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AIRUSE LIFE+: Biomass burning emission factors and chemical profiles
in Southern Europe
Fulvio Amato
C.A. Alves, E. Vicente, C. Gonçalves, M. Duarte, L. Tarelho, T. Nunes, C. Pio, C. Colombi, V.
Gianelle, X. Querol
TFEIP/EIONET Meeting (11th – 12th May)
2
Source apportionment: Biomass burning contribution (2013)
PM10Porto-
TRBarcelona-
UBFlorence-
UBMilan-
UBAthens-
SUB
Contributions to the annual mean 14%(5) <2%(<0.5) 16%(3) 24%(9) 7%(1.4)
Contributions during PM10 exceedances days
25%(16) <2%(<0.5) 30%(22) 35%(28) 1%(0.6)
PM2.5Porto-
TRBarcelona-
UBFlorence-
UBMilan-
UBAthens-
SUB
Contributions to the annual mean 18%(5) <3%(<0.5) 21%(3) 21%(6) 10%(1.2)
Contributions during PM10 exceedances days
33%(22) <3%(<0.5) 33%(23) 26%(14) 2%(0.5)
Contribution of biomass burning to PM10 and PM2.5 levels, mass fractions (%) and µg m-3, in AIRUSE cities
3
Based on forest inventories and information provided by the AIRUSE partners, wood species widely used as biofuels in residential combustion in Southern European countries were burned in traditional appliances (manually fed)
(Fagus sylvatica)European beech
(Quercus pyrenaica)Pyrenean oak
(Populus nigra)Black poplar
Pine(Pinus pinaster)
Eucalypt(Eucalyptus globulus)
Cork oak(Quercus suber )
Golden wattle(Acacia longifolia)
Portuguese oak(Quercus faginea)
Olive(Olea europea)
Holm oak(Quercus ilex rotundifolia)
Briquettes
Biomass burning profiles – biofuels and appliances
4
Traditional brick
fireplace
Traditional cast iron
wood stove
Eco-labelledchimney-typewood stove
Manually fed combustion appliances
5
Emissions from a pellet stove were also measured. In addition to different types of pellets, other alternative biofuels (agro-fuels) that are becoming common in Southern Europe were also burned in this combustion appliance.
4 types of pelletsOlive pit
Shell of pine nutsAlmond shell
Automatically fed combustion appliance
Pellets type I – made of wood (ENPlus certification)Pellets type II to IV – manufactured with residues from the furniture industry and from civil construction, in different proportions
Termocouple T6
Sample Gas (SG) / Pressure
Warm water (out)
Combustion flue gases Cold water (in)
Temperature
S
N2Zero Gas (ZG)
L
UCD0J
I
Pressure
045
000
UCD1
SG
Sam
ple G
as (SG
) / Pressure
UCE1
CO
R
UCD2
K
CO2
O2
HC
Q
O
P
N
Heated sampling line (190ºC)
G
Ice
Bat
h
ZG
Condensed material
Ice
Bat
h
SGSG
MTermocouple T5
Termocouple T4
Termocouple T3
Termocouple T2
D
A
C Air
B
F
E
H
Termocouple T1
A - Stove
B – Grate of the stove
C – Load cell (weight sensor)
D – Air flow meter
E – Thermal insulation of the exhaust duct
F – Exhaust duct (Chimney)
G – Water-cooled gas sampling probe
H – Heated sampling line
I, J, K – Command and gas distribution units (UCD0, UCD1, UCD2)
L – Gas sampling pump
M – Gas condensation unit for moisture removal
N, O, P, Q – Automatic on-line gas analysers (THC, CO2, O2, CO)
R – Electronic command unit (UCE1)
S – Computer data acquisition and control system
Dashed line – Electric circuit,
Continuous line – Pneumatic circuit.
