Speciation of Total Organic Gas
and Particulate Matter Emissions
from Onroad Vehicles in MOVES3



£%	United States

Environmental Protect
Agency


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Speciation of Total Organic Gets
and Particulate Matter Emissions
from Onroad Vehicles in MOVES3

This technical report does not necessarily represent final EPA decisions
or positions. It is intended to present technical analysis of issues using
data that are currently available. The purpose in the release of such
reports is to facilitate the exchange of technical information and to
inform the public of technical developments.

Assessment and Standards Division
Office of Transportation and Air Quality
U.S. Environmental Protection Agency

NOTICE

4>EPA

United States
Environmental Protection
Agency

EPA-420-R-22-017
July 2022


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Table of Contents

1	Introduction	3

1.1	Measuring Hydrocarbons and Particulate Matter	3

1.2	MOVES Speciation Approach	4

1.3	Data Uncertainty and Limitations	4

1.4	Updates to MOVES3	6

1.5	Updates to MOVES3.0.4	6

2	Speciation Glossary	6

2.1	General Terms	7

2.2	Organic Gas Terms	7

2.3	Chemical Mechanism Terms	8

2.4	Particulate Matter Terms	10

2.5	Databases, Models and Tools	11

3	Organic Gas Aggregations and Ratios	12

3.1	Total Organic Gaseous Calculations	13

3.2	Ratios for Evaporative Emissions and Most Exhaust Emissions	14

3.3	Ratios for 2001 -and-Later Light-Duty Gasoline Exhaust	19

3.4	Ratios for Flex Fuel Vehicles using High Ethanol Blends (E85)	23

3.5	Ratios for CNG Vehicles	24

3.6	CH4 Ratios for 2010-and-Later Heavy-Duty Diesel Vehicles	26

4	TOG Chemical Mechanism (CM) Speciation	27

4.1	Overview	27

4.2	Real TOG Speciation Profiles	28

4.3	TOG Chemical Mechanism Species	31

5	PM2.5 Speciation	33

5.1	MOVES PM2.5 Species	33

5.2	PM2.5 Speciation Calculations	34

5.3	PM2.5 Exhaust Speciation Profiles	39

5.4	Brake and Tire Wear Speciation	42

Appendix A Supporting Information for TOG calculations	43

Appendix B CNG CH4/THC and Speciation Constant Parameters for CNG vehicles	50

Appendix C TOG Speciation Map	51

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Appendix D Comparison of ACES Phase 1 and Phase 2 SPECIATE Profiles	54

Appendix E Development of PM2.5 speciation profiles in MOVES	61

E. 1 Development of Gasoline Profiles from the Kansas City Light-duty Vehicle Emissions
Study 62

E.2 Development of E55/59 Profile for Pre-2007 Conventional Diesel	65

E.3 Development of the ACES PM2.5 Profile for 2007 and Newer Technology Diesel	70

E.4 Development of the Compressed Natural Gas (CNG) Profile	72

Appendix F PM10/PM2.5 Factors	75

Appendix G Speciating emissions outside of MOVES	76

6 References	78

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1 Introduction

The United States Environmental Protection Agency's Motor Vehicle Emission Simulator—
commonly referred to as MOVES—is a set of modeling tools for estimating air pollution
emissions produced by onroad (highway) and nonroad mobile sources. MOVES estimates the
emissions of greenhouse gases (GHGs), criteria pollutants and selected air toxics. The MOVES
model is currently the official model for use for state implementation plan (SIP) submissions to
EPA and for transportation conformity analyses outside of California. The model is also the
primary modeling tool for estimating the impact of mobile source regulations on emission
inventories, and thus, provides important inputs to air quality models.

In MOVES, some pollutant emissions are computed directly, based on measured emission
rates1'2. Other pollutants are estimated as a function of the directly computed emissions. This is
true of many of the air toxics, as described in the MOVES air toxics report7. For air quality
modeling purposes, further chemical characterization of TOG and PM2.5 is required. The process
of apportioning aggregate organic gases and particulate matter into sets of separate components
is called "speciation."

Note that MOVES applies speciation to all onroad sources and processes, except for brake and
tire wear particulate matter emissions as discussed in Section 5.4. For nonroad, speciation is
handled differently. Toxics are estimated in the nonroad portion of the model, similar to what is
done for highway sources. However, detailed TOG speciation and speciation of PM2.5 are
conducted as part of post-processing of MOVES nonroad results.3

1.1 Measuring Hydrocarbons and Particulate Matter

In addition to estimating emissions of pollutants that are discrete chemical compounds, such as
carbon monoxide (CO) and sulfur dioxide (SO2), MOVES produces emission rates for
aggregates of individual chemical compounds, including total hydrocarbons (THC), volatile
organic compounds (VOC), total organic gases (TOG) and particulate matter (PM). These
pollutants are operationally defined, meaning that their definition depends on the measurement
technique(s) selected. For example, THC is defined as the hydrocarbons measured by a flame
ionization detector (FID). TOG is defined to include all organic gases.4 Because THC
measurements do not respond fully to carbon-oxygen bonds in oxygenated compounds, such as
aldehydes, alcohols, and ketones, these oxygenates need to be measured separately by gas and
liquid chromatography and added to the THC measurements to calculate TOG. Alternatively,
TOG measurements can be made solely with gas and liquid chromatography methods.21

Similarly, particulate matter is operationally defined as the measured mass collected on a filter
using EPA-defined sampling filter media, conditions, and practices.5'6 PM2.5 refers to particulate
matter emissions collected downstream of a cyclone that removes the particles with aerodynamic
diameter greater than 2.5 microns, while PM10 refers to particulate matter emissions with
aerodynamic diameter less than 10 microns.

a Thus, differences in measurement methods need to be considered when comparing THC to TOG emission
measurements.

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1.2 MOVES Speciation Approach

MOVES produces emission estimates for a subset of species that contribute to TOG and PM2.5.
These include important organic gaseous toxics (e.g., formaldehyde and benzene), and toxic
particle-phase elements (e.g., nickel and manganese). These also include semi-volatile organic
compounds, such as 15 individual polycyclic aromatic hydrocarbons (e.g., benzo(^,/?/,/)perylene)
that can exist in both the gaseous and particle phases under different measurement conditions.
Individual toxic emission rates are detailed in the toxics report7, but are peripherally discussed in
this report in the context of their use in deriving speciated TOG and PM emissions.

MOVES applies TOG and PM2.5 speciation to produce the species need for air quality modeling.
Generally, this speciation is done through a combination of estimation, subtraction of known
pollutants and allocation of the remaining emissions based on profiles from EPA's SPECIATE
database.8 Air quality models such as CMAQb need MOVES emission rates aggregated by
source classification code (SCC), which is defined in MOVES by emission process, source type,
fuel type and road type. However, as discussed in Section 4.2, the speciation profiles used for
allocation are defined at a finer level of detail than SCC. By incorporating the speciation process
within MOVES, MOVES can accurately calculate the speciated components of TOG and PM2.5
at the appropriate level of detail of the speciation profiles and then aggregate the emissions to
SCC.

1.3 Data Uncertainty and Limitations

Speciated emissions are collected in laboratory conditions using laboratory bench instruments
that can analyze bag measurements of volatile organic compounds and can properly handle
particulate matter filters for chemical analysis. Speciated measurements also are based on time-
aggregated bag or filter measurements from engine or chassis dynamometer tests rather than
time-resolved emission measurements (e.g. second-by-second measurements) that are used to
inform emission rates in MOVES from vehicles operating in different operating modes.

As such, the number of vehicles and the range of vehicle operation conditions from which we
have speciated data are more limited than the vehicle samples and operating conditions used to
estimate emission rates of total hydrocarbon and PM2.5 emission rates as documented in the
emission rate reports.1'2 Thus, the speciation results may be heavily impacted by test-to-test and
vehicle-to-vehicle variability, For example, THC emissions for light-duty gasoline vehicle are
based on hundreds or thousands of vehicles for each model year1, and heavy-duty diesel vehicles
measurements are based on hundreds of vehicles operating in real-world operation.2 On the other
hand, the speciation profile for model year 2001 and later light-duty gasoline vehicles is based on
only three vehicles as discussed in Section 3.3C, and the speciation profiles applied to model year
2010 and later diesel vehicles are based on three heavy-duty engines as discussed in Section 3.2.

In addition, available vehicle exhaust speciated measurements tend to be sampled from relatively
new engines or vehicles. However, speciation likely changes as vehicles age. For example, new

b Defined in Section 2.5

0 As discussed in the Toxics report, many of the key toxics are estimated from the fifteen vehicles tested in the Phase
3 of the Epact program.

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vehicles with fully active catalysts likely have higher CH4/THC ratios than older vehicles due to
the relative effectiveness of newer aftertreatment systems in oxidizing the NMHC species as
comparted to more difficult to oxidize methane.9'10 However, we do not have sufficient data to
model age-varying speciation ratios (CH4/THC, NMOG/NMHC and VOC/NMHC) or speciation
profiles, nor have we designed MOVES to handle varying speciation as vehicle age. Similarly,
speciation testing is often conducted using regulatory cycles, while real-world speciation may
differ. For now, our best approach is to select speciation data that are deemed the most
representative of the vehicle fleet by emission process, fuel type, regulatory class, and model
year.

Additional uncertainty comes from applying speciation profiles to technologies and processes
that differ from what was tested. For example, we apply the diesel speciation profile developed
from heavy heavy-duty engines to light-duty diesel emissions. Also, with the exception of the
light-duty gasoline PM2.5 speciation discussed in Appendix E, the speciation profiles are
developed from vehicles that are properly functioning and with low accumulated mileage, but we
apply them to fleet-average emission rates which include higher emissions due to aged and
deteriorated engine and emission control systems. Similarly, the EPAct light-duty gasoline
speciation profile is based on combined emission of start and running emissions. As a result,
there is no resolution between start and running emissions in the speciation profile.

In addition to small sample sizes and limited testing scope, measurement deficiencies contribute
to the uncertainty of MOVES speciated emission emissions. For example, as discussed in
Section 3.2, the 2010-and-later model year heavy-duty diesel total organic gas speciation profile
was corrected to remove three erroneous measurements artifacts. Speciation profiles also may
not measure pollutants because the concentrations were below the detection limits of the
measurement. As discussed in the toxics report7, many individual species are emitted below
detection limits during hot-running operation.

We have attempted to include qualitative discussions of the sources of uncertainty and
application of the speciation data for each of the relevant sections of the report.

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1.4 Updates to I iS3

This document describes all the data and calculations used by MOVES3 in speciation
calculations, including those that are unchanged from previous versions of MOVES. We have
highlighted the updates made in MOVES3 from MOVES2014b.n These changes include:
updates to total organic gases calculations (Section 3), and incorporation of a new TOG
speciation profile for diesel exhaust for 2010 and later model years (Section 3.2 and Section
4.2). These updates were peer-reviewed in September 2017. Updates to the report in response to
the peer-review are summarized in the peer-review materials on the EPA's science inventory
webpage.12

Subsequent to the peer-review, we conducted a further analysis of the speciation of diesel
exhaust for 2010-and- later model years. We adjusted the methane fraction (Section 3.6), and
made revisions to the diesel 2010-TOG speciation profile (Appendix D). We also updated the
speciation profile assigned to diesel refueling emissions as discussed in Section 3.2 and made
clarifications to the text of the report.

1.5 Updates to 3S3.0.4

Starting with version 3.0.4, MOVES3 offers the capability of speciating onroad emissions as a
post-processing step with the objective of facilitating the use of state-of-the-science speciation
profiles and chemical mechanisms without waiting for new public versions of MOVES that
incorporate the latest speciation data. This new feature is geared in particular towards air quality
modelers that wish to translate onroad emissions into chemical mechanism species. The post-
processing of onroad emissions in MOVES3.0.4 is done via post-processing script incorporated
in the Tools menu of the MOVES graphical user interface (GUI).

In terms of the speciation process in MOVES3, the model continues to provide speciated TOG
and PM pollutants and users can continue selecting these pollutants when building the RunSpec.
The only GUI changes that the user will notice is the addition of two new pollutants (Total
Organic Matter and Residual PM) and the removal of chemical mechanisms options in favor of a
single option to generate Residual TOG (NONHAPTOG). These new pollutants must be selected
if the user desires to perform speciation of onroad emissions as a post-processing step. We note
that the addition of new pollutants did not require changes to model calculations as MOVES
already calculated these quantities implicitly during runtime; the effective changes in this version
simply allow the selection of these pollutants as part of the model output. For further details on
speciation outside of MOVES, see Appendix G.

2 Speciation Glossary

In the area of "speciation," many terms have multiple meanings. The definitions below provide
the terms as they are used in the context of speciation in MOVES. We have grouped the terms
into General, Organic Gas, Chemical Mechanism, Particulate Matter, and Databases, Models and
Tools Terms.

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2.1 General Terms

•	Species: Distinct chemical compounds, ions, groups of compounds, or other chemical
entities. In this report, we distinguish "real species," "aggregate species," "CM species,"
and "intermediate species," as explained below

•	Aggregate species: Groups of chemical compounds. These are often defined
operationally or may be defined for modeling purposes. For example, THC, TOG and
VOC are aggregate gaseous species. NonEC is an aggregate particulate matter species.

•	Real species: Species in the normal chemical sense—a pure chemical substance. The
word "real" helps distinguish these species from chemical mechanism species or
aggregated species.

•	Real speciation profile: ideally, a complete listing of the real species and their quantities
of TOG or Particulate Matter. In practice, these profiles are incomplete; a certain fraction
of the mass is unresolved. Such a profile is produced by laboratory analysis of emissions.
This is not a CM speciation profile and is independent of chemical mechanism. Such a
profile does, however, depend on process, fuel, and technology, since the mix of real
species in TOG or PM is different for different emission processes (e.g. evaporative and
exhaust), for different fuels, and for different technologies. The SPECIATE database is
the EPA repository for these profiles.8

2.2 Organic Gas Terins

•	Hydrocarbon (HC): compound containing only carbon and hydrogen13. Because we
cannot precisely measure emissions from combustion emissions using this strict
definition, we often refer to hydrocarbon (HC) emissions synonymously with total
hydrocarbon (THC) emissions which is a defined by the measurement method. For
example, the National Emissions Inventory reports MOVES total hydrocarbon emissions
(THC) as hydrocarbon (HC) emissions. At other times, we also use the term hydrocarbon
more generally to include multiple measurements and definitions of organic gases that are
primarily composed of hydrocarbons, including: non-methane hydrocarbons (NMHC),
non-methane organic gases (NMOG), and total organic gases (TOG). When discussing
HC emission in the MOVES technical reports, we typically only refer to gaseous HC
emissions, and not HC emissions in the particulate phase, which is measured as organic
carbon (OC) and non-carbon organic matter (NCOM).

•	Total Hydrocarbons (THC): "THC is the measured hydrocarbon emissions using a Flame
Ionization Detector (FID) calibrated with propane. The FID is assumed to respond to all
hydrocarbons identically as it responds to propane in determining the concentration of
carbon atoms in a gas sample. Most hydrocarbons respond nearly identically as propane
with notable exceptions being oxygenated hydrocarbons such as alcohols and aldehydes
commonly found in engine exhaust."4 In MOVES, THC is often used synonymously with
hydrocarbon (HC) emissions.

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• Non-Methane Hydrocarbons (NMHC): NMHC = THC - CH4 (methane).

•	Non-Methane Organic Gases (NMOG): NMOG = TOG - CH4 (methane).

•	Total Organic Gases (TOG): Total hydrocarbon (THC) emissions plus oxygenated
hydrocarbons such as alcohols and aldehydes.4

•	Volatile Organic Compounds (VOC): EPA defines VOC as any compound of carbon
(excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or
carbonates, and ammonium carbonate) which participates in atmospheric photochemical
reactions, except those designated by EPA as having negligible photochemical
reactivity.14 In mobile source testing, typically only a few compounds with negligible
photochemical reactivity are measured in significant quantities. For use in MOVES in
defining emission rates and application of speciation profiles, VOC is defined as TOG
minus methane, ethane, and acetone (Equation 9).

2.3 Chemical Mechanism Terms

For MOVES3.0.4 we have removed the option of generating chemical mechanism
species. However, this document will maintain the technical documentation for users that
might still be using earlier versions of MOVES3.

Chemical mechanism (CM): In air-quality models, chemical mechanisms are simplified
representations of the full array of atmospheric chemical reactions. They have been
developed by air-quality modelers to speed up the atmospheric chemistry calculations in
their models. An aspect of these chemical mechanisms is the use of a relatively small set
of "chemical mechanism species," (CM species) into which all the real species can be
mapped, and which serve to model the atmospheric reactions of importance. For the
purposes of MOVES, a chemical mechanism may be thought of as a set of CM species
and the mapping between regular MOVES output species and the CM species. Since the
mapping is table-driven, MOVES has the structure in place to generate onroad vehicle
CM species for any chemical mechanism. MOVES3 produces emissions output for CM
species for the four chemical mechanisms listed in Table 2-1. CB6AE7 is newly added to
MOVES3, the other chemical mechanisms are unchanged from MOVES2014b.

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Table 2-1 Chemical Mechanisms in MOVES3

Chemical
Mechanism

Description

MOVES Status

CB05

Carbon Bond developed in 200515

Unchanged from
MOVES2014b

CB6CMAQ

Carbon Bond Version 616 updated to
model naphthalene as a separate species
from XLK17

Unchanged from
MOVES2014b

SAPRC07T

SAPRC07 updated with additional
toxic species18

Unchanged from
MOVES2014b

CB6AE7

CB6CMAQ updated for the AE7
Aerosol Module in CMAQ19; the
largest impact for the MOVES
speciation profiles is the addition of a
new chemical mechanism species
IVOCd

New in MOVES3

•	Chemical mechanism species (CM species): the species used by chemical mechanisms.
CM species include both artificial constructs (sometimes referred to as "lumped species")
and real species. CM species are unique to particular chemical mechanisms (e.g., CB05,
SAPRC07). All integrated species are mapped to CM species. For each chemical
mechanism, the associated group of CM species can be referred to by the name of the
mechanism, for example, CB05 species.

•	Chemical mechanism speciation profile: the mapping of a real species (e.g., hexane) or an
aggregate species (e.g., TOG) into CM species. The mapping of real species into CM
species has been created by the developers of chemical mechanisms for air quality
modeling. The mapping of real species is independent of emission process and fuel. The
mapping of aggregate species (e.g., residual TOG) represents the sum of the mappings of
the individual real species from the real speciation profiles. The mapping of aggregate
species depends on process and fuel, and is conducted using the Speciate Tool (Section
2.5)

•	Integrated species: Real species for which MOVES produces emissions that are
subtracted from TOG emissions to calculate "Residual TOG." The integrated species are
individually speciated into CM species. MOVES3 integrates the 15 species shown in
Table 2-2. The integrated species include all the organic gases estimated by MOVES,
including naphthalene gas, but excepting all other polycyclic aromatic hydrocarbons

d In addition to adding IVOC to each MOVES profile, CB6AE6 added APIN to profile 8774 (Pre-2007 MY diesel
exhaust)

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Table 2-2 Integrated MOVES Pollutants

pollutantID

Pollutant Name

5

Methane (CH4)

20

Benzene

21

Ethanol

24

1,3-Butadiene

25

Formaldehyde

26

Acetaldehyde

27

Acrolein

40

2,2,4-Trimethylpentane

41

Ethyl Benzene

42

Hexane

43

Propionaldehyde

44

Styrene

45

Toluene

46

Xylene

185

Naphthalene gas

Residual TOGorNonHAPTOG: TOG that remains after subtracting integrated species.
Residual TOG is speciated into CM species using a CM speciation profile constructed
from the real speciation profile from which the integrated species have been removed.
MOVES reports emission rates of residual TOG as NonHAPTOG with pollutantID 88.

Particulate Matter Terms

Primary Exhaust PM2.5 - Total (PM2.5). Primary particulate matter emissions from vehicle
exhaust collected using a filter, measured downstream of a cyclone that removes particles
with mean aerodynamic diameters greater than 2.5 microns. PM2.5 = EC + nonECPM.

Primary Exhaust PM10 - Total (PM2.5). Primary particulate matter emissions from vehicle
exhaust collected using a filter, measured downstream of a cyclone that removes particles
with mean aerodynamic diameters greater than 10 microns.

