soot Generator SOP
August 2011
Rev. 0
• Nitrogen (N2, purity 99.99 %) in a compressed gas bottle or dewar with a pressure
regulator adjusted to the proper pressures required by flow controllers (0-10 L/min
and 0-5 L/min).
• Five mass flow controllers (MFCs), either ordered separately or mass flow control
box (Model PMF-42) from Jing, with installed controllers inside.
6.0 PROCEDURES
6.1 Instrument Setup
1. Connect the input connectors of MFCs for OXIDATION AIR, QUENCH
GAS N2, DILUTION AIR, and MIXING GAS N2 via regulators to the
corresponding gas bottle or gas supply facilities.
2. Connect the input connector of the FUEL gas MFC via a regulator to the fuel
gas bottle (use flame protection valve).
3. Connect the output connectors of the MFCs for OXIDATION AIR, QUENCH
GAS N2, DILUTION AIR, MIXING GAS N2, and FUEL to the corresponding
connectors on the rear panel of the MiniCAST.
4. Make sure there are no leaks, especially for the fuel gas.
5. Completely close (clockwise) the FUEL CONTROL valve (4 in Figure A-2).
6. Connect the MiniCAST to the power supply.
7. Open the main valves of each gas bottle or gas supply facilities to be used.
8. Adjust the regulators of the gas bottles to the corresponding gas pressure
valves shown in Table A-l.
9. Disconnect all particle analyzers from the exhaust outlet or set the exhaust
outlet to ambient conditions.
A-5
-------
Appendix A
Soot Generator SOP
August 2011
Rev. 0
.CAST
V
%
0
3
4
5
Front panel
1. Exhaust pipe
2. Igniter
3. Flame Safety Device
4. FUEL CONTROL valve
5. MAIN VALVE for FUEL GAS
Figure A-2. Front panel of MiniCAST.
Table A-l. Flow and Input Pressure Ranges of MFCs for Device Settings
Gas
CjHg
Mixing gas
{N2 for fuel)
Oxidation
air
Quench
gas (N2)
Dilution
air
Flow rate
(l/min)
0.04-0.08
0-0.50
0.5-2.0
6
10
Input pressure P1
of MFC
3 bar
-30 psig
3 bar
- 30 psig
3 bar
-30 psig
2 bar
-15 psig
2 bar
-15 psig
6.2 Instrument Startup
1. Start computer with Red-y software for MFC manipulation.
2. Set the flow rates of each gas flow to the values shown in Table A-2.
A-6
-------
Appendix A
Soot Generator SOP
August 2011
Rev. 0
Table A-2. Flow Conditions for Starting MiniCAST
1 ¦
tjHs |
Mixing gas !
Ni for fuel J
Oxidation 1
air !
Quench gas •
Dilution air
l/min [
l/min j
l/min i
1 'nun
l/min
©.§6 |
0 J
1,50 j
3 ]
10
3. Turn on the MAIN VALVE (5 in Figure A-2).
4. Depress (open) and hold the flame safety device (3 in Figure A-2) for 4-5
seconds and then release (close) it.
5. After 5-10 s, depress the igniter (red button, 2 in Figure A-2) to ignite the
pilot flame. At the same time, check through the sight glass that a weak blue
pilot flame appears and stays on.
6. After a blue flame appears, immediately depress the flame safety device (3 in
Figure A-2) and keep the button fully depressed. While doing that, the small
blue flame should become larger.
7. While still keeping the flame safety device fully depressed, slowly turn on
(counterclockwise) the FUEL CONTROL valve (4 in Figure A-2).
8. Release the flame failure device and make sure through the sight glass that the
flame is present and stable.
9. Make sure that the soot is coming out of the exhaust outlet and the surplus
soot can be removed by the ventilation system.
10. Change the quench gas flow to 6.5 L/min and wait for 5 min.
11. Select the operation point (Table A-3) and wait 10-15 min of stabilization
time before starting the particle measurements.
12. Do the following if the flame lighting is not successful:
a. Fully close (clockwise) the FUEL CONTROL valve (4 in Figure A-2), set
the flow for propane to 0 L/min, and close the main valve of the propane
gas bottle.
b. Make sure that the installation and the pressure from the gas bottle are
correct.
c. Make sure that the flow of oxidation air is present.
d. Make sure that there are no fuel leaks.
e. Open the main valve of propane gas and repeat steps 2 through 8.
A-7
-------
Appendix A
Soot Generator SOP
August 2011
Rev. 0
An illustrative scheme for the steps required to ignite the flame on the MiniCAST
is shown in Attachment 1.
Table A-3. MiniCAST Operating Points
Results
Gas settings
OP
Panicle
PM
CjH5
Oxi. air
Mix. Gas Ni
Quench gas
Dilution
for fuel
size
Nj
air
[nm]
[mg/mJ]
[ml/min]
li/min]
[ml/min]
tl/min]
[l/minj
1
25.2
60
1.0
350
6.0
10
2
37.1
60
1.1
350
6.0
10
3
46.3
60
1.2
350
6.0
10
4
80.7
11.6
60
1.2
250
6.0
10
5
97.5
60
U
200
6.0
10
6
68.0
60
1.5
300
6.0
10
7
86.4
7.3
60
1.5
280
6.0
10
8
90.1
60
1.5
275
6.0
10
9
107.2
60
1.5
250
6.0
10
6.3 Stop the Operation
1. Turn off the MAIN VALVE (5 in Figure A-2).
2. Set the flow rate of the MFC for fuel gas to zero.
3. Set the flow rates of the MFCs for all other gases used during operation to
zero.
4. Disconnect the MiniCAST from the power supply.
5. Close the main valves of each gas bottle or gas supply facilities.
6. Completely close (clockwise) the FUEL CONTROL valve (4 in Figure A-2).
6.4 Data Logging and Export
1. In the Red-y software, choose the data logger function (Figure A-3).
2. Each device (MFCs) must be selected in the list in order for its data to be
collected (loggers selected are marked with an asterisk in Column "L").
3. Select "data points" to be collected, for example, flow (default), set point, and
temperature.
A-8
-------
Appendix A
Soot Generator SOP
August 2011
Rev. 0
4. Select "kind of logging," for example, "endless" for time unlimited runs.
5. For each device, the minimum data collection interval ("timer") is raised by
500 milliseconds. Thus, in the case of five devices, the minimum interval is
2.5 seconds.
6. Select "directory" where the files will be logged.
7. When ready to start logging, press "Logging; to stop logging press "Stop."
^Getred-y B@S]
File Graph ?
Modbu* | Signals | Ettas j Bala bpgei j| Gas mixer j Pressure leg Jator |
Data points
F Flrw
Logging mode
<• Endless
Timed start/stop
r Start
R7 Setpoint
C Lines/tite 100
fS"j04j20i7
fiT^
r Total
C File/ (Minute »
17 Temp
r stop
I- Valve position
Woiking We
j^JwJioiT
[iljjaf
Timer File
Interval (0>= 500ms) ^ t I
[3 , 9 1099"*! 1 I O St°P
Addi SeiialNo. Type-Code Gas Range Flow Unil Temp. Total I M
1 114593 GSCA9TA-BB22 C3H8 1 50 0 mln/min 2254 X 25.07321 in il
2 117355 GSDASTA-BB22 N2 500 0 mln/min 2095 X 451.41 In x
3 117165 GSC-B9TA-BB23 Air 3 0 In/mm 21.64 X 14590.53 In it
4 117230 GSCC9SA-BB28 N2 10 0 Wnwt 21.3 X 61269.05 In *
5 1117220 |6SC-C4SA-BB12 |A» 120 |0 |h/mn 12062 |T 1171080.5 jln * |
Read Address 5
Figure A-3. Data logger - online view.
A-9
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Appendix A
Soot Generator SOP
August 2011
Rev. 0
7.0 ATTACHMENTS
Illustrative Scheme for Ignition Steps
Step
Rotameter
PARTICLE
CONTROL
Closed
Flame
Failure
device
Press and
hold.
1-2 *
After5-10 sec
Igniter
Flame
check
O
Pilot flame
A-10
-------
Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
Appendix B: Sampling and
Measurement of Nonvolatile Particulate
Matter Mass Using the Thermal/Optical
Transmittance Carbon Analyzer
STANDARD OPERATING PROCEDURE 2104
NRMRL/A PPC D
APPROVED: August 18, 2011
*
5
3)
V
> cjC5
PRO^
o
Z
Ui
O
B-1
-------
Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
TABLE OF CONTENTS
I.0 SCOPE AM) APPLICATION B-3
2.0 METHOD SUMMARY B-3
3.0 DEFINITIONS B-3
4.0 INTERFERENCES B-4
5.0 HEALTH AND SAFETY CONSIDERATIONS B-4
6.0 EQUIPMENT AM) SUPPLIES B-5
7.0 PROCEDURES B-6
8.0 DATA ACQUISITION, CALCULATIONS, AND DATA REDUCTION B-14
9.0 QUALITY CONTROL AND QUALITY ASSURANCE PROCEDURES B-16
10.0 REFERENCES B-22
II.0 ATTACHMENTS B-23
B-2
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) provides instructions for collection and
measurement of nonvolatile particulate matter (PM) mass using the Sunset Laboratory
Inc. (Tigard, OR, USA) thermal/optical-transmittance (TOT) carbon analyzer. The
analytical procedure of the SOP is in accordance with the existing National Institute for
Occupational Safety and Health (NIOSH) Method 5040 for diesel PM analysis.
This method includes determination of organic carbon (OC), elemental carbon (EC), and
total carbon (TC) in PM collected on quartz-fiber filters (QFFs). The PM emitted from
aircraft engines is composed primarily of nonvolatile particles that form inside the engine
combustor, and this method can be used to quantify the emissions of nonvolatile PM
(mostly EC) at the exit plane of aircraft gas turbine engines. It also addresses the
formation of OC as an artifact due to conditioning and transport of the sample. The
Sunset analyzer reports the OC and EC contents in |ig/cm2 of filter area. The instrument
has a detection limit on the order of 0.2 |ig/cm2 filter area for both OC and EC.
This SOP is a step-by-step procedure that describes how to perform the sampling and run
the instrument as well as collect the data and perform calibrations and calculations.
2.0 METHOD SUMMARY
The TOT method is used to speciate carbon in PM collected on QFFs into OC and EC. In
the first (non-oxidizing) heating stage, OC is thermally desorbed from the filter under a
flow of helium with controlled temperature ramps. The oven is then partially cooled, and
the original flow of helium is switched to an oxidizing carrier gas (He/02). In the second
(oxidizing) heating stage, the original EC plus pyrolyzed OC formed during the first
heating stage are oxidized/desorbed from the filter with another series of controlled
temperature ramps. All carbon evolved from the sample is converted to CO2 in an
oxidizing oven immediately downstream from the desorption oven, and the CO2 is
converted to methane (CH4) by a methanator oven before being measured with a flame
ionization detector (FID).
3.0 DEFINITIONS
Organic carbon (OC): Optically transparent carbon at ~ 670 nm removed (through the
thermal desorption or pyrolysis) and char deposited when heating a filter sample to a
preset maximum (850 °C) in a non-oxidizing (He) carrier gas.
Elemental carbon (EC): Carbon that can only be removed from the filter under an
oxidizing carrier gas (He/02). Optically absorbing carbon removed at high temperatures
in a non-oxidizing carrier gas when internal (sample matrix) oxidants are present.
B-3
-------
Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
4.0 INTERFERENCES
Pyrolitically produced elemental carbon (PyC): Laser transmittance is used to
optically correct for pyrolitically produced EC (or char or PyC) formed from organic
compounds during the first (non-oxidizing) part of the analysis. Formation of PyC
decreases the transmittance of the laser beam through the filter. During the oxidizing part
of the analysis, all EC (including PyC) is burned off the filter. The split between OC and
EC is assigned by the calculation software as the time during the analysis when the
transmittance of the laser beam rises back to its initial value at the beginning of the
analysis. Total FID response to the left of the split is assigned to OC, and total FID
response to the right of the split (but before the internal standard peak) is assigned to EC.
PyC is defined as carbon evolved between the addition of oxygen and the OC-EC split. If
the OC-EC split occurs before the addition of oxygen, PyC is zero. An example
thermogram for a filter sample is shown in Attachment 11.1.
The NIOSH 5040 method for diesel PM analysis has fixed residence times at each
temperature step within the He and He/02 phases and a maximum temperature for the He
phase of 870 °C. The NIOSH 5040 temperature profile used in the present study is
documented in Attachment 11.2. Some studies (Chow et al., 2001) argue that 870 °C is
too high and promotes more charring, thus resulting in the OC-EC split shifted to the
right side of the thermogram and higher measured OC concentrations (lower EC)
compared to some other low-temperature protocols (Interagency Monitoring of Protected
Visual Environments [IMPROVE] protocol).
The split between OC and EC can be inaccurate if the sample transmittance is too low.
The EC loading at which this occurs depends on the laser intensity. In general, the OC-
EC split can be inaccurate when EC loadings are above 20 |ig/cm2.
5.0 HEALTH AND SAFETY CONSIDERATIONS
5.1 Before attempting any repairs, turn off power and wait for all heated zones to
cool.
5.2 Do not look directly at the laser source as permanent eye damage can occur.
5.3 Handle all support gas cylinders and regulators with caution. Always have
cylinders properly chained to a safety rack.
5.4 Handle the quartz boat with extreme caution, and regularly clean and maintain the
boat to ensure that it is free of all deposits.
5.5 Inspect the punch regularly for any unevenness around the sharp edges. Punches
with one or more significant notches in the sharp edges should be replaced. Clean
B-4
-------
Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
the punch between samples by nibbing the cutting edges with a piece of clean
quartz filter.
6.0 EQUIPMENT AND SUPPLIES
6.1 Instrumentation
• Sunset Laboratory dual-optics carbon analyzer, including the following:
Computer system that meets Sunset Laboratory's specifications for
running the analyzer, storing the analysis data, and performing
calculations.
Color printer (for printing thermograms).
Sunset Laboratory instrument operation software version 230
(OCECInst230x.exe) or newer.
Sunset Laboratory calculation software version 151 (OCECCalcl51.exe).
• Vacuum pump capable of providing 6 L/min.
6.2 Ancillary Equipment
6.2.1 Sampling
• 47-mm stainless steel filter holder meeting Title 40 Code of Federal
Regulations Part 1065, Subpart B, requirements.
• 47-mm prebaked quartz filters (Tissuequartz™ 2500 QAT-UP from
Pall Corporation, catalog #7202 or equivalent) with associated
polytetrafluoroethylene (PTFE) cassettes meeting Title 40 Code of
Federal Regulations Part 1065, Subpart B, requirements.
• Electronic mass flow controller (MFC; Dwyer Model GFC-1133 or
equivalent) with 9.53-mm (3/8-in.) outside diameter (OD) inlet/outlet
fittings calibrated by the APPCD Metrology Laboratory according to
MOP FV-0237.0 within 1 year of use; MFC readings are recorded by a
computerized data acquisition system (DAS) running the DasyLab®
software package. Approximately 1 meter of stainless steel or Teflon
sampling line to interconnect the above components downstream of
the filter holder.
• Brass or stainless steel three-way switching valve with 9.53-mm (3/8-
in.) OD fittings.
B-5
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
• Brass or stainless steel needle valve with 9.53-mm (3/8-in.) OD
inlet/outlet fittings.
• Sterile Petri dishes (Pall Corporation, catalog #7242 or equivalent).
• Aluminum foil.
• Laboratory timer with 1-s resolution.
• Cassette separator - anodized aluminum (Airmetrics, USA catalog #
600-007 or equivalent).
• Cassette mailers - antistatic (Airmetrics, USA catalog # 600-008 or
equivalent).
• Computerized DAS with DasyLab® software package.
• Vacuum pump suitable of providing ~6 L/min.
6.2.1 Analysis
• Precision punches (nominal area 1.0 cm2 and 1.5 cm2).
• Syringes or automatic pipettors (10 |iL calibrated).
• Forceps with rubber tips (for manipulation of quartz boat).
• Tweezers (for manipulation of quartz filter samples and punches).
• Clean QFFs.
• Analytical balance (capable of weighing to ±0.0001 g) recertified by
the APPCD Metrology Laboratory within 1 year of use.
• Class 1 weights.
6.3 Reagents
• Helium, ultra-high purity (UHP).
• Hydrogen, UHP, or hydrogen generator.
• Oxygen (10%) in helium, premixed, purified.
• Methane (5%) in helium, premixed, certified.
• Air, ultra-zero.
• Sucrose, 99.9% reagent grade.
• Organic-free water.
7.0 PROCEDURES
B-6
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
7.1 Quartz-Fiber Filter Preparation
New QFFs usually have an OC background of 2 to 5 |ig/cm2, which must be
removed prior to analysis. To eliminate this background, purchased QFFs must
be:
• Prebaked in a muffle furnace at 550 °C for 12 hours before sampling.
• Stored in Petri dishes lined with clean aluminum foil (also baked at 550 °C for
12 hours). After baking, aluminum foil is rinsed in n-hexane and dried in the
oven at 100 °C for 10 min. Aluminum foil liners must be cut to cover the
inside surfaces of the Petri dishes so that the filters do not directly touch the
dish when placed inside the lined dishes.
The filters and liners must be handled with Teflon forceps to avoid any
contamination.
7.2 Sampling Procedure
1. Assemble the QFF sampling train as illustrated in Figure B-l and connect
equipment to the stainless steel sampling line provided by others.
3-Way Metering
Valve Valve
Pump
Main Sample Line
Mass Flow
Controller
Part 1065
Stainless Steel
Filter Holder
Figure B-l. Quartz filter sampling train.
2. Install a 47-mm filter cassette containing a prebaked QFF into the filter holder
per the manufacturer's recommendations.
3. Conduct a leak check of the system by removing the sampling line and
installing a vacuum gauge on the inlet of the filter holder. Start the pump with
the three-way valve in the "bypass" (open to atmosphere) position. Before
proceeding, close the metering valve and then just crack the valve to restrict
B-7
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
the rate at which the vacuum is placed on the system to avoid tearing the filter.
Make sure that power is applied to the MFC before proceeding. Switch the
three-way valve to the "sample" (straight through) position, observe the
vacuum gauge until the maximum vacuum is reached, and then switch the
three-way valve back to the "bypass" position. Observe the vacuum gauge for
a period of 2 min. If the vacuum drops more than 127 mm (5 in.) Hg, the
system has a leak. Turn off the pump and slowly release the vacuum by
switching the three-way valve to the "sample" position. Once the vacuum has
been released, remove the vacuum gauge from the sampling train inlet. If a
leak is found, locate and repair the leak and repeat the above procedure.
4. To prepare for sample collection, move the three-way valve to the "bypass"
(open to atmosphere) position and start the pump. When sampling conditions
become stable, switch the three-way valve to the "sample" (straight through)
position and record the start time to the nearest second.
5. Sample for a sufficient period to accumulate at least 0.2 |ig/cm2 of sample
mass (for more accurate results at least 2 |ig/cm2) on the QFF per NIOSH
Method 5040. At the end of this period, move the three-way valve back to
"bypass," stop the timer, and record the end time to the nearest second.
6. Stop the pump and remove the filter cassette from the filter holder. Place it in
a clean and labeled cassette mailer. If another run is to be made, install a fresh
filter cassette in the filter holder and repeat Steps 3 through 6.
7. Remove the filter from the cassette using the cassette separator and place it in
an aluminum foil-lined Petri dish. Samples should be stored in a freezer at ~ -
20 °C until ready for analysis.
8. Collect at least one field blank for every 10 filter samples collected. A field
blank shall consist of installing and immediately removing a QFF cassette in
the filter holder without actually passing any air through the filter.
B-8
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
7.3 Standards Preparation and Analysis
A set of external liquid calibration standards containing sucrose in organic-free
water is used to establish the linearity of the FID response and to calibrate the
gaseous internal standard (5% methane in helium) that is injected at the end of
each analysis.
During TOT analysis of sucrose, some OC (the only kind of carbon in sucrose) is
volatilized and some OC is pyrolyzed during all four of the non-oxidizing heat
ramps. As a result, all OC fractions and PyC show up in the thermogram.
7.3.1 Preparation of Standards
Sucrose Stock Solution: A sucrose stock solution is prepared by
weighing 10.000 ± 0.010 g sucrose into a 1000 mL volumetric flask and
diluting to the mark with organic-free water. (10.000 g of sucrose [C12
H22O11, MW = 342.31] in 1,000.00 mL of solution has a carbon [C, AW =
12.01] concentration of 4.210 |igC/|iL).
10-000 g sucrose s 12x12.01 gC x 1 ml s lolig = 4 n(1 Hic
1000.00 ml solu ' 342,31 g sucrose 103pl 1 g M-1 solu
Calibration Standards: At least three calibration standards that span the
measurement range of the samples are prepared. Calibration standards are
prepared either (1) by weighing appropriate masses of sucrose into a
volumetric flask and diluting to the mark with organic-free water, or (2)
by diluting aliquots of the sucrose stock solution (section la) with organic-
free water in a volumetric flask. A typical set of calibration standards
includes the sucrose stock solution (nominally 4.2 |igC/|iL) and two
dilutions of the sucrose stock solution (to 2.1 |igC/|iL and 0.42 |igC/|iL).
Normally, 10.0 |iL of each standard is used in a calibration analysis, but a
larger volume of the sucrose stock solution could be used to extend the
measurement range.
Sucrose stock solution and sucrose calibration standards are stored in a
refrigerator at <4 °C. New stock solution and calibration standards are
prepared at least every 6 months.
B-9
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
7.3.2 Calibration with External Standards
External standards are used to establish linearity of FID response and to
calibrate the 5 % methane in helium internal standard loop. Prepare and
spike filter punches with external standards for calibration and analyze
them according to the following instructions:
1. A new, clean section of a quartz filter is punched out (1 cm2 punch
area) and the section is placed on the quartz filter boat in the analysis
oven.
(The filter punch section remaining in the oven from the last analysis
can be used instead of a new section of filter).
2. An "Oven Clean" cycle is run to completely clean the filter section;
then an "Instrument Blank" is run.
3. The quartz door to the oven is opened and the quartz filter boat
containing the cleaned filter punch is taken out.
4. Using a precision syringe, a 10.0-|iL volume of a standard sucrose
solution is delivered to the clean filter punch without removing the
punch from the filter boat.
(Deposit the standard at the location on the punch that will be directly
in the path of the laser during analysis).
5. The filter boat is put back into the oven, the quartz door of the oven is
closed, and the filter is allowed to dry completely (10-20 min) inside
the cool oven before the start analysis button is clicked.
6. The filter punch is analyzed as described in next Section 7.4.
7. Sections 3 through 6 are repeated until all three standards have been
analyzed and all of the following criteria have been met:
• The three-point calibration has an R2 > 0.998 (linear least-squares
fit forced through the origin of a plot of total FID area counts vs.
mass of carbon spiked).
• Each of the three analyses shows a percent recovery of 97 % to
103 % of theoretical (|igC measured/|igC spiked).
• Each of the three analyses gives an FID response to the internal
standard within 90 % to 110 % of the average FID response to the
internal standard for the three calibration analyses.
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TOT Carbon Analyzer SOP
September 2011
Rev. 1
• Each of the three analyses gives a response factor (counts/mgC) for
the calibration standard that is within 90 % to 110 % of the average
response factor for the three calibration analyses.
7.3.3 Internal Standard
The response factor (slope = counts/|igC) from the three-point calibration
with external standards (sucrose) and the area acquired for the internal
standard (5 % methane in helium) for the calibrated and fixed-volume
sample loop are both used to calculate the calibration constant (|igC per
sample loop). An aliquot of the internal standard (5 % methane in helium)
is injected near the end of each sample analysis and the acquired standard
and sample area used to calculate the amount of OC and EC in the
analyzed sample.
7.4 TOT Carbon Analyzer Procedure
7.4.1 Preanalysis Checklist
1. Cylinders are checked for sufficient volume and pressure
2. Instrument gas flows are checked on the computer gas flow table.
3. The instrument pressure (psig) is checked prior to analysis (in the off-
line mode it should be in the range 0.15-1 psi).
7.4.2 Work Area Preparation
1. In a designated area near the OC-EC instrument, an area which can be
maintained free of clutter, dust, and chemicals is cleared. The area is
covered with two to three layers of clean aluminum foil. The edges are
taped down so that the foil is secured.
2. The punch, forceps, and aluminum foil are thoroughly cleaned with
acetone at the beginning of each analytical session.
7.4.3 Startup
1. From standby, the CONTINUE button is pressed (if program has been
exited, double clicking on the "OCECINST" icon will start the
analyzer).
2. Set gas flow rates by slowly adjusting the corresponding needle valves
on the instrument's MFC box. Gas flow rates should be set as follows:
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
• He-1 set to 54-58 cc/min.
• He-2 set to 12-15 cc/min.
• He-3 set to 67-70 cc/min.
• He/02 set to 12-15 cc/min.
• Air set to 280-300 cc/min.
• Cal set to 10-14 cc/min.
• Hydrogen - when ready to ignite the flame in the FID, set the
hydrogen flow to 80-100 cc/min. Once the flame has been lit
(usually signaled by a small pop and can be confirmed with
condensation on the forceps), return the flow rate to 40-59 cc/min.
