the southern oxidant study and aerosol study...cloud processing how does aqueous chemistry and cloud...
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The Southern Oxidant and Aerosol Study
Annmarie G. Carlton
Southeast Atmosphere StudiesJune 1 - July 15, 2013
Additionally: EPA’s surface networks, NASA satellites, EPRI network
Smog over Birmingham, TSP ~700 μg m-3.
EPA’s first implementation of the CAA’s
“emergency powers” provision. (The
Birmingham News file/Dave Battle)
40 years later EPA proposed that
Birmingham be certified as
having attained the NAAQS.
Stagnation event 1971
Great Smoky Mountain National Park
Photo courtesy of CIRA
Pre SOS in 1990 Post SOS in 2010
Southern Oxidant and Aerosol StudyJune 1 - July 15, 2013 SOAS + SENEX + TropHONO + NAAMEX = Southeast Atmosphere Studies (SAS)C130 portion of SOAS + TropHONO + NAAMEX = NOMADSS
NSF, NOAA, EPA, EPRI, NCAR, U.S. and European Universities, private companies worked together during the sequester(!).
NSF OFAP request: 160 hours on C130, 2 towers, 110 release sondesand individual investigator proposals
NOAA’s commitment to fly the P3 for SENEX was an early and important impetus
EPA’s anthropogenic influence on PM in the Southeast STAR RFP supported of SOAS. University scientist funded to fly on a NOAA plane
Main ground site is EPRI’s “CTR” SEARCH network site.
SEACR4S campaign repeated some P3 and C130 flight tracks later in summer, extending the intensive period for chemical characterization of the troposphere
SAS timeline
Informal community discussions: Telluride, CO Aug. 2010; AGU, Dec. 2010; J. de Gouw
2010 2011 2012 2013 2014
“SOAS” Rutgers workshop May 2011: EPA: R. Pinder, K. Baker, NOAA: J. de Gouw,
S. Brown; DOE: L. Kleinmann, J. Wang
SENEX campaign announced
AGU Town Hall on SOAS
SOAS OFAP
proposal is accepted,
shares C130 with
TropHONO and
NAAMEX
SOAS/SAS
SOAS
White
Paper
AGU session
(6 sessions) AGU
session
Joint with SEACR4S
(5 sessions) SAS data workshop
AAAR
special
symposium
S. Hunt presentation at AQRS
Overwhelming majority of organic compounds in the atmosphere come from the biosphere. Biogenic hydrocarbons interact with anthropogenic pollution to form pollutants ozone, even resulting in non-attainment.
Last time our community converged on the Southeast U.S. AQ management redefined for O3
– As late as 1988: literature describing how VOC controls are not working for
Atlanta O3: NOx-limited and VOC-limited
– Isoprene is 3% by mass of Atlanta’s VOC inventory, but >30% of the reactivity
SOS Reminders
+ = O3
Emissions from the biosphere interact with emissions from human activity to form particulate matter. Anthropogenic pollution facilitates biogenic SOAformation (Weber et al., 2007; Surratt et al., 2007; Lane et al., 2009; Jimenez and de Gouw, 2009; Carlton
et al. 2010; Spracklen et al., 2011; Shilling et al., 2013).
Motivation behind SOAS in 2013.
+ =
What are the magnitudes,
variations, and controlling
processes for biosphere-
atmosphere fluxes of
oxidants, reactive C & N
across spatial scales
relevant to AQ and climate?
BVOC
Biogenic
SOA
Aqueous
chemistry &
cloud
processing
How does
aqueous
chemistry and
cloud
processing of
BVOCs and
aerosols
influence SOA
properties?
What are the
phys/chem processes
that control BVOC
oxidation? How do
anthropogenic
emissions alter the
distribution of the o-
BVOCs, and what are
the implications for O3,
reactive nitrogen, and
aerosol precursors?
Climate
What are the climate-relevant
properties of BSOA
Precursor
Gases and
aerosol
NOx
SOAS
To what extent do
anthropogenic
influences impact
biogenic (VOC)
SOA formation?
What are the magnitudes,
variations, and controlling
processes for biosphere-
atmosphere fluxes of
oxidants, reactive C & N
across spatial scales
relevant to AQ and climate?
