Transcript Overview of project progress

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)
Source apportionment: Biomass burning contribution (2013)
PM10
Contributions to the
annual mean
Contributions during
PM10 exceedances
days
PM2.5
Contributions to the
annual mean
Contributions during
PM10 exceedances
days
PortoTR
BarcelonaUB
FlorenceUB
MilanUB
AthensSUB
14%(5)
<2%(<0.5)
16%(3)
24%(9)
7%(1.4)
25%(16)
<2%(<0.5)
30%(22)
PortoTR
BarcelonaUB
FlorenceUB
18%(5)
<3%(<0.5)
21%(3)
33%(22)
<3%(<0.5)
Contribution of biomass burning to PM10 and PM2.5 levels,
mass fractions (%) and µg m-3, in AIRUSE cities
35%(28) 1%(0.6)
MilanUB
AthensSUB
21%(6) 10%(1.2)
33%(23) 26%(14) 2%(0.5)
2
Biomass burning profiles – biofuels and appliances
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)
Olive
(Olea europea)
Cork oak
(Quercus suber )
European beech
(Fagus sylvatica)
Pine
(Pinus pinaster)
Golden wattle
(Acacia longifolia)
Pyrenean oak
(Quercus pyrenaica)
Portuguese oak
(Quercus faginea)
Holm oak
(Quercus ilex
rotundifolia)
Briquettes
Black poplar
(Populus nigra)
Eucalypt
(Eucalyptus globulus)
3
Manually fed combustion appliances