Caution: Check the pressure (psig). In the off-line mode, it should be in
the range 0.15-1 psi. While analyzing on-line, it should increase by
approximately 1-2 psi. This oven pressure will change, depending on flow
rates and resistance of the Mn02 oxidizer bed and methanator oven.
3. Wait 20 min for the instrument to warm up and stabilize.
4. Under the Run menu select Clean Oven.
5. After the oven has been cleaned, recheck the flame and the flow rates
of the gases before proceeding.
7.4.4 Ru nning a Blank
1. To run a blank, take a punch (1.5 cm2) from a prebaked (550 °C, 12 h)
QFF using the manual precision punch. If the filters have not been
baked, run the punch through the Clean Oven cycle before analyzing it
as a blank. Handle punches with tweezers only.
2. Before loading a filter punch into the oven, make sure "Safe to put in a
new sample " is displayed in the OC-EC software window. If there is a
red bar displaying " WAIT-Too hot (>75) for new sample ", wait until
the oven cools and the green bar appears.
3. Open the oven port. Be careful not to drop the rubber O-ring
positioned between the oven port sections. Pull the sample holder out
with forceps and place it on the support tray.
4. Place the filter punch on the sample holder using the stainless steel
tweezers.
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
5. Steadily slide the sample holder and sample back into the oven with
the forceps until it is stopped by the tip of the thermocouple. Then pull
the sample holder forward slightly so it does not touch the
thermocouple. Do not tip the sample holder from side to side or risk
losing the sample in the oven port.
6. Close the oven port, making sure the O-ring sealed tightly and check
the pressure reading on the monitor screen to make sure no warning
flag appears (which would indicate a leak).
7. Enter Inst Blank 1 in the Sample ID # field. Enter the date in the file
name of the Output Raw Data File block. Enter the value for Punch
Area (1.5 cm2).
8. Click Start Analysis. Each run will take approximately 13 min.
9. To review the results, click the Shortcut to Calc2PD158 icon on the
right side of the window and choose the correct file date.
10. Click Calculate First Sample. Total carbon (TC) for the blank ideally
should be < 0.05 |ig/cm2, although <0.1 |ig/cm2 is also acceptable. If
the result is higher, the blank filter punch must be reanalyzed.
7.4.5 Running Samples
Quartz filters are stored in a freezer at -15 °C or below. An individual
batch containing up to 50 filters may be kept in a refrigerator during
analysis of that batch. Allow each Petri slide holder containing a quartz
filter sample to warm to room temperature just before opening it to take a
punch from the filter for analysis. Return the quartz filter to the Petri slide
holder and the Petri slide holder to the refrigerator immediately after
starting the analysis. Punches from filter samples should only be placed in
the oven while the computer is in the "Safe to put new sample " mode.
1. To analyze punches from filter samples, perform steps 2 through 8
from Section 7.4.4. In step 7, enter the sample name in the Sample ID
# field.
2. To review the results, click the Shortcut to Calc2PD158 icon on the
right side of the window and choose the correct file date. Click
Calculate First Sample, then calculate Next Sample to view the results
for all analyzed samples.
7.4.6 Shutdown
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TOT Carbon Analyzer SOP
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Rev. 1
1. If intending to return to the analyzer later in the day or at some time
over the next several days, the STANDBY box is clicked on. In
STANDBY, the back oven and methanator oven will be maintained at
a lower than normal operating temperature to increase heating coil life.
Also the laser will be off and the pressure will be near zero, since there
is very little flow.
2. If not intending to use the instrument for several days, EXIT is chosen
from the file menu. This will turn off all power to the ovens, causing
them to cool down. Gas flow rates are set as follows: H2 set to 4-7
cc/min; Air set to off; Cal set to off; He-3 set to trickle flow at 6-8
cc/min; He-2 set to trickle flow at 0-4 cc/min; He-1 set to trickle flow
at 6-8 cc/min; He/02 set to trickle flow at 4- cc/min.
3. When the program is being shut down for more than a few days, all
gases should be turned off except for He-1 and He-3 (approximately
5-10 cc/min each).
8.0 DATA ACQUISITION, CALCULATIONS, AND DATA REDUCTION
8.1 Blank Correction
Final sample results should always be blank corrected. For that purpose, two types
of blanks are used: laboratory and field blanks. The laboratory blank consists of
the prebaked QFFs stored in the aluminum foil-lined Petri dishes in the
laboratory. The field blank is a prebaked QFF subjected to all aspects of sample
collection, transportation, field handling, and preservation as a real sample. Any
measured OC and EC concentration in the blank samples represent contamination
and should be deducted from the real samples.
8.2 Concentrations of Carbon Fractions on the Filter (jigC/cm2)
1. The software application used to run the analyzer (OCECInstxxx.exe)
automatically stores data acquired during an analysis in comma-delimited
ASCII text format for later computation, display, and printing.
2. Results are calculated using a second software application
(OCECCalcxxx.exe) provided by Sunset Laboratory. The data for each
sample can be printed in a graphic form (referred to as a thermogram) with
temperature, laser transmittance and absorbance, and FID profiles. Text output
on the thermogram includes calculated loadings of OC, EC, and TC. The
uncertainty associated with the OC, EC, and TC measurements are also given
on the thermogram. Other text outputs include EC/TC ratio, date, time,
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
calibration constant, punch area, FID1 and FID2 status, calibration area, split
time, manual split time, initial absorbance, absorption coefficient of original
elemental carbon, instrument name, analyst, laser correction factor, and transit
time.
3. The calculation software application (OCECCalcxxx.exe) also creates a tab-
delimited output file with additional data columns. In the output file, several
header rows are followed by one row of data for each analysis. New rows are
added to the bottom of the output file each time the calculation software is
run, so the most recent calculations are always at the bottom of the file.
8.3 Recovery (%) of Sucrose Standards
Sucrose calibration standard (c = 0.421 |ig/|iL) is run at the beginning of each day
and a percent of recovery (|igC measured/|igC spiked) calculated as:
m tot lug/cm2) X 1cm2
% recovery = A x 100
where: mtot is the total (OC + EC) carbon concentration measured (|ig/cm2).
Acceptable % of recovery is from 93 % to 107 %.
8.4 Masses of Carbon Fractions on the Filter (in jigC)
The mass (in |igC) of OC, EC, and TC on the filter are calculated by multiplying
the concentration (c) of each type of carbon (|igC/cm2) by the deposit area (A) of
the filter in cm2.
lit - cA
NOTE: The filter deposit area is 11.76 cm2 for a 47-mm QFF used for sampling in
a filter cassette with a 38.7-mm inside diameter, which defines the deposit area.
.3K "nan
i i i ij
1
i l ""<>¦
The mass calculation of the OC, EC, and TC for the blanks (laboratory and field
blanks) should be done using the same formulas. Carbon mass found in the blanks
must be deducted from the carbon mass calculated for the field samples.
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
8.5 Concentrations of Carbon Fractions in Air
Sample volume is corrected to the EPA standard temperature and pressure (STP)
conditions (T = 25 °C and p = 760 mm Hg). Mass (m, in |ig C) of each type of
carbon on a filter can be divided by the STP volume (Vair)sTP of air sampled (in
m3) to calculate concentrations (Cair) of each type of carbon in the air sampled.
m
^alr ~ nj \
1 alr4tp
8.6 Measurement Uncertainty
Uncertainties of measurements for OC, EC, and TC, each of which contains both
an absolute uncertainty and a relative uncertainty, are calculated by the data
analysis software.
9.0 QUALITY CONTROL AND QUALITY ASSURANCE PROCEDURES
9.1 Thermocouple Temperature Calibration
The thermocouple temperature calibration procedure for the Sunset Laboratory
analyzer is performed annually (earlier if needed) by trained staff or the APPCD
Metrology Laboratory and according to instructions provided by Sunset. The OC-
EC temperature calibration kit consists of the following: precision digital
thermometer, NIST-traceable thermocouple, front oven interface hardware, serial
cable, front oven heating coil, and new version of the software. Temperature
offsets for target temperature ramps are implemented in the new version of the
Sunset OC-EC software, and thus, when the software runs, the thermocouple will
heat the zone in the filter area to match the required protocol (NIOSH 5040).
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TOT Carbon Analyzer SOP
September 2011
Rev. 1
9.2 Calibration of Gas Flow Meters
A calibration is performed at least annually of the gas flow meters for the Sunset
analyzer using APPCD Metrology Laboratory SOP FV-0235.1, which is included
here by reference.
9.3 Instrument Blanks
An instrument blank for the Sunset analyzer is run using a punch from a
precleaned QFF at the beginning of each day. An instrument blank must meet the
following criteria:
• TC for the blank must be < 0.05 |igC/cm2.
• The FID response to the internal standard injected at the end of the instrument
blank analysis must be within 90 % to 110 % of the average FID response to
the internal standard for the last (or current) three-point calibration.
If the instrument blank fails to meet either of the criteria above, determine if the
problem is with the filter or with the instrument. If necessary, initiate corrective
action to identify and solve any instrument problem before repeating the
instrument blank analysis, which must be acceptable before continuing with
analysis of other samples.
9.4 Calibrations
Calibration check samples of the Sunset analyzer are run at the beginning of each
day, and a full three-point calibration is run at least once a week. Determine the
minimum detection limit (MDL) for TC when the analyzer oven or methanator is
changed or annually, whichever comes first.
9.4.1 A complete set of calibration standards (i.e., three different mass loadings)
is run at least once a week. If the least-squares correlation coefficient (R2)
of area counts vs. total mass of carbon, force-fit through the origin (0,0), is
not > 0.998, determine the cause of the nonlinearity, and initiate actions
that will identify and solve any problem that might have arisen. Then the
three-point calibration is repeated, which must yield satisfactory results
before samples are analyzed. In addition, analysis of each of the three
standards must meet all of the following criteria:
• The measured mass of total carbon for the calibration standard is
within 93 % to 107 % of the true value.
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TOT Carbon Analyzer SOP
September 2011
Rev. 1
• The FID response to the internal standard injected at the end of the
calibration standard analysis is within 90% to 110% of the average
FID response to the internal standard for all three calibration standard
analyses.
• The response factor (counts/|igC) for the calibration standard is within
90 % to 110 % of the average response factor for all three calibration
standard analyses.
If any one of the sucrose standards analyses fails to meet any of the above
criteria, repeat the analysis of that standard or, if necessary, initiate
corrective action to solve the problem before analyzing samples.
9.4.2 A sucrose standard calibration check sample is run after the initial
instrument blank each day. The calibration check sample analysis results
are valid if all of the following criteria are met:
• The measured mass of total carbon for the calibration check sample is
within 93 % to 107 % of the true value.
• The FID response to the internal standard injected at the end of the
calibration check sample analysis is within 90 % to 110 % of the
average FID response to the internal standard for the last (or current)
three-point calibration.
• The response factor (counts/|igC) for the calibration check sample is
within 90 % to 110 % of the average response factor for the last (or
current) three-point calibration.
If the sucrose standard calibration check sample analysis fails to meet any
of the above criteria, repeat the analysis of the standard or initiate
corrective action, if necessary, to solve the problem before analyzing
samples.
9.4.3 At least three replicates of a low-level standard (0.421 |ig/|iL) are spiked
on the quartz filter to determine the MDL for total carbon. The spike
volume of that standard should be adjusted to have 5 times the estimated
MDL which is 0.2 |ig/cm2.
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
Determine the variance (S2) as follows:
1
j;
V
ix.
where xt is the z'th measurement of the variable x and x is the average
value of x.
Determine the standard deviation (s) as follows:
Determine the MDL as follows:
where t(n i, « .99) is the one-sided t-statistic appropriate for the number of
samples used to determine (s) at the 99 % level.
If the MDL is > 0.5 |igC/cm2, investigate the source of the problem and
initiate corrective action, if necessary, to correct the problem, then repeat
the MDL. An acceptable MDL must be obtained before samples can be
analyzed.
9.5 Duplicate Sample Analysis
A duplicate punch is run approximately every tenth filter sample (at least 10 % of
samples). Agreement between duplicate TC measurements depends on filter
loading and the uniformity of the deposit. Acceptance criteria for duplicate
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
measurements at higher filter loadings (> 5 |ig/cm2) are based on the relative
percent difference (RPD) of the duplicate measurements, and the acceptance
criterion for duplicate measurements at low filter loadings (< 5 |ig/cm2) is based
on absolute error (± 0.75 |ig/cm2), which dominates the uncertainty of the TC
measurement at low filter loadings. Acceptance criteria for the various
concentration ranges are given in Table B-l.
Table B-l. Acceptance Criteria
Total Carta# Cancettraikm Range 1 Acceptance C>iterion
Virtues greiiier than 10 pg/atr | Less than ICI% RPD
5-10 iipewr | Lens th#n 15% RPD
Values less than 5 pg/citr I Within 0.75% pg/cm
As stated above, nonuniform filter deposit can cause a difference between
duplicate measurements. If the deposit on a filter appears visually to be
nonuniform or if a duplicate analysis is run and the duplicate measurements fail
the appropriate acceptance criterion in the table above, flag the analysis data for
that filter as "Nonuniform Deposit."
9.6 FID Response to Internal Standard
If the Sunset analyzer FID response to the internal standard for any sample
analysis run on a given day is outside the range 95-105 % of the average response
for all samples run that day, discard the results of that analysis and, if necessary,
repeat the analysis with a second punch, if available, from the same filter.
NOTE: An FID response significantly lower than the average occurs when the
ball joint at the front of the instrument leaks during the run.
9.7 Transit Time
During TOT analysis, the laser signal monitors the transmittance of the filter in
real time while FID response to carbon evolved from the filter lags behind
because of the time required for gaseous carbon species to travel from the filter to
the FID. This lag time is called the transit time. The transit time is used by the
calculation software to align FID response properly with laser transmittance for
calculation of OC and EC fractions (by integration of FID response) based on the
OC-EC split time (which is determined solely from the laser transmittance). A
new transit time must be determined whenever the effective volume of the
analysis system between the oven and the FID changes. Such changes include
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
replacement of the oven, replacement of the methanator tube, replacement of the
FID, and replacement or modification of any transfer line between the oven and
the FID.
9.8 Control Charts
Control charts are used to show performance of the Sunset analyzer over time.
1. Measured TC for all instrument blanks by date is plotted.
2. Linearity (R2) of three-point calibrations by date is plotted.
3. Percent recovery for low, mid-level, and high calibration standards as well as
average percent recovery for each three-point calibration by date is plotted;
±10 % bars for average percent recovery are shown.
4. FID response factors for TC for each three-point calibration by date are
plotted. Response factors measured for each standard (to show range) and the
average response factor for all three standards (to show mean) are plotted.
5. Percent recovery for all daily calibration checks by date is plotted.
6. Relative percent difference of duplicate measurements versus average
measured TC for all duplicates is plotted.
9.9 Laser Transmittance
Laser reading (displayed in raw data files under the heading "laser") is an
important indicator not only of EC loading on the filter punch but also of the
condition of the quartz optical flats used for the boat and for the upper and lower
windows of the quartz oven.
1. A laser reading < 1,000 for a filter punch at the beginning of an analysis
indicates a fairly heavy loading of EC in the sample and provides a warning
that the OC-EC split point set by the software could be inaccurate because the
laser response might "bottom out" during the char-forming, non-oxidizing
heating ramp. The absorbance plot on the bottom of the printed thermogram
can be used to check the split point.
2. An initial laser reading > 3,000 for a clean filter punch and a series of final
laser readings that drift slightly upward during the last seconds of an analysis
(as the oven cools) generally indicate that the quartz optical flats (boat and
oven windows) are adequately free of frosting for an accurate assignment of
the OC-EC split. If the initial laser reading is < 3,000 or if the laser reading
drifts slightly downward during the last seconds of an analysis (as the oven
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
cools), the quartz optical flats (boat and oven windows) should be inspected
for frosting and the boat (either oven or both) replaced, if necessary.
9.10 Balance Calibration
Balance performance verification must be performed at the following frequency:
• At least once a year by the APPCD Metrology Laboratory.
• Before weighing any filter by zeroing and spanning the balance with at least
one calibration weight.
• Before and after filter weighing sessions by weighing reference PM sample
filters.
10.0 REFERENCES AND SUPPORTING DOCUMENTATION
National Institute of Occupational Safety and Health. (2003). Diesel particulate matter (as
elemental carbon). Method 5040, Issue 3, available at:
http://198.246.98.21/niosh/nmam/pdfs/5040.pdf.
Chow, J. C., et al. (2001). Comparison of IMPROVE and NIOSH Carbon Measurements,
Aerosol Science and Technology, 34, 23-34.
OC/EC Analyzer Calibration and Analysis Procedures, MOP 2511, May 2009.
Code of Federal Regulations (CFR), Title 40 Part 1065: Engine Testing Procedures.
Standard Operating Procedure for the Determination of Organic, Elemental, and Total
Carbon in Particulate Matter using a Thermal/Optical-Transmittance Carbon Analyzer.
(2004). Center for Air Resources, Engineering and Science (CARES), Clarkson
University, Potsdam, New York, May 10, 2004.
Standard Operating Procedure for the Determination of Organic, Elemental, and Total
Carbon in Particulate Matter using a Thermal/Optical Transmittance Carbon Analyzer.
(2003). OC/EC Laboratory, Environmental and Industrial Sciences Division, Research
Triangle Institute, Research Triangle Park, North Carolina, August 14, 2003.
Procedure for Calibration of a Mass Flow Controller (MFC) Using a Gilibrator®, MOP
FV-0237.0. (2010). U.S. Environmental Protection Agency, National Risk Management
Research Laboratory, Air Pollution Prevention and Control Division, Research Triangle
Park, NC.
Procedure for Calibration of Gas Flow Meters of the Sunset Lab Elemental
Carbon/Organic Carbon Analyzer Using a Gilibrator®, MOP FV-0235.1. (2008). U.S.
Environmental Protection Agency, National Risk Management Research Laboratory, Air
Pollution Prevention and Control Division, Research Triangle Park, NC.
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
11.0 ATTACHMENTS
11.1 Example Thermogram for Filter Sample
OC-EC split
OC and CC
EC
2°ft O.J He
He
890 C Temperature
870
Transmittance
FID
Cli
PC
rJrJ
Time (minutes)
Thermogram for filter sample containing organic carbon (OC), carbonate carbon (CC), and
elemental carbon (EC). Pyrolytically generated carbon is represented here as (PC). The final
peak is the methane (CH4) calibration peak. (Figure from NIOSH 5040 method: Issue 3, 1999.)
B-23
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Appendix B
TOT Carbon Analyzer SOP
September 2011
Rev. 1
11.2 Temperature Profile for the NIOSH 5040 Method
CARRIER
TEMP.
RAMP RATE
RESIDENCE TIME
CARBON
GAS
(°C)
(°C/s)
(s)
FRACTION
Helium
310
4
70
OC1
Helium
475
8
60
OC2
Helium
615
10
60
OC3
Helium
870
8
105
OC4
98% Helium/2% Oxygen
550
9
60
EC1
98% Helium/2% Oxygen
625
10
60
EC2
98% Helium/2% Oxygen
700
12
60
EC3
98% Helium/2% Oxygen
775
13
60
EC4
98% Helium/2% Oxygen
890
8
110
EC5
CalibrationOx
1
110
B-24
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
Appendix C: Development of an
Improved Multi-angle Absorption
Photometer (SuperMAAP)
*
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V
&
PHO^
O
z
ULJ
o
p*
C-1
-------
Appendix C
SuperMAAP Development
December 2016
Rev. 0
TABLE OF CONTENTS
1.0 INTRODUCTION C-3
2.0 INSTRUMENT REQUIREMENTS C-5
3.0 HARDWARE MODIFICATIONS C-6
4.0 SOI I WARi : DEVELOPMENT C-15
5.0 SOFTWARE IMPLEMENTATION C-22
6.0 III. THR CHANGE CORRECTION C-27
C-2
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
1.0 INTRODUCTION
The Thermo Fisher Scientific (Waltham, MA, USA) Model 5012 MAAP is a
commercially available, filter-based absorption photometer that deposits aerosol onto a 2
cm2 area on a quartz-fiber filter (QFF) tape. A 630-nm (670-nm nominal value)
wavelength light-emitting diode (LED) illuminates the area, and multiple photodetectors
measure the transmission and scattering/reflection of the light from the depositing aerosol
layer and the underlying filter. Figure C-l (Petzold et al., 2005) shows a schematic
diagram of the MAAP and the position of the optical sensors. A two stream, radiation
transfer calculation is used to separate the light absorption by the aerosol layer from the
scattered light from the particles and filter matrix. Figure C-2 (Petzold et al., 2005) shows
the radiation processes within the MAAP. A narrow range of mass absorption
coefficients, cabs ~ 6.4-6.6 m2/g, is reported to provide a decent fit between measured
absorption coefficients and collocated particle mass measurements for commercially
produced soot particles and urban particles containing refractory carbon soot collected at
several sites. The standard 5012 MAAP is designed to be operated with a flow rate of 8-
24 L/min and provides measurements of particulate absorption and black carbon (BC)
mass loadings on the time scale of 1, 10, and 30 min. The MAAP is a self-contained
instrument and therefore provides a firmware-determined measurement of the BC mass
loadings on a small LED screen on the front panel. Access to this processed data is
provided using several serial port data output formats. Detailed descriptions of the
standard MAAP are provided in a number of publications such as Petzold et al. (2002,
2005).
A number of research organizations including Aerodyne Research, Inc. (ARI), United
Technologies Research Center (UTRC), National Aeronautics and Space Administration
(NASA)-Langley, and the U.S. Environmental Protection Agency (EPA) National Risk
Management Research Laboratory (NRMRL) have used the Thermo 5012 MAAP to
measure BC emissions from aircraft turbine engines. Since the MAAP was originally
designed for ambient applications, several modifications have been made to the standard
instrument. ARI has implemented the most advanced of these modifications. Working
with Andreas Petzold, formerly of the German Aerospace Center, and Kevin Goohs from
Thermo Fisher Scientific, ARI started using a rapid (~ 1 s) data collection protocol and
developed a data analysis routine within the WaveMetrics Inc. (Tigard, OR, USA)
IgorPro platform. ARI's extensive laboratory and field work experience with the MAAP
has allowed them to identify and address specific instrument-related issues and develop
various sampling protocols that enable rapid, accurate measurements to be made with the
MAAP for a wide range of sampling conditions.
C-3
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
o t
r
r—~|
iH
X*
M
i—i
i i
e.
~
1 1 _
••• n "
Figure C-l. Optical sensor of the MA A P. Left: position of photodetectors at detection
angles 6a = 0°, 0i = 130°, and 62 = 165 0 with respect to the incident light beam (Xmaap =
670 nin). Right: Layout of the MAAP sensor unit with arrows indicating the airflow
through the sensor unit across the filter tape.
back-scattered radiation
Bp
incident radiation
I
\/
multiple
aerosol layer JSEIXJd
II
filter fibers
multiple
reflections
filter matrix [
I
transmitted and forward scattered radiation
PF
Figure C-2. Schematic representation of radiation process to be considered in the two-layer
system consisting of an aerosol-loaded filter layer and the particle-free filter matrix.
C-4
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
However, further work was needed to make the instrument truly useful for source
monitoring applications such as aircraft turbines. Therefore, EPA initiated a separate
research effort to develop an improved version of the MAAP instrument that would be
both useful and user-friendly. In this effort, the goal was to keep the basic instrument the
same as that offered for purchase by Thermo Fisher Scientific but to add whatever
hardware and software is needed to make it more suitable for use during engine
certification. This appendix describes the modifications made to the standard 5012
MAAP, called the "SuperMAAP," under the EPA program.
2.0 INSTRUMENT REQUIREMENTS
As a starting point, EPA organized a workshop to discuss the goals and objectives of the
research and to develop specifications for the modified instrument. Workshop
participants included Andreas Petzold, inventor of the MAAP, and representatives from
ARI, UTRC, and EPA. An outside contractor took detailed minutes to allow free
discussion by the workshop participants. These detailed minutes were then used as the
starting point for the SuperMAAP development process.
During the workshop, the participants agreed on several key objectives for the
SuperMAAP to be of use in engine certification environments:
• Reduce flow through the filter tape to extend the time between filter changes.
• Isolate the MAAP from the main sampling line during filter changes.
• Perform the necessary calculations to determine BC concentration on a 1-Hz basis
and log the data.
• Calculate appropriate statistics from the calculated BC concentrations.
• Provide the ability to manually implement a filter change.
• Monitor the light transmission percentage in real time so that the operator can
determine when an automatic filter change is about to take place.
• Allow for and document some type of quality control (QC) check to tell the operator
the instrument is working properly and ready for use.
• Develop an add-on "package" that incorporates all necessary changes for use in
certification environments.
To meet these objectives, additional hardware and software were identified. With respect
to new hardware, a "box on the box" concept was developed to avoid making any
physical modifications to the standard MAAP instrument. The specific hardware changes
were to add two mass flow controllers (MFCs), filters, an automated three-way valve, and
an isokinetic sampler to the instrument inlet; supply a new sample pump not controlled
C-5
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
by the instrument firmware; and provide a new data acquisition board and DC power
supply for use by the new operating software.
Regarding the new software, the workshop participants decided that code written within
the National Instruments (Austin, TX, USA) Lab View platform would be most
appropriate for this application. The Lab View code would be prepared by an outside firm
most familiar with the subtle nuances required by the ARI data analysis scheme. The
following requirements were established for the new LabView code:
• Process and log the 1-Hz data stream from the RS-232 output.