BVOC
Biogenic
SOA
Aqueous
chemistry &
cloud
processing
Climate
Precursor
Gases and
aerosol
NOx
SOAS
What is the composition and
distribution of aerosol in the
SE U.S.?
What are the
emissions of
aerosol, aerosol
precursors and
greenhouse
gases in the SE
U.S.?
What are the formation
mechanisms of
secondary species (O3
SO4 and organics) in
the SE U.S.?
Which deposition processes
are critical for atmospheric
concentrations of aerosol,
O3 and NOy?
What are the climate-relevant properties of aerosol in the SE U.S.?
SENEX
GHGs
What are the climate-relevant
properties of BSOA
How does
aqueous
chemistry and
cloud
processing of
BVOCs and
aerosols
influence SOA
properties?
To what extent do
anthropogenic
influences impact
biogenic (VOC)
SOA formation?
What are the
phys/chem processes
that control BVOC
oxidation? How do
anthropogenic
emissions alter the
distribution of the o-
BVOCs, and what are
the implications for O3,
reactive nitrogen, and
aerosol precursors?
What are the magnitudes,
variations, and controlling
processes for biosphere-
atmosphere fluxes of
oxidants, reactive C & N
across spatial scales
relevant to AQ and climate?
BVOC
Biogenic
SOA
Aqueous
chemistry &
cloud
processing
Climate
Precursor
Gases and
aerosol
NOx
SOAS
What is the composition and
distribution of aerosol in the
SE U.S.?
What are the
emissions of
aerosol, aerosol
precursors and
greenhouse
gases in the SE
U.S.?
What are the formation
mechanisms of
secondary species (O3
SO4 and organics) in
the SE U.S.?
Which deposition processes
are critical for atmospheric
concentrations of aerosol,
O3 and NOy?
SENEX
GHGs
HONO
pNO3
Establish tropospheric HONO
distribution and budget in various
air masses (continental, oceanic,
urban/industrial plumes).
Collect bulk aerosol samples for
laboratory photochemical
experiments to measure photolysis
rate constants of p-NO3 leading to
HONO and NOx.
Quantify p-NO3 as
daytime HONO
source and a re-
NOx-ification
pathway in the
troposphere.
Examine HONO production
from photo-enhanced
heterogeneous NOx
reactions in urban/industrial
plumes.
Investigate HONO dark formation/nighttime
accumulation and morning-hour photolytic decay
in the PBL and in the FT.
TROPHONO
What are the climate-relevant properties of aerosol in the SE U.S.?
What are the climate-relevant
properties of BSOA
How does
aqueous
chemistry and
cloud
processing of
BVOCs and
aerosols
influence SOA
properties?
To what extent do
anthropogenic
influences impact
biogenic (VOC)
SOA formation?
What are the
phys/chem processes
that control BVOC
oxidation? How do
anthropogenic
emissions alter the
distribution of the o-
BVOCs, and what are
the implications for O3,
reactive nitrogen, and
aerosol precursors?
What are the magnitudes,
variations, and controlling
processes for biosphere-
atmosphere fluxes of
oxidants, reactive C & N
across spatial scales
relevant to AQ and climate?
BVOC
Biogenic
SOA
Aqueous
chemistry &
cloud
processing
To what extent do
anthropogenic
influences impact
biogenic (VOC)
SOA formation?
Climate
Precursor
Gases and
aerosol
NOx
SOAS
What is the composition and
distribution of aerosol in the
SE U.S.?
What are the
emissions of
aerosol, aerosol
precursors and
greenhouse gases
in the SE U.S.?
What are the formation
mechanisms of
secondary species (O3
SO4 and organics) in
the SE U.S.?
Which deposition processes
are critical for atmospheric
concentrations of aerosol,
O3 and NOy?
What are the climate-relevant properties of aerosol in the SE U.S.?
SENEX
GHGs
HONO
pNO3
Establish tropospheric HONO
distribution and budget in various
air masses.
Collect bulk samples for laboratory
photochemical experiments to
measure photolysis rate constants
of p-NO3 leading to HONO and
NOx.
Quantify p-NO3 as
daytime HONO
source and a re-
NOx-ification
pathway in the
troposphere.
Examine HONO production
from photo-enhanced
heterogeneous NOx
reactions in urban/industrial
plumes.
Investigate HONO dark formation/nighttime
accumulation and morning-hour photolytic decay
in the PBL and in the FT.