Intermediate PM2.5 species: Groups of PM2.5 species used to simplify calculations,
improve computation time, and to reduce the size of the emission rate tables. They
include the aggregate species: "non-elemental carbon particulate matter" (NonECPM)
and "non-elemental carbon non-sulfate particulate matter" (NonECnonS04PM),
elemental carbon (EC), sulfate (SO4) and particulate water (H2O). They are used to
compute total PM2.5 emissions and speciated PM2.5 emissions. The EC, nonECPM, SO4,
and H2O species are reported as MOVES outputs.

Elemental Carbon (EC): "A descriptive term for carbonaceous particles based on
chemical composition rather than light-absorbing characteristics. This term is often used
as a synonym for black carbon."20 Elemental carbon is measured through thermal optical
techniques as particle-phase carbon that does not volatize at high temperatures in an

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oxygen-free environment.21 In tailpipe exhaust, EC is one measure of carbonaceous soot
formed from fuel pyrolysis occurring during combustion.22

Organic Carbon (OC): "The mix of compounds containing carbon bound with other
elements; e.g., hydrogen and oxygen. Organic carbon may be a product of incomplete
combustion or formed through the oxidation of VOCs in the atmosphere." Organic
carbon is measured using thermal-optical methods as the particle-phase carbon collected
on a filter that volatizes at high temperatures in an oxygen-free environment.

Organic Matter (OM): Particle-phase organic matter. The mass of the organic material in
particulate: OM = organic carbon (OC) + non-carbon organic matter (NCOM).

Non-Carbon Organic Matter (NCOM): the mass of the oxygen, hydrogen, nitrogen and
other elements present in particle-phase organic matter. OC and NCOM are modeled
separately in air quality models in order to model the degree of oxidation of organic
matter, which depends on the emission source and the chemical transformation in the
atmosphere.23

Non-Elemental Carbon Particulate Matter (nonECPM): The PM2.5 that is not elemental
carbon. This is typically calculated as the difference between PM2.5 mass filter-based
measurements and elemental carbon measurements made using thermal optical
measurements, or surrogate elemental carbon measurements such as photoacoustic
sensors. nonECPM = nonECnonS04PM + SO4 + H2O.

Non-Elemental Carbon, Non-Sulfate Particulate Matter (nonECnonS04PM): MOVES
intermediate species used to represent the PM2.5 mass other than elemental carbon,
sulfate, and associated water. NonECnonS04PM includes organic matter, elements, and
ions. NonECnonS04PM is adjusted for fuel and temperature effects prior to speciation
due to limited data on temperature and fuel effects on individual PM2.5 species in the
exhaust, and to improve computational time.

Databases, Models and Tools

CMAQ: The Community Multiscale Air Quality system (CMAQ) is a photochemical and
transport air quality model. CMAQ is an open source development project sponsored by
the US EPA Atmospheric Science Modeling Division
(https://www.cmascenter.org/cmaq/).

SPECIATE: EPA's repository of organic gas and particulate matter (PM) speciation
profiles from air pollution sources.8 The SPECIATE database contains a record of each
profile including its referenced source, testing methods, a subjective rating of the quality
of the data, and other detailed data that allow researchers to decide which profile is most
suitable for model input (https://www.epa.gov/air-emissions-modeling/speciate)

Speciation Tool: Estimates "split-factors" to translate inventory pollutants such as VOC
to chemical mechanisms species. The Speciation Tool creates the mapping of

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NONHAPTOG emissions from MOVES to the chemical mechanism species, using the
relevant speciation profiles from SPECIATE, re-normalized without the integrated
species.24

• SMOKE: Sparse Matrix Operator Kernel Emissions is a computer program used to
provide model-ready inputs into CMAQ. SMOKE produces gridded, speciated, and
hourly emissions input for use in CMAQ and other air-quality models. For onroad
emissions, MOVES provides the emissions already speciated into the chemical
mechanism species, (https://www.cmascenter.org/smoke/)

• SMOKE-MOVES: "A set of methodologies and software tools to help use output from
MOVES as inputs to SMOKE."25 MOVES is run in rates-mode to produce emission rates
for different meteorological conditions, vehicle speeds (for running emissions), emission
processes, road types, fuel types, and source types at different temporal and geographical
domains to account for local differences in emissions. SMOKE-MOVES combines
MOVES emission rates with respective vehicle activity to estimate emissions that are
input into SMOKE.

3 Organic Gas Aggregations and Ratios

MOVES provides estimates of organic gas emissions in a number of different aggregations.
Table 3-1 shows the composition of various organic gas aggregate classes in MOVES. As the
table shows, the organic gas aggregations differ based on the presence or absence of methane,
ethane, alcohols, and aldehydes. Definitions of these species are also included in the glossary. In
MOVES, total hydrocarbons (THC) is defined as hydrocarbons measured with a Flame
Ionization Detector and includes methane and ethane. MOVES calculates emissions of total
organic gases (TOG), non-methane organic gases (NMOG) and volatile organic compounds
(VOC) using information regarding the organic gas speciation of emissions.

Table 3-1 Relationships among C

rganic Gas Aggregations in MOVES

pollutantID

pollutantName

Acronym

FID-
HC

Methane

Ethane

Acetone

Alcohols

Aldehydes

1

Total

Hydrocarbons

THC

Yes

Yes

Yes

No

No

No

79

Non-Methane
Hydrocarbons

NMHC

Yes

No

Yes

No

No

No

87

Volatile
Organic
Compounds

VOC

Yes

No

No

No

Yes

Yes

86

Total Organic
Gases

TOG

Yes

Yes

Yes

Yes

Yes

Yes

80

Non-Methane
Organic Gases

NMOG

Yes

No

Yes

Yes

Yes

Yes

In MOVES, THC emission rates are the base organic gas emission rates as documented in the
MOVES light-duty exhaust1, heavy-duty exhaust2, and evaporative26 emission rate report from
which each of the other organic emissions are estimated using the calculations documented in the
following section. Gas-phase organic air toxics are calculated from VOC emissions as discussed
in the MOVES air toxics report.7

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3.1 Total Organic Gaseous Calculations

Exhaust regulations for organic gases are often expressed in terms of non-methane hydrocarbons
(NMHC). MOVES calculates both methane and NMHC from the THC emissions using methane-
to-total hydrocarbon ratios (recorded in the CH4THCRatio field of the MOVES
MethaneTHCRatio table) as shown in Equation 1 and Equation 2.

CH4
THC

^4 — THC x ———	Equation 1

( ch4\

NMHC = THC x 1	-

V THCJ

Equation 2

Following the calculation of NMHC, the MOVES algorithm calculates NMOG, VOC and TOG
as shown in Equation 3 through Equation 5.

NMOG

NMOG = NMHC X 		Equation 3

NMHC

VOC

VOC = NMHC X 		Equation 4

NMHC

TOG = NMOG + CH4	Equation 5

In previous versions of MOVES, the data used to calculate CHVTHC was not consistent with the
data used to calculate ratios of organic aggregates.27 In MOVES3, for many of the vehicles and
emission processes, we determined CHVTHC ratios from the SPECIATE profiles that are
currently used in the model. The CHVTHC ratios stored in the MethaneTHCRatio table in
MOVES3 vary by emission process, regulatory class, fuel subtype, and model year. The
methodology to calculate CH4/THC ratios from SPECIATE data is presented in Section 3.2 and
the calculated ratios for each profile are presented in Table 3-2.

Within MOVES, the NMOG/NMHC and VOC/NMHC ratios shown in Equation 3 and Equation
4 are called "speciation constants." In MOVES3, speciation constants were calculated for each
SPECIATE profile used in MOVES in order to be consistent with the updated CH4/THC ratios
included in this release and with the TOG calculation chain.6 These ratios continue to be stored
in the HCSpeciation table which now also includes the key fields regulatory class and fuel
subtype . The new speciation constant parameters are also presented in Table 3-2.

The calculation of NMOG and VOC in previous MOVES versions included additional terms that
represented adjustments to correct for the oxygenated volume in the fuel (oxySpeciation,
volToWtPercentOxy and oxyVolume parameters). In this latest release, different speciation

e Previous to MOVES3, the speciation constant parameters were calculated using either of two methods. The first
method was based on the relative carbon fraction of each species and was first developed for MOBILE4.1. The
second method was based on Equation 1066.635-1 of the CFR. For further details, the reader is directed to the
MOVES2014 speciation report.11

13


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constants are provided for fuel subtypes for different fractions of ethanol in gasoline (EO, E5, E8,
E10, E15, E85), and the previous adjustments made to correct for oxygenated volume in the fuel
were removed, simplifying the equations as shown in Equation 3 and Equation 4. The new
methodology removes the capability of MOVES to adjust NMOG and VOC according to other
oxygenated compounds such as methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE)
and tert-amyl methyl ether (TAME). However, fuel market projections indicate that additives
other than ethanol are unlikely to return to the market, supporting the removal of these
parameters from the model.

We use SPECIATE profiles to derive CH/THC, NMOG/NMHC and VOC/NMHC for all
emissions processes and vehicle classes except exhaust emissions from 2001-and-later light-duty
gasoline vehicles, exhaust emissions from flex-fuel vehicles using E85 fuel, CNG exhaust, and
the CHVTHC fractions for 2010-and-later heavy-duty diesel exhaust, as discussed in the
following subsections.

The speciation profiles in MOVES3 were obtained from the SPECIATE database.8 Each profile
has a detailed list of measured compounds and reports their weight as percentage of TOG. The
calculation of NMOG for each profile was done by simply subtracting CH4 from TOG as shown
in Equation 6.

NMOG = TOG — CH^	Equation 6

The calculation of NMHC is based on Equation 1066.635-1 in the Code of Federal Regulations.
The equation provided in the CFR was rearranged as shown in Equation 7 to solve for NMHC
using NMOG calculated in the previous step as an input.

N	N

ZWlOHCi	\ 1

— X RF0HCi	- > m0CHi	Equation 7

On uri

i=i p0HCi	i=1

Where:

itlnmog = mass of NMOG in the exhaust.
itlnhmc = mass of NMHC in the exhaust.

Pnmhc = 576.816 g/m3 which is the effective Cl-equivalent density of NMHC as specified in
§1066.1005(f).

moHCi = mass of oxygenated species i in the exhaust.

poHCi = Cl-equivalent density of oxygenated species i as specified in 40 CFR 1066.605-1. For
methanol, the density is 1332.02 g/m3; for ethanol, the density is 957.559 g/m3; for acetaldehyde,

14


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the density is 915.658 g/m3; for formaldehyde, the density is 1248.21 g/m3; and for propanol, the
density is 832.74 g/m3.

RFoHCi[THc-FiD] = response factor of a THC-FID to oxygenated species i relative to propane on a
Cl-equivalent basis as determined in 40 CFR 1065.845. The RF for acetaldehyde is 0.5; for
formaldehyde is 0; for ethanol is 0.75; for methanol is 0.63 and for propanol is 0.85.

After NMHC and NMOG are calculated, the calculation of THC is done as shown in Equation 8.
Once THC is calculated, the CH4/THC can then be determined.

NMHC

THC = NMOG X 	 + CH4	Equations

NMOG 4

Finally, VOC is calculated following the definition used in MOVES, where methane (CH4),
ethane (C2H2) and acetone (C3H6O) are subtracted from TOG emissions as shown in Equation 9.

VOC = TOG — CH4 — C2H2 ~ C3H60	Equation 9

Table 3-2 presents the ratios determined for each SPECIATE composite profile. Information on
the data behind each SPECIATE profile is provided in more detail in Appendix A.

Table 3-2 notes the assignment of the derived speciation ratios to different model years,
processes, fuel subtypes, and regulatory classes. For gasoline exhaust, we use profiles 8750a and
8751a to represent gasoline exhaust for 2000 and earlier light-duty vehicles. For other gasoline
regulatory classes (motorcycles and heavy-duty vehicles), the same profiles were used for all
model years.

15


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Table 3-2 Updated CH4/THC and Speciation Constant Parameters from SPECIATE Profiles for MOVES3

Profile
Number

Profile
Description

Emission Process

Fuel
Subtype

Vehicles

CH4/THC
Ratio

NMOG/NMHC
Ratio

VOC/NMH
C Ratio

95120f

Liquid diesel

Evaporative Permeation

Diesel,
biodiesel

All diesel

0

1

1

8750a

Pre-Tier 2 E0
exhaust

Running, starts exhaust and
crankcase

Conventional
Gasoline

Pre-2001 LD gasoline
All MC and non-LD
gasoline

0.142

1.024

0.996

8751a

Pre-Tier 2
E10 exhaust

Running, starts exhaust and
crankcase

RFG, E10, E8,
E5

Pre-2001 LD gasoline
All MC and non-LD
gasoline

0.146

1.037

1.008

8753

E0 Evap

Evaporative (vapors, leaks,
refueling spillage)

Conventional
Gasoline

All gasoline

0

1

1

8754

E10 Evap

Evaporative (vapors, leaks,
refueling spillage)

E10, E8, E5

All gasoline

0

1.071

1.071

8766

E0 Evap
perm

Evaporative Permeation

Conventional
Gasoline

All gasoline

0

1

1

8769

E10 Evap
perm

Evaporative Permeation

E10, E8, E5

All gasoline

0

1.129

1.129

8770

El5 Evap
perm

Evaporative Permeation

E15

All gasoline

0

1.175

1.175

8774

Pre-2007 MY
HDD exhaust

Running, starts, extended
idle exhaust and crankcase

Diesel,
Biodiesel

Pre-2007 diesel

0

1.145

1.124

APU

Pre-2024 APU

Running, starts exhaust and
crankcase

Pre-2007 LD diesel

8775

2007-2009
HDD exhaust

Running, starts exhaust and
crankcase

Diesel,
Biodiesel

2007+ LD diesel

0.589

1.343

1.285

APU

2024+ APU

Running, starts, extended
idle exhaust and crankcase

2007+ HD diesel

95335a

2010+HDD
exhaust

Running, starts exhaust and
crankcase

Diesel,
Biodiesel

2010+ LD diesel

0, Not
Used®

1.085

0.965

Running, starts, extended
idle exhaust and crankcase

2010+HD diesel

16


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Table 3-2 (continued)

Profile
Number

Profile
Description

Emission Process

Fuel Subtype

vehicles

CH4/THC
Ratio

NMOG/NMHC
Ratio

VOC/NMHC
Ratio

8869

E0 Headspace

Refueling displacement
vapor loss

Conventional
Gasoline

All gasoline

0

1

1

8870

E10
Headspace

Refueling displacement
vapor loss

E10, E8, E5

All gasoline

0

1.037

1.037

8871

E15
Headspace

Refueling displacement
vapor loss

E15

All gasoline

0

1.175

1.175

8872

E15 Evap

Evaporative (vapors,
leaks, refueling spillage)

E15

All gasoline

0

1.118

1.118





Evaporative permeation



All gasoline
vehicles running
on high ethanol
blends







8934

E85 Evap



E85, E70

0

1.501

1.501

Evaporative (vapors,
leaks), refueling
displacement and
spillage losses

All gasoline
vehicles running
on high ethanol
blends

f Profile 95120 is based on NMOG and we assume that there is no methane in liquid diesel fuel. In addition, no oxygenated species are measured in the profile
(formaldehyde, acetaldehyde, or ethanol), nor any non-volatile organic compounds (ethane, and acetone), thus the CH4/THC, NMOG/NMHC and VOC/NMHC values
are 0, 1, and 1, respectively.

g MOVES uses a 0.38 CHi/THC ratio based on a literature review discussed in Section 3.6

17


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For vapor venting, fuel leaks, and fuel spillage loss emissions from EO and E10, the speciation
constants are based on SPECIATE profiles from the Auto/Oil Air Quality Improvement
Research Program (profiles 8753 and 8754).h The speciation profiles for refueling displacement
vapor loss (profiles 8869, 8870, and 8871) for EO, E10, and E15 fuels were based on
measurements conducted by EPA.28 ) Profile 8872 used for vapor venting, leaks, and refueling
spillage for El 5 fuels is based on SPECIATE profile 8754 (a composite profile developed from
the Auto/Oil Air Quality Improvement Research Program) and data collected in the EPAct/V2/E-
89 program on E10 and El 5 fuels. For evaporative permeation emissions, MOVES uses
speciation constants developed from three ethanol blend levels (EO, E10, El 5) from the CRC E-
77 program (profiles 8766, 8769, 8770).29 In the CRC E-77 programs the test procedure
specifically separated the evaporative emissions mechanisms, therefore there was an apparent
ethanol effect on permeation but not a clear RVP effect.

The speciation constants for all evaporative emission processes from E85-fueled vehicles are
calculated from SPECIATE profile 8934 developed from the CRC E-80 report.30 The speciation
profile used for diesel refueling emissions, (which only include liquid diesel spillage loss in
MOVES26) was updated in MOVES3 to be based on a liquid diesel SPECIATE profile 95120f

For pre-2007 diesel emissions (both light-duty and heavy-duty), MOVES uses speciation profile
8774, which is based on a review of speciated diesel emissions on pre-2007 model year engine
technologies. MOVES uses the pre-2007 NMOG/NMHC value for diesel auxiliary power units
(APUs; processID 91) for all model years prior to 2024 because they are not subject to the same
control as on-highway diesel engines. For 2007 to 2009 model year light-duty and heavy-duty
diesel vehicles, MOVES uses speciation profile (8775) based on data from Phase 1 of the
Advanced Collaborative Emissions Study (ACES)31, which includes diesel engines equipped
with diesel particulate filter, and is the technology used to meet the heavy-duty 2007 diesel
standards.32 MOVES also applies the ACES Phase 1 speciation profile to 2024 and later
auxiliary power units because it is anticipated they would use diesel particulate filters to meet the
APU PM standards promulgated as part of the Phase 2 medium and heavy-duty greenhouse gas
regulation.33

In MOVES3 we incorporated a new speciation profile (95335a) to 2010 and later diesel vehicles
based the ACES Phase 2 test program.34 This program tested three heavy heavy-duty 2011 model
year engines equipped with diesel particulate filters and selective catalytic reduction systems that
are representative of current diesel technologies used to achieve the 2010 heavy-duty emission
standards. The engines and aftertreatments were tested new, and the emissions of NMHC were
over 99% below the 2010 emission standards. Furthermore, emissions of the majority of
individual organic compounds were below the levels measured from the ACES Phase 1 program,
including methane emissions, which were below the detection limit in ACES Phase 2, but which
contributed over 50% of the TOG emissions in the ACES Phase 1 program.35

h The CRC E-77 program29 observed a significant effect for both RVP and ethanol in the diurnal emissions data
largely due to the vapor venting breakthrough emissions which were vented outside of the SHED using special
procedures as defined in the individual study reports. As noted in the 2017 peer-review12, there is likely an
accompanying effect of RVP on vapor venting emissions (from both vapor venting and fuel displacement venting),
and both RVP and ethanol content should be considered as factors when developing updated vapor venting
speciation profiles in future test programs.

18


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Due to the low level of TOG emissions, the relative error of the speciation fractions of TOG is
high in the ACES Phase 2 program. We have developed methane fractions from a literature
review of emission studies on MY 2010-and-later heavy-duty diesel engines as discussed in
Section 3.6. In addition, we removed alcohol species from the original profile (95335) that are
likely measurement artifacts as documented in Appendix D. In addition, many of the
measurements were near detection limits, and individual species measurements showed
inconsistencies when compared to the emission trends of groups of gaseous hydrocarbons from
ACES Phase 1 (see Appendix D). Given the limited number of tests and low emission levels
measured, it is not possible to determine whether these inconsistencies represent real differences,
test to test variability, or measurement uncertainties.

Despite the uncertainties regarding the Phase 2 speciation profile, we have incorporated it into
MOVES (including the NMOG/NMHC and VOV/NMHC ratios) because it is the most
comprehensive chemical sampling program available for exhaust from MY 2010 and later
heavy-duty diesel technology. We recommend further speciated measurements of modern heavy-
duty diesel engine exhaust, including vehicles with aged and deteriorated aftertreatment systems
that likely emit higher concentrations of organic gas and particulate matter emissions.

3.3 Ratios for 2001-and-Later I mhi-l Xity Gasoline Exhaust

We determined ratios of CHVTHC, NMOG/NMHC and VOC/NMHC for exhaust emissions
from Tier 2 (model year 2001-and-later) vehicles running on gasoline-ethanol blends (0 percent -
15 percent ethanol) using bag-specific data from the EPAct Phase 1 program36 In contrast, the
SPECIATE profiles (8756, 8757, and 8758) developed from the EPACT/V2/E-89 program
combined the start and running emissions (Table 4-1). As presented in this section, the speciation
constants varied significantly by bag, and we determined that it was preferable to use the
resolved speciation constants based on the bag data from the same data set used to derive the
SPECIATE profiles.