• Allow the operator to set the flows below 8 L/min to extend filter life.
• Automatically operate the three-way valve to isolate the instrument from the main
sample line during filter changes.
• Continuously monitor filter life (percent transmission) and provide the capability to
manually change the filter tape to a new spot.
• Provide a real-time display of the data being generated.
• Document QC parameters from the instrument to verify proper operation.
• Generate spreadsheet files of both the raw and processed data.
As part of the new LabView software, a conceptual graphical user interface (GUI) was
also developed during the workshop. This GUI was designed to be user-friendly and
specifically tailored for use during engine certification. Basically, the GUI would allow
the user to start and stop data acquisition for each power condition being tested with the
average concentration of BC and summary statistics available immediately at completion
of the measurements. In addition, the code should also be open source so that it is
accessible to anyone wanting to build a SuperMAAP through a software request to EPA.
3.0 HARDWARE MODIFICATIONS
The hardware modifications identified during the workshop that were added to the
standard 5012 MAAP are shown schematically in Figure C-3. The external hardware is
mounted in a 42- x 44.5- x 40.6-cm light-gauge aluminum enclosure mounted on the top
plate of the standard 5012 MAAP. The flow path for the SuperMAAP was plumbed as
shown in Figure C-3. Photos of the SuperMAAP including the hardware mounting
arrangement are provided in Figure C-4, with a complete parts list shown in Table C-l
and wiring diagrams in Figures C-5 through C-9.
C-6
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
Original SuperMAAP Configuration
teokinti® Sampler
Filter 1
MFC 1
Electrically
Actuated 3-
Way Valve
J
filter 2
MFC s
Filter 3
•
prj- -
"u. »*
\
M«M 5012 IMP'
Com
-2
External Pamip
Figure C-3. Schematic of SuperMAAP hardware additions and signal processing as
developed from user workshop.
C-7
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
Isokinetic
sampler
Figure C-4. Front and back views of the SuperMAAP showing original hardware configuration based on workshop
discussions.
C-8
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
Table C-l. SuperMAAP Parts List
Vendor
Manufacturer
Part Number
Description
Quantity
MKS Instruments, Andover, MA, USA
M100B01353CS1 BV
M100B Mass-Flo economical, analog, elastomer-
sealed MFC
1
MKS Instruments, Andover, MA, USA
M100B01324CS1 BV
M100B Mass-Flo economical, analog, elastomer-
sealed MFC
1
National Instruments, Austin, TX, USA
781424-01
cDAQ-9188, CompactDAQ chassis (8-slot ENET)
1
National Instruments, Austin, TX, USA
779018-01
Nl 9915 DIN rail kit for 8-slot chassis
1
National Instruments, Austin, TX, USA
763000-01
Power cord, AC, US, 120 V AC, 2.3 meters
1
National Instruments, Austin, TX, USA
763068-01
Power cord, 240V, 10A, North American
1
National Instruments, Austin, TX, USA
779002-01
Nl 9421 8-channel 24V 100 US, sinking digital input
module
1
National Instruments, Austin, TX, USA
779012-01
Nl 9263 4-channel +- 10V, 100 kS/s per channel, 16-bit
analog output module
1
National Instruments, Austin, TX, USA
779013-01
Nl 9201 8-channel +- 10V, 500 kS/s per, 12-bit analog
input module
1
Automation Direct, Cumming, GA, USA
FC-33
Signal conditioner, isolator, IN: mA, V/ OUT: mA, V
1
Automation Direct, Cumming, GA, USA
DN-G4
Terminal block; wire-to-wire; screw-cage; 6; 9 mm;
polyamide 6.6; green/yellow
1
Automation Direct, Cumming, GA, USA
DN-D10X
Multi-level clamp terminal block gray, 18-10AWG
14
Automation Direct, Cumming, GA, USA
NON-1/2
250 V AC, 0.5 A fuse, general purpose
2
Automation Direct, Cumming, GA, USA
NON-15
250 V AC, 15 A fuse, general purpose
1
Automation Direct, Cumming, GA, USA
DN-F10L110
Fuse holder terminal block
3
Automation Direct, Cumming, GA, USA
PSE15-215
±15VDC 15W power supply
1
Automation Direct, Cumming, GA, USA
PSE24-130
24VDC 30W power supply
1
Indus. Automation Components, London,
ON, Canada
Valworx 563303
Stainless steel 3-way valve
1
Indus. Automation Components, London,
ON, Canada
Valworx 588125
Wall bracket kit
1
Pall Life Sciences, Port Washington, NY,
USA
12144
HEPA capsule filter
2
Parker Hannifin Corporation,
Greensboro, NC, USA
9922-11 -AAQ
DFU grade AAQ filter
2
Swagelok, Wake Forest, NC, USA
SS-400-2-4
90° elbow, 1/4-in. NPT to 1/4-in. tube
4
Swagelok, Wake Forest, NC, USA
SS-400-3
1/4-in. union tee
3
Swagelok, Wake Forest, NC, USA
SS-1010-3
5/8-in. union tee
1
Swagelok, Wake Forest, NC, USA
SS-400-R-10
1/4-in. to 5/8-in. reducer
2
Swagelok, Wake Forest, NC, USA
SS-400-1-4
1/4-in. NPT to 1/4-in. tube male connector
2
Swagelok, Wake Forest, NC, USA
SS-400-9
1/4-in. 90° union elbow
2
Swagelok, Wake Forest, NC, USA
SS-400-3-4TMT
1/4-in. run tee
1
Swagelok, Wake Forest, NC, USA
SS-1010-6-6
5/8-in. to 3/8-in. reducing union
1
Swagelok, Wake Forest, NC USA
SS-1210-6-6
3/4-in. to 3/8-in. reducing union
1
C-9
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
r«ot
VAU.
*0*7. J5A
^0-
v
pao
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14AVC. UH(K
vccsncD
ru2
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NO
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v
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r »1D.J9VG
^oT4 g&w
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j l lMCOM
~/- 1*0C ».U_*4AVG
7"
C4TB0
-Q.TB0 15V COM
-QT80 -«SV
D
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I***'
Figure C-5. Wiring diagram for Ethernet data acquisition chassis.
C-10
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
_JL3LSt At
-JCSKLB
arttn
Ml ¦
_?ML£aC
I EM I
Ml |
D
B
r**u rot coooa*
mmt »ic» awain
fe
"sns-
W
Figure C-6. Wiring diagram for MFC wiring.
C-11
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
KIRUMXTS
* iWI
1
0"
COw
2
0
J
0
0
S
0
«
0
7
0
a
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DO
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n'» \-
2
-------
Appendix C
SuperMAAP Development
December 2016
Rev. 0
0-
i
0-
i
0-
0-
t
0-
0
1
0
•
0
t
0
WC SETPOSKT
seccu 1
WfC SCTWT 2
-Sib
X ecu 2
i way wtvt sWi
pwtQ Q
i-55—I v/i seuw/
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KHMKl
0-
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0
1
0
4
0
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0
;
0
0
0
-0-
fl» KJC&CX 1
ao» fvo&cx 2
SC COM 1
SIC ecu ?
D
B
Figure C- 8. Wiring diagram for analog input/output.
C-13
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
15V COM
0
0j@ UL
r:
TOIL
¦ WIT
DC
rauD
or
+24V
-24V
iph
r.
@
u:
•MM
0
GND
0
0
GND
0
0
GND
0
0
GND
0
0
GND
0
Mm
A
0
nm
0
m
H
D
B
Ml »¦¦«» ¦ M
¦XU.Sv2.T--
Figure C-9. Wiring diagram for terminal strip.
C-14
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
As shown in Figure C-3, the sample enters the top of the instrument through a 9.5-mm
outside diameter (OD) stainless steel sampling line. Upon entering the instrument, a
subsample of the flow is extracted by an isokinetic probe inserted into a bored-through
16-mm OD stainless steel tee. The excess flow then passes through a filter and bypass
line to an MFC and then the pump. The subsample flow is directed straight through an
electrically operated, three-way, full-flow ball valve to the sensor head of the instrument.
After the flow penetrates the filter tape and exits the analyzer, the flow is then directed to
a second MFC and the external pump.
During automatic tape changes, the head sensor opens and the three-way valve goes to
bypass mode and directs air in-leakage from the open head through a filter to avoid
contaminating the sample flow of any other analyzers on the same sampling line. It was
discovered that this scheme did not isolate the instrument from the other instruments on
the same line. Instead, when the three-way valve activates and the tape head opens up, the
software stops the flow through the instrument, allowing laboratory air to enter the
system through the optical sensor head and cause a pressure fluctuation for the other
instruments. Therefore, a data correction scheme (described in 6.0) was needed along
with hardware/software changes to address the problem. EPA is currently working on
modifications to the original configuration that will be reported in detail in a later
publication.
4.0 SOFTWARE DEVELOPMENT
As stated previously, new Lab View code was written specifically for operation of the
SuperMAAP. The code runs independently of the standard 5012 MAAP firmware but
uses the firmware's raw output as input to calculate MBC and CBC much faster than 1
min as in the standard instrument. The new Lab View code was based on the calculation
scheme developed previously by ARI for their IgorPro program. This calculation scheme
is described below.
Basically, two energy balance equations (taken from Petzold and Schonlinner, 2004)
need to be solved simultaneously to derive the MBC on the filter and the CBC in the
sampled air:
P, Tr +Fr
F - L L (C-la)
Z>(°) 1 -B*B
1 F 1 L M
Bp * Tr +Fr Br
—%r = P, , +— (C-lb)
Bf< l\-B[Bu Bu
Notation
C-15
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
Variables:
F = fraction of forward-scattered radiation
B = fraction of back-scattered radiation
T = fraction of transmitted radiation
P = total fraction of radiation passing through a layer, P = T + F
Subscripts:
L = particle-loaded aerosol filter layer
M = particle-free filter matrix
F = composite system consisting of aerosol-filter layer and particle-free filter
matrix
Superscripts:
(0) = property referring to a blank filter sample
No superscript = particle-loaded filter sample
* = illumination by diffuse radiation
Left-Hand Side
The left-hand side of the equations above is a function of the "signal" data as
follows:
Pp = 2 S(0 = 0)
(C-2)
(C-3)
Therefore:
A.l=/(s(0=o))
\rF J
(C-4)
=f{s{e = 7r\a,p)
(C-5)
C-16
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
where a is the fraction of diffusely scattered radiation and p is filter surface
roughness.
S(o)cc cccos(#-;r) + (l-cc)exp
1 (O-tt)2
2 p2
(C-6a)
Sf 130 ) = 0.2984+ 0.4064a
^ = 165') (C-6b)
where O = 130° was used in theory, but O = 135° was used in practice and actual
calculations below.
Risht-Hand Side
The right-hand side of the main equations consists of nonlinear functions of two
unknowns, v. and SSAl. There are two equations and two unknowns as follows:
= f(rL,SSAL,g)
RHSlm =f(rL,SSAL,g)
where:
tl = optical depth of aerosol-filter layer
SSAl = single-scattering albedo of aero sol-filter layer
g = aerosol asymmetry parameter
4.1 Mass of Black Carbon on Filter (unit conversions not shown)
The MBC is calculated by:
(C-7a)
(C-7b)
MBC = (\-SSAl)^-A
abs
(C-8)
where:
MBC = mass of black carbon (ng) on particle-loaded filter
crabs = aerosol absorption coefficient (m2/g)
C-17
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
A = active filter surface area (m2)
4.2 Concentration of Black Carbon
The CBC is calculated using Equation C-9.
CBC = AMBC/Sample Flow = AMBC/AV
(C-9)
where:
AMBC = difference in mass of black carbon (ng) on particle-loaded filter
between time 1 (ti) and time 2 (t2)
AV = difference in the volume of air sampled during measurement (m3)
between ti and t2
t = clock time
such that CBC is the change in the MBC in time divided by the flow (i.e., change
in sample volume in time).
4.3 Measured Aerosol Absorption Coefficient (Mm1)
The aerosol absorption coefficient (Babs) is calculated by:
CBC = mass concentration of black carbon in sample air (|ig/m3)
-------
Appendix C
SuperMAAP Development
December 2016
Rev. 0
A = active filter surface area (m2)
V = volume of air sampled during measurement (m3)
4.4 LabView Code
The calculation scheme above was implemented in LabView using the RS-232
output from the 5012 MAAP firmware Version 1.29. The output from the
firmware is as follows with an "a " prefix indicating signal for particle loaded
filter, a "b_" prefix indicating signal for blank filter after filter change, and a "c_"
prefix indicating dark current readings:
Maap Date, Maap Time, Maap Flow, a sref, a szero, a si35, a si 65,
bsref b szero, b sl35, b sl65, c sref c szero, c sl35, c sl65,
CBC thermo, MBC thermo, Tl, T2, T4, PI, P3, Volume,
HeizRegePO. 2443
The left-hand side calculations for equations C-la and C-lb above use only
measured signals from raw data. The calculations of normalized signals, S(0) and
S, as a function of angle (0 = 0, 135, and 165°) are:
S(O)(0 = 0) = (b_szero - c_szero)/(b_sref- c_sref)
S(O)(0 = 135) = (b_sl35 - c_sl35)/(b_sref- c_sref)
S(O)(0 = 165) = (b_sl65 - c_sl65)/(b_sref- c_sref)
S (0 = 0) = (a_szero - c_szero)/(a_sref- c_sref)
S (0 = 135) = (a_sl35 - c_sl35)/(a_sref- c_sref)
S (0 = 165) = (a_sl65 - c_sl65)/(a_sref- c_sref)
The calculation of the fractions of radiation transmitted, P, and reflected, B, from
filter layers (blank and particle-loaded filters) for a blank filter are then:
a(0) = (S(O)(0 = 135)/S(O)(0 = 165) - 0.2984 )/0.4064
constl = a(0) * COS(165.0 * % /180.0 - %)
const2 = (1.0 - a(0)) * EXP(-0.5 * (((165.0 * %/180.0 - 7t)/p)A2.0))
S(O)(0 = 7i) = S(O)(0 = 165)/(constl + const2)
P(0)F = 2.0 * S(O)(0 = 0)
C-19
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
B(°)F = S(O)(0 = tc) * (2.0 * a(0) + (1.0 - a(0)) * SQRT(2.0 * tc) * p)
and for a particle loaded filter:
a = (S(0 = 135)/S(0 = 165) - 0.2984)/0.4064
constl = a * COS(165.0 * tt/1 80.0 - tc)
const2 = (1.0 - a) * EXP(-0.5 * (((165.0 * tc/180.0 - Tc)/p)A2.0))
S(0 = 7i) = S(0 = 165)/(constl + const2)
Pf = 2.0 * S(0 = 0)
Bf = S(0 = tc) * (2.0 * a + (1.0 - a) * SQRT(2.0 * tc) * p)
Calculation of the normalized transmission, TRANS, and reflection, REF, are
then:
TRANS = Pf/P(0)f
REF = Bf/B(0)f
Rearranging equations C-la and C-lb (subtracting TRANS and REF from both
sides) and solving the two equations for two unknowns (tl and SSAl) yields:
„ Tl+Fl Pp
0 = F
1_R*R p(°)
1 f (C-la*)
* Tt +Fr B, Bp
0 = P, L L ' L F
LlBu Bf (c.lbt)
These calculations for equations C-la* and C-lb* use the following parameters in
the code:
Filter roughness (p) = 0.50
Asymmetry factor (g) = 0.75
Active filter area (A) = 2 x 10"4 m2
Mass specific absorption coefficient (pabs) = 6.6 m2/g
Fraction of radiation backscattered from particle-free filter matrix (Bm) =
0.70
C-20
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
Initial guess for n (total optical depth of particle-loaded aerosol-filter
layer) = 2.5
Initial guess for SSAl (single scatter albedo of loaded aerosol-filter layer)
= 0.99
The following code uses the initial guesses for tl and SSAl and the parameters
listed above, calculates the variables on the right-hand sides for equations C-la
and C-lb, and is looped (using newly derived tl and SSAl values) to solve the two
equations (C-la* and C-lb*) for two unknowns (tl and SSAl). Note that the
calculations are broken into simple steps.
START LOOP
Tl = EXP( -tl )
const 1 = ( 1.0 - ABS( 1.0 - 2.0 * g )/ 8.0 - 7.0 / 8.0 * ( 1.0 - 2.0 * g ) * ( 1.0 - 2.0 * g ))
beta_L = 0.5 * ( 1.0 - g - 4.0 / 25.0 * constl )
betastar L = 0.5 * ( 1.0 - g / 4.0 * ( 3.0 + POW( g, 3.0 + 2.0 * g * g * g ) ) )
al = 2.0 * ( 1.0 - SSAl * ( 1.0 - betastar_L ) )
bl = 2.0 * SSAl * betastar_L
c = SSAl * beta_L
d = SSAl * ( 1.0 - beta L )
pi = c - al * c - bl * d
p2 = -al *d-bl *c-d
B = al * al - bl * bl
constl = c - pi / ( 1.0 + SQRT(B) )
const2 = ( c - pi / ( 1.0 - SQRT(B) ) ) * POW(TL, 2.0 * SQRT(B) )
const3 = 2.0 * pi * SQRT(B) / ( 1.0 - B ) * POW(TL, 1.0 + SQRT(B) )
const4 = SQRT(B) + al + ( SQRT(B) - al ) * POW(TL, 2.0 * SQRT(B) )
Bl = ( constl - const2 - const3 ) / ( const4 )
C-21
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
const 1 = d + Bl * bl + p2 / (1.0 + SQRT(B))
const2 = d + Bl * bl + p2 / ( 1.0 - SQRT(B) )
const3 = p2 / ( 1.0 - B ) * Tl
Fl = 1.0 / 2.0 / SQRT(B) * ( constl * POW(Tl, -SQRT(B) ) - const2 * POW(Tl, SQRT(B) ) ) +
const3
constl = 1.0 - POW(Tl, 2.0 * SQRT(B) )
const2 = SQRT(B) + al + ( SQRT(B) - al ) * POW(TL, 2.0 * SQRT(B) )
B*l = bl * constl / const2
constl = SQRT(B) - al + B*L * bl
const2 = SQRT(B) + al - B*L * bl
P*L = 1.0 / 2.0 / SQRT(B) * ( constl * POW(Tl, -SQRT(B) ) + const2 * POW(Tl, SQRT(B) ) )
Find Roots solving for new tl and SSAl:
0 = (Tl + Fl )/( 1.0 - B*L * BM ) - Pf / P(0)f
0 = P*L * ( Tl + Fl )/( 1.0 - B*L * BM ) + BL / BM - BF / B<°>f
END LOOP
5.0 SOFTWARE IMPLEMENTATION
The output from the Lab View code consists of a raw and processed data files. The raw
data file includes the 1-Hz RS-232 output string from the instrument firmware plus the
associated software-calculated values of MBC (|ig) and CBC (|ig/m3) as described above
with the sample flow and instrument status. The processed data file provides the time-
weighted average CBC for the period between the user-selected start and stop times. In
this case, however, the CBC is determined by a simple linear regression of the total MBC
values. The CBC is then divided by the total flow measured during the sampling period.
When multiple filter changes are made between the user-selected start and stop times, the
software calculates an average CBC from the individual CBC values obtained for each
period between the filter changes. Also shown in the processed data file are the mean
C-22
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Appendix C
SuperMAAP Development
December 2016
Rev. 0
flow, flow standard deviation (SD), root mean square error of the CBC and correlation
coefficient (R2) for each linear regression performed.
As discussed in Section 4.5 of the main text, the CBC values initially determined by the
SuperMAAP during the testing program proved to be approximately 35 % lower than the
other instruments evaluated. Due to this difference in the measured results, a reevaluation
of the SuperMAAP and its operating software was conducted in an attempt to determine
the basis for the observed differences.
Two basic problems were found that were not evident before the study began. First, the
tape head was determined to contain a substantial leak whereby laboratory air was
introduced into the flow downstream of the filter tape. Based on a recalibration of the
entire flow system, it was determined that approximately 15 % less air was actually
passing through the filter tape than was actually measured by the downstream MFC.
Further experiments with different filter mass loadings showed that this leak was
consistent across all operating conditions and could easily be compensated for in the
MFC calibration. In addition, the existing data set could also be corrected by a simple
calculation. It is generally known that the standard 5012 MAAP is not leak tight, but this
leak was thought to be minimal, which was found not to be the case.
Another problem that was found involved the linear regression of the MBC values used
to determine the average CBC in the Lab View software. The original code calculated the
linear regression over the entire sampling period by simply ignoring the time period(s)
when filter changes occurred. This method created approximately a 9 % difference in the
average CBC from that determined by the ARI method. Therefore, the software code was
revised to calculate individual linear regressions, statistics, and average CBC for each
period between filter changes and then calculate an overall average CBC and statistics
from these values. This revision now provides results that are within 1 ng/m3 of the
results determined by the ARI IgorPro code. In addition, a Lab View post-processor was
developed whereby the existing experimental data can be corrected for this problem and
reported accordingly.
Also as part of the software upgrade (Version 1.3), an additional feature was added to
allow the operator to view the CBC values from the 1-Hz data in real time to determine
stable operating periods for analysis. New code was added to display a 5-s rolling
average CBC continuously in the main window of the measurement screen in addition to
the total MBC. This change allows the operator to be better informed of source operation
and makes the instrument more useful. Figures C-10 through C-13 show the four output
screens from the Version 1.3 Lab View code.
C-23
-------
Appendix C
SuperMAAP Development
December 2016
Rev. 0
The first screen is the file input/output screen (Figure C-10). Here the operator assigns
the storage location for the raw and processed data files, starts the data-logging process,
and enters any desired notations. Also displayed are the date and time from the personal
computer running the Lab View software. The computer time is used in the calculation of
the CBC.
li:07;39AM
Proccwd Onto File
\\C "WAAFiProcwwd
Figure C-10. Updated SuperMAAP file input/output screen.
Next the flow and MBC data are displayed in real time on the main measurement screen
(Figure C-l 1). Also displayed on this screen are the "Start Condition" button, which
starts the sampling time period; the "Stop and Calc" button, which ends sampling and
calculates the average CBC value for the period; the results from the latest sampling
period; the sample temperature and pressure measured by the 5012 MAAP; the total and
MAAP air flow from the two external MFCs; and the filter life gauge showing the
percent transmission through the filter tape. Note that the "Total Flow" is that which
enters the instrument from the sampling line, and the "MAAP Flow" is the flow through
the filter tape on which the average CBC is based. Also shown in the main display is the
5-s rolling average CBC.
C-24
-------
Appendix C
SuperMAAP Development
December 2016
Rev. 0
MMP Inllirtci vt.3
"irmuiTmrnl » Miri in. trrimi I rml>p*r
ItflSSKJW
um/mi
SNjJ l«* Irrw
Lj«il Condition CBC STDcv, R 2
«.s-
-na
f*
JJ-
/
*500
J*
2-5"
2-
-4® §
J
-300 f
yf /
-2tJ0 —
0.5- "
-s»
*0.5-
—
-0
-3
Hk*MO
itt-mm I0C523B SB"54"00' IfcSfe® SO'S&flO II ;DOCO lim:00 l]^H;0D LlOfeOO
Trt*
Change
Filter Life
£Bt
hamifik- 1 rn»p
Vtinitki ftm*
InfjJ Flow
MAW* Tlaw
Figure C-ll. Updated SuperMAAP measurement screen (note yellow status light is on).
As indicated by its title, the status/errors screen (Figure C-12) displays the instrument
operating status, warning status, and error messages produced by the 5012 MAAP
firmware. The instrument is working properly if the three fields on this screen are blank.
The software describes any warnings or errors displayed in these fields and also
illuminates the status and/or error warning light on the main measurement screen (see
Figure C-l 1) to alert the operator.
The last screen of the LabView software is the configure screen (Figure C-13). In this
screen, the operator may enter a total flow from 0 to 20 L/min and a MAAP flow from 0
to 5 L/min to operate the SuperMAAP. Also included on this screen are fields for
entering the slope and intercept of the MFC calibrations, which are then used to
determine the actual total and MAAP flows for display and use in the calculations.
C-25
-------
Appendix C
SuperMAAP Development
December 2016
Rev. 0
11.05:34 UA
1JAB/2012
Operating Status:
Waning Status:
Figure C-12. Updated SuperMAAP status/errors screen (note operating status indication).
MAAP InrlnrfAcc vt S
Set Reodbock
Bypawi Plow SLOPt;
INTERCEPT
MAAP Flow SLOPE B23
MAAP Flow INTERCEPT
LVUj lrrflallfn.il1 |P
Figure C-13. Updated SuperMAAP configure screen.
PIE®
ll:07;C7 AM
a/csms
11 (P"' r SefFlow 0
C-26
MAAP tnterfacevl.3
March 6,2012
-------
Appendix C
SuperMAAP Development
December 2016
Rev. 0
6.0 FILTER CHANGE CORRECTION
After the study was essentially completed, the SuperMAAP was being used in another
project where it was connected to a sample distribution system along with several other
instruments. During sampling, it was discovered that the plumbing and operating scheme
of the instrument did not isolate it from the other instruments during a filter change as
originally intended. Instead, when the three-way valve was activated and the tape head
opened, the software stopped the flow through the instrument, allowing laboratory air to
enter the system through the optical sensor head and causing a pressure fluctuation and
extra dilution for the other instruments that could not be tolerated. (Note that the MAAP
modifications were made exactly as agreed upon during the workshop of experts held
before the start of the study!) Therefore, a data correction method was needed. To
develop this method, a detailed flow characterization and tracer gas study was performed.