Traditional brick
fireplace

Traditional
cast iron
wood stove

Eco-labelled
chimney-type
wood stove
4
Automatically fed combustion appliance

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 pellets
Shell of pine nuts
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
Olive pit
Almond shell
5
Condensed
material
000
HC
N
Pre
UCD0
J
Heated sampling line (190ºC)
E
Combustion flue gases
O2
Heated sampling line (190ºC)
I, J, K – Command and gasZG
distribution units
H
(UCD0,
UCD1,
UCD2)
R – Electronic
command
unit (UCE1)
SG
G
Computer
data
acquisition
and control system
LS––Gas
sampling
pump
T4 removal
M – Gas condensation unit Termocouple
for moisture
N, O, P, Q – Automatic on-line gas analysers
K
(THC, CO2, O2, CO)
• 0.2 m int. diameter
UCD2
Combustion flue gases
/ Pressure
Cold water (in)
Warm water (out)
Heated sampling line (190ºC)
Cold water (in)
Warm water (out)
H
Sample Gas (SG) / Pressure
A - Stove
B – Grate of the stove
C – LoadCO2
cell (weight sensor)
D – Air flow meter
E – Thermal insulation of the exhaust duct
I
F – Exhaust
COduct (Chimney)
N
G – Water-cooled gas sampling probe
J
O
I
H – Heated
sampling
line
UCD1
P
3.3 m height
Zero Gas (ZG)
I, J, K – Command and gas distribution
Termocouple
T3Q N2
K
N
HC
units (UCD0,
UCD1, UCD2)
UCD1
UCD0
SG
SG
J
R
L – Gas sampling pump
O
O2
ZG
Termocouple T2
L
UCE1
N condensation unit for moisture
MHC– Gas
SG
UCD0
P
removal
CO2
M E –JThermal insulation of the exhaust duct
O
O,
on-line gas
Termocouple
T1 P, Q – Automatic
O2
F – Exhaust
ductN,
(Chimney)
K
Q
CO
Temperature
ZG
analysers (THC,UCD2
CO2, O2, CO)
Condensed
G–
Water-cooled
sampling
probe
R –gas
Electronic
command
unit (UCE1)
material
P
CO2
A
Stove
Pressure
R
S – Computer
andUCE1
control
H–
line data acquisition
AirHeated sampling
system
B – Grate
of Qthe stove Temperature
K
CO
Dashed line – Electric circuit,
UCD2
S cell (weight sensor)
C – Load
Continuous line – Pneumatic circuit.
Sample Gas (SG) / Pressure
Termocouple T6
G
Termocouple T6
Sample Gas (SG) / Pressure
Sample Gas (SG) / Pressure
Sample Gas (SG) / Pressure
P
Q
UCD1
Zero Gas (ZG)
N2
Sample Gas (SG) / Pressure
L
F
B
I
I
Condensed
SG
material
Zero Gas (ZG)
N2
045
000
HC
UCD0
J
O2
K
UCD2
Condensed
material
SG
SG
S
R
Pressure
E
Temperature
Termocouple T5 S
Termocouple T4
Termocouple T4
L
A
Termocouple T3
B
SG
Ice Bath
M
Ice Bath
Termocouple T2
B
S
C
D
Termocouple T1
Termocouple T3
C
D
Air
C
Termocouple T2
E
D
Termocouple T1
Air
Condensed
material
Termocouple T4
Pressure
Combustion facility
000
N
O
Pressure
ZG
SG
Ice Bath
E
Ice Bath
M
Termocouple T5
CO2
CO
045
L
O2
UCD2
UCD1
Zero Gas (ZG)
N2
SG
Pressure
•
SG
HC
R
UCE1
CO2
P
045
CO
Q
000
Temperature
UCE1
Ice Bath
F
Ice Bath
M
Termocouple T5
ZG
Sample Gas (SG) / Pressure
Ice Bath
Termocouple T6
G
A
UCD0
SG
Ice Bath
SG
Heated sampling line (190ºC)
Cold water (in)
Warm water (out)
H
A
045
000
F
Combustion flue gases
O
D – Air flow meter
R
Temperature
UCE1
S
T
Z
Dilution air
TCR PM
Air Inlet
V
Pressure (P1)
Thermocouple T8
X
W
Thermocouple T7
Dilution air
TECORA
Electronic flow sampler
PASSIVE CAVITY AEROSOL
SPECTROMETER PROBE
air
Atm
osp
he
ric
T - Dilution tunnel
Combustion flue gases
Y
Heated sampling line (190ºC)
Cold water (in)
Warm water (out)
H
Sample Gas (SG) / Pressure
Termocouple T6
G
Sample Gas (SG) / Pressure
U - Aerosol size distribution probe (PCASP-X)
I
UCD1
Zero Gas (ZG)
N2
V - Venturi system
045
000
F
SG
HC
J
L
O2
ZG
Ice Bath
M
Termocouple T5
Ice Bath
SG
K
W - Pitot tube
CO2
CO
Q
UCD2
Pressure
E
Temperature
S
Termocouple T4
A
Y - TECORA control and data acquisition system
Termocouple T3
B
Termocouple T2
Termocouple T1
C
Z - Blower
D
Air
T
Z
Dilution air
TCR PM
Air Inlet
X
Pressure (P1)
Thermocouple T8
V
W
Thermocouple T7
Dilution air
TECORA
Electronic flow sampler
PASSIVE CAVITY AEROSOL
SPECTROMETER PROBE
mbustion flue gases
At
mo
sp
he
ric
air
Y
Combustion facility
H
Cold water (in)
Warm water (out)
Sample Gas (SG) / Pressure
Termocouple T6
Heated sampling line (190ºC)
R
U
O
P
Condensed
material
X - Sampling head for PM10 or PM2.5 (TECORA)
N
UCD0
SG
UCE1
U
Analytical techniques
Thermal-optical
method
Organic carbon
Elemental carbon
Ion
chromatography
Water soluble
ions
ICP-MS
ICP-AES
Elements
