direct (primary) and indirect (secondary) emissions from biomass and prescribed burning
DESCRIPTION
Direct (Primary) and Indirect (Secondary) Emissions from Biomass and Prescribed Burning. Karsten Baumann School of Earth and Atmospheric Sciences [email protected] 22 January, 2004. Funded in part by DoD/EPA/State P2 Partnership Small Grants Program. - PowerPoint PPT PresentationTRANSCRIPT
Direct (Primary) and Indirect (Secondary) Emissions from Biomass and Prescribed Burning
Karsten Baumann
School of Earth and
Atmospheric Sciences
22 January, 2004
Funded in part by DoD/EPA/State P2 Partnership Small Grants Program.
Co-authors: Mei Zheng, Venus Dookwah, Sangil Lee, Michael Chang
Problem: ESA versus CAA
Military Installations in SE-US occupy habitat of endangered species (red-cockaded woodpecker), and are required to maintain ecosystem by prescribed burning, risking violations of the NAAQS.
Clean Air Act
EndangeredSpecies Act
N
E
S
W10 20 µg m
-3
PM2.5 Eceedance at Columbus-OLC near Fort Benning for SE winds in Winter 2001/02
Manage 94,000 acr, Burn 1/3 per yr, ~ 520 acr/day
PM2.5 Exceedances at Columbus-OLC in Oct-Nov 2001
0.00
Win
d B
arb
40
30
20
10
0WS
(m
/s)
Tm
ax-T
min
(C) 80
60
40
20
0
8h
max O
3 (pp
bv)
ColumbusGIT OLCEPD AirptEPD Crlab
4
6
810
2
4
6
8100
2
4
24h
- P
M2.
5
(µg
m-3
)
10/21/01 10/31/01 11/10/01 11/20/01 11/30/01 12/10/01Time (EST)
1000
800
600
400
200
0
Ft B
enn
ing
(acr bu
rnt)
Griffin MaconAugusta Columbus
wild firesprescribed
Prescribed Burn Study: Objectives and Outlook
• In this initial pilot study, establish understanding of the direct and indirect impact of current burn practices on sub-regional Air Quality.
• Lay foundation for more comprehensive and better focused Phase II Study to optimize burn practices toward minimum AQ impact.
• Create results of general applicability for the benefit of LMBs on other military installations in the SE-US and beyond.
• Learn lessons that help create and implement new revised land management strategies for the benefit of other agencies and institutions that face often times devastating wild fires in other parts of the Nation.
Issues on Local to Global ScalesIn the continental U.S. prescribed burns and forest fires contribute ~37 % to the
total direct fine PM emissions of ~1 Mio t per year*
* Nizich et al., EPA Report 454/R-00-002 (NTIS PB2000-108054), RTP, NC, 2000
Effects on• Health
• Visibility• Air Quality
• Climate
Do prescribed burns reduce the risk
of wild fires?
To what extent does prescribed burning impact local and regional air quality?
VOCs
PMNOx
O3, SOA
Toxics
COCO2
Direct Emissions
1. Savannah GrassLobert et al, Nature 346, 552-554, 1990. Crutzen and Andreae, Science 250, 1669-78, 1990.
Flaming SmolderingCO2 CONOx NitrilesSO2 (HCN, CH3CN)N2O CH4, NMHC
CO/NOx ~ 25, SO2/NOx ~ 0.1
2. Wood/Coal BriquetsStruschka et al, IVD-RdL Univ Stuttgart, Rep.34, 1995
Flaming SmolderingCO/NOx SO2/NOx CO/NOx SO2/NOx
Wood 18 +-9 0.2 +-0.1 48 +-17 0.3 +-0.3Coal 9 +-5 23 +-6 50 +-40 18 +-12
Influence on Remote Locations
400
300
200
100
CO
(
pp
bv
)
121086420NOy (ppbv)
LB Lakes, KY 120 maslslp = 50.2 ±7.1icpt= 123 ±23(R= 0.64)
3000
2500
2000
1500
1000
500
0
CO
(
pp
bv
)
200150100500NOy (ppbv)
Nashville 1995 fire vs all:slp = 10.8 ±0.5 8.3 ±0.14icpt= 215 ±12 202 ±4.9 (R=0.91) (R= 0.90)
Nashville 1994:slp = 9.8 ±0.03icpt= 127 ±1.6(R= 0.96)
400
300
200
100
CO
(
pp
bv
)121086420
NOy (ppbv)
Cove Mt., TN 1250 maslslp = 39.5 ±2.6icpt= 124 ±9.4(R= 0.86)
1600
1400
1200
1000
800
600
400
200
0
CO
(p
pb
v)
100806040200
NOy (ppbv)
Hendersonville downwindfrom Nashville 1994:slp = 11.9 ±0.08icpt= 102 ±1.2(R= 0.89)
Canadian Forest Fires Impacting SE-US in Summer 1995Wotawa and Trainer, Science 288, 324-328, 2000.Open symbols: period 6/30 – 7/4.Increased regional CO background level!Is typically 80-90 ppbv.