Termocouple T6
Sample Gas (SG) / Pressure
Warm water (out)
Combustion flue gases Cold water (in)
Temperature
S
N2Zero Gas (ZG)
L
UCD0J
I
Pressure
045
000
UCD1
SG
Sa m
pl e Ga s (S
G) / P
re ssur e
UCE1
CO
R
UCD2
K
CO2
O2
HC
Q
O
P
N
Heated sampling line (190ºC)
G
Ice
Ba t
h
ZG
Condensed material
Ice
Ba t
h
SGSG
MTermocouple T5
Termocouple T4
Termocouple T3
Termocouple T2
D
A
C Air
B
F
E
H
Termocouple T1
Termocouple T6
Sample Gas (SG) / Pressure
Warm water (out)
Combustion flue gases Cold water (in)
Temperature
S
N2Zero Gas (ZG)
L
UCD0J
I
Pressure
045
000
UCD1
SG
Sam
ple G
as (SG
) / Pre ssu
re
UCE1
CO
R
UCD2
K
CO2
O2
HC
Q
O
P
N
Heated sampling line (190ºC)
G
Ice
Ba
t h
ZG
Condensed material
Ice
Ba
t h
SGSG
MTermocouple T5
Termocouple T4
Termocouple T3
Termocouple T2
D
A
C Air
B
F
E
H
Termocouple T1
Termocouple T6
Sample Gas (SG) / Pressure
Warm water (out)
Combustion flue gases Cold water (in)
Temperature
S
N2Zero Gas (ZG)
L
UCD0J
I
Pressure
045
000
UCD1
SGS
amp le
Ga s (S
G) / P
re ss u re
UCE1
CO
R
UCD2
K
CO2
O2
HC
Q
O
P
N
Heated sampling line (190ºC)
G
Ice
Bat
h
ZG
Condensed material
Ice
Bat
h
SGSG
MTermocouple T5
Termocouple T4
Termocouple T3
Termocouple T2
D
A
C Air
B
F
E
H
Termocouple T1
Termocouple T6
Sample Gas (SG) / Pressure
Warm water (out)
Combustion flue gases Cold water (in)
Temperature
S
N2Zero Gas (ZG)
L
UCD0J
I
Pressure
045
000
UCD1
SG
Sam
pl e G
as ( SG
) / Pressur e
UCE1
CO
R
UCD2
K
CO2
O2
HC
Q
O
P
N
Heated sampling line (190ºC)
G
I ce
Bat
h
ZG
Condensed material
I ce
Bat
h
SGSG
MTermocouple T5
Termocouple T4
Termocouple T3
Termocouple T2
D
A
C Air
B
F
E
H
Termocouple T1
Termocouple T6
Sample Gas (SG) / Pressure
Warm water (out)
Combustion flue gases Cold water (in)
Temperature
S
N2Zero Gas (ZG)
L
UCD0J
I
Pressure
045
000
UCD1
SG
Sam
p le Gas ( S
G) / P
re s su r e
UCE1
CO
R
UCD2
K
CO2
O2
HC
Q
O
P
N
Heated sampling line (190ºC)
G
Ice
Ba t
h
ZG
Condensed material
Ice
Ba t
h
SGSG
MTermocouple T5
Termocouple T4
Termocouple T3
Termocouple T2
D
A
C Air
B
F
E
H
Termocouple T1
E – Thermal insulation of the exhaust duct F – Exhaust duct (Chimney)G – Water-cooled gas sampling probeH – Heated sampling lineA - Stove
B – Grate of the stoveC – Load cell (weight sensor)D – Air flow meter
R – Electronic command unit (UCE1)S – Computer data acquisition and control system
I, J, K – Command and gas distribution units (UCD0, UCD1, UCD2)L – Gas sampling pumpM – Gas condensation unit for moisture removalN, O, P, Q – Automatic on-line gas analysers (THC, CO2, O2, CO)
• 0.2 m int. diameter
• 3.3 m height
Combustion facility
Termocouple T6
Sample Gas (SG) / Pressure
Warm water (out)Cold water (in)
Temperature
S
N2Zero Gas (ZG)
L
UCD0J
I
Pressure
045
000
UCD1
SG
Sam
ple
Gas (S
G) / P
r essure
UCE1
CO
R
UCD2
K
CO2
O2
HC
Q
O
P
N
Heated sampling line (190ºC)
G
Ice
Bat
h
ZG
Condensed material
Ice
Bat
h
SGSG
MTermocouple T5
Termocouple T4
Termocouple T3
Termocouple T2
D
A
C Air
B
F
E
H
Termocouple T1
Atm
osph
eric
air
Co
mbu
stio
n f lu
e ga
ses
Z
Electron ic flow sampler
Y
TECORA
Thermocouple T8