As the first step, a flow characterization was conducted of the entire sampling system and
instrumentation shown in Figure C-3. In this study, the backflow created during a
SuperMAAP filter change was determined using a DryCal flow meter located at the
sample inlet as well as various other points throughout the instrument flow system.
During these measurements, it was determined that only approximately 40 cm3/min of
laboratory air was introduced into the sampling system during a filter change. Since it is
doubtful whether this small amount of dilution air would substantially affect the
measurements made by the other instruments, a tracer gas experiment was designed to
quantitatively assess the measurements made by the other instruments during a
SuperMAAP filter change.
To conduct the tracer gas measurements, compressed N2 gas containing 8720 ppm CO2
was introduced at 4.9 L/min into the bottom of the cyclone (Figure C-3) upstream of the
instruments with the sampling tunnel blower operating at 23 Hz (equivalent to the 100
|ig/m3 target concentration when the MiniCAST burner was used). The CO2
concentration was then measured sequentially at each sampler or instrument location
using a calibrated Horiba Model VA-3000 infrared gas analyzer to obtain the diluted CO2
concentration at each point. These concentrations were measured before, during, and after
at least two filter changes at each location in the system to determine differences in CO2
concentration. Using the data obtained, the difference in the measured concentration was
determined and compared with the other instruments in the system, and a data correction
scheme was developed from the data. Table C-2 shows the data collected during the
tracer gas experiment.
C-27
-------
Appendix C
SuperMAAP Development
December 2016
Rev. 0
Table C-2. Results of SuperMAAP Tracer Gas Study
Segments
Average CO2 (ppm)
Sample Duration
Duration of Filter Change
Teflon filter sample
796 ± 0
SuperMAAP filter change #1
821 ± 7
0:01:58
0:01:31
Teflon filter sample
799 ± 0
SuperMAAP filter change #2
822 ± 6
0:02:12
0:01:43
Teflon filter ambient
382 ± 1
Quartz filter sample
791 ± 0
SuperMAAP filter change #1
799 ± 4
0:02:28
0:01:44
Quartz filter sample
791 ± 0
SuperMAAP filter change #2
799 ± 4
0:02:12
0:01:39
Quartz filter ambient
384 ± 1
MSS sample
794 ± 1
SuperMAAP filter change #1
813 ± 8
0:02:04
0:01:30
MSS sample
793 ± 0
SuperMAAP filter change #2
812 ± 6
0:02:18
0:01:43
MSS ambient
380 ± 0
LII sample
796 ± 0
SuperMAAP filter change #1
812 ± 5
0:02:05
0:01:34
LII sample
794 ± 0
SuperMAAP filter change #2
810 ± 4
0:02:06
0:01:40
LII ambient
379 ± 0
As shown in Table C-2, there was approximately a 3 % higher CO 2 concentration
observed during the SuperMAAP filter change as compared to before and after the
change. However, the higher concentration lasted only approximately 2 min, a factor that
must be considered within the overall test period that could be as long as 7 h. Another
factor that must be considered is the number of filter changes occurring over the test
period. Therefore, using the data in Table C-2, a data correction template was developed
that mathematically determines the total time when the SuperMAAP is undergoing a
filter change (change in duration x number of changes per test) and the percent decrease
in concentration measured by each instrument during that period. These values were then
used to adjust the test averaged PM concentration measured by the two filter samplers,
LII, and MSS considering the overall duration of the test period. The corrected values
obtained using this template are reported in Section 5 of the main document.
7.0 REFERENCES
Petzold, A.; Schonlinner, M. (2004). Multi-angle absorption photometry—a new method for the
measurement of aerosol light absorption and atmospheric black carbon. Journal of Aerosol
Science, 35, 421-441.
C-28
-------
Appendix C
SuperMAAP Development
December 2016
Rev. 0
Petzold, A.; Kramer, H.; Schonlinner, M. (2002). Continuous measurement of atmospheric black
carbon using a multi-angle absorption photometer. Environmental Science and Pollution
Research, Special Issue 4, 78-82.
Petzold, A.; Schloesser, H.; Sheridan, P. J.; Arnott, W. P.; Ogren, J. A.; Virkkula, A. (2005).
Evaluation of multiangle absorption photometry for measuring aerosol light absorption. Aerosol
Science and Technology, 39, 40-51.
C-29
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
Appendix D: Measurement of
Nonvolatile Particulate Matter Mass
Using the Modified Multi-angle
Absorption Photometer (MAAP)—
Thermo Fisher Scientific
STANDARD OPERATING PROCEDURE 2106
NRMRL/A PPC D
APPROVED: September 6, 2011
^4 PRO^^0
D-1
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
TABLE OF CONTENTS
1.0 SCOPE AM) APPLICATION D-3
2.0 METHOD SUMMARY D-3
3.0 DEFINITIONS D-3
4.0 MAAP MODEL 5012 MODIFICATIONS D-4
5.0 EQUIPMENT AM) SUPPLIES D-4
6.0 PROCEDURES D-5
7.0 FUNCTIONALITY TEST D-9
8.0 DATA AM) RECORDS MANAGEMENT I)-10
9.0 REFERENCES D-10
10.0 ATTACHMENTS D-ll
D-2
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) provides instructions for the measurement of
nonvolatile particulate matter (nvPM) mass using the modified Model 5012 multi-angle
absorption photometer (MAAP) manufactured by Thermo Fisher Scientific (Waltham,
MA, USA).
The Model 5012 MAAP measures black carbon (BC) in ambient air. The off-the-shelf
instrument has been specially modified by the Air Pollution Prevention and Control
Division (APPCD) to allow its use for source measurements through the addition of
externally mounted hardware and customized Lab View software (National Instruments,
Austin, TX, USA). Thus, this modified instrument can be used to quantify the emissions
of nvPM at the exit plane of aircraft gas turbine engines. The measurement value of the
MAAP is concentration of BC (|ig/m3).
This SOP outlines a step-by-step procedure that describes how to set up and run the
instrument as well as to retrieve the data during operation of the modified Model 5012
MAAP.
2.0 METHOD SUMMARY
The Model 5012 MAAP measures ambient and source BC concentrations and aerosol
light absorption properties. The instrument is based on the principle of aerosol-related
light absorption and the corresponding BC mass concentration. The MAAP analyzes the
modification of radiation fields caused by deposited particles in the front and back
hemispheres of a glass-fiber filter. The data inversion algorithm is based on a radiation
transfer method and therefore takes into account multiple scattering processes inside the
deposited aerosol and between the aerosol layer and the filter matrix. The reduction of
light transmission, multiple reflection intensities, and air sample volume are continuously
integrated over the sample run period to provide real-time data output of BC
concentration measurements.
3.0 DEFINITIONS
Nonvolatile PM: Particle emissions that exist at gas turbine engine exit plane
temperature and pressure conditions and that do not contain volatile particle contributions
that condense at lower temperatures.
Soot: Carbonaceous particles that are by-products of the combustion of liquid or gaseous
fuels.
D-3
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
4.0 MAAP MODEL 5012 MODIFICATIONS
The following modifications were made by APPCD to the off-the-shelf MAAP
instrument:
• Capability for reduced air flow through the filter tape to extend its useful life.
• Automated isolation of the MAAP from the main sampling line during the filter
changes.
• Incorporation of calculations to determine BC concentrations on a 1-Hz basis and
logging of the data.
• Calculation of the average BC concentration at the end of the run.
• Capability to force a manual filter change at any time during the run.
• Ability to monitor the transmission percentage in real time so that the operator can
determine when a filter change is about to take place.
• Fabrication of an add-on equipment "package" that incorporates the necessary
changes for use in engine certification environments.
5.0 EQUIPMENT AND SUPPLIES
• Modified Model 5012 MAAP.
• Additional hardware (parts list) used to make the "box-on-the-box" (see Figure D-l)
that will be provided as separate documentation.
• Two main power cables (one for the MAAP and a second for the "box-on-the-box").
• RS-232 communication cable.
• External vacuum pump connected to the MAAP.
• Lab View software - Version 1.
D-4
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
Thermo
Figure D-l. Modified MAAP Model 5012 showing the "box-on-the-box."
6.0 PROCEDURES
6.1 Sample Collection and Instrument Operation
1. Turn on both the MAAP and the external vacuum pump.
2. Start the computer with the MAAP software.
3. In the Lab View software, go to the MEASUREMENT screen (Figure D-2)
and click on MANUAL FILTER CHANGE to force this manual operation.
The status light will turn on and the pump will go off during this step.
D-5
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
MAAP Interface v1. ?
12:37:27 FM
01/06/2011
logging
Last Condllion CBC Value, STPev, R^2
RlterLife
06:30.00 09:00:00 09:30:00 10:00:00 10:3000 11:00:00
Time
MAAP Flaw
Figure D-2. MAAP software - Measurement view.
4. Also enter the experiment number (EXP #) in the MEASUREMENT screen.
5. Go to the CONFIGURE screen (Figure D-3) and enter the TOTAL FLOW
and MAAP FLOW. These flows are regulated by mass flow controllers
installed in the "box-on-the-box" and calibrated by the APPCD Metrology
Laboratory according to MOP FV-0237.0 (U.S. EPA, 2010) within 1 year of
use.
6. Go to the FILE I/O screen (Figure D-4) and choose locations for both raw and
processed data files. Press BEGIN LOGGING, which starts data logging for
the raw data file. The raw data file contains all output data from the MAAP
plus the values calculated from those data. Not all raw data are used in the
calculations for the processed data file.
7. Go again to MEASUREMENT view and press START CONDITION. These
data are now used to calculate the concentration of BC (CBC) shown in the
processed data file.
D-6
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
MAAP Interface vt.2
a FBe I/O f~ * Measurement » Status Irrnr* ConfiQUte
a FRe I/O l»
Set Readback
Tola! Flow
MAAP Flow :
Bypass Flow SLOPE
Bypass Flow INTERCEPT
MAAP Flow SLOPE :
MAAP Flow INTERCEPT
EBB
12:40:38 PM
01/06/2011
Ftow Statu* £
Bypass (MbN
MAAP Interface vl.2
May 27,2011
lay/,,
DAQ Initialized i- £
Figure D-3. MAAP software - Configure view.
MAAP Interface vl.2
A VO ¦ ¦ ¦ I Measurement * Status/Errors Configure
EBB
A FUeI/O r- it,
+ —
Processed Data File
' C \MA/VP\Processed files
12:39:06 FM
01/06/2011
Figure D-4. MAAP software - File I/O view.
D-7
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
NOTE: In the middle of the measurement, the Filter Change operation can occur
if the transmission is lower than 20 %, but the filter change will not influence the
calculated results. This operation is handled in the Lab View software program.
8. After the desired sampling time, press STOP and SAVE in the
MEASUREMENT view and STOP LOGGING in the FILE I/O view in order
to stop all data logging. The processed data file is automatically produced and
average values calculated by the software using a linear regression of the mass
of BC on the filter tape divided by the average air flow rate.
9. Before starting a new measurement cycle, make sure that the Filter Change
operation is performed.
6.2 Data Acquisition, Calculations, and Data Reduction
6.2.1 The format for the processed data file is shown in an attachment (Section
10.1). The processed data file contains the following information: Start
and Stop Time (h:min:s), Exp #, number of points used for calculation,
mean flow rate (L/min) and standard deviation (SD), CBC (|ig/m3), and
CBC root-mean-square error (RMSE) and R2 for the linear regression of
the mass of BC calculated by the software.
6.2.2 The software application automatically produces and stores both the raw
and processed data files.
6.2.3 The BC average mass concentrations are generated directly in the
processed data file and expressed as "Black Carbon Concentration CBC
(|ig/m3)." No additional calculation is necessary.
6.3 Troubleshooting
6.3.1 In general, three different types of status messages are possible: operating,
warning, and error (Figure D-5). These messages are not controlled and
cannot be addressed with the new MAAP computer software. They are
created from the MAAP instrument itself.
6.3.2 One of the most common and expected status messages is shown in Figure
D-5 and is caused by a manual or automatic filter change.
6.3.3 Explanation of status messages and correction of errors are described in
the original MAAP Model 5012 instruction manual (Thermo Fisher
Scientific, 2003 or later).
D-8
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
MAAP Interface
Status/Errors
Computer Date 0^36 w\
and Time Cnj22/20ll
Operating Status:
Warning Status:
Figure D-5. MAAP software - Status/Errors view.
7.0 FUNCTIONALITY TEST
The functionality test of the MAAP refers to the emission power of the light-emitting
diode (LED) and to the signal level of the photodetectors. This test is conducted as
follows:
1. Force a manual filter change and then turn off the pump.
2. Go to the SERVICE menu and read the photosensor bit values. The values of the
photodetectors must be in the following ranges:
• Transmission and two reflection diodes between 3000 and 3900.
• Reference diode between 1500 and 3900.
If the values are in this range, the instrument is functioning properly. Otherwise, contact
the instrument manufacturer. For further details, refer to Chapters 2 and 3 of the Thermo
Operating Manual for more specific instructions on setting up the instrument and
D-9
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
operating parameters. This test should be conducted prior to each set of measurements for
QC purposes.
8.0 DATA AND RECORDS MANAGEMENT
8.1 Individual electronic data files are generated for each sample run. All data files
are stored appropriately in the data acquisition system. At the end of each day's
testing, all files generated are archived and identified appropriately.
8.2 Laboratory notebooks are used to document the following:
• Test conditions and times.
• Sampling system parameters.
• Samples collected.
• Background soot concentrations before and after the measuring cycle.
• Any unusual events or difficulties.
8.3 All hand-recorded data (laboratory notebooks and data sheets) must be written
accurately and legibly, and all errors and discrepancies must be noted.
9.0 REFERENCES
Thermo Fisher Scientific. (2003 or later). Model 5012 Multi Angle Absorption Photometer
(MAAP) Instruction Manual, P/N 100076-00. Thermo Scientific Corporation, Franklin, MA.
U.S. Environmental Protection Agency (U.S. EPA). (2010). Procedure for Calibration of a Mass
Flow Controller (MFC) Using a Gilibrator®, MOP FV-0237.0. National Risk Management
Research Laboratory, Air Pollution Prevention and Control Division, Research Triangle Park,
NC.
D-10
-------
Appendix D
MAAP SOP
August 2011
Rev. 0
10.0 ATTACHMENTS
10.1 Processed Data File Format
TEST-G @100 |jg/m3
Start Time
Stop Time
Exp #
#
Points
Mean Flow
Flow SD
CBC
CBC Fit
RMSE
CBC Fit
R2
L/min
|jg/m3
12:22:02
13:24:12
2.1
2855
2.997
0.006
85.343
0.405
1
13:25:52
14:20:11
2.2
2454
2.997
0.006
95.179
0.488
1
14:21:53
15:02:40
2.3
1828
2.997
0.006
92.295
0.565
1
15:04:32
15:22:01
2.4
784
2.996
0.006
96.154
0.844
0.999
12:22:02
15:22:01
2 (avg)
7921
2.997
0.006
91.065
0.511
1
D-11
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
Appendix E: Measurement of
Nonvolatile Particulate Matter Mass
Using the Lll 300 Laser-Induced
Incandescence Instrument
STANDARD OPERATING PROCEDURE 2102
NRMRL/A PPC D
APPROVED: August 6, 2012
^eD sn%
$ A v
% PRO^°
E-1
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
TABLE OF CONTENTS
1.0 SCOPE AM) APPLICATION E-3
2.0 METHOD SUMMARY E-3
3.0 DEFINITIONS E-3
4.0 HEALTH AND SAFETY CONSIDERATIONS E-4
5.0 EQUIPMENT AND SUPPLIES E-4
6.0 PROCEDURES E-8
7.0 DATA AM) RECORDS MANAGEMENT I>13
8.0 QUALITY CONTROL AND QUALITY ASSURANCE I>13
9.0 ATTACHMENTS E-17
E-2
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) provides instructions on the measurement of
nonvolatile particulate matter (nvPM) mass concentration using the LII 300 laser-induced
incandescence instrument from Artium Technologies, Inc. (Sunnyvale, CA, USA).
The LII 300 instrument measures black carbon (BC) soot from air pollution sources. This
method can therefore be used to quantify the emissions of nvPM at the exit plane of
aircraft gas turbine engines. The parameter measured by the LII 300 is mass
concentration of soot (mg/m3).
This SOP is a step-by-step procedure that describes how to set up and run the instrument
as well as to retrieve the data during operation of the LII 300 instrument.
2.0 METHOD SUMMARY
The LII 300 is an instrument for non-intrusive and real-time measurements of soot
particulate concentration and primary particle size. With this technique, a pulsed laser is
used to rapidly heat the soot particles within the measurement volume from the local
ambient temperature to close to the soot vaporization temperature (> 4000 K). Soot
particle incandescence is detected by two detectors using appropriate line filters, and the
signals are recorded for subsequent analysis.
The LII 300 is completely insensitive to liquid particles because they absorb a negligible
amount of laser energy compared to carbon. For carbon particles coated with volatile
material, the volatiles are believed to vaporize early in the laser heating period. For
calibration of the LII, a novel method (self-calibrating) was developed based on absolute
light intensity measurement that avoids the problem of calibration with a known source
of soot particles. That method applies two-color pyrometry principles to determine the
particle temperatures, relating the measured signals to the absolute sensitivity of the
system as determined with a strip filament lamp.
3.0 DEFINITIONS
Nonvolatile PM: Particle emissions that exist at gas turbine engine exit plane
temperature and pressure conditions and that do not contain volatile particle contributions
that condense at lower temperatures.
Soot: Carbonaceous particles that are by-products of the combustion of liquid or gaseous
fuels.
E-3
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
4.0 HEALTH AND SAFETY CONSIDERATIONS
4.1 This device must not be used in any environment where there is a danger of
explosion. Ignitable or explosive exhaust gas mixtures or exhaust gases that are
ignitable or explosive when mixed with air must not be measured with the device.
4.2 Some components can get very hot during operation. If necessary, use heat-
resistant protective gloves.
4.3 Exhaust gas of combustion engines contains toxic substances. If used in a test
cell, ensure appropriate ventilation and proper discharge of the exhaust, which
must meet current industry standards. Make sure to check the leak-tightness of the
probe connectors on both the sampling point and the device.
4.4 The device contains a Class 4 semiconductor laser that is embedded and protected
by suitable measures so that the device has been classified as a Class 1 laser
product. Every service of the laser must be carried out only by service staff
trained in laser safety measures.
5.0 EQUIPMENT AND SUPPLIES
5.1 Instrumentation
• Self-contained LII 300.
• Laser power supply.
• Hand-held controller for the laser power supply.
• External pump capable of supplying flow of approximately 5 L/min.
• Rotameter capable of measuring flow of approximately 5 L/min.
5.2 Ancillary Equipment and Supplies
• Two main cables for 110 V AC.
• Input/output (I/O) cable to connect the LII 300 unit with the laser power
supply.
• Two cooling water hoses: blue and red.
• 9-Pin RS-232 cable to connect the LII 300 unit with the laser power supply.
• Polypropylene tubing (1/4-in. OD) to connect an air supply (50 to 250 psi) to
LII 300 unit.
• BNC connector to connect the LII 300 unit to the laser power supply.
E-4
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
• AIMS software for instrument remote control.
• Wireless router for interconnection of LII 300 unit with the PC.
• Power key switch for laser power supply unit.
• Distilled water (approximately 710 mL).
• Air supply ("shop air") of at least 50 psi (max 250 psi).
• Operational check lamp provided by Artium Technologies, Inc.
5.3 Installation
Refer to Figure E-l for illustration of steps 2 through 10.
1. Connect the laser I/O cable from the laser power supply (#1) to the LII 300
unit (#1 and #2).
2. Connect the blue and red cooling water tubes from the laser power supply unit
(#4 and #5) to the LII 300 unit (#3 and #4).
3. Connect a power cord to the laser power supply (#3) unit and LII 300 unit
(#14).
4. Follow steps 4a through 4g to fill the laser cooling reservoir properly with
distilled water:
a. Connect the fill bottle to the FILL/DRAIN fitting located on the front side
of the laser power supply unit.
b. Connect the fitting with hose to the upper VENT fitting.
c. Add distilled water to the bottle until the water drains from the vent fitting.
d. Disconnect both coolant fittings.
e. Turn the key switch ON and the pump will turn on automatically after
power-up.
f. When the reservoir empties, turn the key switch OFF and repeat steps 4a
through 4d.
g. Add distilled water to the reservoir until the "maximum level" is
maintained in the coolant level window, with the pump running.
5. Connect a 9-pin RS-232 cable from the laser power supply unit (#2) to the
RS-232 connector on the back of the LII 300 unit (#11).
6. Connect an air supply (50 to 250 psi) to the CLEAN DRY AIR connection on
the LII 300 unit (#7).
E-5
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
7. Connect the BNC connector from the laser power supply unit Q-Switch Sync
(#6) to the LII 300 unit (#12).
8. Connect the printer cable from the LII 300 unit (#9) to the wireless router.
9. Connect the external pump (with rotameter) to SAMPLE OUT (#6) on the LII
300 unit.
10. Connect the sample line to SAMPLE IN (#5) position on the LII 300 unit.
11. No. 13 on the LII 300 unit is the optional external heater connection. If not
used, leave cap installed.
12. No. 8 on the LII 300 unit is the spare USB and # 10 spare serial connections.
13. No. 7 on the laser power supply unit is the optional interlock switch. If not
used, leave the BNC cap installed.
14. Connect the hand-held controller to the front of the laser power supply (Figure
E-2). Make sure that the red emergency shutoff button is in the out position.
E-6
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
Figure E-l. Back side of LI I 300 unit (top photo) and laser power supply (two bottom
photos) with marked connections.
E-7
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
Emergency
Shutoff. must be Out
wtien operating
Power Key
Switch
Figure E-2. LII 300 optics enclosure, laser power supply, and hand-held controller front
panel.
6.0 PROCEDURES
6.1 Sample Collection and Instrument Operation
1. Use the key on the front panel (Figure E-2) to turn on the laser power supply
unit (clockwise).
2. Turn on the LII 300 unit by using the power button on the front panel. The red
power light-emitting diode (LED) will come on and remain on.
3. Connect and start the computer with the AIMS software.
4. To set up an external pump on the LII 300 front panel touch screen, choose
"SETTINGS" "SAMPLE CELL" -» "SAMPLE VALVE".
E-8
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
5. Check "Disable ejector vacuum pump" and press the "Open Valve" button.
6. Plug in the pump and check the flow on the rotameter (should be ~ 5 L/min).
7. To control and review device parameters, click on the DEVICE CONTROL
icon (Figure E-3) located on the left side of the window.
8. The user must check the following parameters:
a. Under ACQUISITION, select FREE RUN (as shown in Figure E-3).
b. Under GAIN/FILTERS, select AUTOMATIC GAIN and AUTOMATIC
FILTER.
c. Under STP, enter standard temperature and pressure (STP) all final results
will be calculated using that set of STP conditions.
9. All other options in all other tabs should remain unchanged.
10. Click on the start acquisition button ( ) to start data acquisition.
11. Click on the stop acquisition button ( ) to stop data acquisition.
E-9
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
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Figure E-3. Device control - online view.
6.2 Data Acquisition, Calculations, and Data Reduction
6.2.1 Clicking the DATA LIBRARY icon (Figure E-3) located on the left side
of the window opens folders that contain the results files.
6.2.2 Double clicking any of the files opens them in graphic form under the
RESULTS icon, also located on the left side of the window.
6.2.3 Clicking on the EXPORT icon (left side of window) exports the run file to
the format selected under EXPORT —»¦ PREFERENCES.
E-10
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
6.2.4 Data format depends on the configuration of the export template. The
sample data form with selected mass concentration and primary particle
size (PPS) versus time can be found in Attachment 9.1.
6.2.5 The software application automatically stores data acquired during an
analysis in individual electronic data files for later computation, display,
and printing.
6.2.6 The BC mass concentrations are generated directly and expressed as
concentration of soot in exhaust (mg/m3) at 25 °C and 1013 mbar (760
mm Hg).
6.3 Troubleshooting
6.3.1 The AIMS software displays alerts and recommendations in the Status
Window (Figure E-4).
6.3.2 The Status Window pops up automatically when an alert or error is
received, but it can also be found by pressing F7 or selecting Help —
Show Status Window.
A AIMS - Status Window
Fri Jul 1413:49(0 POT 2006
Em
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Powei Supply k connected to the computer and turned on.
FriJul 14 13.4944 PDT 2006
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Error. Can"! Frd Ul Miciocontaoflw. Make sue Ihe Ul optcaJ boot is
connected to the compter and Jumcd on
FriJul 14 13:4ft 49 PDT 200$
Error Cant FndUl Filter Whee* Make sure Ihe Ul opted bo* ts
connected to the computer and lumed on
Clean Up
Figure 4. Status window - online view.
E-11
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
6.4 Draining Water from the LII 300 and Laser Power Supply
6.4.1 The water from both devices must be drained before shipping the units:
1. Disconnect the quick-disconnect coolant lines from the LII 300 unit
(Figure E-l). Tilt the unit to allow the coolant to drain into a catch
basin.