EPAct Phase 1 was designed to collect data from light-duty vehicles running on low-level
ethanol blends. Three vehicles (MY 2008) were tested to generate data for the three bags
required to create speciated composite profiles. The tests involved 9 runs using fuel with 0
percent ethanol, 6 runs using fuel with 10 percent ethanol and 7 runs using fuel with 15 percent
ethanol. Further information on vehicles, fuels and testing is detailed in the EPAct Phase I
report.36 The data corresponding to the runs used for this analysis is listed in Appendix A.

For ethanol levels between 0-15 percent, the average CH4 and THC emissions were calculated
and subsequently a ratio of means was determined (i.e., CFUavg/THCavg). To verify if there was
a statistically significant trend with ethanol composition, a linear regression between these ratios
and ethanol composition was performed (Figure 3-1). The regression analysis indicated that the
slope was statistically significant (significance level < 0.05) for start emissions but not for
running emissions. Therefore, CH4/THC for starts are specific for each ethanol composition, but
for running an average CH4/THC across all low-level ethanol blends is used. The linear fit for
starts was used to interpolate CH/THC values for E5 and E8 fuel compositions used in
MOVES3 for which no SPECIATE profiles are available.

19


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¦©• running ~starts

Figure 3-1 Relationship between CH-t/THC Ratios and Ethanol Composition for Tier 2

Vehicles using Low-Level Ethanol Blends

The speciated data used to determine NMOG/NMHC and VOC/NMHC for Tier 2 vehicles
corresponds to the same EPAct Phase 1 runs referred to in the determination of CH4/THC ratios
for these vehicles. Data from Bag 3 was subtracted from Bag 1 to determine cold start emissions.
NMOG, VOC and NMHC were calculated for each test following the methodology described in
Section 3.1. The reported speciation constant parameters were determined as a ratio of means
(i.e., NMOGavg/NMHCavg or VOCavg/NMHCavg) for each ethanol composition. The linear
relationship between speciation constant parameters and ethanol composition was statistically
significant for starts (a < 0.05), but not for running emissions (Figure 3-2). Therefore, like the
CH4/THC ratios, we report speciation constant parameters for start emissions (Table 3-3) at each
ethanol composition analyzed, whereas for running emissions (Table 3-4) we report an average
across the ethanol compositions. This approach is supported by a previous study performed by
the Oak Ridge National Laboratory (ORNL)37 which focused on the estimation of NMOG
emissions from 68 vehicles using mid-level ethanol blends. The ORNL study found that given
very low emissions normally measured in bag 2 and the level of scatter associated with them, the
recommended approach was to use a constant NMOG/NMHC ratio across ethanol compositions.

We apply the resulting EPAct Phase 1 speciation constant values for all light-duty gasoline
vehicles in model year 2001 and later. As we note in the discussion of the light-duty PM2.5
speciation profile (Appendix E.l), modern gasoline direct injection vehicles have significantly
different composition of particulate matter emissions. We anticipate that there are also
significant differences in the organic gas speciation. We plan to incorporate light-duty gasoline
organic gas speciation profiles and constants in MOVES and SPECIATE as such data on
representative, in-use vehicles become available.

20


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-9- running starts

¦©• running starts

10

15

10

15

Ethanol (%)	Ethanol (%)

Figure 3-2 Relationship between Speciation Constant Parameters and Ethanol
Composition for Tier 2 Vehicles using Low-Level Ethanol Blends

Furthermore, the reported NMOG/NMHC ratio for 0 percent ethanol level in the ORNL study
was 1.0302 which corresponds to the intercept of the best-fit line for the current analysis. For
comparison purposes, we also determined the NMOG/NMHC ratio for the SPECIATE running
profile 8756 (Tier 2 E0 exhaust) using the methodology described in this report. The
NMOG/NMHC ratio we estimated was 1.038, showing reasonable agreement with the value
determined by the ORNL study.

21


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Table 3-3 CH4/THC and Speciation Constant Parameters for Start Emissions from Tier 2

Vehicles

Bag data
from
profile

Profile
description

Emission
process

Fuel Subtype

Affected
vehicles

CH4/THC
Ratio

NMOG/NMH
CRatio

VOC/NMHC
Ratio

8756

Tier 2 E0
exhaust

Start
exhaust and
crankcase

Conventional
Gasoline

2001+LD
gasoline

0.091

1.014

0.981

N/A

Tier 2 E5
exhaust

Start
exhaust and
crankcase

E5

2001+LD
gasoline

0.098

1.031

0.997

N/A

Tier 2 E8
exhaust

Start
exhaust and
crankcase

E8

2001+LD
gasoline

0.102

1.042

1.007

8757

Tier 2 E10
exhaust

Start
exhaust and
crankcase

E10

2001+LD
gasoline

0.105

1.046

1.014

8758

Tier 2 E15
exhaust

Start
exhaust and
crankcase

E15

2001+LD
gasoline

0.112

1.069

1.030

8855

Tier 2 E85
exhaust

Start
exhaust and
crankcase

E85, E70

Pre-2001 MY
flex-fuel
vehicles
running on high
ethanol blends

0.273

1.511

1.454

8855

Tier 2 E85
exhaust

Start
exhaust and
crankcase

E85, E70

MY 2001+
flex-fuel
vehicles
running on high
ethanol blends

0.273

Not Useda

Not Useda

a MY 2001 and later E85 fueled vehicles use the Tier 2 El 0 NMOG/NMHC and VOC/NMHC ratios as discussed in Section 3.4

22


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Table 3-4 CELt/THC and Speciation Constant Parameters for Running Emissions from Tier

2 Vehicles

Bag data
from
profile

Profile
description

Emission
Process

Fuel Subtype

Affected
vehicles

CH4/TH
CRatio

NMOG/NMHC
Ratio

VOC/NMH
C
Ratio

8756

Tier 2 E0
exhaust

Running
exhaust and
crankcase

Conventional
Gasoline

2001+LD
gasoline

0.338

1.038

0.974

N/A

Tier 2 E5
exhaust

Running
exhaust and
crankcase

E5

2001+LD
gasoline

0.338

1.038

0.974

N/A

Tier 2 E8
exhaust

Running
exhaust and
crankcase

E8

2001+LD
gasoline

0.338

1.038

0.974

8757

Tier2 E10
exhaust

Running
exhaust and
crankcase

E10

2001+LD
gasoline

0.338

1.038

0.974

8758

Tier2 E15
exhaust

Running
exhaust and
crankcase

E15

2001+LD
gasoline

0.338

1.038

0.974

8855

Tier 2 E85
exhaust

Running
exhaust and
crankcase

E85, E70

Pre-2001 MY
flex-fuel
vehicles
running on
high ethanol
blends

0.822

1.234

0.934

8855

Tier 2 E85
exhaust

Running
exhaust and
crankcase

E85, E70

MY 2001+

vehicles
running on
high ethanol
blends

0.822

Not Usedb

Not Usedb

bMY 2001 and later E85 fueled vehicles use the Tier 2 E10 NMOG/NMHC and VOC/NMHC ratios as discussed in Section 3.4

3.4 Ratios for Flex Fuel Vehicles using I ligh Ethanol Blench i! ^x

The CH4/THC ratios and speciation constants used for high-level ethanol blends (E70 and E85),
shown in Table 3-3, were developed from three high-level ethanol fueled vehicles tested as part
of the EPAct/V2/E-89 program.38 The CH4/THC, NMOG/NMHC and VOC/NMHC ratios are
used to estimate CH4, NMHC, NMOG, VOC, and TOG emissions for pre-2001 model year E85
vehicles. The CH4/THC ratios are also used to estimate CH4 and NMHC emissions for 2001 and
later model year vehicles.

The NMOG and VOC emissions from high-level ethanol fueled vehicles for 2001 and later
model year vehicles in MOVES are calculated differently. As discussed in the fuel effects
report51, NMOG and VOC emission rates for high-level ethanol exhaust emissions are based on
the EPAct/V2/E-89 data, plus data from three other testing programs with a total of 19 Tier 2
FFV vehicles tested on both E10 gasoline and E85 fuels. No significant differences were
observed in the NMOG emissions between the Tier 2 vehicles tested on E10 and E85 fuels. As
such, MOVES calculates NMOG and VOC emissions from NMHC emissions calculated using

23


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E10 CH4/NMHC ratios, and fuel effects primarily using E10 fuel properties. 'NMOG and VOC
emissions for E85-fueled vehicles are then calculated using the NMOG/NMHC and
VOC/NMHC ratios from the Tier 2 E10 Profile (8757). We recognize this approach can result in
discrepancies between NMHC and VOC emissions from E85-fueled vehicles particularly if the
methane ratios are significantly different between ratios between the EPAct/V2/E-89 study (3
vehicles), and the larger 19-vehicle dataset.J One of the reasons this approach was taken was due
to the limited data on E85 emissions; it reflects the need for further research on E85 emissions. A
more detailed discussion of NMOG and VOC emissions from high ethanol blend fueled vehicles
is included in the MOVES Fuel Effects Report.51

3.5 Ratios for CNG Vehicles

The speciation values for compressed natural gas (CNG) exhaust are derived from a study
conducted by the California Air Resources Board on a CNG lean-burn transit bus with and
without an oxidation catalyst (Ayala et al. 200343). The derivation of the CNG methane and
speciation constants are documented in Appendix B. In MOVES, we apply the speciation values
from the "without control" tests to pre-2002 model year CNG vehicles, and the values "with the
oxidation catalyst" to 2002 and later vehicles as shown in Table 3-5. The data used to develop
the speciation constants was not complete enough to develop full speciation profiles. In the
absence of mobile-source CNG speciation profile, we use SPECIATE profile 1001kto speciate
the residual TOG (Table 4-1).

Table 3-5 C

14/THC and Speciation Constant Parameters for CNG Exhaust

Profile
Description

Model
Years
affected

Emission
process

CH4/THC
Ratio

NMOG/NMHC
Ratio

VOC/NMHC
Ratio

CNG lean-
burn

1960-2001

Starts and
running
exhaust

and
crankcase

0.886

1.9

1.68

CNG lean-

burn
oxidation
catalyst

2002-2060

Starts and
running
exhaust

and
crankcase

0.959

1.24

0.93

The peer-reviewers of the MOVES2014 Speciation report11 recommended we consider using
more recent studies of CNG vehicles. In response, we compared the CH4/THC, NMOG/NMHC,
and VOC/NMHC developed from Ayala et al. (2003)43, to more recent studies including data on
stoichiometric three-way catalyst (TWC) technology engines as shown in Table 3-6. The
MOVES CH4/THC value falls within the range of recent studies. Larger differences between

1 With the exception of sulfur level, see the discussion in the MOVES3 fuel effects report51

J Only a fraction of the vehicles tested in the 19 vehicle-test sample reported methane measurements. If the methane
fraction is significantly different in the EPAct/V2/E-89 program compared to the 19 vehicle-test sample compared to
the EPAct/V2/E-89 program used to derive the NMOG rates, this could create the observed inconsistency in the
NMOG/NMHC and VOC/NMHC ratios.

k As shown in Table A-4, Speciate profile 1001 is based on a measurements from a stationary CNG engine

24


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studies are observed for the NMOG/NMHC and VOC/NMHC ratios, particularly for the
uncontrolled lean-burn values. The differences can be explained by the fact that the CNG
exhaust from Ayala et al. (2003)43 used in MOVES contain high formaldehyde emissions,
particularly for uncontrolled lean-burn buses, which causes high NMOG/NMHC ratios. The
large variation in these values may also be due to differences in measurement methods,
particularly because non-methane hydrocarbons constitute a small fraction of the total organic
gas emissions from CNG buses.

The MOVES speciation value for the catalyst -equipped engines used for MY 2001 and later, are
slightly outside the range of values obtained in other studies, but still compare relatively well
considering the variability among the different studies. As such, we have maintained the use of
them in MOVES. The variation among the different values could be used to assess the relative
uncertainty of the methane, NMOG, and VOC emissions estimated in MOVES.

Table 3-6 Comparison of CH4/THC and Speciation Constant Parameters for CNG Engines

from several studies

Study

Technology

Model
year

Cycles
tested

CH4/THC
Ratio

NMOG/NMHC
Ratio

VOC/NMHC
Ratio

CEC-201539

Lean-burn

2005

CBDa

0.853

1.062

1.062

Stoichiometric
TWC

2011-2013

CBD

0.881

1.183

1.183

Thiruvengadam
et al.40,41

Stoichiometric
TWC

2008-2009,
2011

UDDSb

0.982

1.096

1.096

Dual-Fuel
High-Pressure
Direct
Injection
(HPDI)

2011

UDDS

0.683

1.031

1.031

CE-CERT42

Stoichiometric
TWC°

2014

UDDS

0.941

NDd

ND

Stoichiometric
TWC

2014

CBD

0.719

ND

ND

Ayala et al.43
(MOVES)

Lean-burn, no
control

2000

CBD

0.886

1.9

1.68

Lean-burn,
Oxidation
catalyst

2000

CBD

0.959

1.24

0.93

Notes:

a Central Business District
b Urban Dynamometer Driving Schedule
0 TWC= Three-way catalyst
d ND: Not Determined

Currently, we do not estimate evaporative or refueling emissions from CNG vehicles in MOVES
and thus, have no CH4/THC, NMOG/NMHC, and VOC/NMHC ratios for these processes. This
is an area for future research.

25


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3.6 CH4 Ratios for 2010-and-Later Heavy-Duty Diesel Vehicles

The pre-2007, 2007-2009, and 2010-and-later model years, CH4/THC ratios for heavy-duty
diesel based on the assigned speciation profiles in Table 3-2 are 0%, 58%, and 0%. The 2010-
and-later speciation profiles (95335a) is developed from the ACES Phase 2 program, where
methane emissions were below the detection limit.35 Methane and NMHC emissions below the
detection limit has also been reported in other studies that measured emissions from MY 2010
and later heavy-duty vehicles.44'87

However, due to the large inconsistency in the methane fractions between the 2007-2009 and
2010-and-later model years, and our relative uncertainty regarding the methane fraction from the
Phase 2 profiles (See Appendix D), we conducted a literature review on methane emissions from
MY 2010 and later heavy-duty diesel trucks. Three different studies from the literature and EPA
certification data reported significant CH4/THC ratios from MY 2010+ heavy-duty exhaust as
shown in Table 3-7. From the reported values, we calculated an average CH4/THC ratio of 38%,
which we use in MOVES3 for all MY 2010 and later diesel-fueled vehicles.

We recognize there is uncertainty regarding representative driving conditions and vehicles.
Quiros etal.(2016,2017)45'46 showed that methane fractions varied by driving cycle, but there
was not a consistent trend in the methane ratios from low to higher load operation. Due to the
wide variety of results, we decided to take an average of each of the cycle-average values from
each of the studies shown in Table 3-7, except for the local drayage value from Quiros etal.45'46
which was deemed an outlier value (90% methane). This approach was deemed the most
reasonable to yield a representative methane fraction for in-use driving.

The vehicles sampled also tended to be vehicles with low mileage accumulation. The reported
odometer readings that were available were relatively low for heavy-duty diesel trucks (less than
200,000 miles). The EPA certification data are obtained from test-engines with fully functioning
aftertreatment systems that have not been applied in-use. In theory, the CH4/THC ratios are
likely to decrease as vehicles age, as the aftertreatment system becomes less efficient at
oxidizing NMHC. However, we don't have the data nor the MOVES structure to support this,
and we are using the methane fraction to represent all vehicle ages for MY 2010-and-later diesel
vehicles.

As discussed in Section 3.2, we are continuing to use the ACES Phase 2 speciation program for
the speciation factors for NMHC from 2010-and-later exhaust (i.e. NMOG/NMHC and
VOC/NMHC ratios, and the speciation profile to estimate the chemical mechanism species from
the integrated species and NONHAPTOG). Most of the studies evaluated did not provide
sufficient speciation measurements from which to develop speciation profiles or even speciation
factors beyond the methane ratios. Future work could develop updated speciation ratios and
profiles from Hays et a/.(2017)47 and other relevant studies.

26


-------


fable 3-7 CH4/TH<

C Ratios for MY 2010+ Heavy-Duty Diesel Trucks

Source

Vehicle

#

Reg
Class

Model
Year

Technology

Odometer

Cycle

CH4/THC
(%)

Quiros et al

201645
Quiros et al
201746

4

HHD

2013-2014

DOC+DPF+SCR

40K to
186K

Hill Climb

18%

Interstate

25%

Regional

20%

Local Drayage

90%

Near Dock

22%

Urban

33%

Hays et al
201747

3

LHD2b3,
LHD45,
MHD

2011

LHD2b3:
DOC+NAC+DPF
LHD45 & MHD:
DOC+SCR+DPF

4K to 35K

CARBMHD
UDDS and
HD-UDDS

42%

Karavalakis

et al 201648

1

HHD

2014

DOC+DPF+SCR

NA

UDDS

68%

HHDDT
Transient

55%

EPA
Certification
Data49-3

9

engine
families

LHD

2016-2019

DOC+DPF+SCR

NA

Transient (TR)
Comb Adj

47%

16
engine
families

MHD

39%

10
engine
families

HHD

46%

Average =

(excluding the Local Drayage from Quiros et al.)

38%

Note: DOC-Diesel Oxidation Catalyst, DPF-Diesel Particulate Filter, NAC-NOx Adsorber Catalyst, SCR-Selective
Catalytic Reduction

a The methane fractions from the EPA certification data were calculated as average of ratios from each engine
family, rather than a ratio of averages, which would yield lower methane fractions

4 TOG Chemical Mechanism (CM) Speciation

4.1 Overview

TOG speciation required for air quality models is different than PM speciation, due to the
concept of chemical mechanisms. Chemical mechanisms (see Section 2.3) are used to simplify
the thousands of individual organic compounds into a manageable set of CM species used for air
quality modeling. PM, on the other hand, is not mapped into CM species, but is split into various
real species and some aggregated groups for use in air quality models (See Section 5).

As defined in Section 2.3, "integrated species" are pollutants from which MOVES directly
calculates chemical mechanism emissions. MOVES maps the gaseous integrated species (e.g.
benzene) and the remaining TOG (referred to as Residual TOG or NONHAPTOG) to the CM
species used by each chemical mechanism, in units of moles, for use by air quality models. In

27


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this report, this mapping process of the Residual TOG to chemical is referred to as TOG
speciation. The calculation of Residual TOG is shown in Equation 10 below.

Residual TOG = TOG - MOVES gaseous integrated species	Equation 10

Currently, we integrate 15 individual MOVES gaseous species, listed in Table 2-2. While a
select list of PAHs, dioxins, and furans are also computed by MOVES, they are not integrated
(with the exception of one PAH species, naphthalene). The other PAHs, dioxins and furans are
not included in the integrated species in part because they compose a small percentage of the
Residual TOG emissions; incorporating them into the integrated species would require additional
data processing without a significant impact on the chemical mechanism estimates.

The profiles used in this process, and the mapping of real species into CM species are discussed
in the following sections.

4.2 Real TOG Specia

A real speciation profile is, in principle, a complete listing of all the real species and their
quantities that make up an aggregate species such as TOG. Of course, the hundred or so
compounds listed in these profiles are not a complete listing, which would likely include
thousands of species. However, they are the major species by mass and reactivity. Such a profile
is produced by laboratory analysis of emissions. These are not CM speciation profiles and are
independent of chemical mechanism.

Table 4-1 summarizes the speciation profiles, based on SPECIATE, that we are using in
MOVES, together with the fuels, affected vehicles, and MOVES emission processes to which
they apply. SPECIATE is the EPA's repository of volatile organic gas and particulate matter
(PM) speciation profiles from air pollution sources.8 The SPECIATE database contains a record
of each profile including its referenced source, testing methods, a subjective rating of the quality
of the data, and other detailed data that allow researchers to decide which profile is most suitable
for model input. Table A-4. lists the referenced sources of the real speciation profiles used in
MOVES.

MOVES applies the speciation profile by model year, fuel subtype, regulatory class and emission
process; Appendix C provides the assignment at this level. Fuel subtype refers to fuel groupings
within the larger fuel types of gasoline, diesel, CNG and E85 as detailed in Table C-3.