Influence on urban areas:- less on slope (mobile src) - more on intercept !Shorter lifetime of NOy: some species (eg HNO3) lost due to surface deposition during transport in PBL.
Regional CO vs Burn Activity in GA during PBS
140
160
180
200
220
240
Dec-02 Jan-03 Feb'03 Mar'03 Apr'03 May'03 June'03
Month
CO
(p
pb
v)
0
5,000
10,000
15,000
20,000
25,000
Bu
rned
Acr
es
Ft Benning (acr)Surr Region (acr)Rest of GA/10 (acr)Ft Gordon (acr)Surr Region (acr)CO bkgrd (ppbv)
Monthly average CO background level derived from CO/NOy regressions at OLC (left) in comparison with prescribed burn areas at Forts Benning and Gordon, their surrounding
counties, and the rest of Georgia (only 10% of true area plotted!).
Direct Emissions of VOCs
Mixing ratios enhanced above local background at Fort Gordon TA21.Fuel: 230 acres of 2 year rough of pine needles, leaves, and woody debris.
0.0
0.1
1.0
10.0
100.0
1000.0
10000.0
100000.0
FLaming (3 h) Smoldering (6 h)
pp
mv,
pp
bv
CO2/COx (%) CO2 CO CH4 AlkanesAlkenes Aromatics Halog HC Biog HC Org NO3
VOC Emission Estimates - Comparison with Mobile Sources
0
1
10
100
1000
10000
Flaming Smoldering Gas Diesel Flaming Smoldering Gas Diesel
Fort Gordon Richmond Fort Benning Muscogee
Em
issi
on
s (
kg
/bu
rn/d
ay
)
Toluene m-Xylene p-Xylene o-Xylene 3-Ethyltoluene4-Ethyltoluene 2-Ethyltoluene Isopropylbenzene Propylbenzene Ethylbenzene
0
10
20
30
40
50
60
70
80
90
100
Flaming Smoldering Gas Diesel Flaming Smoldering Gas Diesel
Fort Gordon Richmond Fort Benning Muscogee
P(S
OA
)-F
rac
tio
n (
%)
Toluene m+p-Xylene o-Xylene 3-Ethyltoluene 4-Ethyltoluene2-Ethyltoluene Isopropylbenzene Propylbenzene Ethylbenzene
Average emissions per burn (~500 acr) compare with daily mobile emissions !3,4-E.toluene higher during smoldering,2-E.toluene highest for gasoline fueled vehicles
Contribution to P(SOA) potential is highest for Toluene from flaming and Xylenes from smoldering, minimal for 2-E.toluene.