2. Blow dry nitrogen gas through the left (blue) coolant connector on the
LII 300 to remove any remaining coolant. Install the shipping cover
over the output of the laser head and the blue coolant port plugs. The
LII 300 is now ready for long-term storage or shipping.
6.4.2 To drain the plumbing in the laser power supply (Figure E-l), attach the
connectors provided with the accessories kit to both cooling lines. Place
the blue-colored hose into a catch basin and turn the power supply key
switch to ON. Allow the pump to run only as long as coolant continues to
flow into the catch basin.
I
i * CAUTION: Do not run the pump motor dry for an extended
period of time as this will cause permanent damage.
When looking at the front of the cabinet, the drain and fill fittings are
located on the left side of the cabinet.
1. Place the water bottle (~ 2 L) below the lower drain fitting of the laser
power supply to catch the waste coolant.
2. Install the white plastic quick-disconnects supplied with the
accessories kit into the fill/drain and vent fittings on the front of the
cabinet. Water should flow out of the lower drain fitting. Be sure to
keep the drain bottle below the level of the power supply unit.
3. With the blue coolant line in the catch basin, blow dry nitrogen into
the red-colored coolant line until no more water exits the power supply
unit. Next, with the red line in a catch basin, blow dry nitrogen into the
blue-colored coolant line until no more water exits the unit.
4. To drain the coolant lines, detach the coolant hoses from the back of
the power supply unit. Hold the end of the coolant hoses (with coolant
change connectors installed in the stainless steel connectors) over a
catch basin. Press the white plastic part that protrudes from the end of
the plastic connectors. When depressing this part, do not cover the
E-12
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
entire end of this connector as it will not allow the coolant to drain
from the lines.
5. Again install the white plastic quick-disconnects supplied with the
accessories kit into the drain and fill fittings on the front of the cabinet.
Water should flow out of the lower drain fitting. Any residual coolant
left in the cooling system after following this procedure is not a
concern. Disconnect the white fittings from the front of the panel. The
coolant is now drained and the power supply unit is suitable for
storage or transport.
7.0 DATA AND RECORDS MANAGEMENT
7.1 Individual electronic data files are generated for each sample run. All data files
are stored appropriately in the data acquisition system. At the end of each day's
testing, all files generated are archived and identified appropriately.
7.2 Laboratory notebooks are used to document the following:
• Test conditions and times.
• Sampling system parameters.
• Samples collected.
• Background soot concentration before and after the measuring cycle.
• Any unusual events or difficulties.
7.3 All hand-recorded data (laboratory notebooks and data sheets) must be written
accurately and legibly, and all errors and discrepancies must be noted.
8.0 QUALITY CONTROL AND QUALITY ASSURANCE
8.1 Quality Control Procedures
The operational check lamp (Figure E-5) is used to check the general operation of
the instrument and to detect any system failures. Before using the check lamp, the
sample cell heater needs to be set to room temperature. To set the sample cell
heater, go to SETTINGS mode on the LII300 front panel, and then choose
SAMPLE CELL -> HEATERS -~ SAMPLING CELL HEATER.
The SAMPLING CELL HEATER option allows the user to change the
temperature of the sampling cell. The set point should be approximately 20 °C.
Cooling of the sample cell can take up to 30 min or longer.
E-13
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
Figure E-5. Operational check lamp.
1. Once the sample cell has returned to room temperature, open the sample cell
access door located on the front panel of the LII 300 unit.
2. Remove the screw from the test cell circled in red and shown on Figure E-6.
3. Plug the USB cable end of the operational check lamp into the USB port on
the front panel of the LII 300 unit while inserting the calibration LED into the
test cell.
4. Use the locking screw to tighten the check lamp into place as shown in Figure
E-7.
5. Then go to SETTINGS mode on the LII 300 front panel, and choose OPTICS
-> OPERATIONAL CHECK.
6. Press the UPDATE button to force the LII 300 to acquire approximately 3
seconds of data and average the signal levels.
7. Compare "Current" to "Factory" values. Devi ation between values should be
<10 % (if higher contact the manufacturer).
E-14
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
Figure E-6. Front panel of the LII300 showing the sample cell access door.
Figure E-7. Front panel of the LII 300 unit showing the operational check lamp.
8.2 Quality Assurance Procedures
8.2.1 Sample Cell Temperature Calibration
E-15
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
The temperature calibration allows the user to calibrate the temperature
sensors on the sample cell. To perform the calibrations, go to SETTINGS
-~ SAMPLE CELL -> TEMPERATURE CALIBRATION. Press the
UPDATE button to force the IJl 300 to perform the action. The
calibration is set to the default offset of 0 and a scale of 1; in this case, the
raw value should equal the corrected value:
tem peratureconwied = (temperatureraw x scale) + offset
8.2.2 Sample Cell Pressure Calibration
The pressure calibration allows the user to calibrate the pressure sensors
on the sample cell. Since the pressure sensor measures pressure relative to
the atmospheric pressure, there is a field in the pressure calibration to
input the local/current atmospheric pressure. To perform the calibrations,
go to SETTINGS -> SAMPLE CELL — PRESSURE CALIBRATION.
Press the UPDATE button to initiate the action. An example of the
calibrated pressure is shown in Figure E-8. The calibration is set to the
default offset of 0 and a scale of 1; in this case, the raw value should equal
the corrected value:
pressurecorrected = (pressureraw * scale) + offset.
Sample Cell Pressure Calibration
Setup Update
Raw:
13.0lbf/in2
Corrected:
13.0 lbf/in2
Offset:
o.o lbf/in2 set
Scale:
1.0 Set
Atm. Press.:
14 7 lbf/in2 set
Gal. Date: 01/07/2011
fol Timo •
1A-95-47
Home Start
j Stop Eject Quit
Figure E-8. Pressure calibration screen.
8.3 Regular Maintenance
Since the LII instrument bases measurements on absolute intensity measurements
of the soot incandescence, window contamination can systematically bias the
results. The windows need to be examined occasionally for contamination. The
E-16
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
LIT 300 unit has three windows: one large horizontal window (Figure E-9A) and
two side vertical windows (Figure E-9B and C).
Figure E-9. Extracting the horizontal sample cell window for cleaning.
The following steps describe how to access and clean the windows:
1. Loosen the thumb screw holding the sample cell door on the front panel of the
LII 300 and remove the door. A safety switch will deactivate the laser when
the door is removed.
2. Unscrew the lockdown thumbscrew on the window frame as shown in Figure
E-9.
3. Grasp the cable and pull out firmly on the window frame and retaining device.
4. Note the proper orientation of the windows in the frame.
5. Remove the window and frame from the the retaining device and clean the
window. A clean cloth may be used, and if there is condensed material on the
window, a solvent may be used. Use a clean cloth to finish cleaning.
6. Replace the window in the frame and reinsert the frame.
7. Lock down the window with the thumbscrew.
8. Place the sample cell doors in their starting position.
9.0 ATTACHMENTS
9.1 Sample Data Form
Time (ms) Mass Concentration (mg/m3) PPS (nm)
E-17
-------
Appendix E
LI I 300 Analyzer SOP
August 2012
Rev. 1
12:01
20:288
0.681
39.6
12:01
21:289
0.212
24.5
12:01
22:288
0.111
55.9
12:01
23:288
0.08
15.5
12:01
24:288
0.158
5.5
12:01
25:288
0.09
12
12:01
26:288
0.065
15
12:01
27:288
0.169
4.1
12:01
28:288
0.242
9.1
12:01
29:288
0.262
10.6
12:01
30:288
1.555
14.7
12:01
31:288
0.978
49.3
12:01
32:288
0.67
24.5
12:01
33:288
2.336
19.1
12:01
34:288
12:01
35:288
2.222
32
12:01
36:288
0.964
9.9
12:01
37:287
0.545
13.3
12:01
39:288
0.819
8.5
12:01
40:288
2.432
125.8
12:01
41:287
3.649
38.6
12:01
42:287
4.414
134.9
12:01
43:287
2.396
50.6
12:01
44:287
2.025
28.8
12:01
45:287
3.221
20
12:01
46:287
2.582
28.2
12:01
47:287
0.926
9.2
12:01
48:287
1.447
10.3
12:01
49:287
0.228
10.7
12:01
50:287
0.047
27.9
E-18
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
Appendix F: Measurement of
Nonvolatile Particulate Matter Mass
Using the AVL 483 Micro Soot Sensor
Photoacoustic Analyzer with AVL
Exhaust Conditioning Unit
STANDARD OPERATING PROCEDURE 2105
NRMRL/APPCD
APPROVED: August 2, 2012
PRO^°
F-1
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
TABLE OF CONTENTS
I.0 SCOPE AM) APPLICATION 1-3
2.0 METHOD SUMMARY 1-3
3.0 DEFINITIONS 1-3
4.0 HEALTH AND SAFETY CONSIDERATIONS F-4
5.0 LIMITS OF APPLICATION 1-5
6.0 EQUIPMENT AND SUPPLIES 1-5
7.0 PROCEDURES F-8
8.0 DATA AM) RECORDS MANAGEMENT 1-12
9.0 QUALITY CONTROL AND QUALITY ASSURANCE 1-13
10.0 REFERENCES F-18
II.0 ATTACHMENTS F-19
F-2
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) provides instructions on the measurement of
nonvolatile particulate matter (nvPM) mass concentration using the AVL 483 Micro Soot
Sensor (MSS) photoacoustic analyzer with AVL exhaust conditioning unit (AVL List
GmbH; Graz, Austria).
The AVL 483 MSS measures black carbon (BC) soot, which is emitted from air pollutant
sources. Thus, this method can be used to quantify the emission of nvPM at the exit plane
of aircraft gas turbine engines. The measured value of the AVL 483 MSS is concentration
of soot in exhaust (mg/m3).
This SOP is a step-by-step procedure that describes how to set up and run the instrument
as well as to retrieve the data during operation of the AVL 483 MSS.
2.0 METHOD SUMMARY
The AVL 483 MSS is based on the photoacoustic effect. With this measurement method,
an intensity modulated "chopped" light beam produces periodic heating (when "on") of
absorbing particles, which dissipate their heat in the "off state. A microphone detects the
resulting pressure fluctuations. Clean air produces a zero signal, avoiding the drawback
of the light extinction method. The microphone signal is linearly related to the BC
concentration in the measuring volume. A more complete description of the
photoacoustic method is provided in various references such as Schindler et al. (2004).
3.0 DEFINITIONS
Measuring device: AVL 483 Micro Soot Sensor (MSS).
Conditioning unit: AVL exhaust conditioning unit.
Nonvolatile PM (nvPM): Particulate matter (PM) emissions that exist at gas turbine
engine exit plane temperature and pressure conditions and that do not contain volatile
particle contributions that condense at lower temperatures.
Soot: Carbonaceous particles that are a by-product of the combustion of liquid or gaseous
fuels.
Operating stages:
Sleep: Power-up stage. All running functions are switched off.
F-3
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
Pause: Warm-up and checking stage. The temperature controls of the measuring
cell and the thermoelectric cooler are switched on. The window pollution, flow
(pump switched on for a short while), and resonance frequency are checked.
Standby: The pump is started. The window pollution and the resonance
frequency are checked again. The average "zero value" is also determined.
Measurement: The analyzed exhaust gas is directed to the measuring cell. The
logging of the measurement data is started.
Zero check: Clean, filtered air ("zero gas") is directed to the measuring cell and
the measurement values are used for the baseline correction.
4.0 HEALTH AND SAFETY CONSIDERATIONS
4.1 This device must not be used in any environment where there is a danger of
explosion. Ignitable or explosive exhaust gas mixtures or exhaust gases that are
ignitable or explosive when mixed with air must not be measured with the device.
4.2 Some components can get very hot during operation, especially if they are located
near the tailpipe. If necessary, use heat-resistant protective gloves.
4.3 Exhaust gas of combustion engines contains toxic substances. If used in a test
cell, ensure appropriate ventilation and a proper discharge of the exhaust. Make
sure to check the leak-tightness of the probe connectors on both the sampling
point and the device.
4.4 The device contains a Class 4 semiconductor laser with invisible radiation of 808-
nm wavelength and a power of up to 2 W. The laser is embedded and protected by
suitable measures so that the device has been classified as a Class 1 laser product.
4.5 All service must be carried out only by service staff trained in laser safety
measures:
• Switch off the measuring device before opening the measuring chamber.
• If one of the LEDs in the measuring chamber is illuminated after the cover has
been opened, the device must be switched off immediately.
• Removal of the cooler unit at the back of the measuring chamber is strictly
forbidden.
F-4
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
5.0 LIMITS OF APPLICATION
5.1 The suction power of the pump is set with a throttling valve so that approximately
3.8 L/min are pulled at the inlet of the pump unit at a negative pressure of 300
mbar. In the measuring unit, the sample flow is split into a by-pass flow and a
measuring flow that passes through the measuring cell. Both flows should be
approximately equal and between 1.8 and 2 L/min.
5.2 The photoacoustic measuring principle limits the pressure in the measuring
chamber and therefore also the pressure at the input of the measuring device to the
ambient pressure of ± 50 mbar. The conditioning unit ensures that the inlet
pressure of the measuring chamber is within that specification and up to a
maximum pressure of 2 bar (rel.).
5.3 The temperature of the exhaust gas at the input of the measuring device must not
exceed 60 °C. The conditioning unit can condition exhaust gas temperatures of
1000 °C (less than 60 s) and 600 °C (in continuous operation).
5.4 The exhaust gas must not contain any condensate droplets and no condensation
water may form in the entire system. The conditioning unit can be used to dilute
the exhaust gas (dilution ranges from 2 to 20) to prevent it from condensing.
5.5 The maximum soot concentration that can be measured is 50 mg/m3 with 1 |ig/m3
sensitivity and a minimum detection limit of 5 |ig/m3.
5.6 Information about the technical data for the measuring device, conditioning unit,
and pressure-reducing unit can be found in Attachment 11.1.
6.0 EQUIPMENT AND SUPPLIES
6.1 Instrumentation
• AVL 483 Micro Soot Sensor (B06529).
• AVL exhaust conditioning unit with pressure-reducing module with dilution
cell (B07354).
• A suitable sampling probe and line (provided by others).
F-5
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
6.2 Ancillary Equipment
• Two main cables for 110 V AC (BV2166).
• CAN connecting cable measuring device - conditioning unit (BV2988).
• Connecting hose measuring device - dilution unit, 2 m (B06533).
• Connecting hose dilution cell, 2m (SS0178).
• Connecting Viton hose measuring device - dilution cell (SS0215).
• Heating for sample line (TM0483S1HT.01).
• PC software - measuring device control software (TM048PCA.01).
• High-performance particulate filters, 10 pes (MM0336).
• Probe filters (for pump unit), 10 pes (MF0478).
• Serial cable for RS-232 connection (BVI854).
• Polyester cleaning cloths (HP0206).
6.3 Installation
1. Refer to Figure F-l for illustration of steps 2 through 5.
2. Connect the power cable with the socket (x7) at the back of the measuring
device (1).
3. Connect the power cable with the socket (x7) at the back of the conditioning
unit (2).
4. Connect the CAN bus (x3) connector of the measuring device (3) and the
CAN bus (x3) connector of the conditioning unit (4) using the CAN
connecting cable.
5. Connect the serial cable to the COM1 (xl) interface at the back of the
measuring device (5).
F-6
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
1 Power supply (x7) of measuring device
2. Power supply (x7> of conditioning unit
3 . CAN Bus (x3) of measuring device
4 , CAN Bus (x3) of conditioning unit
5 COM1 (xl) of measuring device
Figure F-l. Connections between measuring device and conditioning unit - back side.
6. Connect EXHAUST IN on the conditioning unit with EXHAUST OUT on the
measuring unit using the quick-connect hose (Figure F-2).
7. Connect the sample inlet tube to the EXHAUST IN pipe on the measuring
device.
F-7
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
Figure F-2. Connections between measuring device and conditioning unit - front side.
7.0 PROCEDURES
7.1 Sample Collection and Instrument Operation
1. Connect and start the computer with the AVL software.
2. Turn on both the measuring device and the conditioning unit.
3. In the AVL software (Figure F-3), go to drop down menu SETTINGS, click
on USER, and select REMOTE.
4. Click the PAUSE button. Approximately 25 min is needed to warm up. A
resonance test and zero value determination will automatically be performed
when the device is ready for measurement.
F-8
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
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Figure F-3. AVL device control software - online view.
5. During warm-up, select FILE -> DEVICE CONFIGURATION -* LOG
SETTINGS (Figure F-4) to input the file name, desired location, logging
channels, etc:
a. Select the channels that need to be logged. When NO DILUTION is
selected, the common channel selections should include concentration
sensor, flow, absolute pressure, gas temperature, and zero signal.
b. Select "Auto logging during measurement."
c. Select "New file for each measurement."
d. Choose logging speed of 1 Hz.
e. Click on SELECT FILE to change the file name and location. You can
select either CSV or TXT as the file type.
F-9
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
TCP/IP settings Log settings Password
Logfie:
Channel Selection
Filter time
Filter type
Set point dilution ratio
Peak concentration dil. corrected
Peak concentration sensor
K V Rflferpnrp
< >
Select File.
»
«
State Ctannel
Q Concentration sensor
Loggng speed:
| | User defined
1 Hz
~ flirto. togging during measurement
d] Auto. togging during peak meas.
New file for each measurement
OK
Cancel
Apply
Figure F-4. Log settings - online view.
6. Once the device is warmed up, place it in STANDBY position (~ 60 s to
stabilize).
7. Instead of ONLINE VIEW shown in Figure F-3, select SERVICE VIEW
(NUMERICAL) and record the following values:
a. Zero signal (window pollution): 0.0-1.4 mV.
b. Resonance frequency: ~ 4100 Hz.
c. Max. raw meas. value: 230-30 mV.
d. Measuring cell temp, at test; ~ 52 °C.
8. Once the values have been recorded during STANDBY, choose SETTINGS
—>¦ CONDITIONING. For 0 dilution select NO DILUTION in the menu and
click APPLY. For a dilution ratio of 2-20, select CONDITIONING UNIT, set
the dilution, and click APPLY.
9. Record the background soot concentration shown at the end of the STANDBY
cycle.
10. Start sampling by selecting the MEASUREMENT option. Measuring cycles
should not be longer than 30 to 60 min to avoid significant window pollution.
11. When the testing is finished, select ZERO CHECK and let the device run for
30-60 seconds. If the measuring value has drifted (for example, because of
window pollution), the original zero value will not be reached. In this case, the
F-10
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
measuring value obtained in the operating state ZERO CHECK can be used
for the baseline correction.
12. Select either PAUSE (for long breaks) or STANDBY (to get unit ready for
next measurement) to stop logging and measuring.
13. At the end of the day, put the unit in either PAUSE or SLEEP and close the
program.
14. Turn off both the measuring device and the conditioning unit.
Data Acquisition, Calculations, and Data Reduction
7.2.1 Data format depends on the channel selection (Section 7.1, step 5a).
7.2.2 The software application automatically stores data acquired during an
analysis in individual electronic data files for later computation, display,
and printing. A data form sample can be found in Attachment 11.2.
7.2.3 The BC mass concentrations are generated directly and expressed as
concentration of soot in exhaust (mg/m3) at 0 °C and 1013 mbar (760 mm
Hg). To recalculate that value to the EPA standard temperature and
pressure (STP) conditions (25 °C and 760 mm Hg), the following formula
must be applied:
Cstp= 1 qQ2 (mg/m3) = C x 0.92 (mg/m3)
where:
Cstp is the soot concentration under STP conditions (25 °C and 760
mm Hg).
C is the soot concentration at 0 °C and 760 mm Hg generated by
the instrument.
1.092 is the number representing the ratio of temperatures Tstp/T in
K (298K/273K).
F-11
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
7.3 Troubleshooting
7.3.1 In general, two different types of messages are possible: errors and
warnings.
7.3.2 Messages with an error and warning code smaller than 100 refer to the
measuring device, and messages with a code greater than 100 refer to the
conditioning unit.
7.3.3 In the event of either warning or error, the red status LED on the device
flashes.
7.3.4 Warnings inform the user that a maintenance action is required. The user
should eliminate the error as soon as possible. When a warning is
generated, the device firmware does not take any actions and the currently
running actions are continued.
7.3.5 Three different types of errors are possible: operating, device, and
commissioning errors. Device errors and some operating errors are
detected by the firmware, and the firmware takes actions to correct them.
7.3.6 Error and warning codes are listed in Attachment 11.3 together with a
short description and required corrective action.
7.3.7 For detailed explanations of each error code as well as how to recognize
and correct the commission errors (firmware does not recognize them),
please refer to the instrument manual.
7.3.8 If an error cannot be rectified by simple maintenance actions and persists,
the failure must be resolved by a service technician.
DATA AND RECORDS MANAGEMENT
8.1 Individual electronic data files are generated for each sample run. All data files
are stored appropriately in the data acquisition system. At the end of each day's
testing, all files generated are archived with proper identification.
8.2 Laboratory notebooks are used to document the following:
• Test conditions and times.
• Sampling system parameters.
F-12
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Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
• Samples collected.
• Background soot concentration before and after the measuring cycle.
• Any unusual events or difficulties.
8.3 All hand-recorded data (laboratory notebooks and data sheets) must be written
accurately and legibly, and all errors and discrepancies must be noted.
QUALITY CONTROL AND QUALITY ASSURANCE
9.1 Quality Control Checks
9.1.1 Calibration Check
The entire sensor sensitivity (the intensity of the laser beam and the
sensitivity of the microphone) is checked by means of an absorber
window. The calibration check should be carried out at least once a month
or once a week, depending on the instrument use.
1. The measuring device should be warmed up and in the operating state
PAUSE or STANDBY
2. Change to the operating state SLEEP.
3. Switch off the measuring device.
4. Open the lid of the measuring device.
5. Remove the five screws of the measuring chamber cover.
6. Lift off the cover of the measuring device.
7. Remove the window on the right-hand side (Figure F-5 [1]) by turning
the quick lock.
8. Insert the absorber window (blue calibration window on the cover of
measuring device, Figure F-5 [3]) so that the writing on the series
number sticker is horizontal.
F-13
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
1,2- Measuring cell windows
3 - Absorber window
Figure F-5. Measuring cell and absorber windows (open lid view).
9. Close the cover, refasten the five screws, and close the lid of the
measuring device.
10. Switch on the measuring device and change to the operating state
SLEEP.
11. In the software, select the menu item SERVICE/MAINTENANCE -
CALIBRATION CHECK (Figure F-6).
12. Click on START CALIBRATION CHECK (check takes - 20 min).
13. The deviation of the measured value expressed as DEVIATION OF
CALIBRATION CHECK should be approximately 2-3 %, not to
exceed 10 %. In the event of deviations exceeding 10 %, it is
recommended to return the instrument to AVL for a factory
recalibration.
F-14
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
Calibration check
Reference value absorber window:
3.350 :
mg/m3
Start calibration check
Measuring value absorber window
Deviation of calibrstfion check:
mg/m3
%
] | | (0 ] OK Cancel Apply
Figure F-6. Calibration check - online view.
14. After the calibration check, the device is in the operating state SLEEP.
Switch off the measuring device and lift off the cover.
15. Remove the absorber window and fix it on the cover of the measuring
device.
16. Fix the standard window and close the cover.
17. Retighten the five screws and close the lid.
9.1.1 Zero Check
In the STANDBY operation state, the window pollution is checked
automatically before each measurement by measuring the primary signal
values (in mV) with clean air in the measuring cell. The window pollution
is checked to determine whether these values are below 1.5 mV.
1. Zeroing should be performed again after each measurement cycle
(measuring time of 30 to 60 min) by switching to the STANDBY or
ZERO CHECK operating stage.
2. To record the values for the zero signal, select SERVICE VIEW
(TECHNICAL).
3. In the ONLINE VIEW, concentration after zeroing should be < 0.01
mg/m3. If the value exceeds 0.05 mg/m3, massive pollution occurred
during the test run and/or the device has been operated over a very
long period without switching into the STANDBY operating state. In
F-15
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
this situation, the windows have to be cleaned (see Regular
Maintenance, Section 9.2.5).
4. During each measurement, the primary signal is automatically
corrected with the zero value (baseline correction).
Quality Assurance Procedures
To ensure that quality data are being collected the following procedures should be
considered.
9.2.1 Resonance Test
The system automatically performs a check of the resonance frequency of
the microphone in the measuring cell at the end of the operating state
PAUSE. A manual execution of this function can be performed from the
same operating state for a repeated check.
1. Select the menu item SERVICE/MAINTENANCE -~ SERVICE
TESTS -> RESONANCE TEST -~ START RESONANCE TEST.
2. At the end of the test, values should be as follows:
• Resonance frequency: ~ 4100 Hz.
• Max. raw meas. value: 230-30 mV.
• Measuring cell temp, at test: ~ 52 °C.
9.2.2 Linearity Check of Microphone
This check can be initiated from the operating states SLEEP and PAUSE.
1. Select the menu item SERVICE/MAINTENANCE -> LINEARITY
CHECK -> START LINEARITY CHECK.
2. When the linearity check is completed, the regression coefficient is
displayed and should be higher than 0.95. Smaller regression
coefficients indicate a loudspeaker or microphone fault.
9.2.3 Linearity Check of Laser
This check can be called from the SLEEP operating state.
1. Install the absorber window (see Section 9.1.1).
F-16
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
2. Select the menu item SERVICE/MAINTENANCE -> LINEARITY
CHECK -> LINEARITY CHECK LASER -~ START LINEARITY
CHECK LASER.