Regulatory class refers to vehicle type as defined in Table C-2. Emission process refers to the
emission's physical mechanism. As listed in Table C-l, MOVES has twelve emission processes
that are relevant for TOG speciation. Within each process, emission rates can potentially vary by
operating mode. Running exhaust has different operating modes to represent idling, coasting, and
operating with different engine loads. Start exhaust has different operating modes to differentiate
a continuum of starts between cold, warm, and hot starts. The operating modes are defined in the
light-duty1 and heavy-duty exhaust2 emission rate report and the evaporative report.26 In
MOVES, different TOG and PM speciation profiles can be applied to different processes, but not
to individual operating modes.

28


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Table 4-1 Speciation Profiles Used for Onroad TOG Emissions'

Profile

Profile
Description

Fuel

Affected Vehicles

Emission Process

1001

CNG Exhaust

CNG

All CNG Transit Buses

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust,
Crankcase Start Exhaust

95120m

Liquid Diesel

Diesel

All Diesel

Evap Permeation, Evap Fuel Vapor
Venting, Evap Fuel Leaks, Refueling
Displacement Vapor Loss, Refueling
Spillage Loss

8753

E0 Evap

E0

All Gas

Evap Fuel Vapor Venting, Evap Fuel
Leaks, Refueling Spillage Loss

8754

E10 Evap

E10

All Gas

Evap Fuel Vapor Venting, Evap Fuel
Leaks, Refueling Spillage Loss

8756

Tier 2 E0
Exhaust

E0

2001+LD Gas

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust,
Crankcase Start Exhaust

8757

Tier 2 E10
Exhaust

E10

2001+LD Gas

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust,
Crankcase Start Exhaust

8758

Tier 2 E15
Exhaust

E15

All Gas

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust,
Crankcase Start Exhaust

8766

E0 Evap
Permeation

E0

All Gas

Evap Permeation

8769

E10 Evap
Permeation

E10

All Gas

Evap Permeation

8770

El5 Evap
Permeation

E15

All Gas

Evap Permeation

8774

Pre-2007 MY
HDD Exhaust

Diesel

Pre-2007 HD Diesel

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust,
Crankcase Start Exhaust, Crankcase
Extended Idle Exhaust, Extended Idle
Exhaust

8774

Pre-2007 MY
HDD Exhaust

Diesel

Pre-2024 APU

Auxiliary Power Exhaust

8774

Pre-2007 MY
HDD Exhaust

Diesel

Pre-2007 LD Diesel

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust,
Crankcase Start Exhaust

8775

2007-2009
HDD Exhaust

Diesel

2007-2009 LD Diesel

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust,
Crankcase Start Exhaust

8775

2007-2009
HDD Exhaust

Diesel

2007-2009 HD Diesel

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust,
Crankcase Start Exhaust, Crankcase
Extended Idle Exhaust, Extended Idle
Exhaust

1 Appendix C provides a complete mapping of the TOG speciation profiles to modelYearGroupID, processID,
fuelSubTypelD, and regClassID.

m While MOVES maps the liquid diesel profile to several processes, MOVES only estimates emissions from
refueling spillage loss. The other evaporative and refueling processes from diesel vehicles have zero emissions.

29


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Table 4-1 (continued)

Profile

Profile
Description

Fuel

Affected Vehicles

Emission Process

8775

2007-2009
HDD Exhaust

Diesel

2024+ APU

Auxiliary Power Exhaust

95335a

2011 HDD
Exhaust

Diesel

2010+ LD Diesel

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust, Crankcase
Start Exhaust

95335a

2011 HDD
Exhaust

Diesel

2010+ HD Diesel

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust, Crankcase
Start Exhaust, Crankcase Extended Idle
Exhaust, Extended Idle Exhaust

8855

Tier 2 E85
Exhaust

E70, E85

E70, E85

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust, Crankcase
Start Exhaust

8869

E0 Headspace

EO

All Gas

Refueling Displacement Vapor Loss

8870

E10

Headspace

E10

All Gas

Refueling Displacement Vapor Loss

8871

E15

Headspace

E15

All Gas

Refueling Displacement Vapor Loss

8872

El5 Evap

E15

All Gas

Evap Fuel Vapor Venting, Evap Fuel
Leaks, Refueling Spillage Loss

8934

E85 Evap

E70, E85

E70, E85

Evap Permeation, Evap Fuel Vapor
Venting, Evap Fuel Leaks, Refueling
Displacement Vapor Loss, Refueling
Spillage Loss

8750a

Pre-Tier 2 E0
Exhaust

EO

Pre-2001 LD Gas

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust, Crankcase
Start Exhaust

8750a

Pre-Tier 2 EO
Exhaust

EO

All MC and non-LD Gas

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust, Crankcase
Start Exhaust

8751a

Pre-Tier 2
E10 Exhaust

RFG, E10

Pre-2001 LD Gas

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust, Crankcase
Start Exhaust

8751a

Pre-Tier 2
E10 Exhaust

RFG, E10

All MC and Non-LD Gas

Running Exhaust, Start Exhaust,
Crankcase Running Exhaust, Crankcase
Start Exhaust

30


-------
4.3 TOG Chemical Mechanism Species

The mapping of real species to CM species is mechanism-specific. Each chemical mechanism is
based on a mapping of real organic gas species to one or more CM species. The atmospheric
chemistry is then modeled using these CM species. As outlined in Table 2-1, MOVES3 can
output chemical mechanisms using following four mechanisms: CB05, CB6CMAQ, SAPRC07T,
and CB6AE7. All the species in each real speciation profile of TOG are mapped to the chemical
mechanism species associated with each chemical mechanism. Then all the occurrences of each
CM species for each mechanism are added up to give molar quantities of chemical mechanism
species (lumped species) for each chemical mechanism.

While the original "real speciation profiles" include the "integrated species," the MOVES
estimates for the 15 integrated species listed in Table 2-2 are based on as much or more detailed
and accurate information than available from applying the real speciation profiles. Therefore, we
independently calculate and subtract these species from the real speciation profiles and then
develop CM speciation for the residual TOG (referred to as NONHAPTOG). For example, the
benzene fraction estimated by MOVES for light-duty gasoline vehicles accounts for the benzene
content in the gasoline fuel, whereas the benzene fraction estimated in the TOG speciation
profiles is based on the benzene level in the tests conducted for the speciation measurements.

The CM speciate profiles are generated outside MOVES using the Speciation Tool.24 After
separately mapping the integrated species and the residual TOG to CM species, MOVES adds all
CM species together to produce CM species output. All chemical mechanism species output is in
units of moles. MOVES emission rates are combined with activity in the SMOKE-MOVES
process (Section 2.5), and emissions are subsequently spatially gridded and allocated to the
hourly level in SMOKE11, to then be used by an air quality model, such as CMAQ. Figure 4-3 is a
diagram of the process of TOG speciation conducted by MOVES for air quality modeling.

n Defined in Section 2.5

31


-------
Speciation profiles
with all measured species
(e.g., based on EPAct data)

MOVES

Acetaldehyde

Formaldehyde

Benzene

Other
individual
species to be
integrated



Speciation of
each
integrated
species

speciation

Speciation of
Residual TOG

with
renormalized
profile

¥ /

s

Summed CM species

Speciate

Tool

Tool for mapping
measured species into
CM species

New CM species profiles
renormalized without
integrated species

Figure 4-3. Diagram of the Process of TOG Speciation for Air Quality Modeling as it

occurs with MOVES

32


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5 PM2.5 Speciation

5/1 MOVES PM2.5 Species

MOVES estimates the 18 PM2.5 species outlined in Table 5-1.

)le 5-1 AE6 Chemical Mechanism PM2.5 Species

Ta

PM2 5 Species

AE6 Species
Name

Primary organic carbon

POC

Elemental carbon

PEC

Sulfate

PS04

Nitrate

PN03

Ammonium

PNH4

Non-carbon organic matter

PNCOM

Iron

PFE

Aluminum

PAL

Silicon

PSI

Titanium

PTI

Calcium

PCA

Magnesium

PMG

Potassium

PK

Manganese

PMN

Sodium

PNA

Chloride

PCL

Particulate water

PH20

Primary unspeciated PM2 50

PMOTHR

Similar to the methods used to speciate total organic gases, MOVES uses speciation profiles to
estimate individual PM2.5 species. The PM2.5 Speciation profiles were developed to directly
estimate the species used for the CMAQ Aerosol Module, version 6, or "AE6;"24 all other
measured PM2.5 species are aggregated into PMOTHER.0 If needed, post-processing can be
used to aggregate the AE6 species into the PM2.5 species used with the Comprehensive Air
Quality Model with Extensions (CAMx).24

0 Primary unspeciated PM2 5 (PMOTHR) is calculated as 1- sum(AE6 species fractions) and can include both
unspeciated PM2 5 mass as well as measurements of other PM2 5 species that are not included in the AE6 chemical
mechanism species..

33


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5.2 PM2.5 Speciation Calculations

Figure 5-1 and Figure 5-2 provide an overview of the algorithm used to calculate speciated and
total exhaust PM emission rates in MOVES. The steps used to calculate PM2.5 emissions and
PM2.5 speciation are outlined in nine steps below. Steps 1 - 4 are outlined in Figure 5-1.

Base EC and
NonECPM
exhaust emission
rates

at 12

by polProcessID,
OpModelD,
ageGroupID,
SourceBinID

EC, NonECS04PM, S04, and
H20 exhaust emissions
adjusted by fuel and
temperature effects. Effects
differ by polProcessID
SourceType,fuelTypelD,
modelYearRangelD

NonEC
nonS04
PM

S04 fraction

by polProcessID,
SourceType,
fuelTypelD,
modelYearRangelD

Figure 5-1 Flow Chart of Calculation of the Intermediate PM2.5 Emission Rates

Step 1. MOVES stores PM2.5 exhaust emission rates in the emissionRateByAge table by
pollutant process (start, running, extended idle), operating mode, sourcebin (fuelType, engine
technology, regulatory class, model year), and vehicle age. MOVES stores the base exhaust rates
for PM2.5 in two primary components (EC and nonECPM), so that the EC/PM2.5 ratio can vary
across operating modes.p2

p Within MOVES, modal EC/PM ratios are developed for conventional diesel vehicles (pre-2007) as documented in
the MOVES3 heavy-duty exhaust report.2 Modal EC/PM2 5 ratios have not been developed for other vehicle types
(gasoline, CNG, ethanol, and 2007+ diesel), and the EC and NonECPM emission rates for these sourcetypes and
fuels have a constant ratio across operating modes.

34


-------
Step 2. MOVES calculates sulfate (SO4) and particulate water (H2O) emissions as a fraction of
nonECPM. The sulfate to nonECPM fraction (SulfatenonECPMFraction) used in MOVES is
derived from the PM2.5 speciation profiles documented in Table 5-5. MOVES stores this value in
the sulfateFraction MOVES table. The sulfate calculator, documented in the MOVES fuel effects
report,51 adjusts the sulfate fraction based on the default or user-supplied fuel sulfur level. The
remaining nonECPM is renamed nonECnonS04PM. This intermediate species contains organic
matter, elements, ions, and the unspeciated portion of PM2.5

Step 3. The intermediate PM species are adjusted for ambient temperature effects such as
inefficient oxidation of emissions at cool catalyst temperatures and additional fuel needed to start
an engine at cold temperatures. The temperature effects can differ by intermediate species,
process (e.g. start exhaust, running exhaust, extended idle), model year groups, and fuel type.
Currently, temperature effects only apply to gasoline and ethanol-blend fueled vehicles.
Currently, the EC, nonECnonS04PM, SO4, and H2O emissions are each adjusted using the same
temperature adjustments, because our data does not support individual temperature
adjustments.61 The temperature effects are documented in the Emission Adjustments report.50

Step 4. MOVES adjusts the intermediate species (EC and NonECnonS04PM) according to the
fuel properties and the applicable fuel effects (e.g., EPAct fuel effects model for 2001 and later
light-duty gasoline). The fuel adjustments and calculators are described in the Fuel Effects
Report.51

Steps 5 - 8 are outlined in Figure 5-2.

35


-------
r	i

NonEC
nonS04
PM

S04
H20



Exhaust and crankcase intermediate
PM2.5 species. Individual ratios for EC,
NonECnonS04PM,S04, and H20. Ratios
differ by polProcessID SourceType,
fuelTypelD, modelYearRangelD

Speciated PM2.5 emissions

by ProcessID (start/running/extended
idle exhaustand

start/running/extended idle crankcase
emissions),

SourceTypelD,fuelTypelD,
modelYearRangelD

PM10 calculated
from totalPM2.5.

PM10/PM2.5 factors
by ProcessID,
SourceTypelD,
fuelTypelD,
modelYearRangelD

s	



S04/H20 r



Exhaust



Factor



S04/H20



Crankcase

V

Factor

Total
Crankcase I
PM2.5 ^

Figure 5-2 Flow Chart of Calculation of Exhaust and Crankcase PM2.5 and PM10 Emission
Rates, and PM2.5 Exhaust and Crankcase Speciation

Step 5. Exhaust and crankcase emissions are calculated from the intermediate exhaust PM2.5
species (EC, NonECnonS04PM, SO4, and H2O), after the intermediate exhaust species have been
adjusted for fuel effects and temperature effects. The exhaust and crankcase emissions are

36


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calculated from the intermediate exhaust rates with exhaust and crankcase ratios that can vary
according to pollutant, process, source type, fuel type, and model year range. Example crankcase
ratios for heavy-duty diesel vehicle are shown in Table 5-2.

For most vehicles types (including pre-2007 and 2010_+ heavy-duty diesel, gasoline, and CNG
vehicles), this step accounts for the PM crankcase emissions that are not measured in the exhaust
emission rates (i.e., the exhaust and crankcase ratios sum to greater than one for each PM
subspecies). The exhaust emissions remain constant in this step.

For 2007-2009 MY heavy-duty diesel engines, crankcase emissions are assumed to be included
in the tailpipe exhaust emissions in the certification data. The exhaust and crankcase emission
ratios are used to split the PM rates into exhaust and crankcase emissions. For 2007-2009heavy-
duty diesel, the exhaust and crankcase ratios sum to one for each PM subspecies.

The exhaust and crankcase ratios are applied by intermediate subspecies, to account for
differences in PM2.5 speciation between crankcase and tailpipe particulate matter emissions. For
example, MOVES models higher EC/PM composition for exhaust than for crankcase emissions
for pre-2007 conventional11 diesel, using the exhaust and crankcase ratios as shown in Table 5-2.
For MY 2007-2009 heavy-duty diesel vehicles, the exhaust and crankcase ratios are the same
across intermediate PM2.5 species, yielding the same PM2.5 composition for exhaust and
crankcase emissions. This is intended because the PM2.5 speciation profile is estimated from
measurements that contained both tailpipe exhaust and crankcase exhaust emissions.2

The sources of the crankcase emission factors are documented in the light-duty exhaust1 and
heavy-duty exhaust emissions rates reports.2

q We use the term "conventional diesel" to refer to diesel trucks which lack exhaust aftertreatment systems such as
diesel particulate filters (DPF), diesel oxidation catalysts (DOC), and selective catalytic reduction systems (SCR)
that modern diesel trucks use to meet the EPA 2007/2010 heavy-duty emission standards.

37


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Table 5-2 Example Heavy-duty Diesel Exhaust and Crankcase Ratios by Pollutant, Process,
		Model Year Group, and Source Type	





1960-2006
Heavy-duty diesel (all
heavy-duty source types)

2007-2009
Heavy-Duty diesel (all heavy-duty
source types except single unit trucks)3

Pollutant



Start

Running

Extended
Idle

Start

Running

Extended
Idle

EC



1

1

1

1

0.971

0.707

nonEC
nonS04-PM

Exhaust

1

1

1

1

0.971

0.707

S04

1

1

1

1

0.971

0.707

H20



1

1

1

1

0.971

0.707

EC



0.007

0.004

0.007

0

0.0290

0.293

nonEC
nonSCVPM


-------
PM2.5 profiles in Table 5-5, by removing EC, SO4, and H2O and then renormalizing the
remaining species. These values are stored in the MOVES pmSpeciation tables, with a column
key 'inputPollutantID' specifying that the PM speciation profile is based on nonECnonS04
(pollutantID 120). The data sources and derivation for the PM2.5 profiles are documented in
Appendix E.

Step 9. Although not shown in Figure 5-1 or Figure 5-2, MOVES can calculate additional
particulate-phase species, required for the National Emission Inventory (NEI) and National Air
Toxics Assessment (NATA). Listed in Table 5-4, these include: manganese, nickel, chromium,
arsenic, and particulate mercury. The metals are emitted in exhaust as PM2.5, but they are
calculated with a separate calculator than the other PM2.5 species. The emission rates for these
metals are not chained from NonECS04PM, but are independent mass/distance rates as
documented in the Air Toxic Emissions Report.7 The mass of these compounds is not used in the
summation to calculate PM2.5 due to the very small mass, but they are important PM2.5 exhaust
species from a health effects perspective. Of the toxic metals, CMAQv5.1 only requires
manganese as a required PM2.5 species. By default, MOVES calculates manganese emission rates
when the user requests PM2.5 speciation. Chromium, nickel, arsenic, and particulate mercury
emission rates are produced when requested by the user.

Table 5-4 Metal Particulate Air Toxics Produced by MOVES

Pollutant

Chromium 6+

Manganese	

Nickel	

Particulate Hg
Arsenic

5.3 PM2.5 Exhaust Speciation Profiles

Table 5-5 lists the PM2.5 speciation profiles used in MOVES with the SPECIATE database
profilelD. As discussed earlier, these profiles only estimate the AE6 Chemical Mechanism PM2.5
species, with the other measured species and unspeciated mass being considered as part of the
unspeciated PM2.5 species (PMOTHR).

39


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Table 5-5 Mi

3VES PM2.5 Exhaust Speciation Profiles

Profile ID

Profile Name

Source Data

8992

Light-duty
Gasoline Exhaust
- Start

Kansas City PM characterization Study. Final Report. EPA 420-R-
08-009. U.S. EPA, April 2008. Available at:
http://www.epa.gov/oms/emission-factors-research/index.htm.

8993

Light-duty
Gasoline Exhaust-
Hot Stabilized
Running

Kansas City PM characterization Study. Final Report. EPA 420-R-
08-009. U.S. EPA, April 2008. Available at:
http://www.epa.gov/oms/emission-factors-research/index.htm.

8994

Conventional
HDD - Idle

Clark, N.N. and Gautam, M. HEAVY-DUTY Vehicle Chassis
Dynamometer Testing for Emissions Inventory, Air Quality
Modeling, Source Apportionment and Air Toxics Emissions
Inventory. August 2007. CRC Report. No. E55/59

8995

Conventional
HDD - Hot
Stabilized
Running

Clark, N.N. and Gautam, M. HEAVY-DUTY Vehicle Chassis
Dynamometer Testing for Emissions Inventory, Air Quality
Modeling, Source Apportionment and Air Toxics Emissions
Inventory. August 2007. CRC Report. No. E55/59

8996

2007 and Newer
Diesel Exhaust
Composite

Khalek, I. A.; Bougher, T. L; Merrit, P. M.; Phase 1 of the
Advanced Collaborative Emissions Study. CRC Report: ACES
Phase 1, June 2009.

95219a

CNG transit bus
exhaust from a
lean-burn engine -
no aftertreatment

Okamoto, R. A.; Kado, N. Y.; Ayala, A.; Gebel, M.; Rieger, P.;
Kuzmicky, P. A.; Kobayashi, R.; Chemical and Bioassay Analyses
of Emissions from Two CNG Buses with Oxidation Catalyst.
http://www.arb.ca.gov/research/veh-emissions/cng-diesel/cng-
diesel.htm.

95220a

CNG transit bus
exhaust from a
lean-burn engine
- oxidation
catalyst

Okamoto, R. A.; Kado, N. Y.; Ayala, A.; Gebel, M.; Rieger, P.;
Kuzmicky, P. A.; Kobayashi, R.; Chemical and Bioassay Analyses
of Emissions from Two CNG Buses with Oxidation Catalyst.
http://www.arb.ca.gov/research/veh-emissions/cng-diesel/cng-
diesel.htm.

The PM2.5 profiles used for the applicable source type, fuel, pollutant process, and model year
ranges are described in Table 5-6 and detailed in Table D-l.