XTCR PM Air Inlet
T
Thermocouple T7
Pres sure (P
1 )
W
UPASSIVE CAVITY AEROSOL SPECTROMETER PROBE
Dilution air
Dilution air
V
Termocouple T6
Sample Gas (SG) / Pressure
Warm water (out)Cold water (in)
Temperature
S
N2Zero Gas (ZG)
L
UCD0J
I
Pressure
045
000
UCD1
SG
Sam
ple
Ga s (S
G) / P
res sure
UCE1
CO
R
UCD2
K
CO2
O2
HC
Q
O
P
N
Heated sampling line (190ºC)
G
Ice
Bat
h
ZG
Condensed material
Ice
Bat
h
SGSG
MTermocouple T5
Termocouple T4
Termocouple T3
Termocouple T2
D
A
C Air
B
F
E
H
Termocouple T1
Atm
osph
eric
air
Co
mbu
stio
n flu
e ga
ses
Z
Electronic flow sampler
Y
TECORA
Thermocouple T8
XTCR PM Air Inlet
T
Thermocouple T7
Pressu re (P
1)
W
UPASSIVE CAVITY AEROSOL SPECTROMETER PROBE
Dilution air
Dilution air
V
T - Dilution tunnel
U - Aerosol size distribution probe (PCASP-X)
V - Venturi system
W - Pitot tube
X - Sampling head for PM10 or PM2.5 (TECORA)
Y - TECORA control and data acquisition system
Z - Blower
Combustion facility
Analytical techniques
Thermal-optical method
Ion chromatography
ICP-MSICP-AES
GC-MS
Water solubleions
Organic carbonElemental carbon
Elements
Organic speciation
HPLC-electrochemistry,HPAEC/ESI-MS,
HPAEC-PADor GC-MS
Anhydrosugars
9
PM emission factors
0
200
400
600
800
1000
1200
Fireplace Traditionalwoodstove
Eco-labelledwoodstove
Pellet stove
mg
MJ-1
(dry
bas
is)
0
200
400
600
800
1000
1200
Fireplace Traditionalwoodstove
Eco-labelledwoodstove
Pellet stove
mg
MJ-1
(dry
bas
is)
Particle emissions from the fireplace were about 3, 9 and 12-fold higher than those from the traditional woodstove, eco-labelled appliance and pellet stove, respectively.
Emissions from the traditional woodstove exceeded 5 to 6 times those of the two more modern combustion devices
10
PM emission factors
0
20
40
60
80
100
120
140
160
180
200
Pellet - typeI
Pellet - typeII
Pellet - typeIII
Pellet - typeIV
Olive Pit Shell of PineNuts
AlmondShell
mg
MJ-1
(dry
bas
is)
0
20
40
60
80
100
120
140
160
180
200
Pellet - typeI
Pellet - typeII
Pellet - typeIII
Pellet - typeIV
Olive Pit Shell of PineNuts
AlmondShell
mg
MJ-1
(dry
bas
is)
PELLET STOVE: only one type of pellets, with ENplus quality seal, complies with the limits stipulated in countries where certification of combustion appliances is required
(e.g. 50 mg MJ-1 in Denmark and Switzerland, 35 mg MJ-1 for wood fuels and 25 mg MJ-1 for pellets in Austria, and 27 mg MJ-1 in Germany).
11In the fireplace and the old type stove, OC dominated the emissions, while more efficient combustion in the eco-labelled and pellet stoves contributed to 1.3 to 4.7-fold higher EC relative fractions in PM. An increase of EC emissions with increasing combustion temperature is generally observed.
Chemical composition of PM
0
10
20
30
40
50
60
70
Maritime pine Golden wattle Eucalypt Cork oak
(OC+
EC)/
PM10
(%w
t.)
Eco-labelled woodstove
0102030405060708090
(OC+
EC)/
PM2.
5(%
wt.
)
Fireplace
EC OC
0102030405060708090
(OC+
EC)/
PM2.
5(%
wt.
)
Woodstove
0
10
20
30
40
50
60
70
Pellet I Pellet II Pellet III Pellet IV Olive Pit Shell ofPine Nuts
AlmondShell
(OC+
EC)/
PM10
(%w
t.)