TROPHONO
Hg0
Constrain
emissions of Hg
from major
source regions
in the US.
Hg2+
Quantify distribution &
chemical transformations of
speciated Hg in the
troposphere.
NAAMEX+ + + = Southeast Atmosphere Studies (SAS)
What are the climate-relevant
properties of BSOA
How does
aqueous
chemistry and
cloud
processing of
BVOCs and
aerosols
influence SOA
properties?
What are the
phys/chem processes
that control BVOC
oxidation? How do
anthropogenic
emissions alter the
distribution of the o-
BVOCs, and what are
the implications for O3,
reactive nitrogen, and
aerosol precursors?
RH + OH R RO2
O2+NO
+HO2
+RO2
“Big” Picture
VOCs + NOx + hv O3 + particles + …
“High NOx”
“Low NOx”
Model predictions must correctly predict concentrations for the rightreasons. This is essential to ensure appropriate model response tosimulated control strategies and is critical to development of cost-effective air quality management plans.
+NO3
Moving Forward
Reaching across scientific discipline workhsop at GFDL: “Southeast Atmosphere Studies Workshop: Intensive Observation Period Modeling to Improve Mechanistic Representation of Trends”
Are we still asking the most critical and open important science questions?
What are high level questions we can answer with our robust data set? Are we getting the most out of this resource?
What are the important scientific details can we “finally figure out” and “nail down”?
How do we impact future the development of effective air quality management strategies?
Organic Aerosol Formation in the Humid,
Photochemically-Active Southeastern US: SOAS
Experiments and Simulations
Barbara Turpint, Annmarie Carlton, Neha Sareen
Rutgers University – New Brunswicktnow at University of North Carolina – Chapel Hill
ANTHROP
OGENIC
BIOGENIC
Organic+Oxidants:Gases.OH,O3,NO3
Water-solublegases
Water-solublecompounds
+.OH
(Aqueous-phase)
SecondaryOrganicAerosol(SOAAQ)Clou
dDrople
t
Evapora
on
(Par cle-phase)
H2O
H2O
.OH
.OH.OH
.OH
.OH
.OH
.OH
.OH.OH
.OH
.OH.OH
Brent,AL
Dept of Environmental SciencesTurpin–Carlton Specific Aims - SOAS:
1) Model aerosol liquid water concentrations
2) Model water-soluble gases
3) Conduct aqueous OH oxidation experiments with
ambient SOAS mixtures of water-soluble gases
(WSOG) to identify precursors/products
4) Collaborate, provide intellectual leadership and
share data to achieve the SOAS science goals
Condensation
VOC Oxidant (O3, OH, NO3
,…) SOA+
SVOC1,2, …
WSOC1,2, …
(isoprene,monoterpenes,
SESQ)
VOCs + NOx + hv O3 + particles + …
Polar gases also partition to polar solvents water SOAaq
Majority of partitionable atmospheric organic compounds are small, water-soluble gases (Grosjean et al., 1996; Nolte et al., 2001: Zhang et al., 2007) and globally, particle phase liquid water mass >>2-3x organic aerosol mass (Liao and Seinfeld, 2007).
Why is Southeastern U.S. the ideal region for this study?
condensed-phase𝐬𝐞𝐦𝐢𝐯𝐨𝐥𝐚𝐭𝐢𝐥𝐞𝐨𝐫𝐠𝐚𝐧𝐢𝐜𝐬
gas-phase𝐬𝐞𝐦𝐢𝐯𝐨𝐥𝐚𝐭𝐢𝐥𝐞𝐨𝐫𝐠𝐚𝐧𝐢𝐜𝐬
Lots of aerosol water Lots of WSOCg (glyoxal …) Lots of semi-volatile organic compounds
[Carlton and Turpin, 2013, ACP]
WSOCgWSOCp CMAQ used in site selection
CMAQ predictions for all of the ground sites extracted and uploaded to ftp in ICARTT format
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0 2 4 6 8 10 12 14 16 18 20 22
0
10
20
30
40
50
Hours past midnight
Wate
r µg/m
^3
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Water model comparison for SOAS
ISORROPIA SMPS
Wate
r (µ
g m
-3)
Hours past midnight
ISORROPIA ran with measured data input SMPS data from Nguyen et al., 2014
adjusted to SEARCH RH using P&K eqn.