40


-------
Table 5-6 Application of M(

3YES PM2.5 Speciation Profiles

Profile
ID

Description

Fuel

Affected
Vehicles

Emission Process

8992

Light-duty Gasoline
Exhaust - Start

All
gasoline
vehicles
(E0 to
E85)

All model years

Running exhaust; crankcase
running exhaust.

8993

Light-duty Gasoline
Exhaust- Hot Stabilized
Running

All
gasoline
vehicles
(E0 to
E85)

All model years

Start exhaust; crankcase start
exhaust.

8994

Conventional HDD - Idle

Diesel

Pre-2007 and all
MY auxiliary
power units

Running exhaust; crankcase
running and extended idle
exhaust; auxiliary power unit

8995

Conventional HDD - Hot
Stabilized Running

Diesel

Pre-2007

Start exhaust; crankcase start
exhaust.

8996

2007 and Newer Diesel
Exhaust Composite

Diesel

2007+

Start exhaust; crankcase start
exhaust. Running exhaust;
crankcase running and
extended idle exhaust;
auxiliary power unit

95219a

CNG transit bus exhaust
from a lean-burn engine -
no aftertreatment

CNG

pre-2002 model
year

Start exhaust; crankcase start
exhaust. Running exhaust;
crankcase running and
extended idle exhaust;
auxiliary power unit

95220a

CNG transit bus exhaust
from a lean-burn engine
- oxidation catalyst

CNG

2002+ model
year

Start exhaust; crankcase start
exhaust. Running exhaust;
crankcase running and
extended idle exhaust;
auxiliary power unit

MOVES uses two light-duty gasoline profiles to characterize PM2.5 emissions from all gasoline
vehicles, including motorcycles, light-duty passenger cars and trucks, and medium and heavy-
duty gasoline trucks and buses.

The pre-2007 diesel profiles are used to represent all pre-2007 on-highway diesel vehicles in
MOVES, including light-duty passenger cars and trucks, medium, and heavy-duty trucks, and
diesel buses. Tailpipe exhaust and crankcase nonECnonS04 emissions emitted during extended
idle and start are speciated using the Idle Profile (8994). Tailpipe exhaust and crankcase
nonECnonS04 emissions emitted during running operation are speciated using the running
profile (8995). In addition, the idle profile (8994) is used to characterize nonECnonS04
emissions from diesel-powered auxiliary power units used on heavy-duty diesel trucks.

The ACES Phase 1 profile (8996) is used for all 2007-and-later diesel sources, including light-
duty passenger cars and trucks, medium- and heavy-duty trucks and diesel buses. The ACES

41


-------
Phase 1 16-hour cycle is used to develop the profile, which includes both exhaust and crankcase
emissions, as well as start, extended idle and running emission processes. For this reason, the
composite profile is also used to speciate all emission processes for 2007-and-later diesel
engines. It should be noted that while PM speciation data for 2010 and later diesel engines is
available from the ACES Phase 2 test program, we did not update PM speciation to incorporate
these data because the ACES Phase 2 emissions data did not collect any active regeneration
events, and thus, had minimal sulfate emissions. Testing done by California Air Resources
Board53 has shown active regeneration events occur on 2010+ technology on-highway diesel
trucks, but at a lower frequency than 2007-2009 model year trucks. During active regeneration,
fuel is injected into the aftertreatment system to raise the temperature to burn off the soot
collected in the diesel particulate filter, which increases emissions of particulate matter (mostly
sulfate). Thus it is important that sulfate emissions be represented in the PM2.5 profile to
represent real-world regeneration events.54

The CNG compression ignition profile is applied to the pre-2002 model CNG heavy-duty
vehicles, and the CNG profile with oxidation catalyst profile is applied to the 2002+ model year
CNG heavy-duty vehicles.

5.4 Brake and Tire Wear Speciation

Brake and tire wear PM2.5 are not speciated within MOVES. For developing the emissions
modeling platform, SPECIATE Profiles 95462 and profile 95460 developed from Schauer et al.
200667 are applied to brake wear and tire wear PM2.5 emissions in the moves2smk postprocessor
that prepares the emission factors for processing in SMOKE.55

42


-------
Appendix A Supporting Information for TOG calculations

Table A-l and Table A-2 summarize the data56 used to generate CH4/THC ratios for Tier 2
vehicles running on low-level ethanol blends as described in Section 3.3. In Table A-2, "cold
start" refers to the difference between Bags 1 and 3. Running data corresponds to stabilized
emissions from Bag 2. In the particular case of running emissions, seven tests (shown in grey in
Table A-l and Table A-2) were not considered in the analysis because the reported CH4 emissions
were higher than the reported THC emissions, possibly because measurements were close to the
detection limit of the instrument.

Table A-l Data56 Used to Generate CH4/THC Ratios for Tier 2 Vehicles Running on Low-

Level Ethanol Blends

Bag data
from
profile

Run
Number

Ethanol

(%)

Bagl -

-Bag 3

Bag 2

EPAct
Phase 1

CH4
(g/mi)

THC

(g/mi)

CH4
(g/mi)

THC

(g/mi)



3162

0

0.048

0.427

0.006

0.016



3169

0

0.050

0.570

0.006

0.017



3179

0

0.024

0.299

11.001

0.000



3190

0

0.027

0.355

0 001

0 000

8756

3205

0

0.042

0.369

O 00(i

0.0:4



3215

0

0.043

0.430

0.006

0.026



3223

0

0.019

0.236

0.001

0.002



3231

0

0.017

0.211

0.001

0.004



3239

0

0.030

0.382

0.00 |

0.000



3280

10

0.031

0.351

O OO I

0 000



3291

10

0.029

0.343

0.001

0.001

8757

3302

10

0.045

0.362

0.005

0.014

3313

10

0.049

0.382

0.006

0.021



3326

10

0.016

0.163

0.001

0.004



3339

10

0.016

0.165

0.001

0.003



3480

15

0.058

0.448

0.007

0.018



3492

15

0.053

0.424

0.007

0.014



3508

15

0.017

0.141

0.001

0.002

8758

3516

15

0.017

0.209

0 001

0 00:



3542

15

0.052

0.494

O OO I

0.000



3553

15

0.043

0.379

0.001

0.000



3568

15

0.022

0.248

O OO I

0.000

43


-------
Table A-2. Data56 Used to Generate Speciation Constant Parameters for Tier 2 Vehicles
		 Running on Low-Level Ethanol Blends			

Bag data
from
profile

Run
Number
EPAct
Phase 1

Ethanol

(%)

Cold
Start
NMOG
(g/mi)

Cold
Start

voc

(g/mi)

Cold
Start
NMHC
(g/mi)

Running
NMOG

(g/mi)

Running
VOC

(g/mi)

Running
NMHC
(g/mi)

8756

3162

0

0.345

0.332

0.338

0.009

0.008

0.008

3169

0

0.468

0.453

0.458

0.010

0.010

0.010

3179

0

0.256

0.250

0.255 0.001

0.001

0.001

3190

0

0.284

0.276

0.282

0.001

0.001

0.001

3205

0

0.314

0.301

0.306

0.013

0.012

0.013

3215

0

0.360

0.346

0.353

0.013

0.012

0.013

3223

0

0.197

0.190

0.196

0.001

0.001

0.001

3231

0

0.168

0.162

0.165

0.004

0.004

0.004

3239

0

0.295

0.287

0.294

0.001

0.001

0.001

8757

3280

10

0.312

0.305

0.301

0.001

0.001

0.001

3291

10

0.315

0.306

0.301

0.000

0.000

0.000

3302

10

0.331

0.320

0.317

0.007

0.006

0.006

3313

10

0.345

0.332

0.327

0.008

0.007

0.007

3326

10

0.144

0.139

0.137

0.000

0.000

0.000

3339

10

0.159

0.154

0.151

0.000

0.000

0.000

8758

3480

15

0.390

0.372

0.363

0.012

0.011

0.012

3492

15

0.371

0.354

0.348

0.012

0.011

0.012

3508

15

0.143

0.137

0.133

0.001

0.001

0.001

3516

15

0.188

0.182

0.172

0.000

0.000

0.000

3542

15

0.433

0.420

0.410 0.000

0.000

0.000

3553

15

0.328

0.317

0.310 0.000

0.000

0.000

3568

15

0.239

0.232

0.221 0.000

0.000

0.000

Table A-3. documents the CHVTHC and speciation constant parameters for all the sources in
MOVES (by including the data from Table 3-2, Table 3-3, Table 3-4, and Table 3-5 ). In
addition, it specifies the MOVES variables that are used to define the CH4/THC and
speciationConstants within the MethaneTHCRatio and HcSpeciation tables, respectively.

44


-------
Table A-3 CH4/TH

C and Speciation Constant Parameters and Their Relationship to MOVES Variables

Profile
number

Profile
description

modelYear
-GroupID

processID

fuelSubTyp
elD

regClassID

CH4/THC

NMOG/NMH
C

VOC/NMHC

95120

Liquid
Diesel

1960-2060

11

20,21,22

0

0

1

1

12,13,18,19

20,21,22

10,20,30,40,41,
42,46,47,48

0

8750a

Pre-Tier 2
E0 exhaust

1960-2000

1,2,15,16

10

20,30

0.142

1.024

0.996

1960-2060

10,40,41,42,46,
47,48

8751a

Pre-Tier 2
E10 exhaust

1960-2000

1,2,15,16

11,12,13,14

20,30

0.146

1.037

1.008

1960-2060

10,40,41,42,46,
47,48

8753

E0 Evap

1960-2060

12,13,19

10

10,20,30,40,41,
42,46,47,48

0

1

1

8754

E10 Evap

1960-2060

12,13,19

12,13,14

10,20,30,40,41,
42,46,47,48

0

1.071

1.071

8766

E0 Evap
perm

1960-2060

11

10

0

0

1

1

8769

E10 Evap
perm

1960-2060

11

12,13,14

0

0

1.129

1.129

8770

El5 Evap
perm

1960-2060

11

15,18

0

0

1.175

1.175

8774

Pre-2007
MY HDD
exhaust

1960-2006

1,2,15,16,1
7,90

20,21,22

40,41,42,46,47,
48

0

1.145

1.124

1960-2023

91

46,47

1960-2006

1,2,15,16

20,30

8775

2007-2009
HDD
exhaust

2007-2009

1,2,15,16

20,21,22

20,30

0.589

1.343

1.285

2024-2060

91

46,47

2007-2009

1,2,15,16,1
7,90

40,41,42,46,47,
48

95335a

2010+HDD
exhaust

2010-2060

1,2,15,16

20,21,22

20, 30

0

1.085

0.965

1,2,15,16,1
7,90

40,41,42,46,47,
48

45


-------
Table A-3 (continued)

Profile
number

Profile
description

modelYear
GroupID

processID

fuelSubTyp
elD

regClassID

CH4/THC

NMOG/NMH
C

VOC/NMH
C

8869

E0
Headspace

1960-2060

18

10

10,20,30,40,41,4
2,46,47,48

0

1

1

8870

E10
Headspace

1960-2060

18

12,13,14

10,20,30,40,41,4
2,46,47,48

0

1.037

1.037

8871

E15
Headspace

1960-2060

18

15,18

10,20,30,40,41,4
2,46,47,48

0

1.175

1.175

8872

E15 Evap

1960-2060

12,13,19

15,18

10,20,30,40,41,4
2,46,47,48

0

1.118

1.118

8934

E85 Evap

1960-2060

11

50,51,52

10,20,30,40

0

1.501

1.501

12,13,18,1
9

10,20,30,40

46


-------
Table A-4 Data Sources for the SPECIATE8 Profiles used in MOVES

Profile
ID

Profile
Name

Source Data

Additional Documentation

1001

Internal
Combustion
Engine -
Natural Gas

Oliver, W. R and S. H. Peoples, Improvement of the
Emission Inventory for Reactive Organic Gases and
Oxides of Nitrogen in the South Coast Air Basin,
Volumes I and II, Final Report (Prepared for California
Air Resources Board), May 1985.



95120

Liquid Diesel
- California
composite

Gentner, Drew R, Gabriel Isaacman, David R Worton,
Arthur WH Chan, Timothy R Dallmann, Laura Davis,
Shang Liu, et al. "Elucidating Secondary Organic
Aerosol from Diesel and Gasoline Vehicles through
Detailed Characterization of Organic Carbon
Emissions." Proceedings of the National Academy of
Sciences 109, no. 45 (2012): 18318-23. DOI:
10.1073/pnas. 1212272109



8750a

Gasoline
Exhaust -
Reformulated
gasoline (pre-
Tier 2)

Kansas City PM characterization Study. Final Report.
EPA 420-R-08-009. U.S. EPA, April 2008. Available
at: http://www.epa.gov/oms/emission-factors-
re s e arch/inde x. htm.

Emission Profiles for EPA SPECIATE Database.
EPA Contract No. EP-C-06-094. Environ
Corporation, January 2008. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2005-0161, Document ID: EPA-HQ-
OAR-2005-0161-2710.

8751a

Gasoline
Exhaust - E10
ethanol
gasoline (pre-
Tier 2)

Kansas City PM characterization Study. Final Report.
EPA 420-R-08-009. U.S. EPA, April 2008. Available
at: http://www.epa.gov/oms/emission-factors-
re s e arch/inde x. htm.

Emission Profiles for EPA SPECIATE Database.
EPA Contract No. EP-C-06-094. Environ
Corporation, January 2008. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2005-0161, Document ID: EPA-HQ-
OAR-2005-0161-2710.

8753

Gasoline
Vehicle -
Evaporative
emission -
Reformulated
gasoline

Auto/Oil Air Quality Improvement Research Program.
Coordinating Research Council, 1990-1997. List of
reports at: http://www.crcao.com/reports/auto-
oil/default.htm

Emission Profiles for EPA SPECIATE Database.
EPA Contract No. EP-C-06-094. Environ
Corporation, January 2008. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2005-0161, Document ID: EPA-HQ-
OAR-2005-0161-2710.

8754

Gasoline
Vehicle -
Evaporative
emission -
E10 ethanol
gasoline

Auto/Oil Air Quality Improvement Research Program.
Coordinating Research Council, 1990-1997. List of
reports at: http://www.crcao.com/reports/auto-
oil/default.htm

Emission Profiles for EPA SPECIATE Database.
EPA Contract No. EP-C-06-094. Environ
Corporation, January 2008. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2005-0161, Document ID: EPA-HQ-
OAR-2005-0161-2710.

8756

Gasoline
Exhaust - Tier
2 light-duty
vehicles using
0% Ethanol -
Composite
Profile

Data Collected in EPAct Fuel Effects Study Pilot
Phases 1 and 2. Memorandum to the Tier 3 Docket.
U.S. EPA, 2013 Available at:
http://www.regulations.gov. Docket ID: EPA-HQ-
OAR-2011-0135.

Exhaust Emission Profiles for EPA SPECIATE
Database: Energy Policy Act (EPAct) Low-Level
Ethanol Fuel Blends and Tier 2 Light-Duty
Vehicles. EPA Report No. EPA-420-R-09-002.
U.S. EPA, 2009. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2005-0161, Document ID: EPA-HQ-
OAR-2005-0161-2711.

8757

Gasoline
Exhaust - Tier
2 light-duty
vehicles using
10% Ethanol -
Composite
Profile

Data Collected in EPAct Fuel Effects Study Pilot
Phases 1 and 2. Memorandum to the Tier 3 Docket.
U.S. EPA, 2013 Available at:
http://www.regulations.gov. Docket ID: EPA-HQ-
OAR-2011-0135.

Exhaust Emission Profiles for EPA SPECIATE
Database: Energy Policy Act (EPAct) Low-Level
Ethanol Fuel Blends and Tier 2 Light-Duty
Vehicles. EPA Report No. EPA-420-R-09-002.
U.S. EPA, 2009. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2005-0161, Document ID: EPA-HQ-
OAR-2005-0161-2711.

8758

Gasoline
Exhaust - Tier
2 light-duty
vehicles using
15% Ethanol -
Composite
Profile

Data Collected in EPAct Fuel Effects Study Pilot
Phases 1 and 2. Memorandum to the Tier 3 Docket.
U.S. EPA, 2013 Available at:
http://www.regulations.gov. Docket ID: EPA-HQ-
OAR-2011-0135.

Exhaust Emission Profiles for EPA SPECIATE
Database: Energy Policy Act (EPAct) Low-Level
Ethanol Fuel Blends and Tier 2 Light-Duty
Vehicles. EPA Report No. EPA-420-R-09-002.
U.S. EPA, 2009. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2005-0161, Document ID: EPA-HQ-
OAR-2005-0161-2711.

47


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Table A-4 (continued)

Profile
ID

Profile
Name

Source Data

Additional Documentation

8766

Diurnal

Permeation

Evaporative

Emissions

from Gasoline

Vehicles

using 0%

Ethanol -

Combined -

Composite

Profile

Evaporative Emissions from In-use Vehicles: Test Fleet
Expansion. CRC E-77-2b. SWRI Project No.
03.14936.05. Final report. Available at:
http ://www. epa. gov/otaq/emission-factors-research/



8769

Diurnal

Permeation

Evaporative

Emissions

from Gasoline

Vehicles

using 10%

Ethanol -

Combined -

Composite

Profile

Evaporative Emissions from In-use Vehicles: Test Fleet
Expansion. CRC E-77-2b. SWRI Project No.
03.14936.05. Final report. Available at:
http ://www. epa. gov/otaq/emission-factors-research/



8770

Diurnal
Permeation
Evaporative
Emissions
from Gasoline
Vehicles
using 15%
Ethanol -
Combined

Evaporative Emissions from In-use Vehicles: Test Fleet
Expansion. CRC E-77-2b. SWRI Project No.
03.14936.05. Final report. Available at:
http ://www. epa. gov/otaq/emission-factors-research/



8774

Diesel
Exhaust
Emissions
from Pre-
2007 Model
Year Heavy-
Duty Diesel
Trucks

Heavy-duty Vehicle Chassis Dynamometer Testing for
Emissions Inventory, Air Quality Modeling, Source
Appointment and Air Toxics Emissions Inventory. CRC
Project No. E-55/E-59, Phase II Final Report.
Coordinating Research Council, July 2005. Available at:
http://www.crcao.com/publications/emissions/index.html



8775

Diesel

Exhaust

Emissions

from 2007

Model Year

Heavy-Duty

Diesel

Engines with
Controls

Phase 1 of the Advanced Collaborative Emissions Study.
Coordinating Research Council, July 2009. Available at:
http://www.crcao.com/publications/emissions/index.html



8855

Gasoline
Exhaust - Tier
2 light-duty
vehicles using
85% Ethanol -
Composite
Profile

EPAct/V2/E-89: Assessing the Effect of Five Gasoline
Properties on Exhaust Emissions from Light-Duty
Vehicles Certified to Tier-2 Standards: Final Report on
Program Design and Data Collection. EPA-420-R-13-
004. U.S. EPA, April 2013. Available at:
http://www.epa.gov/otaq/models/moves/epact.htm.



8869

Gasoline
Headspace
Vapor - 0%
Ethanol (E0)
Combined -
EPAct/V2/E-
89 Program

Hydrocarbon Composition of Gasoline Vapor Emissions
from Enclosed Fuel Tanks, Report No. 420-R-l 1-018.
U.S. EPA, December 2011. Available at:
http://www.regulations.gov, Docket ID: EPA-HQ-OAR-
2011-0135, Document ID: EPA-HQ-OAR-2011-0135-
0027.

Mobile Source Hydrocarbon Speciation Profiles
for the Tier 3 Rule NPRM and Anti-backsliding
Study Air Quality Modeling. Memorandum to
the Docket. U.S. EPA, 2013. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2011-0135, Document ID: EPA-HQ-
OAR-2011-013 5-0089.

48


-------
Table A-4 (continued)

Profile
ID

Profile
Name

Source Data

Additional Documentation

8870

Gasoline
Headspace
Vapor - 10%
Ethanol (E10)
Combined -
EPAct/V2/E-
89 Program

Hydrocarbon Composition of Gasoline Vapor Emissions
from Enclosed Fuel Tanks, Report No. 420-R-l 1-018.
U.S. EPA, December 2011. Available at:
http://www.regulations.gov, Docket ID: EPA-HQ-OAR-
2011-0135, Document ID: EPA-HQ-OAR-2011-0135-
0027.