Pellet stove
12
Water-soluble ions
2%
Elements 0.4%
EC9%
OM89%
Pine, Fireplace
Water-soluble ions
11%Elements
2%
EC15%
OM72%
Pine, Eco-labelled stoveAlkanes0.24%
Alkenes0.010%
PAHs1.5%
Phenolic compounds
2.6%Alcohols0.022%
Acids44%
Sugars48%
Other compounds
4.3%
Alkanes2% Alkenes
1%
PAHs13%
Phenolic compounds
1%
Alcohols2%
Acids60%
Sugars18%
Other Compounds
3%
Chemical composition of PM (manually fed appliances)
Higher mass fractions of inorganic constituents, EC and polyaromatics in PM from more efficient combustion devices
Organic compounds, such as sugars and acids, completely dominate emissions from old-type appliances that operate at lower temperatures
13
Chemical composition of PM (pellet stove)EC7%
OM 52%
Elements and their oxides
39%
Undetermined2%
Pellets type I
EC3.2%
OM 57%
Elements and their oxides
32%
Undetermined7.8%
Olive pit
EC41%
OM 37%
Elements and their oxides
22%
Shell of pine nuts
Much higher inorganic PM10 mass fractions (up to 42%)
Under typical conditions, organic particles are most relevant in poorly operated
manual wood combustion devices, while inorganic particles are most dominant in automatic biomass combustion devices
operated at high temperatures
23 parent-PAHs, 11 NPAHs and 15 OPAHs in PM10 were quantified
0
5000
10000
15000
20000
25000
30000
35000
40000
Eucalypt,devolatilisation
Eucalypt, flaming+ smouldering
Pine,devolatilisation
Pine, flaming +smouldering
µg
kg-1
of f
uel
bu
rned
, dry
bas
is
Woodstove
parent-PAHs
OPAHs
NPAHs
0
100
200
300
400
500
600
700
800
900
Pellets typeI
Pellets typeII
Pellets typeIII
Pellets typeIV
Olive pit Shell ofpine nuts
Almondshell
µg
kg-1
of f
uel
bu
rned
, dry
bas
is
Pellet stove
parent-PAHs
OPAHs
NPAHs
Polycyclic aromatic compounds
15
BaP (and PM) emission factors
nd – not detected; --- not determined
FIREPLACE Softwood Hardwood Briquettesg PM2.5 kg-1 biofuel 7.02 16.9 13.8µg BaP kg-1 biofuel 260 475 31.4
TRADITIONAL WOODSTOVE Softwood Hardwood Briquettesg PM2.5 kg-1 biofuel 3.64 13.5 9.02µg BaP kg-1 biofuel 46.7 322 85.3
ECO-LABELLED STOVE Softwood Hardwood Briquettesg PM10 kg-1 biofuel 1.12 2.06 ---µg BaP kg-1 biofuel 1543 146 ---
PELLET STOVE Pellets I Pellets II Pellets III Pellets IV Olive pit Shell of pine nuts Almond shellg PM10 kg-1 biofuel 0.49 1.51 1.77 1.35 3.12 2.19 2.07
µg BaP kg-1 biofuel 4.43 nd nd 4.61 nd 17.2 9.19
Combustion of resinous wood (softwood) at higher temperatures in the eco-labelled stove produces very intense flames, contributing to oxygen-starved conditions and, consequently, to higher PAH emissions
16
0
50
100
150
200
250
mg/
g PM
2.5
Woodstove
0.0
0.5
1.0
1.5
2.0
2.5
Pelletstype I
Pelletstype II
Pelletstype III
Pelletstype IV
Olive Pit Shell ofPineNuts
AlmondShell
mg/
g PM
10
Pellet stove
0
50
100
150
200
250
Maritime pine Golden wattle Eucalypt Cork oak
mg/
g PM
10
Eco-labelled stove
Levoglucosan
Levoglucosan is not a suitable tracer for automatically fired combustion appliances in which high temperatures are reached.
Levoglucosan-to-mannosan ratios
Authors Levo/Man
Schmidl et al., 2007
Fagus sylvatica Quercus robur
Picea abies Larix decidua
14.8 ± 2.2 14.4 ± 2.7 3.6 ± 0.35 3.9 ± 0.1
Fine et al., 2004Hardwood Softwood
19 - 26 5.4 ± 3.7
This study
(eco-labelled stove)
Eucalyptus globulus
Pinus pinaster
Quercus suber Acacia longifolia
34.9 3.0 24.8 10.4
Much lower levoglucosan/mannosan ratios in softwood (in blue) than in hardwood smoke particles
Potassium
0.0
0.5
1.0
1.5
2.0
2.5
K (w
t% P
M2.