Mas
s E
mis
sion
Rat
e (g
/kg
of b
iom
ass
burn
ed)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15Carbonyls Cyclic compounds Branched Alkanes n-Alkynes Aromatics n-Alkanes n-Alkenes
Pinu
s tae
da
Tsug
a he
tero
phyl
la
Pinu
s pon
dero
sa
MH
FF
FPSP
WG
LP
Biomass Litter CompositesMHFF… mixed hardwood (oak) forest foliageFPSP… Florida palmetto & slash pineWGLP… wiregrass & longleaf pine
Direct (Primary) PM Emissions from Foliar Fuel Combustion in Lab
Hays, Geron et al., ES&T 36, 2281-2295, 2002
POC
High-Vol Sampling and GC/MS AnalysesQuantification of >100 Particle-phase Organic Compounds
RetenePimaric acidAbietic acidSandaracopimaric acidLevoglucosan
0
100
200
300
400
500
600
700
2/5/03 12:00 2/5/03 17:00 2/5/03 22:00 2/6/03 3:00 2/6/03 8:00
Sample Start Time [EST]
Co
nc
en
tra
tio
n (
ng
m-3
)
n-Alkanes Hopanes Steranes
PAHs Resin acids Arom carboxy acids
Other compounds Levoglucosan Branched alkanesn-Alkanoic acids Alkenoic acids Alkanedioic acids
Five consecutive 5-h samples taken at OLC between February 5th 1200 and 6th 1300
Influence from February 5th Burn: Source Apportionment
1200
1000
800
600
400
200
0
CO
(pp
bv) P
B (acres)
2/2 2/3 2/4 2/5 2/6Sun Mon Tue (m/dd) Wed Thu
60
50
40
30
20
10
0
NO
NO
y O
3 (
pp
bv)
16
12
8
4
0
PM2.5
(g m-3
) Un-ID Others LOA OOE OC EC NH4+ NO3- SO4=
8
4
0WS
(m
s-1
)0.00
-20
-10
0
10
20
amb
T (C
)
Low P front moving through GA on 3rd and 4th, with cold dry air moving in behind it from NE, causing below normal T under clear skies. Prescribed burning of 937 acres on 2/5 1200 at ~28 km to east, smoldering until 2/6 am. 0
1
2
3
4
5
6
7
8
2/5 1200 2/5 1700 2/5 2200 2/6 0300 2/6 0800Sample Start Time (EST)
Org
an
ic C
arb
on
(u
g m
-3)
Diesel exhaust Gasoline exhaust Wood combustion
Vegetative detritus Other OCNighttime avg
53% wood
?
?
VOCs
PMNOx
O3, SOA
Toxics
COCO2
Secondary organic aerosol (SOA):Organic compounds, some highly oxygenated, residing in the
aerosol phase as a function of atmospheric reactions that occur in either gas or particle phases.
SOA formation mainly depends on:Emissions & forming potential of precursors
aromatics (BTX, aldehydes, carbonyls)terpenes (mono-, sesqui-)other biogenics (aldehydes, alcohols)
Presence of other initiating reactantsO3, OH, NO3, sunlight, acid catalysts
Mechanisms (with half hr to few hr yields):Gas-to-particle conversion/partitioning
e.g. terpene oxidationHeterogeneous reactions
aldehydes via hydration and polymerization, forming hemiacetal/acetal in presence of alcohols
Particle-phase reactionsacetal formation catalytically accelerated by particle sulfuric
acid (Jang and Kamens, ES&T, 2001)
Photochemical Processes Leading to O3 and PM
SOA
NOz
An Assessment of Tropospheric Ozone Pollution, A North American Perspective, NARSTO, National Acad. Press, 2000.
0
5
10
15
20
25
30
35
20-Ja
n
21-Ja
n5-F
eb6-F
eb
10-M
ar
24-M
ar
27-M
ar
13-Apr
15-Apr
17-Apr
29-Apr
29-M
ay
Period
PM
2.5
(g
m-3
)
[K+] [Na+] [Ca2+] [NH4+] [Cl-] [NO3-] [SO4-2] EC Acetate Formate Oxalate OC OOE
PM2.5 Mass & CompositionIndividual Burn Events and Acres Burned
January May 2003
No-Burn Background
937 acres
1256 acres
3770 acres 4006 acres
504 251
Burning early in the season seems advantageous
PM2.5 Mass & CompositionOM/OC & [O3-max] Averages per Burn Event
January May 2003
0
5
10
15
20
25
Jan
Feb
Mar
, 1st
Mar
, 2nd
Apr, 1
st
Apr, 2
ndM
ay
Period
PM
(
g m
-3)
0
10
20
30
40
50
60
70
80
90
100
O3 (p
pb
v)
Others [NH4+] [NO3-] [SO4-2] EC LOA OC OOE Max O3
OM/OC 1.9 1.5 2.2 1.6 1.9 2.1 2.0
Higher PM mass and OM/OC with higher [O3] later in the season
PM2.5 Wind Roses: Seasonal Differences Across GAIndications for Regional Transport?