Mobile Source Hydrocarbon Speciation Profiles
for the Tier 3 Rule NPRM and Anti-backsliding
Study Air Quality Modeling. Memorandum to
the Docket. U.S. EPA, 2013. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2011-0135, Document ID: EPA-HQ-
OAR-2011-0135-0089.

8871

Gasoline
Headspace
Vapor - 15%
Ethanol (El 5)
Combined -
EPAct/V2/E-
89 Program

Hydrocarbon Composition of Gasoline Vapor Emissions
from Enclosed Fuel Tanks, Report No. 420-R-l 1-018.
U.S. EPA, December 2011. Available at:
http://www.regulations.gov, Docket ID: EPA-HQ-OAR-
2011-0135, Document ID: EPA-HQ-OAR-2011-0135-
0027.

Mobile Source Hydrocarbon Speciation Profiles
for the Tier 3 Rule NPRM and Anti-backsliding
Study Air Quality Modeling. Memorandum to
the Docket. U.S. EPA, 2013. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2011-0135, Document ID: EPA-HQ-
OAR-2011-0135-0089.

8872

Gasoline
Vehicle -
Evaporative
emission -
El 5 ethanol
gasoline -
Calculated

Auto/Oil Air Quality Improvement Research Program.
Coordinating Research Council, 1990-1997. List of
reports at: http://www.crcao.com/reports/auto-
oil/default.htm

EPAct/V2/E-89: Assessing the Effect of Five Gasoline
Properties on Exhaust Emissions from Light-Duty
Vehicles Certified to Tier-2 Standards: Final Report on
Program Design and Data Collection. EPA-420-R-13-
004. U.S. EPA, April 2013. Available at:
http://www.epa.gov/otaq/models/moves/epact.htm.

Mobile Source Hydrocarbon Speciation Profiles
for the Tier 3 Rule NPRM and Anti-backsliding
Study Air Quality Modeling. Memorandum to
the Docket. U.S. EPA, 2013. Available at:
http://www.regulations.gov. Docket ID: EPA-
HQ-OAR-2011-0135, Document ID: EPA-HQ-
OAR-2011-013 5-0089.

8934

Evaporative
Emissions
from Flexible-
Fuel Gasoline
Vehicles
using 85%
Ethanol

Exhaust and Evaporative Emissions Testing of Flexible-
Fuel Vehicles. Final report. CRC Report CRC-E-80.
Coordinating Research Council, Inc. August 2011.
Report and program data available at
http://www.crcao.org/publications/emissions/index.html



95335

Diesel
Exhaust -
Heavy-heavy
duty truck -
2011 model
year

Khalek, I., Blanks, M., and Merritt, P. M. (2013). Phase
2 of the Advanced Collaborative Emissions Study.
Prepared by Southwest Research Institute for the
Coordinating Research Council and the Health Effects
Institute, November 2013. Available at www.crcao.org.



49


-------
Appendix B CNG CH4/THC and Speciation Constant
Parameters for CNG vehicles

SPECIATE 5.18 does not contain a TOG speciation profile from modern CNG exhaust
emissions. We used hydrocarbon speciation data from Ayala et al. that measured a 2000 MY
transit bus with a Detroit Diesel Series 50G engine with and without an oxidation catalyst
collected on the CBD cycle.43 This data allows us to isolate the impact of the oxidation catalyst.
Studies have shown that the speciation of hydrocarbon can be drastically different between
uncontrolled CNG buses and CNG buses with oxidation catalysts. For example, formaldehyde
emissions can be quite large from uncontrolled CNG buses57'58, but are significantly reduced
with oxidation catalysts.43 Large formaldehyde emissions have a large impact on the NMOG
and VOC emissions estimated from THC emissions from CNG buses because THC-FID
measurements have a small response to formaldehyde concentrations.59

We used the CBD test cycle to be consistent with our analysis of the criteria emission rates
documented in the heavy-duty emission rate report.2 NMOG and VOC conversion factors are
listed in Table B-l. The NMOG values are calculated using Equation 7. The VOC emissions are
calculated from subtracting the ethane and acetone from the NMOG values. The emissions of
hazardous air pollutants, including formaldehyde and acetaldehyde, are also estimated from this
study as documented in the MOVES3 Toxics Emissions Report.7

Table B-l Hydrocarbon Speciation Values for CNG Transit Emissions with No Control

and with Oxidation Cata

yst from Ayala et al. (2003)43

Measured values
(mg/mile)

No Control

Oxidation
Catalyst

THC

8660

6150

CH4

7670

5900

C2H6

217

72.2

Formaldehyde

860

38.4

Acetaldehyde

50.7

32.6

Calculated values (mg/mile)





NMHC

990

250

NMOG

1881.0

309.0

VOC

1658.5

232.1

Ratios





NMOG/NMHC

1.90

1.24

VOC/NMHC

1.68

0.93

50


-------
Appendix C TOG Speciation Map

Table C-4 provides a speciation map between MOVES TOG profiles and the distinguishing
factors used in MOVES. To help interpret this table, we have also provided tables that describe
the MOVES processes, fuel subtypes, and regulatory classes and list their id codes.

Model YearGroupID is simply the first model year of the group, followed by the last model
year.

Table C-l MOVES Processes Relevant for Speciation Profiles'*

processID

Process Name



1

Running Exhaust

Exhaust emissions from a running vehicle

2

Start Exhaust

Exhaust emissions that occur at engine start

11

Evap Permeation

migration of hydrocarbons through materials in the fuel
system

12

Evap Fuel Vapor Venting

Escape of vapors that are generated through heating of
gasoline fuel system

13

Evap Fuel Leaks

Fuels escaping gasoline fuel system in a non-vapor form

15

Crankcase Running Exhaust

Combustion products and oil droplets from compression
ignition engines that are vented to the atmosphere rather
than routed through the exhaust

16

Crankcase Start Exhaust

17

Crankcase Extended Idle Exhaust

18

Refueling Displacement Vapor Loss

Displaced fuel vapors when liquid fuel is added to the
vehicle tank

19

Refueling Spillage Loss

Vapor emissions from any liquid fuel that is spilled during
refueling

90

Extended Idle Exhaust

Idle emissions during "hotelling" of long-haul combination
trucks

91

Auxiliary Power Exhaust

Auxiliary power unit emissions during hotelling of long-
haul combination trucks

s Not a complete list of MOVES emission processes.

51


-------
Table C-2 Regulatory Classes in MOVES3

regClassID

Regulatory Class Name

Description

0

Doesn't Matter

Doesn't Matter

10

MC

Motorcycles

20

LDV

Light-Duty Vehicles

30

LDT

Light-Duty Trucks

41

LHD2b3

Class 2b and 3 Trucks (8,500 lbs < GVWR <= 14,000
lbs)

42

LHD45

Class 4 and 5 Trucks (14,00 lbs. < GVWR <= 19,500
lbs.)

46

MHD

Class 6 and 7 Trucks (19,500 lbs. < GVWR < =33,000
lbs.)

47

HHD

Class 8a and 8b Trucks (GVWR > 33,000 lbs.)

48

Urban Bus

Urban Bus (see CFR Sec. 86.091 2)

49

Gliders

Glider Vehicles60

Table C-3 Fuel Subtypes in MOVE S3

fuelSubtypelD

fuelTypelD

fuelSubtypeDesc

10

1

Conventional Gasoline

11

1

Reformulated Gasoline (RFG)

12

1

Gasohol (E10)

13

1

Gasohol (E8)

14

1

Gasohol (E5)

15

1

Gasohol (E15)

20

2

Conventional Diesel Fuel

21

2

Biodiesel (BD20)

22

2

Fischer-Tropsch Diesel (FTD100)

30

3

Compressed Natural Gas (CNG)

40

4

Liquefied Petroleum Gas (LPG)

50

5

Ethanol

51

5

Ethanol (E85)

52

5

Ethanol (E70)

90

9

Electricity

52


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Table C-4 TOG Speciation

Map

Profile

Profile Description

modelYear-
GroupID

processID

fuelSubTypelD

regClassID

1001

CNG Exhaust

19602060

1,2,15,16

30

48

95120m

Liquid Diesel

19602060

11

20,21,22

0

95120m

Liquid Diesel

19602060

12,13,18,19

20,21,22

10,20,30,40,41,42,46,47,48

8753

E0 Evap

19602060

12,13,19

10

10,20,30,40,41,42,46,47,48

8754

E10 Evap

19602060

12,13,19

12,13,14

10,20,30,40,41,42,46,47,48

8756

Tier 2 E0 Exhaust

20012060

1,2,15,16

10

20,30

8757

Tier 2 E10 Exhaust

20012060

1,2,15,16

12,13,14

20,30

8758

Tier 2 El5 Exhaust

19602060

1,2,15,16

15,18

10,20,30,40,41,42,46,47,48

8766

EO evap permeation

19602060

11

10

0

8769

E10 evap permeation

19602060

11

12,13,14

0

8770

El5 evap permeation

19602060

11

15,18

0

8774

Pre-2007 MY HDD
exhaust

19602006

1,2,15,16,17,90

20,21,22

40,41,42,46,47,48

8774

Pre-2007 MY HDD
exhaust

19602060

91

20,21,22

46,47

8774

Pre-2007 MY HDD
exhaust

19602006

1,2,15,16

20,21,22

20,30

8775

2007+ MY HDD
exhaust

20072009

1,2,15,16

20,21,22

20,30

8775

2007+ MY HDD
exhaust

20072009

1,2,15,16,17,90

20,21,22

40,41,42,46,47,48

95335a

2010+MY HDD
exhaust

20102060

1,2,15,16

20,21,22

20,30

95335a

2010+MY HDD
exhaust

20102060

1,2,15,16,17,90

20,21,22

40,41,42,46,47,48

8855

Tier 2 E85 Exhaust

19602060

1,2,15,16

50,51,52

10,20,30,40,41,42,46,47,48

8869

E0 Headspace

19602060

18

10

10,20,30,40,41,42,46,47,48

8870

E10 Headspace

19602060

18

12,13,14

10,20,30,40,41,42,46,47,48

8871

El5 Headspace

19602060

18

15,18

10,20,30,40,41,42,46,47,48

8872

El5 Evap

19602060

12,13,19

15,18

10,20,30,40,41,42,46,47,48

8934

E85 Evap

19602060

11

50,51,52

0

8934

E85 Evap

19602060

12,13,18,19

50,51,52

20,30,40

8750a

Pre-Tier 2 E0 exhaust

19602000

1,2,15,16

10

20,30

8750a

Pre-Tier 2 E0 exhaust

19602060

1,2,15,16

10

10,40,41,42,46,47,48

8751a

Pre-Tier 2 E10 exhaust

19602000

1,2,15,16

11,12,13,14

20,30

8751a

Pre-Tier 2 E10 exhaust

19602060

1,2,15,16

11,12,13,14

10,40,41,42,46,47,48

53


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Appendix D Comparison of ACES Phase 1 and Phase 2
SPECIATE Profiles

We initially developed profile 95335 from the ACES Phase 2 profile as recommended by the
MOVES2014 peer-reviewers.11 However, there are inconsistencies between the ACES Phase 1
and 2 profiles. For example, ACES Phase 1 is composed of over 50% percent methane, while
the ACES Phase 2 profile has zero percent methane (Updated in Section 3.6). Other anomalies
in the ACES Phase II profile included benzene is not detected (ND) in the ACES Phase II
profile (from which we then assumed benzene=0), while ethanol comprises over 3% of the TOG
emissions. As suggested by one of the 2017 peer-reviews12, to better understand the
consistency of these changes, we compared emission trends among different groups of gaseous
hydrocarbons (Tables D-5) and individual compounds (Table D-6 through D-10) between the
ACES Phase 1 and Phase 2 profiles.

While relative amounts of olefins and aromatics substantially increased in the Phase 2 profile
relative to Phase 1, paraffins, aldehydes and ketones decreased. However, there was
inconsistency in emission changes among individual compounds in all chemical groups. For
example, propane increased by more than a factor of four from ACES Phase 1 to ACES Phase
2, but hexane decreased by 69%. Similarly, while the total weight percentage of olefins
decreased, both ethene and propene increased as a proportion of total organic emissions.
Carbonyl compounds consistently decreased with the exception of acetaldehyde which
increased by 3%.

We did not attempt to impute minimum values in the cases where the species were not detected
in one of the profiles. Our speciation profiles consist of the weight percentage of total organic
emissions for each detected species as opposed to an absolute emissions value (in mg/mi or
similar unit); therefore, it is not straightforward to apply a below detection limit value to not
measured species

Within SPECIATE profile 95335, the mass fraction of three alcohol species, ethyl alcohol
(ethanol), isopropyl alcohol (2-propanol), methyl alcohol (methanol), sum to 7% of the total
TOG emissions. We do not believe these alcohol species are produced in modern heavy-duty
exhaust; instead they are likely an artifact of measurement during sampling or analysis in the
laboratory. With agreement from one of the 2017 peer-reviewers12, we created a new profile
(95335a) from 95335 where the mass fractions for the alcohol species are set to zero and we re-
weighted the remaining non-alcohol species.

While it is difficult to predict how complex emission control systems may affect individual
compounds, the inconsistent pattern of hydrocarbon measurements suggests that there are
potential significant uncertainties in the measurements. Additional sources of uncertainty in the
ACES phase 2 profile are due to the small number of engines tested (three), the low
concentrations of organic gas emitted with new 2010-compliant engines and aftertreatment
systems causing many measurements to be near the detection limits. Although ACES Phase 2 is
currently our best data source for the speciation of advanced technology diesels, the data should
still be interpreted with caution. As we discussed in the main text, we recommend further work

54


-------
to improve the confidence of speciation of exhaust from modern heavy-duty diesel engines,
including from engines with aged and deteriorated aftertreatment systems.

Table D-5 Comparison of Groups of Compounds from diesel exhaust speciation from

ACES Phase 1 and ACES Phase 2).

Compound Group

ACES Phase 1
(Weight %)

ACES Phase II
(Weight %)

% Change:
Phase I to
Phase II

Paraffins (total)

67.09

33.07

-51%

Olefins (total)

6.13

33.09

440%

Aromatics (total)

5.77

17.37

201%

Aldehydes/Ketones (total)

16.66

7.83

-53%

Unknown

4.35

1.56

-64%

Other



7.07



55


-------
Table D-6 Comparison of Individual Compounds from diesel exhaust speciation from

ACES Phase 1 and ACES Phase 2): Parafins





ACES Phase

ACES

% Change:

CAS

Name

1 (Weight

Phase II

Phase I to





%)

(Weight %)

Phase II

74-82-8

methane

51.64'





74-84-0

Ethane

1.34

10.11

655%

96-37-7

methylcyclopentane

0.02





112-40-3

dodecane

2.34

0.36

-84%

1120-21-4

undecane

1.75





106-97-8

N-butane

1.10

0.17

-85%

109-66-0

N-pentane

1.01

3.06

201%

78-78-4

Isopentane (2-Methylbutane)



0.88



124-18-5

decane

0.38

0.12

-68%

111-84-2

nonane

0.28

2.72

873%

74-98-6

Propane

0.51

2.75

441%

75-28-5

Isobutane

0.50

1.03

108%

3522-94-9

2,2,5 -trimethy lhexane

0.04





590-73-8

2,2 -dimethy lhexane

0.66





589-43-5

2,4 -dimethy lhexane

0.42





589-34-4

3-methy lhexane

0.15

0.26

76%

108-87-2

methylcyclohexane

0.89

0.77

-13%

619-99-8

3 -ethy lhexane

0.08





110-54-3

n-hexane

0.24

0.07

-69%

96-14-0

3-methylpentane

0.14





107-83-5

2-methylpentane

0.13

0.59

336%

79-29-8

2,3-dimethylbutane

0.09





15869-87-1

2,2-dimethyloctane

0.00

0.30

26037%

111-65-9

octane

0.20

0.36

80%

565-75-3

2,3,4-trimethylpentane

0.54





560-21-4

2,3,3 -trimethy lpentane

0.52





540-84-1

2,2,4-trimethy lpentane

0.37

0.37

-1%

565-59-3

2,3-dimethylpentane

0.35





562-49-2

3,3 -dimethy lpentane

0.00





590-35-2

2,2-dimethylpentane

0.02





1068-19-5

4,4-dimethylheptane

0.16





1072-05-5

2,6-dimethylheptane

0.20

0.82

303%

589-81-1

3-methylheptane

0.07





592-27-8

2-methylheptane







142-82-5

heptane

0.28

0.09

-66%

463-82-1

2,2-dimethylpropane

0.68





75-83-2

2,2-dimethylbutane



2.40



4 This differs from the 58% CH4/THC reported in Table 3-2 because the 51% reports the fraction of methane/TOG.
We calculated THC from TOG using the methods described in Section 3.2

56


-------
Table D-6 (Continued)





ACES Phase

ACES

% Change:

CAS

Name

1 (Weight

Phase II

Phase I to





%)

(Weight %)

Phase II

767-58-8

1-methy lindane







2216-33-3

3-methyloctane



0.16



584-94-1

2,3 -dimethy lhexane







108-08-7

2,4-dimethylpentane



1.45



591-76-4

2-methy lhexane



0.41



124-11-8

1-nonene



0.06



2213-23-2

2,4-dimethylheptane



0.61



4032-94-4

2,4-dimethyloctane



0.63



3221-61-2

2-methyloctane



0.19



583-48-2

3,4-dimethy lhexane



0.22



90622-57-4

C9-cl2 isoalkanes



1.51



2532-58-3

Cis-1,3 -dimethy Icy clopentane



0.46





Cis-l,trans-2,4-







16883-48-0

trimethylcyclopentane



0.06



1759-58-6

Trans-l,3-dimethylcyclopentane



0.07



57


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Table D-7 Comparison of Individual Compounds from diesel exhaust speciation from
	 ACES Phase 1 and ACES Phase 2): Olefins		

CAS

Name

ACES Phase 1
(Weight %)

ACES Phase
II (Weight

%)

% Change:
Phase I to
Phase II

74-85-1

ethene

3.07

9.55

212%

763-29-1

2-methy 1-1 -pentene

0.01





115-07-1

propene

0.94

4.31

359%

74-86-2

acetylene

0.58

0.82

42%

115-11-7

2-methylpropene

0.97

13.33

1268%

106-99-0

1,3-butadiene

0.04





590-19-2

1,2-butadiene







592-41-6

1-hexene

0.01





7688-21-3

Cis-2-hexene







4050-45-7

Trans-2-hexene







106-98-9

1-butene

0.03





590-18-1

cis-2-butene



0.53



624-64-6

trans-2-butene







513-35-9

2-methyl-2-butene



3.01



691-37-2

4-methy 1-1 -pentene

0.06





625-27-4

2-methyl-2-pentene

0.03





7385-78-6

3,4-dimethyl-1 -pentene

0.07





107-40-4

2,2,4-trimethyl-2-pentene

0.04





142-29-0

cyclopentene

0.01





816-79-5

3-ethyl-2-pentene

0.01

0.50

4963%

107-00-6

1-butyne

0.25





542-92-7

cyclopentadiene

0.02





627-20-3

Cis-2-pentene



0.17



110-83-8

Cyclohexene



0.87



58


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Table D-8 Comparison of Individual Compounds from diesel exhaust speciation from
	 ACES Phase 1 and ACES Phase 2): Aromatics		

CAS

Name

ACES Phase 1
(Weight %)

ACES Phase
II (Weight

%)

% Change:
Phase I to
Phase II

71-43-2

benzene

0.61





108-88-3

toluene

1.24

1.52

22%

95-47-6

o-xylene

0.65

0.37

-44%

108-38-3; 106-42-3

m/p-xylenes

1.04

6.65

539%

527-53-7

1,2,3,5 -tetramethy lb enzene

0.16





95-93-2

1,2,4,5-tetramethylbenzene

0.08

1.25

1526%

95-63-6

1,2,4-trimethylbenzene

0.75

0.18

-76%

25551-13-7

trimethylbenzene







526-73-8

1,2,3 -trimethylbenzene

0.06

4.54

7737%

108-67-8

1,3,5 -trimethylbenzene







1758-88-9

1,4-dimethyl-2-ethylbenzene

0.12





620-14-4

1 -Methy 1-3 -ethy lbenzene

0.08





622-96-8

1 -Methyl-4-ethy lbenzene







611-14-3

1 -methyl-2-ethy lbenzene

0.05

0.02

-56%

103-65-1

Propy lbenzene



0.72



100-41-4

ethy lbenzene

0.31

0.92

194%

98-19-1

tert-butyl-m-xylene

0.13





100-42-5

styrene







98-82-8

isopropy lbenzene



0.52



538-93-2

(2 -methy lpropy l)benzene

0.20

0.12

-43%

535-77-3

1 -Methy 1-3 -isopropy lbenzene

0.05





527-84-4

1 -methyl-2-isopropy lbenzene

0.06





1074-43-7

1 -Methy 1-3 -propy lbenzene

0.02





03968-85-2

2-methyl-butyl-benzene

0.05





1074-92-6

t-1 -Butyl-2-Methylbenzene

0.03





91-20-3

Naphthalene

0.07





141-93-5

1,3-diethylbenzene (meta)







105-05-5

1,4-diethylbenzene (para)







0

Isomers of diethylbenzene







104-51-8

buty lbenzene









1,2,4-trimethylbenzene







25155-15-1

Isopropy ltoluene







28729-54-6

Propyltoluene







7364-19-4

1 -tert-butyl-4-ethy lbenzene



0.56



59


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Table D-9 Comparison of Individual Compounds from diesel exhaust speciation from
ACES Phase 1 and ACES Phase 2): Aldehydes/Ketones

CAS

Name

ACES Phase 1
(Weight %)

ACES Phase
II (Weight

%)

% Change:
Phase I to
Phase II

50-00-0

formaldehyde

10.05

2.20

-78%

75-07-0

acetaldehyde

3.36

3.45

3%

107-02-8

acrolein

0.50

0.30

-41%

67-64-1

acetone

0.76

1.01

34%

100-52-7

benzaldehyde

0.79

0.03

-96%

123-38-6

propionaldehyde

0.15

0.24

58%

78-93-3

Methyl ethyl ketone (2-butanone)

0.16

0.08

-50%

123-72-8

butyraldehyde

0.16

0.11

-30%

66-25-1

hexanaldehyde

0.11

0.04

-64%

590-86-3

isovaleraldehyde

0.08

0.03

-69%

104-27-0

M- & p-tolualdehyde

0.49

0.13

-75%

110-62-3

valeraldehyde

0.05

0.14

208%

4170-30-3

Crotonaldehyde



0.02



28351-09-9

Dimethylbenzaldehyde



0.02



529-20-4

o-Tolualdehyde



0.04



Table D-10 Comparison of Individual Compounds from diesel
ACES Phase 1 and ACES Phase 2): Other/Un

jxhaust speciation from
mown

CAS

Name

ACES Phase 1
(Weight %)

ACES Phase
II (Weight

%)

% Change:
Phase I to
Phase II

64-17-5

Ethyl alcohol (ethanol)



3.19



67-63-0

Isopropyl alcohol (2-Propanol)



1.74



67-56-1

Methyl alcohol (methanol)



2.14



N/A

C-6 Compounds



1.42



N/A

C-8 Compounds



0.14



N/A

Unknown

4.35





60


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Appendix E Development of PM2.5 speciation profiles in
MOVES

This report includes the derivation of each PM2.5 profiles used in MOVES to estimate AE6
chemical mechanism PM2.5 species.