5)
Fireplace Woodstove
0
2
4
6
8
10
12
Maritime pine Golden wattle Eucalypt Cork oak
K+(w
t% P
M10
)
Eco-labelled woodstove
0
5
10
15
20
25
30
Pelletstype I
Pelletstype II
Pelletstype III
Pelletstype IV
Olive Pit Shell ofPineNuts
AlmondShell
K (w
t% P
M10
)
Pellet stoveProportion of K in PM10 inorganic fraction from the pellet stove: 66 (pellets I) – 88% (almond shell)
K may be a good tracer for smoke particles from more efficient combustion systems, but not for all biofuels
19
0.169
5.29
2.91
1.70
0.027 0.005 0.0110
1
2
3
4
5
6
Pelletstype I
Pelletstype II
Pelletstype III
Pelletstype IV
Olive pit Shell ofpine nuts
Almondshell
Pb
0.81
5.98
3.56 3.26
0.05 0.134 0.0640
1
2
3
4
5
6
7
Pelletstype I
Pelletstype II
Pelletstype III
Pelletstype IV
Olive pit Shell ofpine nuts
Almondshell
Zn
0.128 0.054
1.70
5.10
0.0120.248
bdl0
1
2
3
4
5
6
Pelletstype I
Pelletstype II
Pelletstype III
Pelletstype IV
Olive pit Shell ofpine nuts
Almondshell
Fe
0.001
0.079
0.0300.022
0.001 bdl bdl0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
Pelletstype I
Pelletstype II
Pelletstype III
Pelletstype IV
Olive pit Shell ofpine nuts
Almondshell
As
PM10 mass fractions of trace elements (wt.%)
Standards need to be established in the EU for elemental composition of commercial wood pellets and chips to avoid the inclusion of extraneous materials. Only Germany has standards containing extensive trace element limits.
Average OC-normalised concentrations of some tracers (mg/g OC)
Other organic tracers
Tracers Equipment Softwood Hardwood
Vanillic acid Fireplace 2.01 1.58
Traditional woodstove 8.26 2.73
Eco-labelled stove 15.0 7.79
Syringic acid Fireplace 0.07 7.77
Traditional woodstove 0.18 6.59
Eco-labelled stove 1.75 29.9
Stigmasterol Fireplace --- 0.61
Traditional woodstove --- 0.28
Eco-labelled stove --- 0.43
Retene Fireplace 3.99 0.11
Traditional woodstove 9.75 0.19
Eco-labelled stove 14.3 0.15
21
Conclusions (1)
Chemically treated material should not be allowed in any quality class of pellets; all pellets sold at the market must have quality certification.
Emission requirements for the eco-labelling or certification of small-scale combustion appliances must be mandatory in all countries. Traditional residential appliances should be replaced by certified equipment.
www.airuse.eu provides updated and speciated EFs (including condensables), for several domestic heating appliances and fuel types (softwood, hardwood, pellets, alternative agrofuels)
22
Conclusions (2)
Some of the identified organic compounds can be used as tracers of biomass burning and to distinguish between soft- or hardwood ( syringyl and vanillyn compounds, retene, stigmasterol).
Levoglucosan and their stereoisomers are not formed at the higher temperatures achieved in efficient, automatically fired, combustion aplliances. Good tracer only for traditional, batch operated, devices.
Differences in source profiles of organic compounds between wood types and combustion appliances deserves consideration in receptor modelling techniques, such as CMB, to apportion the contribution of biomass burning to ambient aerosol concentrations.
Other organic tracers
Average OC-normalised concentrations of RESIN ACIDS (mg/g OC)
RESIN ACIDS Equipment Softwood Hardwood
Pimaric acid Fireplace 218 6.90
Traditional woodstove 146 10.2
Eco-labelled stove 4.70 ---
Isopimaric acid Fireplace 24.0 0.87
Traditional woodstove 17.8 2.01
Eco-labelled stove 31.2 0.32
Abietic acid Fireplace 19.2 0.40
Traditional woodstove 12.0 3.34
Eco-labelled stove 1.50 0.30
Dehydroabietic acid Fireplace 187 8.84
Traditional woodstove 119 7.17
Eco-labelled stove 5.44 0.12
25
0
5
10
15
20
25
Vanillin Vanillic acid Syringic acid Coniferylalcohol
Isopimaric acid Dehydroabieticacid
Abietic acid
µg
com
pou
nd
mg-1
OC
Pellets type I
Pellets type II
Pellets type III
Pellets type IV
Olive pit
Shell of pine nuts
Almond shell
Other organic tracers – automatically fed appliance