3. When the linearity check is completed, the regression coefficient is
displayed and should be higher than 0.95. Smaller regression
coefficients indicate a laser or laser driver fault.
9.2.4 Calibration of Conditioning Unit
Calibration is automatically carried out during every change from SLEEP
to PAUSE. A manual execution of this function is used for a repeated
check and can be called from operating states PAUSE and READY.
Select the menu item SERVICE/MAINTENANCE -> CONDITIONING
UNIT CALIBRATION -> START CALIBRATION.
9.2.5 Regular Maintenance
9.2.5.1 Replace the fine filters (MM0336) in the measuring device (three
filters) and the conditioning unit (one filter) when the soot layer is
visible or error 28 appears (flow warning). Turn the transparent
cover of the filter housing counterclockwise and remove the cover
and the fine filter. Replace the fine filter and reassemble the filter
housing.
9.2.5.2 Purge or replace the sampling lines when significant pollution is
visible. Automatic purging is performed at each transition from the
operating state SLEEP to PAUSE. If the tube (inlet on the front of
the measuring device, Figure F-2 [3]) is still evidently polluted
after it has been purged, it must be replaced.
9.2.5.3 Clean the measuring cell and glass tube in the measuring cell when
the zero signal exceeds a value of 1.5 mV (error code 25).
1. Wear soft cotton gloves when performing the cleaning
procedures.
2. Switch off the measuring device and open the lid.
3. Remove the five screws of the measuring cover and lift off the
cover.
4. Remove the measuring cell windows on both sides (Figure F-5
[1] and [2]) by turning the quick lock.
F-17
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
5. Gently clean both measuring windows with a new cleaning
cloth (HP0206).
6. Insert a cotton tip (HP0207) into the glass tube on the right-
hand of the measuring cell.
7. Clean the glass tube by moving the cotton tip back and forth.
8. Remount both measuring cell windows and close the cover.
9. Retighten the five screws and close the lid.
9.2.5.4 Perform a leak check after each new installation and
commissioning of the device. This operation can be performed
from the SLEEP and PAUSE operating states.
1. Close the entry of the sampling line or the sampling probe.
2. In the software, select menu item SERVICE/MAINTENANCE
-> SERVICE TESTS -~ LEAK CHECK —>START LEAK
CHECK.
3. The green color next to the leak rate and leak rate conditioning
unit values appears when the leak check is passed.
10.0 REFERENCES
Schindler, W., Haisch, C., Beck, H. A., Niessner, R., Jakob, E., & Rothe D. (2004). A
photoacoustic sensor system for time resolved quantification of diesel soot emissions.
SAE 2004-01-0968.
F-18
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
11.0 ATTACHMENTS
11.1 Technical Data for Equipment
AVL MICRO SOOT SENSOR
Measured quantity
Soot concentration ("elementary carbon") <50 mg/m3
Display resolution (digital)
0.001 mg/m3
Data rate
Digital: max. 5 Hz
Analog: 100 Hz
Noise
s 0.01 mg/m3(defined as 3 times the standard deviation (SD) of the measurement variation of the
zero signal [clean, filtered air] with 1 s data smoothing)
Resolution of the measurement value
s 0.01 mg/m3 (defined as 3 times the SD of the measurement variation of the zero signal [clean,
filtered air] with 1 s data smoothing)
Drift
s 0.01 mg/m3 per hour (defined as change of the average of the zero signal [clean, filtered air] over
1 h)
Voltage supply
230 V AC version, 50/60 Hz
Power consumption: 500 VA max.
Fuses: 2 * 5 A T (slow blow)
100/115 V AC version, 50/60 Hz
Power consumption: 500 VA max.
Fuses: 2* 10 A T (slow blow)
Fuses (main board)
F1: 3.15 A T (slow blow)
F2: 6.3 A T (slow blow)
F3: 3.15 A T (slow blow)
F4: 5 A T (slow blow)
F5: 1 A T (slow blow)
F6: 3.15 A T (slow blow)
F7: 5 A T (slow blow)
Ambient temperatures
Operation: 5 ... 43 °C
Storage: -5 ... 70 °C (other temperature ranges on request)
Humidity during operation
Corresponding to a humidity of maximum 95 % at 25 °C.
F-19
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
If this cannot be achieved, clean and dry shop air must be supplied at the relevant connector of the
device.
Protection class
IP34
Tolerance of the exhaust input pressure
-50 ... +50 mbar
Permissible exhaust temperature at the inlet
+20 ... +60 °C
Humidity of the measured exhaust gas
max. 90 % at s 52 °C, non-condensing
Dimensions
Measuring unit: 19" * 5 HU * 530 mm (W * H * D)
Pump unit: 19" * 4 HU * 320 mm (W * H * D)
Weight: Measuring unit: approx. 20 kg
AVL EXHAUST CONDITIONING UNIT
Output
Dilution ratio (DR)
Dilution ratio (DR)
2 ... 20
Exactness DR
max. ±3 % in the range dilution ratio (DR) = 2 ... 10
max. ±10 % in the range dilution ratio (DR) = 10 ... 20
Interfaces
CAN bus
DIO
Analog Out
RS-232
Shop air input
1 ± 0.2 bar (rel.)
Flow: > 4 l/min
Voltage supply
230 V AC version, 50/60 Hz
Power consumption: 500 VA max.
Fuses: 2 x 5 A T (slow blow)
100/115 V AC version, 50/60 Hz
Power consumption: 500 VA max.
Fuses: 2 x 10 A T (slow blow)
Fuses (main board)
F1: 5 A T (slow blow)
F-20
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
F2: 3.15 A T (slow blow)
F3: 5 A T (slow blow)
F4: 5 A T (slow blow)
F5: 1 A T (slow blow)
Ambient temperatures
Operation: 5 ... 40 °C
Storage: -5 ... 70 °C
Protection class
IP34
Dimensions
AVL Exhaust Conditioning Unit: 19" «4HUx 530 mm (W * H * D)
Weight
Measuring unit: approx. 15 kg
PRESSURE REDUCING UNIT
Maximum exhaust gas temperature
up to 1000 °C (<1 min), 600 °C (continuous operation)
Maximum exhaust gas backpressure
up to 2000 mbar (rel.)
Pressure pulsations
±1000 mbar, but max. 50 % of exhaust gas backpressure
Blown-off quantity
~ 20 l/min at 1000 mbar and 600 °C
Weight
2 kg
11.2 Data Form Sample
////////////////////////////////#######////////////////////////////////////####
### Micro Soot Sensor Log-File ###
### Log-File-Version: 1.0###
### Firmware-Version: V1.30 ###
### DUI-Version: 2.0###
### Serial number: S/N0273 ###
### Log-File
started:
1/11/11 2:09:23 PM###
Illlll (Mil/
II II II — — ——— — —————————————— — —————— — —————— — —— If If If
### Y_y_GasTemp [°C] ###
### Y_y_M_NSAbs [mV] ###
### Y_y_M_Concentration [mg/m3]###
### Y_y_AbsPressure [mbar] ###
F-21
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
### Y_y_Flow [l/min] ###
Illlll (Mil/
II II II — — ————— — ———————————— — —————— — —————— — —— If If If
### State description ###
###0... invalid###
### 1...valid###
### 2...valid under reservation ###
IIIIIIIIIIII ll#MII IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII MM
Absolute
Zero
Date
Time
Concentration
pressure
Flow
signal
Gas
[dd/mm/yy]
[hh:mm:ss.t]
sensor [mg/m3]
[mbar]
[l/min]
[mV]
temperature [°C]
1/11/2011
09:24.8
-0.007
950
1.96
0.232
45.1
1/11/2011
09:25.8
0
952
1.96
45.2
1/11/2011
09:26.8
-0.001
953
1.96
0.231
45.2
1/11/2011
09:27.8
0
953
1.96
0.231
45.2
1/11/2011
09:28.8
0
952
1.96
0.231
45.2
1/11/2011
09:29.8
0
952
1.96
0.231
45.1
1/11/2011
09:30.8
-0.001
953
1.96
0.231
45.2
1/11/2011
09:31.8
-0.001
953
1.96
0.231
45.2
1/11/2011
09:32.8
0
952
1.96
0.231
45.2
1/11/2011
09:33.8
0
953
1.96
0.231
45.1
1/11/2011
09:34.8
-0.001
953
1.96
0.231
45.2
1/11/2011
09:35.8
-0.001
952
1.96
0.231
45.2
1/11/2011
09:36.8
0
952
1.96
0.231
45.2
1/11/2011
09:37.8
0
953
1.96
0.231
45.2
11.3 Error and Warning Codes and Descriptions
11.3.1 Errors
F-22
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
&»,}. CCKite
Description
Action
1
ADC hardware error
-wwr . n 1'" < " £?=> -
ml reached
Repine# t» mmn board.
hhM jW ' 1 erx
Device slays in "Paws# or .-SU'iv s
not reacted.
Replace lie man board.
3
rhidwum mm EE-P8QM
Of* - r-n,r if ? FF^ '1* r+,f«r>"^,y.i-
steles setectei*..
CaMmAor required.
4
i 3,w flic- i» e
steep, *' * '~11018,8 ep6f
Itoswera
?
&ror tftsfilfisfeciMs: oootor
Qe v„v
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
105
enw oodet 107, 121 mxS 125 miy bedteplay«l
As offtfwwafe version 1:11';
Cu>»iOC4tOn In ©SWWWdPjMI wiift ItlSS WW,
mmr «ftss tor and 125 may be dtopteyrt w
106
MFOcoo**^*^
Y or PWj ood pwtctw® to
SLEEP.
IB?
No alutkwi ar a*ilabte
Ito error a. reported wfwrv swilelifig «»«*
trom PAUSE to STAND-BY or from STANO-BY
f-fcAfc'i? l* ,-e vv'tothensle-
108
COj aenaor Drue-out
109
MFMfew-ait {««.of iiummi verwon f.lf)
tew# «tay» in 11* relevant operating Hals.,
arror <«te 121 «Bf be rtspttryod «s welt
F-24
-------
Appendix F
AVL Photoacoustic
Analyzer SOP
July 2012
Rev. 1
11.3.2 Warnings
fciK*
Description
j
Device pmmMr wanning
mm taKbntm pwbww m#* be- iej(r<5 ? >' »e• ?»«,<<(• «u H't
"
Sampling toe temperature <** of imilt
MMMurfrtg ert temperature en* of dm*
[13
Vfatage supply error
Tl* eternal veMaoe* «k 1* cheeked wrth AADC.
fteialiwe eallwafiofi too Hgh
1120
^1
MFM tow out of limit (0 ... 545B « ± 10 * of mm*
mean mtUB mmmgmi aver 1E3 s ir 'wanriQ sti«e ME-O.i^E-
MENT
( "
Serwee warning (after iDOQ operating tens!
£ I'l ll.HK, If «V-1 « 1
1 *24
Low woltage of the buffer iiMtery on fie main boant
1
Ho dtofiwi airavatteiMe (wamlfta »atme PALIS®
Citation oet temperaiwe out of tin*
1 !*T
Z' 11 jf r,T r >~tT-
"k*
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
Appendix G: Sampling and
Measurement of Nonvolatile Particulate
Matter Mass Using the Filter-Based
Gravimetric Method
STANDARD OPERATING PROCEDURE 2103
NRMRL/APPCD
APPROVED: August 18, 2011
^60Sr«*.
>
PRO^
G-1
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION G-3
2.0 METHOD SUMMARY G-3
3.0 DEFINITIONS G-3
4.0 INTERFERENCES G-4
5.0 EQUIPMENT AND SUPPLIES G-4
6.0 PROCEDURES G-5
7.0 DATA ACQUISITION, CALCULATIONS, AND DATA REDUCTION G-l 1
8.0 QUALITY CONTROL AND QUALITY ASSURANCE PROCEDURES G-13
9.0 REFERENCES G-l 4
G-2
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
1.0 SCOPE AND APPLICATION
This standard operation procedure (SOP) provides instructions on collecting and
measurement of nonvolatile particulate matter (nvPM) mass using the standard filter-
based gravimetric method. The existing procedures described in Title 40 Parts 1065 and
86 of the Code of Federal Regulations (CFR) are used as guidance for the PM sampling
and filter weighing procedures of the SOP.
This SOP is a step-by-step procedure that describes how to perform the sampling and
weighing of the filters (loaded with PM and unloaded) as well as to analyze the data and
perform all necessary calibrations and calculations.
2.0 METHOD SUMMARY
Preconditioned and preweighed polytetrafluoroethylene (PTFE) filters (Whatman catalog
no. 7592-104 or equivalent) are used to collect the nvPM mass from the main sample
stream at a flow rate of approximately 50 L/min. The filters are post-conditioned and
weighed, and the PM mass collected on them is used as a reference mass to evaluate
other PM mass collection methods (e.g., multi-angle absorption photometry; laser-
induced incandescence, photoacoustic analysis, and filter sampling with carbon burn-off)
employed during the same experiments.
A prebaked quartz-fiber filter (QFF) is used as a backup filter placed in line after the
PTFE filter. After sampling, the QFFs are analyzed using the procedure described in SOP
2104 and therefore that procedure is not repeated here. Studies have found that QFFs can
adsorb the semivolatile organic carbon (OC) (Turpin et al., 1994) in addition to the PM
OC (positive sampling artifacts). Therefore, the semivolatile OC mass measured on the
backup filter is used to correct for the total OC measured, as described in SOP 2104.
3.0 DEFINITIONS
Organic carbon (OC): Optically transparent carbon at approximately 670 nm removed
(through thermal desorption or pyrolysis) and char deposited when heating a filter sample
to a preset maximum (850 °C) in a non-oxidizing (helium) carrier gas.
Nonvolatile PM (nvPM): Particle emissions that exist at gas turbine engine exit plane
temperature and pressure conditions and that do not contain volatile particle contributions
that condense at lower temperatures.
G-3
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
4.0 INTERFERENCES
Personnel should avoid activities that could contribute to free airborne particles or static
electricity. Particular attention should be given to clothing worn when preparing or
weighing filters. Many cloth materials and clothing items have been shown to contribute
significantly to static effects. These include lab coats and wool sweaters, pants, and shirts
and clothes made of polyester, acrylic, or nylon. In addition, avoid dirty or dusty
clothing, cut-off blue jeans, soft Vibram-soled shoes, and rubber-soled sneakers.
Recommended clothing includes non-aged or non-brushed denim, cotton twill weave
pants and shirts, 100% cotton shirts or sweat shirts, and hard-soled leather shoes.
5.0 EQUIPMENT AND SUPPLIES
• Vacuum pump suitable of providing approximately 45 L/min.
• Two 47-mm stainless steel filter holders meeting Title 40 CFR Part 1065, Subpart B,
requirements.
• 47-mm PTFE filters (Whatman catalog no. 7592-104 or equivalent) with associated
cassettes meeting Title 40 CFR Part 1065, Subpart B, requirements.
• 47-mm prebaked quartz-fiber filters (Tissuequartz™ 2500 QAT-UP, 47 mm from Pall
Corporation catalog no. 7202 or equivalent) with associated cassettes.
• Orifice flow meter incorporating 9.53-mm (3/8-in.) outside diameter (OD) inlet/outlet
fittings and differential pressure (dP) cell (Omega Model PX658-10D5V or
equivalent), including plastic isolation valves and tubing for interconnection,
calibrated by the APPCD Metrology Laboratory according to MOP FV-0201.1 within
1 year of use. Orifice meter readings are recorded by a computerized data acquisition
system (DAS) running the DasyLab® software package.
• Absolute pressure transducer (Omega Model PX309-015A5V or equivalent)
calibrated by the APPCD Metrology Laboratory according to MOP PR-0400.0 within
1 year of use. Absolute pressure readings are also recorded by the DAS.
• Brass or stainless steel three-way switching valve with 9.53-mm (3/8-in.) OD fittings.
• Two-way brass or stainless steel needle valve with 9.53-mm (3/8-in.) OD inlet/outlet
fittings.
• Approximately 1 meter of 9.53-mm (3/8-in.) OD stainless steel or Teflon sampling
line to interconnect the above components downstream of the filter holder.
• Tweezers (for manipulation of PTFE [with grounding strap] and quartz filters).
• Analytical microbalance with l-|ig readability and 5-g capacity (Sartorius ME5 or
equivalent) installed in a temperature- and humidity-controlled weigh room (see
G-4
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
specifications below). The microbalance shall be recertified by the APPCD
Metrology Laboratory within 1 year of use.
• Class 1 calibration weights.
• Aluminum foil.
• Sterile Petri dishes (Pall Corporation catalog no. 7242 or equivalent).
• Static eliminator consisting of two polonium-210 units (Nuclespot P-2042 from NRD,
USA or equivalent) positioned upside down on stainless steel holders and separated
by approximately 1 inch.
• Cassette separator - anodized aluminum (Airmetrics, USA catalog no. 600-007 or
equivalent).
• Cassette mailers - antistatic (Airmetrics, USA catalog no. 600-008 or equivalent).
• Powder-free nitrile gloves.
• Laboratory timer with 1-s resolution.
• NIST-traceable barometer certified by the APPCD Metrology Laboratory within 1
year of use.
• Environmental weighing chamber meeting the specifications outlined in Section 6.1.
6.0 PROCEDURES
6.1 Weighing Room Specifications
Design and specifications of the weighing room should meet those listed in Title
40 CFR Part 50, Appendix L, Section 8.0. The ambient conditions within the
room should be maintained at an average temperature of 20-23 °C and a mean
relative humidity (RH) of 30-40%. Control of the internal environment should be
maintained within ± 2 °C and ± 5% RH as measured over a 24-h period.
Verification of the temperature and RH specifications must be certified at least
annually using NIST-traceable standards per the EPA document Quality
Assurance Guidance Document 2.12: Monitoring PM2.5 in Ambient Air Using
Designated Reference or Class I Equivalent Methods.
To isolate the balance from external noise and vibration, it should be mounted on
a vibration-isolation platform. Static electric charge in the balance environment
should be minimized with use of an electrically grounded balance, 300 series
stainless steel grounded tweezers for handling filter media, and electrically
grounded, static-electricity neutralizers for the sampling media.
G-5
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
6.2 Preconditioning and Tare Weighing of PTFE Filters
6.2.1 Preconditioning
Before weighing filters, take the following steps to prepare the PTFE
filters, weighing environment, and equipment:
1. Write down the date/time, temperature, pressure and RH in the
weighing room before measurement.
2. The ambient temperature of the room should be maintained at 20w-23
±2 °C over 24 h. The RH should be maintained at 30-40 % ± 5 %
over 24 h.
3. To avoid contamination, remove any unnecessary items and clean any
dirty areas.
4. Put on powder/static-free latex gloves and any necessary garments
needed to minimize human-produced contamination while handling
filters.
5. Use a Kimwipe (or equivalent low-particulate wipe) to wipe the areas
where forceps, filters, and Petri dishes will be placed and around the
balance. Wipe the forceps that will be used for filter handling.
6. All new filters should be equilibrated prior to weighing. They should
also be inspected for holes or other defects prior to use. This can be
done by holding the filter up to the light with forceps and looking for
holes. If the new filter passes inspection, place it in a numbered
(labeled) Petri slide. Arrange new filters in sets (e.g., sets of 10) and
place them in a clean area for equilibration for a minimum of 48 h
prior to obtaining tare weights. The Petri slide tops should remain
partially open during the equilibration.
7. Place any filter trays, standard weights, laboratory notebooks, or any
other items needed for weighing on the weighing table or within reach
of the table.
8. It is required that at least two unused reference filters remain in the
weighing room at all times in covered, but unsealed petri slides to
verify the cleanliness of the PM-stabilization environment. These
reference filters shall be placed in the same area as the sample filters.
The Petri slide tops should be partially open at the same time as the
sample filters for preconditioning and weighed at the same time as the
sample filters. If the average weight of the reference filter pairs
G-6
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
changes between the clean and used sample filter weighings by more
than 40 |ig, then all sample filters and background filters in the process
of stabilization shall be discarded and tests repeated. The reference
filter pairs should be changed at least once a month, but never between
the clean and used sample filter weighings. The reference filters
should be the same size and made from the same material as the
sample filters.
6.2.2 Balance Setup
1. Put on a pair of powder-free nitrile gloves and leave them on for the
remainder of the weighing session.
2. Unload the pan, close the draft shield, and zero the microbalance.
When the balance shows zero readout, press the FKey. A "C" will now
be displayed. The built-in calibration weights are internally applied by
servomotor and removed at the end of calibration. If external
interference affects the calibration procedure, you might obtain a brief
display of the error message "Err 02." In this case, re-zero and then
press the FKey again when zero readout appears. An acoustic signal
indicates the end of calibration.
3. With the balance reading zero, weight the working standard weights
(such as the 100 mg and 200 mg weights) and record the data, making
note of the measurement units.
4. When satisfactory results are obtained from the standard weights,
place the standards in their designated container, cover, and move
them out of the way until the end of the weighing session when they
will be used again.
6.2.3 Tare Weighing
1. Arrange filters in sets (e.g., sets of 10) within easy reach of the balance
to minimize unnecessary movements during the weighing.
2. Equilibrate the microbalance by opening the door for 5 s and then
closing the door. Repeat this step at least three times.
3. Set up two polonium strips using the special gooseneck holder with
one source positioned upside down above and aimed directly at the
other. They should be approximately 1 in. apart to maximize the static-
reducing effect of the polonium. Hold a filter with grounded tweezers
between the sources to expose both sides of the filter at least 20 s
G-7
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
before moving the filter to the balance pan. It is preferable to expose
all filters identically to the polonium strips and to not flip the filters for
polonium exposure.
4. First weigh the reference filters to gauge the long-term stability of the
weighing room. The standard for repeatability between one weighing
session and the next is ± 0.011 mg for the filters/room to be "in
control".
5. Develop an organized sequence to follow for every session so that
each filter gets weighed in the same fashion as the others and so that
there are no mix-ups on filter ID (whether it has been weighed or not),
placement on storage tray, or entries in the data log.
6. When weighing a filter, note that the balance adjusts when the filter is
placed on the balance pan. Watch the display after the initial increase
in numbers and watch for the unit symbol (such as g for gram, mg for
milligram, or |ig for microgram) to appear at the end of the number
sequence. Once the stability symbol appears, wait 10 s. If the number
has not changed within 10 s, then record the weight. If the number
does change, wait another 10 s. Repeat this step until the number does
not change within the 10-s interval.
7. After weighing a filter, place it in the same Petri slide and tightly close
the top on the slide.
8. Close the door on the balance and allow the display to settle back to
zero to check the stability of the balance. If at any time the balance
fails to resettle, it must undergo the calibration process and the filters
of that group must be weighed again.
9. After weighing an entire set of filters, it is necessary to reweigh a few
random filters from that lot. Be sure to record this QA reweigh data,
too. A minimum of two filters per 10 should be chosen by an
independent operator and reweighed. If either of the two is unable to
meet the previous measurement within ± 0.004 mg, the entire lot of 10
filters must be reweighed and the reweigh performed again.
10. After filter weighing is completed, reweigh the working standard
weights and reference filters, record the results, and compare these
measurements with the ones taken at the beginning of the weigh
session. The second measurements should be within ± 0.003 mg of the
first ones.
G-8
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
11. After weighing is completed, place the reference filters in their Petri
slides, close the tops and keep them closed until new filter sets are
ready for conditioning.
12. Make sure all laboratory equipment is put away, and gather all items
that need to be taken out of the laboratory.
13. Write down the date/time, temperature, and RH before leaving the
weighing room.
6.3 Preparation of Quartz-Fiber Filters
New QFFs usually have an OC background of 2 to 5 |ig/cm2, which must be
removed prior to analysis. Use the following procedure to eliminate this
background for newly purchased QFFs:
1. Prebake in a muffle furnace at 550 °C for 12 h before sampling.
2. Store in Petri dishes lined with cleaned aluminum foil (also baked at 550 °C
for 12 h). After baking, rinse aluminum foil in n-hexane and dry in the oven at
100 °C for 10 min. Aluminum foil liners must be cut to cover the inside
surfaces of the Petri dishes so that the filters do not directly touch the dish
when placed inside the lined dishes.
Filters and liners must be handled with Teflon forceps to avoid contamination.
6.4 Sampling Procedure
1. Install one or more preweighed PTFE filters and prebaked quartz filters into
separate filter cassettes in the laboratory while wearing nitrile gloves;
transport the filter cassettes to the test location, as appropriate.
2. Assemble the sampling train as illustrated in Figure G-l and connect this
equipment to the main stainless steel sampling line provided by others.
G-9
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
Absolute
Pressure 3-Way Metering
Transducer Valve Valve
Pump
Main Samp!
Line
Isolation
Valves
Pari 1065
Stainless Steel
Filter Holder
(quartz filter)
Part 1065
Stainless Steel
Fitter Holder
(PTFE filter)
Differential
Pressure
Transducer
Figure G-l. Sampling train.
3. Install a 47-mm filter cassette containing a preweighed PTFE filter into the
front filter holder per the manufacturer's recommendations.
4. Install a 47-mm filter cassette containing a prebaked QFF (backup filter) into
the back filter holder per the manufacturer's recommendations.
5. Conduct a leak check of the system by removing the sampling line and
installing a vacuum gauge on the inlet of the PTFE filter holder. Start the
pump with the three-way valve in the "bypass" (open to atmosphere) position.
