Terrestrial emissions of isoprene
Paul Palmer
Division of Engineering and Applied Sciences, Harvard University
http://www.people.fas.harvard.edu/~ppalmer
NO
HO2OH
NO2
O3hv
HC+OH HCHO + products
NOx, HC, CO
Tropospheric O3 is an important climate forcing agent
IPCC, 2001
Level of Scientific Understanding
Natural VOC emissions (50% isoprene) ~ CH4 emissions.
GEIA EPA BEIS2
7.1 Tg C 2.6 Tg C
MEGAN
3.6 Tg C
[1012 atom C cm-2 s-
1]
Isoprene emissions July 1996
Isoprene oxidation products (e.g. HCHO) provide constraints on
estimated emissions
GOME isoprene emissions (July 1996) agree with surface measurements
ppb0 12
r2 = 0.53
Bias -3%
GEIA BEIS2
r2 = 0.65
Bias -30%
Mod
ele
d H
CH
O [
pp
b]
Observed HCHO [ppb]
Modeling the terrestrial biosphere
April Sep
LA
IPAR – direct and diffuse (GMAO)
MODIS/AVHRR LAI
Canopy model (Guenther 1995)
Alt
itu
de
Emission
Temperature:
Instantaneous (G95)
10-day avg (Petron ‘01)
Fixed base emission factors (Guenther 2004)
Emissions
Monthly mean LAI (AVHRR/MODIS)
MEGAN (isoprene)Canopy model
Leaf ageLAI
TemperatureBase factors
MODEL BIOSPHERE
GEIAMonoterpenes
MBOAcetoneMethanol
GEOS-CHEMGlobal 3D CTM
PAR, T
Emissions
Global 3-D Modeling Overview•Driven by NASA GMAO met data
•2x2.5o resolution/30 vertical levels
•O3-NOx-VOC-aerosol chemistry
May
Jun
Jul
Aug
Sep[1012 atom C cm-2 s-
1]
VOC emissions
during 2001
growing season
IsopreneMonoterpenes MBO
GEOS-CHEM
NOx = 1 ppb
NOx = 0.1 ppb
isoprene
Use this analysis to parameterise source of HCHO from monoterpenes
HCHO production from biogenics using the MCM
0 20 40 60 80 100 120 1400.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
Cum
mu
lativ
e H
CH
O Y
ield
fro
m is
opr
ene
oxi
da
tion
(per
C)
TIME (HOURS)
NOX = 0.1 PPB
NOX =1 PPB
Figure 18. Formation of HCHO from isoprene. Vertical lines denote midnight of each day
HOURS
0.5
Cu
mu
lati
ve H
CH
O y
ield
[p
er
C]
0 2 4 6 8 10 12 14 16 18 20 220.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
HC
HO
YIE
LD
PE
R C
RE
AC
TE
D
DAYS
NOX= 1 PPB NOX= 100 PPT pinene (
pinene similar)
DAYS
0.4
0.33
Y become closer at t progresses further
Mike Pilling and Jenny Stanton, Leeds University
•Nadir-viewing SBUV instrument
•Pixel 320 x 40 km2
•10.30 am cross-equator time (globe in 3 days)
•O3, NO2, BrO, OClO, SO2, HCHO, H2O, cloud
Global Ozone Monitoring Experiment
•HCHO slant columns fitted: 337-356nm
•Fitting uncertainty < continental signalsHCHO JULY 1997
Isoprene
Biomass Burning
May
Jun
Jul
GEOS-CHEM GOME
Aug
Sep
GEOS-CHEM GOME
HCHO column [1016 molec cm-
2]
GROWING SEASON 2001
HCHO column signal from monoterpenes is comparable to GOME
column uncertainty
HCHO data over the Ozarks
c/o Y-N. Lee, Brookhaven National Lab.
MissouriIllinois
Kansas
[ppb]
Aircraft data @ 350 m July 1999
OZARKS
SOS 1999
[1016 molec cm-
2]
GOME
Relating HCHO Columns to VOC Emissions
kHCHO HCHOEVOC = _______________kVOCYieldVOCHCHO
VOC source
Distance downwind
HCHO Isoprene
-pinenepropane
100 km
VOC
HCHOhours
OH
hours
h, OH
Ultimate Yield Y (per
C)
Approx. Time to Y
isoprene
~0.5 2-3 hrs
pinene
~0.3 3-4 days
pinene
~0.25 3-4 days
MBO ~0.4 3-4 days
Master Chemical Mechanism
Wind direction associated with largest [HCHO] in 1998
intensive
EVALUATE GOME DATA USING LONG-TERM ISOPRENE FLUX DATA
PROPHET RESEARCH SITE (MI)Maple, beech, birch, basswood, mixed aspen, bog conifers (lower, wet areas), and pine and red oak (drier upland regions). Average height near 20 m. Overstory age of the hardwood forest is approximately 75 years.
Long term in situ isoprene flux measurements at PROPHET site during
2001
Y2K1 Day
HCHO column [1016 molec cm-2]
Isoprene flux [1012 molec cm-2 s-1] Measured
(WSU) MEGAN GOME
+/- uncertainty
Isoprene flux [1012 molec cm-2 s-1]
Measured (WSU) MEGAN GOME
Using observed isop flux:HCHO column regression better agreement with GOME
May June July August September
1996
1997
1998
1999
2000
2001
HCHO column [1016 molec cm-
2]
Interannual variability of the seasonal cycle
GO
ME H
CH
O C
olu
mn
[10
16 m
ole
c c
m-2]
Days 2K1
Southeast US 32-38N; 265-280W
In situ observations over Atlanta GA provide some verification of large
interannual variability
GO
ME H
CH
O C
olu
mn
[1
01
6 m
ole
c cm
-2]
PAMS (EPA) Isoprene Concentration (10-12 LT)
[ppbC]
r = 0.75 n=14
Mean values associated with individual values > 30 ppbC
Lance McCluney,
EPA
What is driving this variability?
Curve based on greenhouse data (Guenther)
2nd-order polynomial fit to HCHO columns
r=0.9
Closing Remarks
• GOME HCHO data provide constraints on natural VOC emissions
• Data consistent with seasonal and interannual variability observed with in situ measurements
• Improved understanding and quantification of air quality and climate
• Just the beginning…need to relate model-observation discrepancy to a better understanding of the underlying processes