34.4
34.2
34.0
33.8
33.6
33.4
33.2
33.0
32.8
32.6
32.4
32.2
32.0
-85.5 -85.0 -84.5 -84.0 -83.5 -83.0 -82.5 -82.0
Atlanta
FAQS measurement sites GA-EPD monitoring sites coal burning power plants point sources w/ CO:NOx > 1
20x20 km
N
E
S
W9 18
µg m-3
15.813.4Griffin
Period 2001+ 02MAY-OCT NOV-APR
N
E
S
W9 18
µg m-3
16.715.5Macon SBP
N
E
S
W9 18
µg m-3
Columbus OLC 16.6 19.3
N
E
S
W9 18
µg m-3
15.014.2Augusta RP
…Similarity to Daytime O3
34.4
34.2
34.0
33.8
33.6
33.4
33.2
33.0
32.8
32.6
32.4
32.2
32.0
-85.5 -85.0 -84.5 -84.0 -83.5 -83.0 -82.5 -82.0
Atlanta
FAQS measurement sites GA-EPD monitoring sites coal burning power plants point sources w/ CO:NOx > 1
20x20 km
Period 2001+ 02MAY-OCT NOV-APR
N
E
S
W30 60
ppb
38.228.5Macon SBP
N
E
S
W30 60
ppb
Columbus OLC 30.7 19.8
N
E
S
W30 60
ppb
30.222.2Augusta RP
N
E
S
W30 60
ppb
44.236.1Griffin
Findings Progressively increasing fine PM mass and organics fraction correlate with increased temperature, solar radiation, and O3, indicating increased oxidizing potential, hence increased potential for SOA formation.
Strongest direct impact from prescribed burning emissions at OLC site encountered at night under clear skies nocturnal inversion and slow moving easterly component flow (along the Upatoi Creek); the contribution from the PB source indicators is then ~52 % to total OC.
VOCs with low Ps (C>6), esp. toluene and xylenes are being emitted at similar quantities per average burn day than the daily emissions of the mobile sources of the respective county, Muscogee (Fort Benning) and Richmond (Fort Gordon); the P(SAO) potential is highest for toluen followed by xylenes.
The regional CO background is closely correlated with open burning activities in Georgia, suggesting i) substantially longer smoldering phases than originally assumed, ii) similar source behavior across the entire SE-US??
Supplementary Material
Seasonal Differences in Diurnal Cycles: O3 & PM2.5
00:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00
Time (EST)
WINTER HALF NOV-APRMac '01/'02 '00/'01Col '01/'02 '00/'01Aug '01/'02 '00/'01
WINTER HALF NOV-APRGrif '01 Tift '01Mac '01 '00Col '01 '00Aug '01 '00
PM2.5 Sources Near Columbus Driving Nighttime Averages in Winter 2001/02
Winter
25
20
15
10
5
0
PM
2.5
(
g m
-3)
00:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00
Time (EST)
SUMMER HALF MAY-OCTGrif '02Mac '02 '01 '00Col '02 '01 '00Aug '02 '01 '00
70
60
50
40
30
20
10
0
O3
(pp
bv)
SUMMER HALF MAY-OCTTift '02 '01Grif '02 '01Mac '02 '01
'00Col '02 '01
'00Aug '02 '01
'00
Summer
OLC site upgradeResearch site at
Oxbow Meadows Environmental Learning Center
upgraded for PM source apportionment and in situ
gas phase sampling
3’
4’
a/c
11’
8’
Stair step
4’ 14’
Guy wired8m Towertilt down
10’ Gate
45’ x 40’ Fence
N
10’ x 12’ Shelter
4 additional 20 A circuit breakers
33’ x 7’ level Platform~ 1’ above ground
4 quadruple outlets on individual breakers
Particle Composition Monitor “PCM”
Channel 1:
NH3
Na+, K+, NH4+, Ca+2
Channel 2:
HF, HCl, HONO, HNO3, SO2,
HCOOH, CH3COOH, (COOH)2
F-, Cl-, NO3-, SO4
=,
HCOO-, CH3COO-, C2O4=
Channel 3:
EC, OC, WSOC, “SVOC”
Additional higher resolution
CO, NO, NOy, O3, PM-mass,
and basic meteorology
Canister Sampling and GC/FID Detection of Volatile Organic Compounds
VOC
Collaborating withProf. Don Blake, UC Irvine, CA 92697 http://fsr10.ps.uci.edu/GROUP/group.html
C2-C6 n-alkanes, alkenes, branched alkenes, alkynesisoprene
Cyclic compoundsmonoterpenes (-, -pinene)
Aromatics, organic nitrates, halogenated speciesmethylchloride
Quantification of >60 compounds, incl. CO2 for “fire” samples
Other OrganicCarbon{SOA}30%
WoodCombustion
39%
MeatCooking
6%
VegetativeDetritus
2%
GasolineExhaust
3%
Diesel Exhaust 20%
Source Contributions to Organic Carbon (OC)in Ambient PM2.5
Pensacola, FL October 1999Measured average [PM2.5] = 16.6 g m-3
[OC] = 4.6 g m-3
Zheng et al., ES&T 2002