Strategically Targeted Research in Intelligent Built Environmental Systems
EPA Contracts # CR 83199201-0 & X-83269001-0
Fate Formation And Transport Of Indoor PM
EPA04 T2.2
Larry Tavlarides & Meera Sidheswaren, Syracuse University
and
Phil Hopke & Xi Chen, Clarkson University
http://www.eqstar.org
http://www.syracusecoe.org
Task 2.2 Introduction
 Epidemiological studies link “reactive” fine particles to human health
hazards including mortality (Pope and Dockery, 1996; USEP, 1997),
especially those generated indoors (Long et al., 2001)
 Important to know chemistry of particle formation, the nature of
VSVOC’s formed, and the fate of VSVOC’s due to interactions with
room surfaces and secondary organic aerosols (SOA’s)
 Terpene and terpene-alcohol ozone reaction systems will be studied
as these compounds exist in room fresheners, perfumes and laundry
softeners.
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Formation of SOA
Initial Models
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Formation of SOA
More Complete Models – Odum et al., ES&T 1997; Liang et al ES&T 1997
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Objectives: Task 2.2.4
Ozone Reactions of Linalool and Adsorption of VOC and SVOC By-Products on
Surfaces and SOA
 Understand the kinetic mechanism which describes the gas phase
reaction of linalool with ozone. These studies will be performed in the
150 ft3 stainless steel chamber.
 Determine the adsorption and desorption behavior of VSVOCs on
building surfaces. These studies will also be performed in the same
chamber with all walls exchanged with building materials.
 Characterize the growth of SOAs due to the adsorption of VSVOCs
and develop size distribution and growth dynamic models.
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Reaction Pathway Study
HO
CH3
O
O
O
H2C
CH3
H3C
+
H2C
CH3
CH3
H3C
OH
HO
H3C
H3C
CH3
O
O
O
O
Branch 1
O
O
Branch 2
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Reaction Pathway Study: Branch 1
H2C
HO
CH3
H3C
CH3
O
O
O
CH2
CH2
H3C
CH3
+
CH3
O
O
O
H3C
CH3
CH
CH3
+
CH2
O
O
O
OH
OH
CH3
HO
O
O
CH2
O
HO
CH2
CH3
O
CH3
HO
H3C
O
CH3
O
OH
CH3
O
HO
O
O
O
O
O
O
HC
HO
O
H2C
O
O
+
O
O
O
HO
O
CH3
CH
HO
H2C
CH3
O
HO
+
O
O
HO
CH3
H3C
CH3
O
OH
O
O
CH3
O
HO
H2O
O
HO
H2C
O
+
CH
HO
HO
O
CH3
O
+
HO
O
CH3
O
H2C
CH3
O
O
HO
O
O
O
H2O
H3C
H2O
CH3
O
HO
O
O
CH3
CH3
O
O
O
O
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Reaction Pathway Study: Branch 2
H3C
OH
H3C
H3C
O
O
O
CH3
HO
CH2
O
O
CH3
HO
+
CH3
O
CH2
CH3
HO
+
O
CH3
HC
CH3
O
O
O
CH3
H3C
O
OH
CH3
O
O
HO
O
CH3
HO
CH3
H3C
O
O
O
O
CH3
H3C
O
OH
H3C
CH
O
O
+
CH3
O
HO
OH
O
C
O
O
O
H3C
O
+
OH
CH3
H3C
O
O
O
O
H3C
H3C
OH
HO
O
H3C
OH
CH3
H3C
HO
O
OH
+
H3C
CH3
O
OH
O
HO
O
OH
CH
O
H3C
O
O
O
H3C
O
H3C
+
CH3
O
H3C
HO
O
CH3
H3C
O
O
H3C
OH
OH
O
HO
O
O
H3C
O
OH
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Mass Spectra of Some Products
2-Ethenyl-5-methyl-5-hydroxytetrahydrofuran
2-(3-H)-Furanone-5-ethenyldihydro-5-methyl-
2-Furancarboxylicacidtetraydro-1-methyl-5-oxo
2-Hydoxy2,3-dimethylsuccinic acid
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Particle Phase Analysis
Similar to the analysis by Leungsakul et al., 2005
CH2
CH2
CH3
+
CH3
O
O
OH
Seed 1
+ H2O
O
CH
O
O
H 3C
H3C
CH3
HO
+ H2C
CH3
CH3
O
CH3
+ H2O
CH3
H 3C
O
Seed 2
H 3C
O
H 2C
O
O
HO
CH O
HO
CH3
+
CH3
H2 O
Seed 3
+ H2O
O
O
O
H 3C
H3C
O
H2C
O
OH
Seed 4
CH3
+
+
O
H3C
CH
H 3C
O
O
O
CH2
HO
O
CH3
Seeds + 0.05
O
CH3
CH2
+
CH3
0.52
O
+ 0.28
O
HO
O
+ 0.11
HO
HO
H3C
O
O
CH3
+ 0.14
CH3
O
OH
O
Secondary Organic Aerosols
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Experiments: Conducted at 22-24 °C
Sl.no
Linalool
Concentration,
ppb
Ozone
Concentration, Humidity
ppb
1
492 ± 7
~502
22-25%
Batch
2
512 ± 10
~298
22-25%
Batch
3
108 ± 5
~100
22-25%
Continuous
(RT: 10mins)
Mode of
Operation
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Particle Size Distribution
Particle Size Distribution : Linalool Concentration: 500ppb, Ozone
Concentration: 500ppb and Humidity: 25%
40000
60 mins: 131nm
35000
25000
15mins: 76nm
20000
15000
120 mins: 213nm
BG: 76nm
240 mins: 404nm
10000
5000
25
28
.9
33
.4
38
.5
44
.5
51
.4
59
.4
68
.5
79
.1
91
.4
10
5.