For comparison purposes, the seven PM2.5 profiles developed for MOVES are presented in
Table E-l. The remainder of this appendix explains how each profile was derived.

Table E-l PM2.5 Profiles developed for MOVES



Light-duty Gasoline
Exhaust - Start (8992)

Light-duty Gasoline
Exhaust- Hot Stabilized
(8993)

Conventional HDD- Idle
(8994)

Conventional HDD- Hot
Stabilized Running (8995)

2007 and Newer Diesel
Exhaust Composite (8996)

CNG transit bus exhaust
from a lean-burn engine -
no aftertreatment (95219a)

CNG transit bus exhaust
from a lean-burn engine -
aftertreatment (95220a)

Elemental Carbon
(EC)

44.37%

14.00%

46.40%

78.97%

9.98%

9.25%

11.12%

Organic Carbon (OC)

42.64%

55.70%

34.74%

14.52%

22.33%

36.99%

37.45%

Non-carbon Organic
Matter (NCOM)

8.53%

11.14%

6.95%

2.90%

4.47%

7.40%

7.49%

S04

0.95%

7.19%

5.27%

1.03%

59.91%

0.64%

1.04%

N03

0.26%

0.29%

1.25%

0.18%

0.00%





NH4

0.43%

2.78%

1.74%

0.36%

0.00%





Fe

0.31%

1.83%

0.34%

0.13%

0.64%

0.25%

0.25%

A1



0.32%

0.06%

0.06%

0.11%

0.89%

0.89%

Si



0.32%

0.30%

0.22%

0.09%

0.46%

0.59%

Ti



0.03%

0.01%

0.01%

0.02%





Ca

0.39%

1.44%

0.58%

0.35%

0.47%

0.21%

0.44%

Mg

0.02%

0.14%

0.13%

0.01%

0.14%





K



0.09%

0.26%

0.02%

0.05%





Na

0.01%

0.04%

0.31%

0.03%

0.99%





CI

0.02%

0.10%

0.38%

0.13%

0.04%





unspeciated
(PMOTHR)

2.09%

4.58%

1.28%

1.09%

0.78%

43.90%

40.74%

61


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E.l Development of Gasoline Profiles from the Kansas City
Light-duty Vehicle Emissions Study

The Kansas City Light-duty Vehicle Emissions Study (KCVES) is the primary source of PM2.5
emission rates for light-duty vehicles in MOVES.1 The KCVES sampled PM2.5 emissions from
496 vehicles recruited in a stratified random sample. The KCVES also measured speciated
PM2.5 on a subset of 99 of these vehicles. An overview of the vehicles included in this
"chemical subset" is included in Table E-2.

Table E-2 Vehicle Sample Size in the Kansas City Light Duty Vehicle Emissions Study

Vehicle
Type1

Strata

Model
Year
Group

% of KC
LDGV
Vehicle
Population

% of KC
LDGV
Vehicle
Miles
Traveled
(VMT)

Summer Round
Sample

Winter Round
Sample

Full
Sample

Chemical
Subset

Full
Sample

Chemical
Subset

Truck

1

pre-1981

1.1%

0.6%

2

2

10

3

2

81-90

3.7%

2.4%

21

4

33

3

3

91-95

7.2%

6.5%

18

6

33

7

4

96-2005

28.6%

34.2%

39

8

59

11

Car

5

pre-1981

1.3%

0.7%

6

5

17

3

6

81-90

7.4%

4.6%

49

4

40

5

7

91-95

13.4%

11.2%

39

6

44

9

8

96-2005

37.3%

39.8%

87

14

41

9





Sum =

100%

100%

261

49

277

50

The derivation of the PM2.5 gasoline profile for MOVES is documented in Sonntag etal.
(2013).61 A summary of the speciation derivation is included in this report, as well as a
discussion on implementing the profile into the MOVES framework. Two gasoline profiles are
developed to maintain differences between start and running processes. Minor differences were
detected between the PM2.5 compositions between seasons, which were confounded by the
different vehicles tested in each season. The analysis used equally weighted data from the
summer and winter tests to calculate a profile that incorporates data from both seasons.

We discovered high concentrations of silicon in some of the PM2.5 measurements— likely due to
contamination from silicone rubber couplers used in KCVES. The silicone contamination
occurred primarily on bag 2 of the LA-92 drive cycle which was used for developing the
running PM2.5 speciation profile and emission rates. The silicone contamination was larger for
trucks than cars due to their higher exhaust temperatures. The effect of the silicone
contamination was removed from the developed profile using the silicon emissions
measurement by X-ray florescence. The primary exhaust PM2.5 emission rates were corrected in
MOVES to account for the silicone contamination.1 After removing the silicone contamination
from the speciated data, no significant differences were detected between passenger cars and
light-duty trucks, and the data from the cars and trucks were pooled to develop single start and
running PM2.5 speciation profiles for all light-duty gasoline vehicles.

62


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While differences in the PM2.5 compositions were detected among model year groups, the
speciation sample size was deemed too limited to accurately capture the impact of deterioration
and high-emitting vehicles within each model-year group. Instead fleet-average profiles were
calculated to better capture the impact of deterioration within all model year groups and to avoid
over-fitting the data to model year group trends. Malfunctioning high-emitting vehicles are
known to contribute a significant share of in-use PM emissions from light-duty
vehicles.62'63'64'65 High-emitting gasoline emissions have a highly variable PM composition due
to failed emission control systems, excessive oil consumption, and poor fuel control. Previous
analysis of the KCVES suggested that the speciation subsample (102 tests) provides a
reasonable estimate of the total PM mass compared to the full sample (522 tests), but the
speciation sample underestimated the high emitting vehicles in the newer model year groups.66
Other test programs have confirmed that high emitting gasoline vehicles also occur in vehicle
fleets such as 1990-era vehicles with electronic fuel injection.62'63'64 By using all the data in a
fleet-average approach, we incorporated the impact of deteriorated vehicles on the fleet-average
PM2.5 emissions.

The fleet-average PM speciation profiles are calculated using seasonal, vehicle-miles-traveled
(VMT), and PM mass-weighting. The PM profile is calculated using the ratio of the means, also
referred to as a mass-normalized emission profile.67 The ratio of means is calculated by first
calculating the mean emission rate of the total PM2.5, and the mean emission rate of each PM
species (EC, OC, Fe, etc.). Then the speciation profile is calculated, by calculating the ratio of
the mean emission rate from each species, to the mean PM2.5 emission rate, e.g., mean
(EC)/mean(PM). The vehicle tests from each season are equally weighted, and averaged
according to the calculated contribution to annual VMT in the Kansas City MSA (Table E-2).
By using VMT and mass weighting, the profile scales up the contribution of older and higher
emitting vehicles according to their high PM emissions, but also scales their down their
contribution based on the relatively small number of vehicle miles traveled associated with
these vehicles. For application in MOVES, the fleet-average profile is used to characterize
PM2.5 emissions across all model year groups, and all ages of vehicles used to represent
deterioration.

Because the PM2.5 speciation varied significantly by model year group,61 the fleet average
speciation profile is sensitive to the averaging assumptions. As mentioned above, we did not
maintain the difference in speciation in model year groups, due to concern that the model-year
groups would not be representative of the PM emissions as the vehicles aged. Given the
uncertainty of the PM speciation profiles, we thought it would be unreasonable to model
differences in PM speciation according to different ages of vehicle fleets in different areas in the
US. For simplicity, we assume that the fleet-average PM2.5 profile from Kansas City to be
representative of the US gasoline fleet.

We recognize the need to incorporate speciation data on newer vehicles. For the next generation
of vehicles, the composition of PM is expected to become increasingly dominated by black
carbon emissions from both low-emitting port-fuel injected vehicles62'68'69'70 and gasoline-direct
injection (GDI) vehicles.71'72'73 We plan on incorporating light-duty gasoline PM profiles to
MOVES and SPECIATE as such data on representative, in-use vehicles become available.

63


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The developed PM2.5 profiles used in MOVES for gasoline exhaust are included in Table E-3..
The number of samples for each PM2.5 species are also shown. EC was measured on each
vehicle test and has a much greater sample size than the other species. The EC and nonECPM
emission rates in MOVES are consistent with the EC fractions listed here.

For application in MOVES, only the PM2.5 species required by CMAQv5.1 are reported. Metal
emission rates for Mn, Cr, and Ni for gasoline vehicles based on the KCVES are provided in the
Air Toxics Report.7 The PM2.5 ratios that were not significantly greater than 0 at the 95 percent
confidence intervals were reported as 0, which removed five PM2.5 species pollutants from the
start profile. Fuel samples analyzed for 171 of the vehicles tested in KCVES yielded an average
fuel sulfur content of 161.2 ppm. Fuel sulfur content in the US is now much lower after
implementation of the Tier 2 74 and Tier 375 Gasoline Sulfur Standards (30 ppm beginning 2006-
2008, and 10 ppm in 2020). In MOVES, the baseline sulfate emissions estimated from the PM2.5
profile are adjusted according to the fuel sulfur content as discussed in the fuel effects report.51

Details on the data, quality control measures, and statistical methods used to develop the profile
are documented in the Sonntag etal. (2013).61 The paper also introduces methods to identify
significant measurements, correct for organic carbon positive artifact, control for contamination
from the testing environment on the PM2.5 speciation profiles, and impute missing PM2.5 species
in the KCVES measurements from other light-duty gasoline PM emission studies. Speciation
factors for additional PM2.5 species (P, Cu, Zn, Br, Mo, and Pb) that are not included in
MOVES are also presented.

Table E-3 Gasoline PM2.5 Profile for Start and Running Emissions Weighted Average

using Vehicle Miles Traveled (VMT)

PM Species

Start (8992)

Running (8993)



n

mean ratio +/- 95% CI

n

mean ratio +/- 95% CI

Elemental Carbon (EC)

484

44.37%

+/- 4.30%

531

14.00%

+/- 2.68%

Organic Carbon (OC)

66

42.64%

+/- 6.63%

99

55.70%

+/- 4.02%

Non-carbon Organic Matter (NCOM)

66

8.53%

+/- 1.33%

99

11.14%

+/- 0.80%

S04

66

0.95%

+/- 0.24%

99

7.19%

+/- 1.90%

N03

66

0.26%

+/- 0.08%

99

0.29%

+/- 0.08%

NH4

66

0.43%

+/- 0.10%

99

2.78%

+/- 0.73%

Fe

66

0.31%

+/- 0.21%

99

1.83%

+/- 0.53%

A1







99

0.32%

+/- 0.10%

Si







99

0.32%

+/- 0.10%

Ti







99

0.03%

+/- 0.01%

Ca

66

0.39%

+/- 0.14%

99

1.44%

+/- 0.26%

Mg

66

0.02%

+/- 0.02%

99

0.14%

+/- 0.02%

K







99

0.09%

+/- 0.03%

Mn







99

0.02%

+/- 0.02%

Na

66

0.01%

+/- 0.00%

99

0.04%

+/- 0.01%

CI

66

0.02%

+/- 0.01%

98

0.10%

+/- 0.04%

Unspeciated (PMOTHR)

66

2.09%

+/- 1.75%

99

4.56%

+/- 1.10%

64


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E.2 Development of E55/59 Profile for Pre-2007
Conventional Diesel

An PM2.5 profile for pre-2007 conventional11 diesel trucks was developed from the CRC E55/59
Study: Heavy-Duty Vehicle Chassis Dyno Testing for Emissions Inventory.76 The E55/59
program is the current source for PM2.5 emission rates for medium- and heavy-duty pre-2007
model year conventional diesel trucks in MOVES, and is the source of the conventional pre-
2007 diesel TOG speciation profiles. By using the E55/59 study for PM2.5 speciation profiles,
we are using consistent data with both the PM2.5 emission rates and the TOG speciation profiles
in MOVES.

The E55/59 PM2.5 profile includes measurements from eight heavy-duty trucks, ranging from
1985 to 2004 model year as shown in Table D-4. The E55/59 average sulfur content is 172 ppm.
The CRC E55/59 study was conducted from 2001-2005 in several phases. Chemical
characterization of PM2.5 emissions was conducted for nine of the 75 trucks tested in the E55/59
study, ranging from 1985 to 2004 model year.

Table

£-4 Vehicle Information from t

ie Speciated E55/59 Trucks

Phase

ID

Medium/
Heavy-
Duty

Vehicle
Model
Year

Vehicle
Manufacturer

Engine
Model
Year

Engine
Model

Engine
Power
(hp)

Engine
Disp.
(Liter)

Engine
Manufacturer

Odometer
Reading
(mi)

1

1

H

1994

Freightliner

1994

Series
60

470

12.7

Detroit

639105

1

2

H

1995

Freightliner

1995

3406B

375

14.6

Caterpillar

241843

1

3

H

1985

International

1985

NTCC-
300

300

14

Cummins

501586

2

39

H

2004

Volvo

2003

ISX

530

14.9

Cummins

45

2

40

H

2004

Freightliner

2003

Series
60

500

14

Detroit

8916

2

41

M

1998

Ford

1997

B5.9

210

5.9

Cummins

13029

2

42

H

2000

Freightliner

1999

3406

435

14.6

Caterpillar

576998

2

43

H

1995

Peterbilt

1994

Series
60

470

12.7

Detroit

899582

2

44

H

1989

Volvo

1989

3406

300 (est.)

14.6

Caterpillar

811202

In all, 65 tests were conducted on the nine trucks selected for PM speciation. Phase 1 tested
three heavy heavy-duty diesel trucks (HHDDTs) for PM speciation on four modes of the Urban
Dynamometer Driving Schedule (UDDS), including: idle, creep, transient and cruise. Phase 2
tested six additional heavy heavy-duty diesel trucks, and one medium heavy-duty diesel truck
(MHDDT). In Phase 2, the HHDDTs were also tested on the UDDS, as well as a high-speed
cruise mode added after Phase 1. The MHDDT was tested on MHDDT schedule developed by
the California Air Resources Board that included two transient modes and a cruise mode. For
chemical speciation, some tests were repeated in sequence to collect additional mass on the

65


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filter, including extended idle and extended creep. In Phase 2, the speciation data was not
collected for the creep mode.76

The total and speciated PM2.5 emissions data from the E55/59 study was compiled from the
speciation database compiled in CRC Report No. E75-2: Diesel Unregulated Emission
Characterization Report77 and from Table 17 of the E55/59 Phase 1 report.78 The data reduction
steps used to develop a PM2.5 speciation profile from the E55/59 speciated data are outlined in
the following Steps: 1-4.

Step 1. We first calculated the average PM2.5 profile for each individual truck and four generic
classifications of test cycle, namely: idle, creep, cruise, and transient. The composite UDDS
cycle is classified as a transient cycle, similar to the classification conducted of speciation
profiles by E75-2.76 The truck and test cycle average PM profiles are calculated as ratios of the
means, also called a PM mass-weighted profile. In this manner, idle tests that contain three
repeat idle cycles contribute more to the average than tests that include only one idle cycle. The
average profile for each vehicle/test cycle classification is shown in Figure D-l. Thirty average
speciation profiles were calculated from the 65 tests as shown in Figure D-l. Typically, each
truck/cycle average contains two tests.

E

~3)

o
a)

T3

o
E
~3)
af
ro
Q1
c
o
'(/)
CO

'E

LD

31
31
21
21
11
11
CK
0:1

6"
5-
4-
3-

2-
1-

0-

1-

11

1r<

01

0^

0^

0:

01.

3^

3^

2:

21

I

II
0:
0:1

I

I

39

HI

40

41

42

43

44

I

I

70

Pollutant. ID

PM2.5

Elemental carbon
Organic carbon
| ions
| S04-2
I elements

MR MR MR MR MR MR MR MR MR

Figure D-l Average PM2.5 Speciation Profiles by Truck and Test Cycle from the E55/59
Program. M = Measured total PM2.5, R = Reconstructed Total PM2.5 from the Speciated

Measurements

Step 2. We removed the average PM2.5 profiles with suspect data. As shown in Figure D-l, the
MMHDT truck (Truck 41) had very low PM emissions on the transient cycle, and a very large

66


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contribution of ammonium to the idle cycle. This PM composition does not compare well with
previous data in the literature79, so the medium-duty truck was removed from further analysis.

Step 3. We calculated a median PM profile using the individual truck/test-cycle PM profiles
calculated in steps 1 and 2. The median is used rather than the mean due to the small sample
(eight trucks), in contrast to the variety of truck technologies, exhaust control systems, and ages
of the trucks in the real-world fleet. A mass-weighted mean would have been dominated by the
results for Truck 3 and Truck 44, which had the highest PM emission rates. Instead we
calculated the median of the PM fractions, and not a fraction of the median emission rates. In
this manner, the final PM speciation profile is not overly dependent on any one vehicle.
Additionally, there may be systematic differences between the Phase 1 and Phase 2
measurements that could impact a mass-weighted profile. By calculating the PM2.5 species
fraction before computing the median, any differences impacted the absolute PM2.5 emission
rates between phases do not impact the resulting speciation profile.

Step 4. We adjust the median profile to account for unmeasured PM2.5 species including metal-
bound oxygen and non-carbon organic matter. The additional oxygen mass associated with the
metal oxides are calculated using the oxide state assumptions in Sonntag etal. (2013)61
reproduced in Table E-5.