Before proceeding, close the metering valve and then just crack the valve to
restrict the rate at which the vacuum is placed on the system to avoid tearing
the filters. Close the isolation valves to the differential pressure transducer (if
this is not done, the transducer can be damaged), and switch the three-way
valve to the "sample" (straight through) position. Observe the vacuum gauge
until the maximum vacuum is reached and then switch the three-way valve
back to the "bypass" position. Observe the vacuum gauge for a period of 2
min. If the vacuum drops more than 127 mm Hg (5 in. Hg), the system has a
leak. Turn off the pump and slowly release the vacuum by switching the three-
way valve to the "sample" position. Once the vacuum has been released, open
the isolation valves to the differential pressure transducer and remove the
vacuum gauge from the sampling train inlet. If a leak is indicated, find and
repair the leak and repeat the above procedure.
6. To prepare for sample collection, move the three-way valve to the "bypass"
(open to atmosphere) position and start the pump. When sampling conditions
become stable, switch the three-way valve to the "sample" (straight through)
position and record the start time to the nearest second.
7. Sampling time is limited by requirements in SOP 2104 and the minimum
detection limit of the Sunset OC/EC analyzer. Because of these limitations,
G-10
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
sample mass on the PTFE filter must be from 900 to 1000 |ig. At the end of a
sampling period, move the three-way valve back to "bypass" and record the
end time to the nearest second.
8. Stop the pump and remove the filter cassettes from the filter holders. Place
them in clean, labeled cassette mailers. If another run is to be made, install
fresh filter cassettes in the filter holders and repeat Steps 5 through 8.
9. Remove the PTFE filters from the cassette mailers. Place them in the
originally used and labeled Petri slides, and place the QFFs in the aluminum
foil-lined Petri dishes. Use the cassette separator for easy opening of the filter
cassettes. QFFs should be stored in a freezer until ready for analysis.
10. Collect at least one field blank of each filter type for every 10 samples
collected. A field blank consists of installing a filter into the sampling train in
the normal fashion and immediately recovering it without any air passing
through the filter. The field blanks should be handled and analyzed in the
same manner as the samples collected (see below).
6.5 Post-Conditioning and Total Weighing of PTFE Filters
6.5.1 Sampled PTFE filters should be brought to the balance room at least 24 h
before weighing for equilibration with Petri slide tops left partially open.
6.5.2 The same protocol for entering and leaving should be followed including
recording the pressure, temperature, and RH before entering and after
exiting. At this time, also make sure the lid of the reference filter is left
open for equilibration.
6.5.3 To weigh the total mass on the filters, repeat steps 1 through 13 in Section
6.2.3.
DATA ACQUISITION, CALCULATIONS, AND DATA REDUCTION
7.1 Buoyancy Correction of PM Sample Media
Given that the net PM mass is calculated by subtracting the unloaded filter mass
from the sample-loaded filter mass, the two buoyancy corrections will cancel each
other under normal ambient conditions (i.e., ambient pressure changes of ± 10-20
mm Hg). Thus, a buoyancy correction should be calculated only in the cases when
absolute filter mass is important and of interest for the analyst. In that situation,
the buoyancy correction should be calculated according to the formulas listed in
Title 40 CFR Part 1065, Subpart G (1065.690).
G-11
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
7.2 Blank Correction
Final sample results should always be blank-corrected. For that purpose, two
types of blanks are used: laboratory and field blanks. Laboratory blanks are
preconditioned and preweighed filters stored in labeled Petri slides in the
laboratory. Field blanks are preconditioned and preweighed filter subjected to all
aspects of the sample collection, transportation, field handling, and preservation
as a real sample. Any measured PM mass in the blank samples represents
contamination and should be deducted from the real samples.
7.3 Net Particulate Matter Weight
The net PM weight of each filter should be equal to the corrected gross filter
weight minus the corrected tare filter weight and minus any PM mass that comes
from contamination and is measured on the field blank filters.
7.4 Average Air Flow Rate
The average flow rate of the air passing through the filter is corrected to EPA
standard temperature and pressure (STP) conditions of 25 °C and 760 mm Hg. It
is calculated from the orifice meter and absolute pressure and tunnel temperature
readings by:
Pa Tstp
Qstp = Qavg
*stp 1 a
where:
Qavg = average flow rate calculated from the orifice meter (m3/min)
Pa = absolute pressure (mm Hg)
Ta = temperature (K)
Pstp = standard pressure = 760 mm Hg
Tstp = standard temperature = 298.15 K
7.5 Concentrations of Particulate Matter in Air
The concentration of PM can be calculated from the net PM weight and the total
volume of air sampled as:
G-12
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
^ (mf — mt)
CpM " Qstp t
where:
Cpm = PM concentration (|ig/m3)
mf = corrected filter final weight (|ig)
mt = corrected filter tare weight (|ig)
Qstp = standard air flow rate through the filter as measured by the orifice
meter during the sampling period (m3/min)
t = total sampling time (min)
QUALITY CONTROL AND QUALITY ASSURANCE PROCEDURES
8.1 Laboratory and Field Blanks
Laboratory and field blanks are run in parallel with each sample to eliminate
contamination that comes from the same environments where the sample filter is
exposed.
8.2 Reference Filters
Reference filters are filters that remain in the weighing room on the same place
and over the same preconditioning time as the sample filters. The purpose of these
filters is to verify the cleanliness of the PM stabilization environment and to
detect any unusual events that might have effects on PM mass on sample filters.
8.3 Balance Performance Verification
Balance performance must be verified:
• At least once a year by the APPCD Metrology Laboratory.
• Before weighing any filter by zeroing and spanning the balance with at least
one calibration weight.
• Before and after filter weighing session by weighing reference PM sample
filters.
8.4 Reweighing of Filters
G-13
-------
Appendix G
Filter-Based
Gravimetric SOP
July 2012
Rev. 1
After weighing the entire set of filters, 20 % of them are subjected to reweighing.
If any reweighs do not meet the previous measurement within ± 0.004 mg, the
entire set of filters must be reweighed. Following the same procedure, an
independent person should reweigh 10 % of all filters and record the weights. Any
reweighs that do not meet the repeatability criteria of ± 0.004 mg require that all
filters in that respective set should be reweighted.
REFERENCES AND SUPPORTING DOCUMENTATION
Code of Federal Regulations (CFR), Title 40: Protection of Environment; Part 1065 -
Engine testing procedures.
Code of Federal Regulations (CFR), Title 40: Protection of Environment; Part 86 -
Control of emissions from new and in-use highway vehicles and engines (continued).
Sampling and measurement of non-volatile particulate matter mass using the
thermal/optical - transmittance carbon analyzer. SOP No. 2104, U. S. Environmental
Protection Agency, National Risk Management Research Laboratory, Air Pollution
Prevention and Control Division, Research Triangle Park, NC, 2011.
Turpin, B. J.; Huntzicker, J. J.; Hering, S. V. (1994). Investigation of organic aerosol
sampling artifacts in the Los Angeles Basin. Atmos. Environ., 28, 3061-3071.
Calibration of Gas Flow Rate Measurement Devices Using the DHI Molbox/Molbloc™
System. MOP No. FV-0201.1, U. S. Environmental Protection Agency, National Risk
Management Research Laboratory, Air Pollution Prevention and Control Division,
Research Triangle Park, NC, 2008.
General Procedure for Calibrating/Evaluating Pressure Measurement Devices Using the
Mensor APC600 Automated Pressure Calibrator. MOP No. PR-0400.0, U. S.
Environmental Protection Agency, National Risk Management Research Laboratory, Air
Pollution Prevention and Control Division, Research Triangle Park, NC, 2009.
Quality Assurance Guidance Document 2.12: Monitoring PM2.5 in Ambient Air Using
Designated Reference or Class I Equivalent Methods. U. S. Environmental Protection
Agency, National Exposure Research Laboratory, Human Exposure and Atmospheric
Sciences Division, Research Triangle Park, NC, November 1998.
G-14
-------
Appendix H
SMPSSOP
December 2016
Rev. 0
Appendix H: Operation of the TSI
Scanning Mobility Particle Sizer (SMPS)
Model 3936
MISCELLANEOUS OPERATING PROCEDURE 1412
NRMRL/A PPC D
srX
£ Q \
1321
V PRO^
H-1
-------
Appendix H
SMPSSOP
December 2016
Rev. 0
TABLE OF CONTENTS
1.0 SCOPE AM) APPLICATION 11-3
2.0 METHOD SUMMARY 11-3
3.0 INSTRUMENT AM) SOFTWARE SETUP 11-3
4.0 DATA COLLECTION 11-5
5.0 DATA PROCES SING 11-6
H-2
-------
Appendix H
SMPSSOP
December 2016
Rev. 0
1.0 SCOPE AND APPLICATION
This procedure is for experiments conducted using the TSI (Shoreview, MN, USA)
Model 3936 Scanning Mobility Particle Sizer (SMPS) and Aerosol Instrument Manager
(AIM) Version 5.2 software. The purpose of this document is to provide a written and
repeatable procedure for the operation of the SMPS using the AIM software.
2.0 METHOD SUMMARY
The Model 3936 SMPS consists of the Model 3080 electrostatic classifier (EC), the
Model 3025A condensation particle counter (CPC), and associated plumbing. This
facility currently uses two 3696 SMPS systems, one with a long differential mobility
analyzer (DMA) Model 3081 and another with the nano-DMA Model 3085. Both
systems are covered in this document.
For more specific and detailed information relating to the setup, operation, and
maintenance of this instrument, refer to the Model 3936 SMPS Instruction Manual. This
manual is stored with the instrument.
3.0 INSTRUMENT AND SOFTWARE SETUP
3.1 Instrument Setup
1. Turn on the CPC and EC.
2. Set analog output to HOST on the CPC.
3. Set the voltage control to "Analog Ctrl" on the EC.
4. Turn the TSI SMPS 3936 on and allow at least 30 min. for warm-up.
5. Set aerosol and sheath flow rates as appropriate by referring to the
Recommended Operating Parameters table located on page 4-4 of the Model
3936 SMPS Instruction Manual.
6. Perform a SMPS system check, which can be found on pages 4-6 and 4-7 of
the Model 3936 SMPS Instruction Manual.
The instrument is ready for sampling after the TSI SMPS software is set up.
3.2 Software Setup
1. Open the AIM Version 5.2 software.
2. Select File/New and enter the file name.
3. Select Open or press Enter.
H-3
-------
Appendix H
SMPSSOP
December 2016
Rev. 0
4. Select File/Properties OR Run/Properties and verify or enter the following
SMPS Properties:
Hardware Settings
Classifier Model
Impactor Type
CPC Model and Flow Rate
DMA Flow Rate (L/min):
Sheath
Aerosol
Scan Time (s):
Up
Retrace
3080
Enter cut point for serial no. of impactor
3025A
6 L/min (default)
0.6 L/min (default)
150 (adjust based on size range)
30
Size Range Bounds (Diameter) Select "Set to Max Range" button
Scheduling
Scans per Sample
Number of Samples
Physical Properties
Gas Properties
Particle Density (g/cc)
Multiple Charge Correction
Title
Instrument ID
1
120
Select "Set to Defaults for Air" button
As appropriate for the aerosol (nominally=l)
"On"
As appropriate for the experiment
As appropriate
As needed
Comments
5. Select OK or press Enter.
6. Select View / Size Data / Graph.
7. Select View / Units / Concentration (dW).
8. Select View / Weight / Number.
9. Select Format / Channel Resolution / (32 or 16) channels/decade.
H-4
-------
Appendix H
SMPSSOP
December 2016
Rev. 0
10. Select Run / Auto Export to File and enter the following Dialog properties:
Data Types Number / Concentration (dW)
Delimiter Comma
11. Select OK or press Enter.
12. Enter the Export As properties:
Save in: Create directory if necessary
Save as type: Delimited text file (.txt)
File name: Create Filename
13. Select Save or press Enter.
4.0 DATA COLLECTION
4.1 Start Data Collection
After choosing the Run / Start data collection command, there is an approximate
delay of 4 s before data collection begins. (As an example, to start data collection
at 11:10:00, select the Start data collection command at 11:09:56).
4.2 Stop Data Collection
1. Select Run / Finish current sample.
2. Select File / Save.
3. Select File / Close.
4.3 Instrument Software Shutdown
Select File / Exit.
4.4 Instrument Hardware Shutdown
Standard practice is to keep the SMPS operating unless an extended period of
inactivity is expected.
1. Turn OFF the system vacuum pump.
2. Turn Off the classifier (switch is located on the back).
3. Unplug the CPC.
H-5
-------
Appendix H
SMPSSOP
December 2016
Rev. 0
5.0 DATA PROCESSING
The AIM software writes data into two files: raw data (with extension *.S80) and display
format (with extension *.P80). Raw data is exported as it is collected into a comma-
delimited text file format. Raw data files and processed (exported) data files are managed
per instructions contained in the appropriate QAPP/test plan. In general, raw data and
exported text files are transferred from the instrument computer to a central computer.
Data transfer is a simple drag and drop procedure. Processed data is generated from the
exported text file using Microsoft Excel.
H-6
-------
Appendix I
Blowers/Pumps
Calibration Curves
December 2016
Rev. 0
Appendix I: Blowers/Pump Calibration
Curves
srX
* O \
*1 PRO^
1-1
-------
Appendix I
Blowers/Pumps
Calibration Curves
December 2016
Rev. 0
The x-axis represents blower reading (Hz) or pump adjustment (rotameter reading) and the y-axis
the calibrated standard volume of air passing through the tunnel at that condition.
1500
1300
Big blower calibration
y= 37.38X+ 1.3497
R2 = 0.9999
£
1100
900
700
0.
_l
V)
500
10
15 20 25 30
35 40 45
Hz
Small blower calibration v = i6.7i4x - 4.9277
R2 = 1
900
S 700
Q.
—i
V)
500
300
10
20
30
40
50
60
Hz
1-2
-------
Appendix I
Blowers/Pumps
Calibration Curves
December 2016
Rev. 0
50.00
Pump calibration
y = 0.3969x-19.032
R2 = 0.9968
40.00
E
Q.
"3> 30.00
20.00
10.00
80
100 120 140
Rotameter reading
160
180
1-3
-------
Appendix J
Flow Adjustment and
Software Verification
December 2016
Rev. 0
Appendix J: Experimental Verification
of Lll Recalibration and SuperMAAP
Flow Adjustment and Software
Changes
t... j
Kafe?
PRO^
J-1
-------
Appendix J
Flow Adjustment and
Software Verification
December 2016
Rev. 0
After completing the baseline study, several issues were discovered with the LII and
SuperMAAP that required further investigation and corrective action. This investigation
revealed that the following were needed: corrections to the data to reflect new calibration
constants for the LII, a slight flow adjustment and software change for the SuperMAAP,
and minor temperature corrections to the Micro Soot Sensor (MSS) data. After these
corrections were made to the entire data set, a limited evaluation was conducted in the
laboratory to compare the post-processed data to new experimental data obtained after
implementation of the necessary changes to the LII and SuperMAAP. For the LII, this
evaluation involved three repeat tests at 50 and 500 |ig/m3, both with and without use of
the catalytic stripper (CS), the results of which were compared to the corrected data for
the same experimental conditions in the baseline study. The results of the experimental
verification are provided below. Note that these data have not been corrected for the
SuperMAAP filter change problem discussed in Appendix C.
1.0 VERIFICATION OF LII RESULTS
To validate the LII post-processing method, the post-processed results provided by
Artium Technologies were compared to new experimental data collected at target
concentrations of 50 and 500 |ig/m3 as shown in Figures J-l and J-2. The LII data were
plotted against the organic carbon (OC)-corrected Teflon filter results in Figure J-l and
the NIOSH Method 5040 results in Figure J-2 for experiments conducted with and
without use of the CS. As can be seen from Figure J-l for Teflon filter data, a difference
of 6 to 19 % in slope was observed between the post-processed results and the new
experimental data, depending on CS use. For the comparison against NIOSH in Figure J-
2, the difference ranged from 6 to 12 %, again depending on CS operation. It should also
be noted that the MiniCAST was repaired shortly before performing experiments with the
CS, which probably had at least some influence on the LII measurement results. The
average OC/total carbon (TC) ratio was approximately 69 % before MiniCAST servicing
and approximately 81 % after (during repeated CS experiments) using the same operating
parameters. The other instruments (MSS and NIOSH 5040) did not register any
significant changes in the slope before and after MiniCAST repair, however.
Although the comparison of experimental to post-processed data was not as good as
expected for the stripped MiniCAST aerosol, the unstripped aerosol produced slopes
within 6 % regardless of whether the comparison was against the OC-corrected Teflon
filter results or the NIOSH 5040 results, indicating good agreement. These results would
suggest that there should be little problem using post-processed data. For the data with
use of the CS, the deviation in slope was 12 to 19 % and thus not as good as for the
unstripped aerosol. In this case, a change in the MiniCAST exhaust particles after
servicing might have caused changes in the operation of the stripper, thus negatively
J-2
-------
Appendix J
Flow Adjustment and
Software Verification
December 2016
Rev. 0
impacting the data obtained. As discussed in the main text, the stripper did not provide
anywhere near the expected OC reduction and its operation was found to be highly
idiosyncratic. For this reason, we considered the post-processed LII stripper data to be
adequate for use without repeating the entire experimental matrix.
J-3
-------
Appendix J
Flow Adjustment and
Software Verification
December 2016
Rev. 0
•• LB PC-Bt-PTCCe B Wti
¦ LDExpertrr»ental
PGBt-PTC-CSBBSIil
y = t.iaaa*
R*-= (L597B
Exjrerfnejital
y = 1.1322*
R== 0.9977
Exc«rtn»ntas
y = 1.2542X
R: = 0.3993
nt-u
PDBt-PTD'»B99!S
y = t.0«15X
Rr= 0.8957
10(1 2® 500 «Q 5Q0 SCfl 7M
OC - Corre cted Tefto n FiIte r Co ncentrati on (pg/m^
L8POBt-PrCi8BB8tf
•LBExpwlirantal
230 330 «D 533 see 700 SOD
OC - Corrected Teflon Filter Co ncentrati on Ijjg'm1)
Figure J-l. Comparison of LII post-processed data to new experimental results based on
Teflon filter measurements for tests (a) with stripper and (b) without stripper.
J-4
-------
Appendix J
Flow Adjustment and
Software Verification
December 2016
Rev. 0
Eicpeftrcan tei
U! Po Ert-PrccfcB BeU
¦ LHExjwrtmantel
y= 1.326?*
R== 0.3974
PcBt-Prc-ceB Bfl-a
y=
R-= 0.9903
100 200 200 400 500 000
NIO SH 5 040 EC Con centrati on {jjgfrn3)
LII POBt-PfO«8BB«l
Po Bft-Proce b b«J
Y=1.19Q9x
RI = 0.3901
E «arrant#
y= 1.1324*
Rz= 09371
NIOSH 5040 EC Con centrati on jjigftn3)
Figure J-2. Comparison of LII post-processed data to new experimental results based on
NIOSH 5040 measurements for tests (a) with stripper and (b) without stripper.
J-5
-------
Appendix J
Flow Adjustment and
Software Verification
December 2016
Rev. 0
2.0 VERIFICATION OF SUPERMAAP RESULTS
A similar evaluation was also conducted for the SuperMAAP, except only data collected
with the CS (three tests at 50 |ig/m3 and three at 500 ug/m ! concentrations) are shown in
Figures J-3 and J-4. The unstripped results were highly suspect and thus deleted from this
analysis. As shown in the figures, both slopes (experimental and post-processed) were
almost the same when compared with OC-corrected Teflon results and within 7% when
compared with NIOSH EC. These results indicate good agreement between repeated
laboratory experiments and the computer-based post-processing method using the newly
developed Lab View post-processor. These results allowed us to use the post-processed
SuperMAAP results without repeating all experiments.
s MAAP Post-Processed
* MAAP Experimental
Post-Processed
y=<0.9 Mix
R= = 0.3371
100 200 300 400 500 600
OC- Corrected Teflon Filter Concentration (|jgynrr!)
^ Experimental ¦
y = 0.334fix
R==fl.93«J
Figure J-3. Comparison of SuperMAAP post-processed data to new experimental results
based on Teflon filter measurements for tests with stripper.
J-6
-------
Appendix J
Flow Adjustment and
Software Verification
December 2016
Rev. 0
» MAA P Post-Processed
« MAAPExperimental
Experimental
y =0.9879*
R== 0.9908
Post-Processed
y= 1.0644*
R== 0.9973
0 100 200 300 400 500 600 700
NIOSH5040 EC Concentration (tig/rn5)
Figure J-4. Comparison of SuperMAAP post-processed data to new experimental results
based on NIOSH 5040 measurements for tests with stripper.
J-7
-------
Appendix K: APPCD Metrology
Laboratory Calibration Reports
NRMRL/APPCD
£
5
3)
V
> c^C5
PRO^
O
Z
Ui
O
K-1
-------
Appendix K
December 2016
Rev. 0
US EPA APFCD Metrology Lab
Flow Rate Evaluation Report
De\ ice Under Test Micro Soot Measuring System
Mir., Model AVL, B06529
Serial Number 273
Met Lab ID 03743
Affiliation & 1»I NRMRL, APPCD, ECPB. John Kinsey
Requestor Jelica Pavlovic
Report File AVL 03743 2011 -04-25 qa.xls
MOP# FV-0237.0
Comments
Calibration Date
Location
Notebook, pa Re
4/25/2011
High Bay
2273, p. 70
Ambient Conditions During Calibration
T emperature between 20 °C and 24 "C
RH between 30 % and (50 %
Pressure between 1,000 hPa and 1,005 hPa
Flow rate was evaluated at a single point. The unit was found to operate within the manufacturer's specified tolerances of
10% of target flow rate
Data and Results
Reference Flow Rate.
LPM PUT Flow Rate. I.PM Difference. 1-PM
3.819 3.80 -0.02
Difference from Target was 4X5 %
Test Equipment
Device Calibration Due SN Uncertainty (2K)
Gilibrator 2 6 LPM cell 11/8/2011 1011020-S ±1.0% Reading
Page 1
K-2
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Flow Rate Calibration Report
Device Under Test QFF Flow Rate
Mfr., Model Dwyer, GFC1133
Serial Number G1013521C
Met. Lab ID 02811
Affiliation & PI NRMRL, APPCD, ECPB, John Krnsey
Requestor Jelica Pavlovik
ReportFile MFC028112011-07-06qa.xls
MOP # FV-0237.0
Comments
Calibration Date
Location
Notebook, page
7/6/2011
Soot Tunnel Lab
2273, p. 119
Ambient Conditions During Calibration
Temperature between 21 °C- and 25 °C
RH between 20 % and 50 %
Pressure between 1,001 hPa and 1,007 hPa
MFC flow rate response was compared to flow rate measured with a Bios DryCal. A strong vacuum (23 "Hg) was pulled on
the outlet of the MFC to draw room air through the DryCal then the MFC. This calibration is only valid for 5 SLPM to 20
SLPM and in the configuration in which it was calibrated.
Correction Equation and Uncertainty
Use the equation format below to correct a device response.
y = m * x + b
Coefficients for correcting a device response, y = corrected response (SLPM) and x = device response (Volts)
m = 10.011, b =-0.335
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Flow rate was corrected to standard conditions of 25.0 °C (77 °F) and 1013.25 hPa (1 atm.).
Combined Expanded Uncertainty for this calibration was ±0.38 % of reading and ± 0.29 SLPM.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device Calibration Due SN Uncertainty (2K)
DryCal, 0.05-50 L/min 10/3/2012 H1688 ±1% of reading
Calibrated by Mike Tufts
Page 1
K-3
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name QFF Flow Rate
MetLab ID 02811
Calibration Date 7/6/2011
Reference Corrected DUT DUT Error after
DUT Response, Volts Measurement, SLPM Reading, SLPM Correction, SLPM
1.889 18,75 18.58 -0.17
1,470 14.18 14.38 0,20
0.977 9.31 9.45 0.14
0.694 6.63 6.62 -0.01
0,555 5,25 5.22 -0.03
0.622 6,01 5.89 -0.12
Page 2
K-4
-------
Appendix K
December 2016
Rev. 0
Error Chart
QFF Flow Rate
MetLab ID 02811
7/6/2011
0 10.0 12.0
How Kate, SLPM
~ DUT Error after Correction, SLPM
Page 3
K-5
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Flow Rate Calibration Report
Device Under Test Small Soot Tunnel Blower
Mfr.. Model Fuji Electric, VFC200A-7W
Serial Number 10577484
Met Lab ID 03735
Affiliation & PI NRMRL, APPCD, ECPB, John Kinsey
Requestor Jelica Pavlovic
Report File blower 03735 2011-04-28 qa.xls
MOP# FV-0236.0
Comments
Calibration Date
Location
Notebook, page
4/28/2011
high bay
2273, p. 69 & 75
Ambient Conditions During Calibration
Temperature between 18 °C and 22 °C
EH between 30 % and 60 %
Pressure between 1,001 hPa and 1,007 hPa
Calibration was performed by comparing blower frequency drive set points to flow rate measured with the M175 Roots
meter. Calibration gas was room air.