5
12
1.
9
14
0.
7
16
2.
5
18
7.
7
21
6.
7
25
0.
3
28
9
33
3.
8
38
5.
4
44
5.
1
51
4
59
3.
5
68
5.
4
0
14
.1
16
.3
18
.8
21
.7
Particle Count
30000
Particle Mean Diameter
Background
After 15 mins
After 60 mins
After 120 mins
After 240mins
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Particle Size Distribution
Particle Size Distribution : Linalool Concentration: 500ppb, Ozone
Concentration: 300ppb, Humidity: 25%
30000
60 mins: 131nm
Particle Count, #/cm3
25000
20000
15mins: 76nm
15000
120 mins: 213nm
BG: 76nm
10000
240 mins: 404nm
5000
0
Particle Mean Diameter, nm
Background
After 15 mins
After 60 mins
After 120 mins
After 240 mins
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Particle Size Distribution
Linalool Concentration: ~100 ppb; Ozone Concentration: ~100 ppb Time of
Sampling : Continuous.
Time Scale:
Reading 1: 15mins
Reading 19: 285mins
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Yield Model
Linalool Concentration: 500ppb, Ozone Concentration: 500ppb, Humidity: 25%
(T. Hoffmann, J. Odum, et al., 1997)
Yield Model of Secondary Organic Aerosol
0.8
0.7
0.6
Yield %
0.5
0.4
0.3
0.2
0.1
0
0
50
100
Time, mins
Simulated Yield
Actual Yield
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Batch Injection of Linalool in Mid-size Chamber
Decay of Linalool in the Mid-Size Chamber During
Flushing
600
600
500
500
Linalool Concentration, ppb
Linalool Concentration, ppb
Concentration of Linalool in the Mid-size Chamber monitored
after a pulse injection
400
300
400
300
200
200
100
100
0
0
0
0
100
200
300
400
Time, mins
500
600
700
800
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
Time, mins
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T2.2.4: Results
 The 150 ft3 chamber has been built, commissioned and is fully
functional. Diffusion cell for continuous linalool injection is being
fabricated.
 Gas and particle phase analyses using GC-MS technique have been
developed.
 Initial qualitative analyses of products for preliminary estimation of the
reaction pathway has been completed in the 100 L chamber.
 Two major products of linalool ozone reaction have been synthesized
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T2.2.4: Future Work
 Quantification of significant linalool ozone products
 Proposed experiments for the particle size distribution and yield of
SOA’s in the 150 ft3 chamber will be executed.
 Obtain sorption data for suggested building materials to quantify
particle adsorption on surfaces.
 Obtain parameters for secondary organic aerosol growth models and
describe the dynamics of aerosol formation.
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Formation of Indoor Particles
a-Pinene and Ozone
 There have been many studies of the a-Pinene and Ozone system.
 However, many of these studies have been performed to provide
critical reaction rate constants for chemical transport models.
 Thus, the reactions with ozone need to be separated from the
reactions with hydroxyl radical.