RH < 99%
CMAQ Modeling
• CMAQv5.0.1
• June 6-June 15 2013
• SAPRC07 updated with “explicit” isoprene gas
phase oxidation chemistry (Xie et al., ACP, 2013)
• Heterogeneous organic chemistry (Pye et al., ES&T, 2013)
• WRFv3.4
• BEISv3.14
• Point and other anthropogenic species based on
NEI2008v3.1 and “grown” (forecasting ‘runs’)
• 12km x 12km grid for the ConUS
accumulation mode organic PM
AOLGB
AORGC
∙OH
dis
solu
tio
n
cloud water
VOCs
EMIS
SIO
NS
EMIS
SIO
NS
isoprene
sesquiterpenes
monoterpenesSV_TRP1
SV_ISO1
SV_SQT
+O3P, NO3
+∙OH
pathways do not contribute to SOA
+∙OH,O3
ASQT
ATRP1
AISO1
EMIS
SIO
NS
SV_TRP2
SV_ISO2 AISO2
+HO2ISOPOOH
+OH
IEPOX
AIETET
+H2O
AIEOS+SO4
2-
AIEON+NO3-
AIDIM
+NO MACR
+OH,NO2
MPAN +∙OH MAE + HMML
AIMGA
AIMOS
AIMON
ATRP2
SOA formation pathways from biogenically-derived VOCs in CMAQ’s AERO 6
+O3 O3P, NO3
Glyoxalmethylglyoxal
(Xie et al., ACP, 2013) (Pye et al., ES&T, 2013)
WSOG species SV species
• Formaldehyde (HCHO)
• Acetone (ACETONE)
• Acetaldehyde (CCHO)
• Methyl ethyl ketone (MEK)
• Methyl vinyl ketone (MVK)
• Methacrolein (MACR)
• Glyoxal (GLY)
• Methylglyoxal (MGLY)
• Acetic acid (CCOOH)
• Methanol (MEOH)
• Isoprene epoxydiol (IEPOX)
• Methacrylic acid epoxide (MAE)
• Hydroxymethylmethyl-α-lactone (HMML)
• Alkane (SV_ALK)
• Xylene (SV_XYL*)
• Toluene (SV_TOL*)
• Benzene (SV_BNZ*)
• Terpene (SV_TRP*)
• Isoprene (SV_ISO*)
• Sesquiterpene (SV_SQT)
* multiple species
20
0
10
ppb
0
1
2
WSOG species
Surface layer
Semi-volatile species
CMAQ modeling
WSOG species4000
0
2000
ppb
0
200
400
Vertical total
Semi-volatile species
CMAQ modeling
[Ci]p=HiRTLCi(g)
35
30
25
20
15
10
5
0
WS
OG
(p
pb
V)
6/6
00:0
0
12:0
06/7
00:0
0
12:0
06/8
00:0
0
12:0
06/9
00:0
0
12:0
06/1
0 0
0:0
0
12:0
06/1
1 0
0:0
0
12:0
06/1
2 0
0:0
0
12:0
06/1
3 0
0:0
0
12:0
06/1
4 0
0:0
0
12:0
06/1
5 0
0:0
0
12:0
0
Time
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
SV
(p
pb
V)
WSOG SV
At surface layer, model predicts WSOG an order of magnitude
greater than semi-volatile species at Brent ground site
SV
WSOG
35 3.5
Modeling Summary
IEPOX is only recently discovered in ambient PM and modeling results suggest it dominates the WSOCg in wet aerosols in the SEU.S.
Model estimates depend on organic gas ‘solubility’, the extent to which this is accurately predicted remains an open question.
What happens to the partitioned material Barbara Turpin
Log [Po atm]
-7 -6 -5 -4 -3 -2 -1 0
O/C
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Isoprene
O
Methacrolein
O
MVK
HO
O
C5 Hydroxy
carbonyl
OH
OOH
OH
HO
O
OH
Recycling
OrgPeroxEpoxide
OO
MGLY
OO
GLY
OHO
Glycolaldehyde
1st
G Products
1st
G Products
2nd
G Products
OH (Fragmentation)(Oxidation)
(Fragmentation)OH
3hrs
10-14hrs
3hrs1.3 days
1-3 days
OH
Example: isoprene + OH radicals
Expect gas phase chemistry to produce WS gases
Dept of Environmental SciencesLab experiments with selected precursors
Wet aerosols:
acid and ammonium catalyzed oligomerization
organosulfate formation
radical-radical reactions
Dilute cloud chemistry:
Oxidation – organic acid formation
Droplet evaporation:
e.g., amines and aldehydes
What are the important precursors in the
real atmosphere? Can we identify more?