Table E-5 Oxide States Assumed for Calculation of Metal-Bound Oxygen

Element

Oxide Form 1

Oxide Form 2

Oxide Form 3

Oxide/Element
Mass Ratio

Na

Na20





1.35

Mg

Mg





1.0

A1

A1203





1.89

Si

Si02





2.14

P

P04





3.07

CI

CI





1.0

K

K20





1.20

Ca

Ca





1.0

Ti

Ti02





1.67

Cr

Cr203

Cr03



1.69

Mn

MnO

Mn02

\11120

1.63

Fe

FeO

Fe203



1.36

Ni

NiO





1.27

Cu

CuO





1.25

Zn

Zn





1.0

Rb

Rb20





1.09

Br

Br





1.0

Mo

Mo02

Mo03



1.42

Pb

PbO

Pb02



1.12

67


-------
For the Phase 1 samples, the molar concentration of ammonium balances within 5 percent of the
molar concentrations of 2*SC>4 + NO3. This is what would be expected if the ammonium exists
as ammonium sulfate [NH^SCU and ammonium nitrate, NH4NO3. For the Phase 2 samples,
ammonium balances within 25 percent of the molar concentrations of 2*SC>4 + NO3. Due to the
relatively good agreement between the measurements, it appears that the sulfate on the filter
exists as ammonium sulfate. As such, we did not account for sulfate-bound water contributing
to filter mass.

The sum of the PM fractions from the median profiles is greater than one. To achieve mass
balance, we are scaled down the organic carbon fraction to correct for positive artifact inherent
in organic carbon (OC) filter measurements, as was done in previous work including for the
light-duty gasoline profile61 and analysis of emissions from other combustion sources.80 We
calculated the organic matter (OM) as the remainder of the PM2.5 using Equation 11.

OM% = 100 — EC% — elements% — metal bound oxygen% — ions% Equation

Then, we split the OM into OC and non-carbon organic matter (NCOM) using the following
relationship: OM = 1.2 * OC used by Kleeman etal. (2000)81 and developed from work
conducted on medium-duty diesel emissions79, as shown in Equation 12 and Equation 13.

OC% = Q OM%

NCOM% = OM%

The initial and corrected OC/PM factors are shown in Table E-6. The adjusted OC speciation
factors are smaller than the initially measured OC/PM fraction, which is expected due to the
higher affinity for OC artifact to collect on the quartz fiber filters, as compared to the Teflon
filters used to measure PM2.5 mass.82

Table E-6 Impact of Mass-Balance Correction on Organic Carbon and Organic Matter

Emission Rates

PM factors

IDLE

CRUISE

TRANSIENT

Initial OC/PM factor

54.1%

36.3%

30.1%

Mass-balance OM/PM factor

41.7%

36.1%

17.4%

Corrected OC/PM factor

34.7%

30.1%

14.5%

The resulting profiles for the PM2.5 species are located in Table E-7. The Start/Extended Idle
profile is based on the idle test cycles, and the running emissions are based on the transient
cycles. These cycles are selected for use for modeling these emission processes because they
have similar PM characteristics (EC/PM) ratio as the PM2.5 MOVES emission rates for
conventional diesel as discussed next.

Equation

12

Equation

13

68


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Table E-7 PM2.5 Profiles for Pre-2007 Diesel Exhaust Developed for MOVES2014



Idle (Profile
8994)

Running

(Profile

8995)

Elemental Carbon

46.40%

78.97%

Organic Carbon

34.74%

14.52%

NonCarbon OM

6.95%

2.90%

S04

5.27%

1.03%

N03

1.25%

0.18%

NH4

1.74%

0.36%

Fe

0.34%

0.13%

Al

0.06%

0.06%

Si

0.30%

0.22%

Ti

0.01%

0.01%

Ca

0.58%

0.35%

Mg

0.13%

0.01%

K

0.26%

0.02%

Na

0.31%

0.03%

CI

0.38%

0.13%

CMAQ5.0 unspeciated

1.28%

1.09%

In MOVES, the EC/PM fraction from the Idle profile (8994) is used for idle emissions from
running (opModelD 1, processID 1) and extended idle (processID 90). It is also used to speciate
the PM from start emissions (processID 2) and auxiliary power emissions (processID 91). The
running profile is used to speciate the PM from all other operating modes from running
emissions (processID 1).

Table E-8 compares the profiles developed from the E-55/59 study to measurements made at
CE-CERT (Shah et al. (2004)83), a composite profile developed by Schauer etal. (2006)67 from
the DOE Gasoline/Diesel PM Split Study, and the NFRAQS heavy-duty diesel profile
(SPECIATE Profile 91106). The EC/PM fraction from the E55/59 transient cycle compares
well to both the composite profiles. The E55/59 idle profile has a substantially lower EC/PM
fraction than the composite profiles, with a corresponding higher fraction of organic matter. The
cold/start idle profile from CE-CERT (Shah et al. (2004)) also shows an even lower EC/PM
fraction during idle than high load conditions. The MOVES sulfate fractions appear to be more
aligned with the DOE Split study, which could be due to newer technology diesel and lower
altitude testing. Elements and ion emission rates compare well to the DOE gasoline/diesel PM
split study.

69


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Table E-8 Comparison of MOVES Conventional Pre-2007 Diesel Profiles with other PM2.!

Conventional Diesel Profiles



MOVES
E-55/59

CE-CERT 2004a

DOE

Gasoline/
Diesel PM
Split Study

Northern
Front Range
Air Quality
Study



Idle (8994)

Running
(8995)

Cold
start/Idle

Running
(Transient)

Composite

Composite
(91106)

Elemental carbon

46.4%

79.0%

13.3%

68.0%

72.7%

77.1%

Organic matter

41.7%

17.4%

81.4%

33.5%

24.1%

17.6%

SO4-2

5.3%

1.0%





1.3%

0.3%

CI + NH4 + N03

3.4%

0.7%





0.4%

0.1%

Elements

2.1%

1.1%





1.5%

0.5%

Note:

a. Organic matter estimated using the 1.2 * OC, other components not measured.

E.3 Development of the ACES PM2.5 Profile for 2007 and
Newer Technology Diesel

The PM2.5 speciation profile for 2007-and-later technology is based on Phase 1 of the Advanced
Collaborative Emissions Study (ACES) Report.31 The purpose of the ACES report was to
characterize criteria and toxic emissions from advanced technology diesel engines and control
systems. Phase 1 of ACES tested four heavy-duty diesel engines each equipped with a catalyzed
diesel particulate filter (C-DPF). The PM2.5 profile is based on a 16-hour cycle which is
composed of FTP and CARB 5-Modes, developed specifically to gain sufficient PM mass to
measure the emission rates of trace metals and toxics and to capture diesel particulate filter
regeneration events. The PM2.5 measurements from the 16-hour cycle include the exhaust
measurements downstream of the C-DPF and crankcase blow-by emissions. Crankcase blow-by
emissions contributed 38 percent of the combined crankcase and tailpipe PM2.5 emissions on the
FTP cycle.

The SPECIATE contractor (Abt Associates) developed the PM2.5 profile from the ACES
program Phase 1 with input from the US EPA, with the intent of maintaining consistency with
the summarized results in the ACES Phase 1 report. The 16-hour results yielded the most
accurate measurements at the low levels of PM2.5 and are used to represent all PM2.5 emission
processes from 2007-and-newer on-highway diesel vehicles.

The following decisions were made to develop a profile to be consistent with the results in the
ACES Phase 1 report.

1. The original measurements were used rather than background or tunnel corrected
measurements. EC and OC were not corrected for background, or backup quartz filters.
Background correcting the EC/OC filters caused negative EC/OC emission rates on
three of the four engines. The ACES researchers did not report OC corrected by a
backup-quartz filter because of concern of under-representing OC emissions.84
Similarly, species for elements and ions were not corrected for tunnel blanks. Using

70


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uncorrected OC measurements likely contributed to the mass of the sum of the speciated
measurements being higher than Teflon filter measurements.85 By using the original
measurements, rather than the background or tunnel corrected measures, we are likely
overestimating the emissions from some of the individual species that are subject to
positive artifact like OC. The ACES researchers discuss possible approaches for
correcting the measured OC emission rates and mention this as an area for future work
for 2007-and-later diesel engines.

2.	Unmeasured species that likely contribute to particulate matter were not included in the
profile, including sulfate-bound water and metal-bound oxygen from the profile. The
PM collected on the filter were analyzed for nitrate and ammonium, however no
ammonium or nitrate was detected.31 In the absence of these species, the sulfate is
expected to exist as hydrated sulfuric acid. Khalek et al. 201184 reported that accounting
for the water-bound sulfate would increase the summed mass of the individual species
37 percent beyond the measured filter mass. Rather than lowering the factors for other
species by including the sulfate-bound water, it was excluded from the profile.
Converting the measured organic carbon to organic matter and accounting for the oxide
state of the elements was considered by Khalek et al. (2011)84, but was not conducted
due to the uncertainty of reconciling the filter mass and the sum of the measured species.

3.	According to the SPECIATE database, the profile was normalized to the gravimetric
mass of PM. Gaseous and particulate phase sulfate are combined in the PM profile.

More information on the profile itself can be found in the SPECIATE database, and the
database's supporting documentation outlines specific procedures for creating PM
profiles.86

The ACES Profile is included in the SPECIATE database as profile #5680. This profile is the
basis of SPECIATE profile 8996 used in MOVES with one adjustment. MOVES needs organic
matter reported as OC and non-carbon organic matter (NCOM). We treated the reported OC in
the SPECIATE profile 5680 as OM, and calculate OC and NCOM using the same split
(Equation 12) as used for pre-2007 diesel and light-duty gasoline. The species not needed by
MOVES from the ACES Phase 1 profile are summed into the unspeciated fraction. The
speciation values are presented in Table D-9. Metal emission rates for manganese, chromium,
and nickel from MOVES are derived from the ACES Phase 1 data.7 They are estimated using
the metals calculator with mass/distance emission rates, and are not reported in the SPECIATE
profiles.

71


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Table E-9 SPECIATE PM2.5 Profile 8996 Developed from the 16-hour Cycle from Four

Heavy-duty Diese

Engines with Catalyzed-DPFs in the ACES Phase 1 Program



Weight %

Elemental Carbon

9.98%

Organic Carbon

22.33%

Non Carbon Organic Matter

4.47%

Sulfate

59.91%

Nitrate

0.00%

Ammonium

0.00%

Iron

0.64%

Aluminum

0.11%

Silicon

0.09%

Titanium

0.02%

Calcium

0.47%

Magnesium

0.14%

Potassium

0.05%

Sodium

0.99%

Chlorine

0.04%

Unspeciated

0.78%

The ACES Phase 1 derived EC fraction of 9.9% falls within the range of EC fraction of total
carbon emissions (2 to 20%) reported from Thiruvengadam et al. 2016.87

E.4 Development of the Compressed Natural Gas (CNG)
Profile

The California Air Resource Board (CARB) conducted several emission characterization
studies on compressed natural gas vehicles. In our profile development, we used only the data
reported by CARB for a CNG New Flyer bus with a 2000 MY Detroit Diesel (DDC) Series 50G
engine, equipped with and without an oxidation catalyst. Using a single profile provides
consistency in the PM characterization estimates and assures that the organic carbon emissions
are reduced with implementation of oxidation catalyst controls. CARB also conducted tests on a
CNG bus with a 2001 Cummins Westport engine. Other studies that reported EC/OC did not
measure emission rates for elements.88

We developed the profiles shown in Table E-10 with and without catalyst to estimate the impact
of oxidation catalyst control. CARB characterized the PM emissions on a steady-state cycle,
and a central business district cycle (CBD). We used the CBD data, which was consistent with
the criteria pollutant analysis in the heavy-duty emissions report2 and was considered more

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representative of typical transit bus behavior.11'89 The PAH/OC ratios documented in the
MOVES3 toxics report7 were also developed from the CARB measurements on the DDC 50G.

Table E-10 PM2.5 Speciation Profiles for CNG Compressed Ignition Transit Bus Exhaust

Pollutant

Uncontrolled
(95219)

Oxidation

Catalyst

(95220)

Elemental Carbon (EC)

9.25%

11.12%

Organic Carbon (OC)

36.99%

37.45%

Non-carbon Organic Matter (NCOM)

7.40%

7.49%

S04

0.64%

1.04%

aluminum

0.89%

0.89%

calcium

0.21%

0.44%

chromium

0.25%

0.25%

cobalt

0.39%

0.40%

iron

0.25%

0.25%

nickel

0.04%

0.00%

phosphorus

0.04%

0.15%

silicon

0.46%

0.59%

zinc

0.14%

0.20%

Unspeciated PM2 5

43.04%

39.74%

We used PM, EC, OC, and element emission rates for two repeat tests both with and without the
oxidation catalyst.90'91 CARB measured 13 elements by X-ray fluorescence but no ions (sulfate,
ammonium, or nitrate) were measured. The sulfate emissions were estimated by assuming that
all elemental sulfur is in the form of sulfate. This assumption is consistent with sulfate and
elemental sulfur measurements reported for natural gas combustion in the speciate database
(SPECIATE 91112). We assume that the missing ammonium and nitrate emissions are zero,
based on the negligible ammonium and nitrate measurements from modern spark-ignition CNG
buses equipped with three-way catalysts.92 Sodium and magnesium were the largest elements
measured (sodium was over 7 percent of the PM2.5 measured in the uncontrolled test), which is
likely due to known measurement artifact for XRF measurements of sodium and magnesium.
As such the sodium and magnesium emission rates are reported as zero.

The use of the oxidation catalyst reduced the PM2.5 emission rates from 28 mg/mile to 20.3
mg/mile on the CBD cycle (a 27.5 percent decrease). As shown in Table E-10, the composition
of the PM2.5 stayed fairly constant. The EC and OC fractions between the two control conditions
are not statistically different. Both profiles contain a large amount of unspeciated PM2.5
emissions. The source of the large unspeciated PM2.5 emissions is unknown but may be
attributed to the different sampling media for the total and speciated PM2.5 emissions, which is
amplified at the low PM2.5 concentrations measured from CNG exhaust. The absence of ion
measurements may also be a contributing factor.

u The CNG profile was developed for MOVES2014, where transit buses were the only source type that were run on
CNG fuels. In MOVES3, CNG is modeled in all of the heavy-duty source types except combination trucks as
documented in the population and activity report.89

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The real-world variability in the PM2.5 composition is larger than the developed profiles suggest.
The OC/PM fraction for the 2001 Cummins Westport with oxidation catalyst was 61.9 percent,
which is much larger than that measured on the 2000 Detroit diesel engine. Lanni et al. (2003)88
reported that the OC/PM fraction on three CNG transit buses with DDC Series 50G engines
ranged from 29 percent to 74 percent of the PM2.5. The EC emissions measured by Lanni el al.
(2003)88 were below the detection limit, but the presented results compare well with the 2001
Cummins Westport measured by CARB (12.7 percent EC/PM). The sulfate fraction for the
oxidation catalyst presented in compares well with the sulfate fraction reported for the 2001
Cummins Westport by CARB91 (2.8 percent), and by Lanni et al. (2003)88 (1.5 percent to 2.4
percent).

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Appendix F PM10/PM2.5 Factors

The gasoline PM10/PM2.5 factor is based on measurements of 1991-1997 model year vehicles
tested by Norbeck et al. (1998).93 This ratio estimates that roughly 10 percent of the PM emitted
from gasoline vehicles is in the coarse range, which agrees with the size-distributions reported
from cascade impactor measurements on light-duty gasoline exhaust from Schauer et al.
(2008).94

The diesel PM10/PM2.5 factor is based on a 1985 EPA report95, which reports that 92 percent of
particulate mass is measured below a 2.5 |im cut-off. Although derived from measurements on
older technologies, the diesel PM10/PM2.5 ratio compares well with observations of the particle
size distribution of diesel exhaust by Kittelson et al. (1998)96, who states that the coarse mode
contains 5-20 percent of the total aerosol mass. Unfiltered crankcase emissions published by
Donaldson Company Inc. (2011)97 have similar reported mass distributions with ~ 93 to 97
percent of the cumulative mass particles smaller than 2.5 |im. In contrast, Tatli and Clark
(2008)98 report that the particle mass size distribution is significantly different from crankcase
and tailpipe diesel emissions for particles below 1 |im. Due to the limited information on
coarse-mode crankcase particulate emissions, we assume the same PM10/PM2.5 fraction for
diesel crankcase emissions.

Filtered diesel crankcase and exhaust emissions are expected to have smaller PM10/PM2.5 ratios,
due to the higher filter capture efficiency of coarse mode particles.97'99 However, the same
PM10/PM2.5 ratios are used for the later model year groups, due to limited coarse mode
particulate exhaust measurements, and limited information on the failure rates of these
technologies in real-world use.

No information was available on the PM10/PM2.5 ratios for CNG emissions, and the gasoline
ratio is used for CNG emissions. Table F-l contains the selected exhaust PM10/PM2.5 ratios used
in MOVES.

Table F-l PM10/PM2.5 Ratios for Primary Exhaust and Crankcase Emissions by Fuel Type

Fuel

PM10/PM2.5

Gasoline, E85, CNG

1.130

Diesel

1.087

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Appendix G Speciating emissions outside of MOVES

Post-processing of onroad emissions to speciate residual TOG and PM requires the selection of
these pollutants when designing the MOVES RunSpec. As defined in section 2.3, residual TOG
(NONHAPTOG, pollutantID = 88) corresponds to the remaining TOG mass after MOVES has
applied fuel and temperature effects to calculate gaseous integrated species. Similarly, the new
Residual PM (nonECnonS04nonOM, pollutantID = 124) corresponds to the remaining PM
mass after MOVES has applied fuel and temperature adjustments, and has calculated particulate
integrated species: EC, SO4 and the newly defined total organic matter (TOM, pollutantID =
123). TOM is simply the sum of two existing MOVES pollutants: NCOM and OC. We have
opted to aggregate these species into the new TOM pollutant to facilitate the speciation of
organic matter under the Reactive Organic Carbon framework100 during post-processing
downstream from MOVES.

During the speciation step within MOVES, residual TOG and PM are matched to specific
speciation profiles by fuel subtype, emission process, regulatory class and model year (see
Figures 4-3 and 5-2). To mimic this step during postprocessing outside of MOVES, we have
added a new table (rocSpeciation table) to the MOVES default database that records the latest
mapping of emissions to traditional speciation profiles, as well as new parameters for the
speciation of organic matter within the ROC framework. The rocSpeciation table contains the
following columns: fuel SubtypelD, regClassID, processID, minModelYearlD,
maxModelYearlD, pmSpeciationProfilelD, CROCCode, CROCOMratio,
togSpeciationProfilelD, GROCCode and GROCNMOGratio. The first five columns
characterize the vehicle emission source; togSpeciationProfilelD and pmSpeciationProfilelD
indicate the traditional speciation profiles8 associated with each vehicle emission source as
discussed in previous sections of this document; the "Code" columns specify the ROC
speciation profiles101 (listed in EPA's SPECIATE5.2 8) associated with a given vehicle emission
source and the "Ratio" columns contain adjustment factors applied within the post-processing
script to generate Condensable Reactive Organic Carbon (CROC) mass and Gaseous Reactive
Organic Carbon (GROC) mass.

The new rocSpeciation table is not used by MOVES and it is only intended to be used by the
post-processing script. For modelers planning to speciate onroad emissions outside of MOVES,
in addition to selecting the appropriate pollutants, they must also specify output by SCC,
regulatory class, fuel type, emission process and model year for the postprocessing script to run.

The post-processing script generates a SQL database with NONHAPTOG, Residual PM and
TOM speciated emissions. The speciated emissions are grouped into SMOKE SCCs to facilitate
the combination with vehicle activity within SMOKE-MOVES. A diagram of the new
workflow for the post-process is shown in Figure G-l. Further details on how to run the script
and how to use the output are provided in the instructions associated with the post-processing
speciation script included in the MOVES GUI.

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MOVES
inputs

MOVES

TOM
Residual PM
NONHAPTOG

MOVES Output:
Emissions
per SCC

rocSpeciation
table

I

Profile
Weighting
Script

Generates
profile % per
SCC

(GSREF-COMBO)

SPECIATE

Speciation
Profiles

I

Explicit

Compound

Profiles

Speciation
Tool

Transforms

explicit
compound
profiles into
chemical
mechanism
species (GSPRO)

SMOKE-
MOVES

Gridded
emissions of
chemical
mechanism
species

Figure G-l. Diagram showing the new workflow to post-process the speciation of onroad emissions into
chemical mechanism species and how it interacts with other modeling platform tools.

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