 For example, Presto and Donahue (ES&T 2006) summarize much of
the prior data along with their chamber results where a hydroxyl
radical scavenger like butanol has been added to the chamber
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Formation of SOA
a-Pinene and Ozone
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Formation of Indoor Particles
Current Progress
 Much of this year has been used to develop and test the experimental
systems:
 Chamber
 Ozone Generation
 Reactive VOC Generator
 Particle Measurement System
 Particle Composition Measurements
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Formation of SOA
a-Pinene and Ozone
Experiment 1
Experiment 2
a-pinene (ppb)
59.6±4.8
67.6±9.6
Ozone (ppb)
45.8±0.2
33.8±0.7
Temperature (oC)
21-23
20-21
Relative humidity
28-36%
23-32%
0.53
0.53
Air exchange rate (h-1)
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Formation of SOA
a-Pinene and Ozone – Experiment 1
4500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
3
Particles /cm
4000
3500
3000
2500
2000
1500
1000
500
icle
t
Par
0
80
70
60
50
40
30
e
Siz
20
)
(nm
10
0
1
2
3
o
Time (h
4
5
6
7
8
urs)
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Formation of SOA
a-Pinene and Ozone - Experiment 2
3
Particles /cm
3000
0
500
1000
1500
2000
2500
3000
2500
2000
1500
1000
500
icle
t
Par
0
80
70
60
50
40
30
e
Siz
20
)
(nm
10
0
1
2
4
3
5
6
7
8
s)
our
Time (h
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Formation of SOA
a-Pinene and Ozone
Number Concentration(#/cm3)
50000
59.6± 4.8ppb a-pinene ґ 45.8± 0.2 ppb O3
67.6 ± 9.6ppb a-pinene ґ 33.8± 0.7 ppb O3
40000
30000
20000
10000
0
0
2
4
6
8
10
Time elapsed(hr)
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Formation of SOA
a-Pinene and Ozone
Figure from Fan et al., ES&T 2003.
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Formation of Indoor Particles
Current Progress
 Thus, initial results appear comparable with prior flow through
chamber results.
 We need to extend the time to longer periods to examine steady-state
behavior.
 We need to measure ROS concentrations resulting from the new
particle formation.
 In other studies, we have been examining the nature of the reaction
products for a-pinene and ozone.
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Formation of Indoor Particles
Future Work
 We will continue the work with a-pinene and ozone to obtain the
D(Particle Formation) v D(Hydrocarbon Reacted) to provide results
without the OH scavenger to provide curves relevant to indoor air
modeling.
 To explore other possible reactive VOCs, we have started to explore
the presence of compounds in a series of commercial air fresheners
 Analysis of a number of commercial air freshener products by GC/MS.
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Possible SOA Precursors Found
Limonene
Terpineol Methyl-cinnamaldehyde
Linalyl butyrate
a-Isomethylionone
Beta-Ionone
Hexenylsalicylate
Eugenol
Rose Oxide
Linalyl anthranilate
a-bergamotene
Muurolene
Cis-verbenol
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Results
 Many of these compounds have more than one double bond.
 These compounds behave differently from the single double bond
compounds.
 As an example, some chamber studies have been made on terpineol
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Formation of SOA
Terpinolene and Ozone
Time-dependent growth curves and final growth curve do not overlap;
time-dependent growth curves show the contribution of the secondary reactions
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Results
 These time-dependent growth curves for terpinolene ozonolysis
cannot be fit with Odum equation, confirming that this model is only
valid when the data represent final SOA growth.
 We will need to consider further how best to model the multiple stage
reaction systems that the multiply double bonded compounds
represent.
 We need to decide what species to pursue following the completion of
the a-pinene-ozone work
 Terpineol
 Others?
SAC Review 07/31-08/01/07 - 32
Discussion and Questions
 Questions?
 Suggestions?
SAC Review 07/31-08/01/07 - 33
Formation of SOA
a-Pinene and Ozone
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Formation of SOA
a-Pinene and Ozone
Time series of ozone concentration in the chamber
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Formation of SOA
a-Pinene and Ozone
Time series of a-pinene concentrations from the diffusion cell
for three different diffusion lengths
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Characterization of ROS Species
Figure 4.11: Representative direct mass-spec of the filter extract solution
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Characterization of ROS Species (Contd.)
a-Isomethylionone
Hexenylsalicylate
a-bergamotene
Muurolene
Cis-verbenol
Linalyl butyrate
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Experimental Set-up
 Experimental Apparatus
 100L / 4274.5L stainless steel chamber
 Injection ports to inject linalool
 API 400 Ozone generator
 Dynacalibrator/Diffusion cell for Linalool generation
 Analysis Techniques
 API 440 Ozone Analyzer
 ppB RAE for VOC monitoring
 Tenax sorbents
 Samples pulled out through an ozone trap using handheld socket pump (ozone
trap made of potassium iodide)
 PFPH coated Tanex for estimation of lower aldehydes (S.A. Hang Ho, J. Z. Hu,
2004)
SAC Review 07/31-08/01/07 - 39
Experimental Set-up (Contd.)
 Analysis Techniques
 ATD-GC/MS
 ATD: Perkin Elmer Turbomatrix 300 (Sorption Temperature @ 210 oC)
 GC-MS: Thermoelectron (Trace GC Ultra/DSQ)
 GC Column: Restek 5MS
 Temperature of Operation: Ramp to 200 C(@ 25oC/min) and holdup for 10
mins
 Particle Collection
 TSI 3086 Nano-Aerosol Sampler (Sampling size range: 2nm-100nm)
 Teflon Filter/Membrane Filter:>200nm
 Analysis using GC/MS after extracting particles with methanol using overnight
Soxhlet Extraction
SAC Review 07/31-08/01/07 - 40