Dept of Environmental SciencesTurpin–Carlton Specific Aims - SOAS:
1) Model aerosol liquid water concentrations
2) Model water-soluble gases
3) Conduct aqueous OH oxidation experiments
with ambient SOAS mixtures of water-soluble
gases (WSOG) to identify precursors/products
4) Collaborate, provide intellectual leadership and
share data to achieve the SOAS science goals
Mist Chamber Sampling at SOAS
in
WSOG mix close to Henry’s law equilibrium
based on WSOG vs collection time before campaign
and 1 run with 2 in parallel (w/in 11%)
FT ICR MS-MS
10000
8000
6000
4000
2000
CIM
S s
ign
al
35x103302520151050
Time (s)
Background25°C 39°C
56°C
74°C
93°C
114°C
140°C
160°C
Oxalic acid Formic acid
Glyoxal CSTR mimic pH 7
10000
8000
6000
4000
2000
CIM
S s
ign
al
45x1034035302520151050
Time (s)
Background 25°C
39°C
56°C
74°C
93°C
114°C
(Oxalic acid)
(Formic acid)
Glyoxal CSTR mimic pH 3
± NH4OH
Ortiz-Montalvo et al., ES&T 2013
Oxalic acid likely to
remain in gas phase
at SOAS
CIMS
Evolved
oxalic acid
pH 3
CIMS
Evolved oxalic acid
pH 7
Gas-phase oxidation of 2-hexenal (or 3-hexenal)
O O
OH
OH
O’Conner et al., PCCP 2006
O
HO O
OH
Gas-phase oxidation of (E)-2-methyl but-2-enal
Jimenez et al., AE 2009
Lanza et a.,, CPL 2008
IEPOX – signature peaks in ESI-MS(+)
60x103
50
40
30
20
10
0
ES
I- M
S a
bu
nd
acn
e
40035030025020015010050
m/z (+)
3000 µM IEPOX 300 µM IEPOX DI blank
71
83
101
141
159
237
259
377
197201 219 297
[IEPOX + Na + H2O]+
[IEPOX + Na]+
IEPOX not seen in SOAS mist chamber samples – but is seen by ESI-MS
•Tentatively identified OH-reactive water soluble polyols,
possible oxidation products of isoprene, green leaf
volatiles
•IEPOX, ISOPOOH probably too reactive to be preserved
in the mist chamber samples
•Complex WSOG mixtures produced oxalate, pyruvate
•Cloud-produced oxalate probably in gas phase at SOAS,
in particle phase if a salt
We conclude:
Carlton, ….Turpin et al. (2016) The Southeast Atmosphere Studies (SAS):
Coordinated Investigation and Discovery to Answer Critical Questions about
Fundamental Atmospheric Processes, Bulletin of the American
Meterological Society, in preparation.
Sareen, N., Carlton, A.M.G., Felipe, H., Lopez-Hilfiker, D., Mohr, C.,
Thornton, J.A., Zhang, Z., Gold, A., Surratt, J.D., Lim, Y.B., Turpin, B.J.
(2015) Identifying precursors and aqueous organic aerosol formation
pathways during the SOAS campaign, Atmospheric Chemistry Physics
Discussion, submitted.
Sareen, N., Waxman, E.M., Turpin, B.J., Volkamer, R., Carlton, A.G. (2015)
Dominance of isoprene epoxydiol (IEPOX) as an aerosol precursor in the
Southeastern United States: model simulations, ES&T, in preparation.
EPA-STAR Publications
Acknowledgements
SOAS2013.rutgers.edu
NCAR’s EOL
ARA, Karsten Bauman
City of Brent, AL
Yong Bin Lim, Jeff Kirkland, Diana Ortiz,
Sara Duncan
Jason Surratt, Avram Gold, Zhenfa Zhang,
Faye McNeill, Joel Thornton
83541201