Col l ection Fcumlion and Uncertainty
Use the equation format below to correct a device response.
y = A2 * x"2 + A1 * x + AO
Coefficents for correcting a device response, y = corrected response (CFM) and x = device response (Hz)
A2 = -3.488E-04, A1 = 6.180E-01, AO = -0.660
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Combined Expanded Uncertainty for this calibration was ± 0.76 % of reading and ± 0.15 CFM.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device
Rot ts Meter 5M175
ASL F250
ASL T-loo SPRT A
Heise HQS-2, 0-30 PSIA
Calibration Due
9 25 2(U5
6 10 2011
3 9 2012
7'11-2008
SN
0521990
216^ 01S 1204
400054
20400
Uncertainty (2 k)
±1 o° o
±0 02 "C
±002 r
±0 38 mmHg
Calibrated by Mike Tufts
Page 1
K-6
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name Small Soot Tunnel Blower
MetLab ID 03735
Calibration Date 4/28/2011
Reference Corrected DUT DUT Error after
DUT Set Point, Hz Measurement, CFM Reading, CFM Correction, CFM
40,0
23,51
23.50
-0,01
55.0
32,40
32.27
-0,12
45.0
26.42
26.44
0,02
35,1
20.57
20.60
0,03
25,0
14.54
14.57
0,03
20.0
11.69
11.56
-0.12
10.0
5.45
5.49
0.04
60.0
35.13
35.16
0.04
Page 2
K-7
-------
Appendix K
December 2016
Rev. 0
Error Chart
Small Soot Tunnel Blower
MctLab ID 03735
4/28/2011
15.0 20.0
Flow Rate, CFM
~DUT Error after Correction, CFM
Page 3
K-8
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Flow Rate Calibration Report
Device Under Test Large Soot Tunnel Blower
Mfr., Model Fuji Electric, VFC400A-7W
Serial Number 0311J77486120
Met. Lab ID 03744
Affiliation & PI NRMRL, APPCD, ECPB, John Kinsey
Requestor Jelica Pavlovic
Report File blower 03744 2011-04-27 qa.xls
MOP # FV-0236.0
Comments
Calibration Date
Location
Notebook, page
4/27/2011
high bay
2273, p. 69 & 75
Ambient Conditions During Calibration
Temperature between 1S °C- and 22 °C
RH between 30 % and 60 %
Pressure between 1,001 hPa and 1,007 hPa
Calibration was performed by comparing blower frequency drive set points to flow rate measured with the Ml 75 Roots
meter. Calibration gas was room air.
Correction Equation and Uncertainty
Use the equation format below to correct a device response.
y = A2 *xA2 + A1 *x + A0
Coefficents for correcting a device response, y = corrected response (CFM) and x = device response (Hz)
A2 = -8.632E-04, A1 = 1.386E+00, A0 =-1.182
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Combined Expanded Uncertainty for this calibration was ± 0.89 % of reading and ± 0.18 CFM.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device
Roots Meter 5M175
ASL F250
ASL T-100 SPRT A
Heise HQS-2, 0-30 PSIA
Calibration Due
9/25/2015
6/10/2011
3/9/2012
7/11/2008
SN
0521990
2169 018 1204
400054
20400
Uncertainty (2 K)
±1.0%
±0.02°C
±0.02 °C
±0.38 mmHg
Calibrated by Mike Tufts
Page 1
K-9
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name
MetLab ID
Calibration Date
Large Soot Tunnel Blower
03744
4/27/2011
DUT Set Point, Hz
10.0
20.1
30.0
40.1
50,0
60.0
Reference
Measurement, CFM
12.53
26,44
39.63
52.90
66.02
78.8.9
Corrected DUT
Reading, CFM
12.59
26.33
39.62
53.01
65.96
78.87
DUT Error after
Correction, CFM
0,06
-0,12
-0,01
0.11
-0.06
-0.02
Page 2
K-10
-------
Appendix K
December 2016
Rev. 0
Error Chart
Large Soot Tunnel Blower
MetLab ID 03744
4/27/2011
40.0 50.0
Flow Rate, CFM
~DUT Error after Correction, CFM
Page 3
K-11
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Flow Rate Calibration Report
Device Under Test LII Rotameter
Mfr., Model Dwyer, none
Serial Number none
Met Lab ID 03040
Affiliation & PI NRMRL, APPCD, ECPB, John Kinsey
Requestor Jelica Pavlovic
Report File rotameter 03040 2011-05-04 qa.xls
MOP# FV-0237.0
Comments
Calibration Date
Location
Notebook, page
5/4/2011
High Bay
2273, p. 78
Ambient Conditions During Calibration
Temperature between 19 °C and 23 °C
EH between 30 % and 60 %
Pressure between 1,004 hPa and 1,009 hPa
Calibration was performed by comparing rotameter readings to the DryCal measured flow rate. The rotameter was read at
the center of the ball. Calibrated only at the anticipated flow rate of the LII.
Range: 0,5 to 10LPM
Correction Equation and Uncertainty
Use the equation format below to correct a device response.
y=m*x+b
Coefficients for correcting a device response, y = corrected response (SLPM) and x = device response (LPM)
m = 0.88, b = -2.3
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Flow rate was corrected to standard conditions of 25 0 C177 F) and li>12 25 hPa (1 atm.).
Combined Expanded Uncertainty for this calibration was ±0.15 SLPM.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device Calibration Due SN Cnciriainty (2 k)
DtyCal, 0.05-50 L/min 10/3/2011 H1688 ±1% of reading
Calibrated by Mike Tufts
Page 1
K-12
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name LII Rotameter
MetLab ID 03040
Calibration Date 5/4/2011
Reference Corrected DUT DUT Error after
DUT Set Point, LPM Measurement, SLPM Reading, SLPM Correction, SLPM
8.0 4.77 4.74 -0.03
8.5 5.24 5.18 -0.06
9.0 5.66 5.62 -0,04
9,5 6.16 6.06 -0.10
10,0 6.51 6.50 -0.01
Page 2
K-13
-------
Appendix K
December 2016
Rev. 0
Error Chart
L1I Rotameter
MetLab ID 03040
5/4/2011
0.50
0.40
0.30
Flow Rate, SLPM
~ DUT Error after Correction, SLPM
Page 3
K-14
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Flow Rate Calibration Report
Device Under Test
Sample Dump Rotameter
Calibration Date 5/4/2011
Mfr., Model
Dwyer, RMC-104-SSV
Location High Bay
Serial Number
none
Notebook, page 2273, p. 78
Met. Lab ID
03747
Affiliation & PI
NRMRL, APPCD, ECPB, John Kinsey
Ambient Conditions During Calibration
Requestor
.Taleica Pavlovic
Temperature between 19 °C and 23 °C
Report File
rotameter 03747 2011-05-04 qa.xls
EH between 30 % and 60 %
MOP#
FV-0237.0
Pressure between 1,004 hPa and 1,009 hPa
Comments
Calibration was performed by comparing rotameter readings to the DryCal measured flow rate. The rotameter was read at
the center of the ball.
Correction Equation and Uncertainty
Use the equation format below to correct a device response.
y=m*x+b
Coefficients for correcting a device response, y = corrected response (SLPM) and x = device response (SCFH)
m = 0.397, b = -19.0
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Flow rate was corrected to standard conditions of 25 0 C177 F) and li>12 25 hPa (1 atm.).
Combined Expanded Uncertainty for this calibration was ±1.2 SLPM.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device Calibration Due SN Uncertainty (2K)
DiyCal, 0.05-50 L/min 10/3/2011 H1688 ±1% of reading
Calibrated by Mike Tufts
Page 1
K-15
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name Sample Dump Rotameter
MetLab ID 03747
Calibration Date 5/4/2011
Reference Corrected DUT DUT Error after
DUT Set Point, SCFH Measurement, SLPM Reading, SLPM Correction, SLPM
100.0
21.40
20.70
-0.70
120,0
27.80
28.64
0,84
140.0
36.30
36.58
0.28
150,0
40.50
40.55
0,05
160,0
44.20
44.52
0,32
170,0
49.10
48.49
-0.61
Page 2
K-16
-------
Appendix K
December 2016
Rev. 0
Error Chart
MetLab ID 03747
5/4/2011
30.0
How Kate, SLPM
~ DUT Error after Correction, SLPM
Page 3
K-17
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Pressure Calibration Report
Device Under Test Orifice Plate dP Sensor
Mfr., Model Omega Engineering, PX653 - 10D5 V
Serial Number 20927145
Met Lab ID 03686
Affiliation & PI NRMRL, APPCD, ECPB, John Kinsey
Requestor Jelica Pavlovic
Report File PT 03686 2011-07-21 qa.xls
MOP# PR-0400.0
Comments
Calibration Date
Location
Notebook, page
7/21/2011
High Bay
2273, p. 127
Ambient Conditions During Calibration
Temperature between 21 "C and 25 °C
EH between 20 % and 500 o
Pressure between 997 hPa and 1,003 hPa
Calibration was performed by comparing differential pressure transducer voltage response to pressure conditions generated
with the Mensor APC 600.
CoiTedion FcumUon and Uncertainty
Use the equation format below to correct a device response.
y = A3 *x '3 - A2*xA2 + Al *x + A0
Coefficents for correcting a device response, y = corrected response ("H20) and x ™ device response (Volts)
A3 = -2.600E-03, A2 = 2.299E-02, A1 =2.4012E+00, AO = -2.3854
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Combined Expanded Uncertainty for this calibration was ± 0.003 "H20.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device
Mensor APC 600 10 "H20 dP cell
Calibration Due
1/14/2012
SN
621603-2
Uncertainty (2 k)
±0,01 % FS
Calibrated by Mike Tufts
Page 1
K-18
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name Orifice Plate dP Sensor
MetLab ID 03686
Calibration Date 7,21/2011
Reference Corrected DUT DUT Error after
DUT Response, Volts Measurement, "H20 Reading, "H2Q Correction, "H20
1 802
2.000
2(i(il
0UO1
2613
4 000
4 000
oooo
3 424
6.000
6ooo
0 000
4 215
8 111 SI!
7.998
4) .002
5 t)S3
10.000
10.000
0.000
4 644
9.000
9.000
0.000
3.830
7.000
7.002
0 002
3.018
5.000
5.000
0 000
2.207
3.000
2.999
-0 001
1.394
1.000
1.000
o ooo
0.985
0.000
0.000
0 000
Page 2
K-19
-------
Appendix K
December 2016
Rev. 0
Error Chart
Orifice Plate dP Sensor
MetLab ID 03686
7/21/2011
Pressure, "1120
• DUTError after Correction, "H20
Page 3
K-20
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Flow Rate Calibration Report
Device Under Test MFM431
Mfr., Model Omega Engineering, FMA1728
Serial Number G17431
Met Lab ID 02212
Affiliation & PI NRMRL, APPCD, ECPB, John Kinsey
Requestor Jelica Pavlovic
Report File MFM 02212 2011-05-24 qa.xls
MOP# FV-0201.1
Comments
Calibration Date
Location
Notebook, page
5/24/2011
High Bay
2273, p. 94
Ambient Conditions During Calibration
Temperature between 18 °C and 22 °C
EH between 30 % and 60 %
Pressure between 997 hPa and 1,003 hPa
The correlation for this calibration was between mass flow meter response and flow rate measured with a DryCal flow
calibrator. Compressed dried house air was used as the calibration gas.
This unit was interfaced to channel #2 of an IOtech cube. It was referred to as MFM431 in Pdaq
Correction Fcumlion and Uncertainty
Use the equation format below to correct a device response.
y = A2 * x"2 + A1 * x + AO
Coefficents for correcting a device response, y = corrected response (SLPM) and x = device response (Volts)
A2 = 0.1372, A1 = 9.500, AO = 0.123
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Flow rate was corrected to standard conditions of 25 0 C177 F) and li>12 25 hPa (1 atm.).
Combined Expanded Uncertainty for this calibration was ± 0.70 % of reading and ± 0.26 SLPM.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device Calibration Due SN Uncertainty (2K)
DtyCal, 0.05-50 L/min 10/3/2011 H1688 ±1% of reading
Calibrated by Mike Tufts
Page 1
K-21
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name MFM431
MetLab ID 02212
Calibration Date 5/24/2011
Reference
DUT Response, Volts Measurement, SLPM
1.904
18,93
2.958
29.51
3.821
38.32
4,884
49.79
4,572
46.44
3,578
35.98
2,515
24.65
1,453
14.13
0.988
9.64
Corrected DUT
DUT Error after
Reading, SLPM
Correction, SLPM
18.71
-0.22
29.42
-0.09
38.42
0.10
49.79
0,00
46.42
-0.02
35.87
-0.11
24.89
0.24
14.21
0.08
9.64
0.00
Page 2
K-22
-------
Appendix K
December 2016
Rev. 0
Error Chart
MFM431
MetLab ID 02212
5/24/2011
30.0 40.0 50.0
Flow Rate, SLPM
• DUT Error after Correction, SLPM
Page 3
K-23
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Flow Rate Calibration Report
Device Under Test
MFM392
Calibration Date 5/24/2011
Mfr., Model
Omega Engineering, FMA1728
Location High Bay
Serial Number
G17392
Notebook, page 2273, p. 93
Met Lab ID
02213
Affiliation & PI
NRMRL, APPCD, ECPB, John Kinsey
Ambient Conditions During Calibration
Requestor
Jelica Pavlovic
Temperature between 18 °C and 22 °C
Report File
MFM 02213 2011-05-24 qa.xls
EH between 30 % and 60 %
MOP#
FV-020U
Pressure between 997 hPa and 1,003 hPa
Comments
The correlation for this calibration was between mass flow meter response and flow rate measured with a DryCal flow
calibrator. Compressed dried house air was used as the calibration gas.
This unit was interfaced to channel #3 of an IGtech cube. It was referred to as MFM392 in Pdaq
Correction Fcumiion and Uncertainty
Use the equation format below to correct a device response.
y = A2 * x"2 + A1 * x + AO
Coefficents for correcting a device response, y = corrected response (SLPM) and x = device response (Volts)
A2 = 0.5830, A1 = 9.353, AO = 2.590
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Flow rate was corrected to standard conditions of 25 0 C177 F) and li>12 25 hPa (1 atm.).
Combined Expanded Uncertainty for this calibration was ± 0.39 % of reading and ± 0.30 SLPM.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device Calibration Due SN Cnciriainty (2 k)
DtyCal, 0.05-50 L/min 10/3/2011 H1688 ±1% of reading
Calibrated by Mike Tufts
Page 1
K-24
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name MFM392
MetLab ID 02213
Calibration Date 5/24/2011
Reference Corrected DUT DUT Error after
DUT Response, Volts Measurement, SLPM Reading, SLPM Correction, SLPM
1.734
20.63
20.56
-0.07
1,491
17.87
17.83
-0.04
1.257
15.02
15.27
0.25
1,011
12.63
12.65
0,02
0,762
10.20
10.06
-0.14
0.504
7,61
7.46
-0.15
0.250
4.83
4.97
0.14
Page 2
K-25
-------
Appendix K
December 2016
Rev. 0
Error Chart
MFM392
MctLab ID 02213
5/24/2011
15.0 20.0
Flow Rate, SLPM
• DUT Error after Correction, SLPM
Page 3
K-26
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Flow Rate Calibration Report
Device Under Test Orifice Plate
Mfr., Model In-house, none
Serial Number none
Met Lab ID 03706
Affiliation & PI NRMRL, APPCD, ECPB, John Kinsey
Requestor Jeliea Pavlovic
Report File OP 03706 2011-05-23 qa.xls
MOP# FV-0201.1
Comments
Calibration Date
Location
Notebook, page
5/23/2011
High Bay
2273, p. 92
Ambient Conditions During Calibration
Temperature between 18 °C and 22 °C
EH between 30 % and 60 %
Pressure between 1,001 hPa and 1,007 hPa
The correlation for this calibration was between the square root of the orifice plate differential pressure response and flow
rate measured by the Molbloc flow calibration system. Compressed dried house air was used as the calibration gas.
This pressure transducer was interfaced to channel #1 of an lOtech cube. It was referred to as dP m Pdaq
dP cell: s/n 20927145, model #PX653-10D5V, MetLab ID02686
An additional step is required when using the equations below with an OP. The square root of the dP reading must be
calculated before the first equation is applied. The result of the second equation must be squared to determine a set point.
Correction Equation and Uncertainty
Use the equation format below to correct a device response.
y=m*x+b
Coefficents for correcting a device response, y = corrected response (SLPM) and X ™ device response (SQRT "H20)
m = 15.636, b = 1.374
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Flow rate was corrected to standard conditions of 25 0 C177 F) and li>12 25 hPa (1 atm.).
Combined Expanded Uncertainty for this calibration was ±1.3 % of reading and ± 0.15 SLPM.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device Calibration Due SN Cnciriainty (2 k)
DiyCal, 0.05-50 L/min 10/3/2011 H1688 ±1% of reading
Calibrated by Mike Tufts
Page 1
K-27
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name Orifice Plate
MetLab ID 03706
Calibration Date 5/23/2011
DUT Response,
Reference
SQRT"H20
Measurement, SLPM
1.798
29.59
2.012
32.90
2.226
36.22
2,378
38.53
2,524
40.83
2,534
41.00
2.574
41.65
2.661
42.88
2.521
40.80
1.488
24.50
Corrected DUT
DUT Error after
Reading, SLPM
Correction, SLPM
29.48
-0.11
32.83
-0.07
36.17
-0,05
38.56
0,03
40.84
0,01
40.99
-0.01
41.62
-0.03
42.99
0.11
40.79
-0.01
24.63
0.13
Page 2
K-28
-------
Appendix K
December 2016
Rev. 0
Error Chart
Orifice Plate
MetLab ID 03706
5/23/2011
35.0
Flow Kate, SLPM
~ DUT Error after Correction, SLPM
Page 3
K-29
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Pressure Calibration Report
Device Under Test PT Tutinel
Mfr., Model Omega Engineering, PX309-015A5V
Serial Number 0114081007
Met Lab ID 03713
Affiliation & PI NRMRL, APPCD, ECPB, John Kinsey
Requestor Jelica Pavlovic
Report File PT 03713 2011-05-24 qa.xls
MOP# PR-0400.0
Comments
Calibration Date
Location
Notebook, page
5/24/2011
High Bay
2273, p. 95
Ambient Conditions During Calibration
Temperature between 18 °C and 22 °C
EH between 30 % and 60 %
Pressure between 997 hPa and 1,003 hPa
The correlation for this calibration was between the pressure transducer response and the pressure condition generated by the
Mensor APC600.
This unit was interfaced to channel #4 of an IOtech cube. It was referred to as PT007 in Pdaq.
Correction FquHlion and Uncertainty
Use the equation format below to correct a device response.
y = A2 * x"2 + A1 * x + AO
Coefficents for correcting a device response, y = corrected response (mmHg) and x = device response (V)
A2 = 0.0897, A1 = 154.42, AO = 1.186
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Combined Expanded Uncertainty for this calibration was ±0.14 mmHg.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device
Mensor APC 600 15 PSIA cell
Calibration Due
1/15/2012
SN
621604-2
Uncertainty (2 k)
±0,01 % FS
Calibrated by Mike Tufts
Page 1
K-30
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name PT Tunnel
MetLab ID 03713
Calibration Date 5/24/2011
DUT Response, V
3.225
1,287
2,255
4.191
5.157
Reference
Measurement, mmHg
500.00
200.00
350,00
650.00
800.00
Corrected DUT
Reading, mmHg
500.07
200.02
349.92
649.95
799.99
DUT Error after
Correction, mmHg
0,07
0,02
-0,08
-0.05
-0.01
Page 2
K-31
-------
Appendix K
December 2016
Rev. 0
Error Chart
PT Tunnel
MetLab ID 03713
5/24/2011
200.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0
Pressure, mmllg
750.0 800.0
•DUT Error after Correction, mmHg
Page 3
K-32
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Temperature Calibration Report
Device Under Test Soot Tunnel T-Type TC
Mfr., Model Omega Engineering, T-type
Serial Number none
Met. Lab ID 03742
Affiliation & PI NRMRL, APPCD, ECPB, John Kinsey
Requestor Jeliea Pavlovic
Report File TC 03742 2011-04-20 qa.xls
MOP# TH-0301.0
Comments
Calibration Date
Location
Notebook, page
4/20/2011
high bay
2183, p. 132
Ambient Conditions During Calibration
Temperature between 19 °C and 23 "C
EH between 30 % and 60 %
Pressure between 1,000 hPa and 1,005 hPa
Calibration was performed by comparing the response of the T-type thermocouple an data acquisition system to the
conditions generated by a Hart 9170 Metrology Well.
Correction Equation and Uncertainty
Use the equation format below to correct a device response.
y=m*x+b
Coefficents for correcting a device response, y = corrected response (°C) and x = device response (°C)
m = 0.997, b =-0.055
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Combined Expanded Uncertainty for this calibration was ±0.12 °C.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device Calibration Due SN Cnciriainty (2 k)
Hart 9170 Metrology Well 12/2/2011 B0B515 ±0.1 °C
Calibrated by Mike Tufts
Page 1
K-33
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name Soot Tunnel T-Type TC
MetLab ID 03742
Calibration Date 4/20/2011
DUT Response, °C
30,13
40.18
35.19
25,16
15,15
5.08
10.07
20.07
Reference
Measurement,'
30.000
40.000
35.000
25.000
15.000
5.000
10.000
20.000
Corrected DUT
Reading, °C
29.99
40.01
35.03
25.03
15.05
5.01
9.98
19.96
DUT Error after
Correction, °C
-0.01
0.01
0.03
0,03
0,05
0,01
-0.02
-0.04
DUT Error before
Correction, °C
0.13
0.18
0.19
0.16
0.15
0.08
0.07
0.07
Page 2
K-34
-------
Appendix K
December 2016
Rev. 0
1- 0.00 -
£
Error Chart
Soot Tunnel T-Type TC
MetLab ID 03742
4/20/2011
1 em per at ure, °C
~DUT Error after Correction, °C
¦ DUT Error before Correction, °C
Page 3
K-35
-------
Appendix K
December 2016
Rev. 0
US EPA APPCD Metrology Lab
Flow Rate Calibration Report
Device Under Test
Mfr., Model
Serial Number
Met. Lab ID
Affiliation & PI
Requestor
Report File
MOP#
MAAP MFC
MKS, M100B01353CS1BV
21t)98222
037+1
NRMRL, APPCD, ECPB, John Kinsey
Jelica I'avlovic
MFC 03745 2012-02-28 rpt maap.xls
FV-0237.0
Calibration Date
Location
Notebook, page
2/28/2012
Soot Tunnel Test Facility
2319
Ambient Conditions During Calibration
Temperature between 21 °C and 25 °C
RH between 10 % and 40 %
Pressure between 1,011 hPa and 1,016 hPa
Comments
Calibration was performed by comparing mass flow controller display set point to the flow rate measured with a diyCal flow
rate calibrator. The dryCal was positioned at the inlet of the MAAP.
Flow rate data was collected at set tr 1 different filter transmittance levels to determine how filter loading effected sample flow
rate. Fliter loading did not effect sample flow rate.
Correction Equation and Uncertainty
Use the equation format below to correct a device response.
y = m * x + b
Coefficients for correcting a device response, y = corrected response (SLPM) and x = device response (Volts)
m = 9.193E-01, b =-0.188
Correction equations were derived from least squared methods and will reduce systematic bias from DUT measurements.
Combined Expanded Uncertainty for this calibration was ±1.0 % of reading.
Combined Expanded Uncertainty includes random errors after correction, DUT resolution, and uncertainty of reference
devices. It is expressed at a coverage factor of 2 representing a confidence interval of approximately 95%.
Test Equipment
Device Calibration Due SN Uncertainty (2K)
DryCal, 0.05-50 L/min 5/30/2013 H1688 ±1% of reading
Calibrated by Mike Tufts
Page 1
K-36
-------
Appendix K
December 2016
Rev. 0
Measurement Results
DUT Name MAAP MFC
MetLab ID 03745
Calibration Date 2/28/2012
Reference
DUT Response, Volts Measurement, SLPM
4 50
3,95
5.0U
4,42
3 111
3.04
4.50
3.95
3,50
3.04
3.50
3.03
4.50
3.95
4,50
3.95
5.00
4.42
3.50
3.03
4.50
3 94
3.50
3 03
3.50
3 03
4,50
3 95
4.50
3 94
5.00
4,41
3.50
3.03
4.50
3.94
3.50
3,03
3,50
3.03
4.50
3,94
4.50
3.94
5,00
4.41
3,50
3.03
4.50
3.94
3.50
3.03
3.50
3.03
4.50
3.94
4.50
3.94
Corrected DUT
DUT Error after
Reading, SLPM
Correction. SLPM
3.95
0.00
4.41
-0.01
3.03
-0.01
3.95
0 00
3.03
-0.01
3.03
0,00
3.95
0 00
3.95
-0 01
4.41
-0 111
3.03
0 00
3.95
0,00
3.03
0,00
3.03
0.00
3.95
0.00
3.95
0.01
4.41
0.00
3.03
0.00
3.95
0.01
3.03
0.00
3.03
0,00
3.95
0.01
3.95
0,01
4.41
0.00
3.03
0.00
3,95
0.01
3.03
0.00
3,03
0.00
3.95
0,01
3.95
0.01
Page 2
K-37
-------
Appendix K
December 2016
Rev. 0
Error Chart
MAAP MFC
MetLab ID 03745
2/28/2012
-
\
~
~
Flow Rate, SLPM
~DUT Error after Correction, SLPM
Page 3
K-38
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