HPLC-electrochemistry,
HPAEC/ESI-MS,
HPAEC-PAD
or GC-MS
GC-MS
Anhydrosugars
Organic speciation
PM emission factors
1200
mg MJ-1 (dry basis)
1000
800
600
400
200
0
Fireplace
Traditional
woodstove
Eco-labelled
woodstove
Pellet stove
 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
9
PM emission factors
200
mg MJ-1 (dry basis)
180
160
140
120
100
80
60
40
20
0
Pellet - type Pellet - type Pellet - type Pellet - type
I
II
III
IV
Olive Pit
Shell of Pine
Nuts
Almond
Shell
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).
10
Fireplace
EC
(OC+EC)/PM10 (%wt.)
70
OC
(OC+EC)/PM2.5 (%wt.)
90
80
70
60
50
40
30
20
10
0
Eco-labelled woodstove
Woodstove
90
80
70
60
50
40
30
20
10
0
Pellet stove
70
60
(OC+EC)/PM10 (%wt.)
(OC+EC)/PM2.5 (%wt.)
Chemical composition of PM
50
40
30
20
10
60
50
40
30
20
10
0
Pellet I
0
Maritime pine Golden wattle
Eucalypt
Cork oak
Pellet II Pellet III Pellet IV Olive Pit Shell of Almond
Pine Nuts Shell
In the fireplace and the old type stove, OC dominated the emissions, while more efficient combustion in
11 An
the eco-labelled and pellet stoves contributed to 1.3 to 4.7-fold higher EC relative fractions in PM.
increase of EC emissions with increasing combustion temperature is generally observed.
Chemical composition of PM (manually fed appliances)
Watersoluble ions
2%
Elements
0.4%
Watersoluble ions
11%
Elements
2%
EC
9%
EC
15%
OM
72%
OM
89%
Other
compounds
4.3%
Alkanes Alkenes PAHs
0.24% 0.010% 1.5%
Sugars
48%
Acids
44%
Phenolic
compounds
2.6%
Alcohols
0.022%
Pine, Fireplace
Other
Alkanes
Compounds 2%
3%
Alkenes
1%
PAHs
13%
Sugars
18%
Pine, Eco-labelled stove
Phenolic
compounds
1%
Alcohols
2%
Acids
60%
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
12
Chemical composition of PM (pellet stove)
Undetermined
2%
Elements and
their oxides
39%
EC
7%
OM
52%
Undetermined
7.8%
Elements and
their oxides
32%
Pellets type I
EC
3.2%
OM
57%
Olive pit
Elements and
their oxides
22%
EC
41%
OM
37%
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
Shell of pine nuts
Much higher inorganic PM10 mass fractions (up to 42%)
13
Polycyclic aromatic compounds
23 parent-PAHs, 11 NPAHs and 15 OPAHs in PM10 were quantified
Woodstove
35000
OPAHs
30000
NPAHs
25000
20000
15000
10000
5000
0
µg kg-1 of fuel burned, dry basis
parent-PAHs
40000
µg kg-1 of fuel burned, dry basis
Pellet stove
900
parent-PAHs
800
OPAHs
700
NPAHs
600
500
400
300
200
100
0
Eucalypt,
devolatilisation
Eucalypt, flaming
+ smouldering
Pine,
devolatilisation
Pine, flaming +
smouldering
Pellets type Pellets type Pellets type Pellets type
I
II
III
IV
Olive pit
Shell of
pine nuts
Almond
shell
BaP (and PM) emission factors
FIREPLACE
kg-1
g PM2.5
biofuel
µg BaP kg-1 biofuel
g PM2.5 kg-1 biofuel
µg BaP kg-1 biofuel
kg-1
g PM10
biofuel
-1
µg BaP kg biofuel
Pellets I
kg-1
g PM10
biofuel
0.49
µg–BaP
kg-1 biofuel
4.43
nd
not detected;
--- not determined
Softwood
Hardwood
7.02
16.9
260
475
TRADITIONAL WOODSTOVE
Softwood
Hardwood
3.64
13.5
46.7
322
ECO-LABELLED STOVE
Softwood
Hardwood
1.12
2.06
1543
146
PELLET STOVE
Pellets II
Pellets III
Pellets IV Olive pit
1.51
nd
1.77
nd
1.35
4.61
3.12
nd
Briquettes
13.8
31.4
Briquettes
9.02
85.3
Briquettes
----Shell of pine nuts
Almond shell
2.19
17.2
2.07
9.19
Combustion of resinous wood (softwood) at higher temperatures in the ecolabelled stove produces very intense flames, contributing to oxygen-starved
conditions and, consequently, to higher PAH emissions
15
Levoglucosan
Woodstove
250
mg/g PM2.5
200
150
100
50
0
250
Eco-labelled stove
2.0
mg/g PM10
200
mg/g PM10
Pellet stove
2.5
150
1.5
1.0
0.5
100
0.0
50
Pellets
type I
Pellets
type II
0
Maritime pine Golden wattle
Eucalypt
Pellets
type III
Pellets Olive Pit Shell of Almond
type IV
Pine
Shell
Nuts
Cork oak
Levoglucosan is not a suitable tracer for automatically fired
combustion appliances in which high temperatures are reached.
16
Levoglucosan-to-mannosan ratios
Authors
Levo/Man
Fagus sylvatica
Quercus
robur
Picea abies
Larix decidua
14.8 ± 2.2
14.4 ± 2.7
3.6 ± 0.35
3.9 ± 0.1
Schmidl et al., 2007
Fine et al., 2004
This study
(eco-labelled stove)
Hardwood
Softwood
19 - 26
5.4 ± 3.7
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
2.5
12
Woodstove
Eco-labelled woodstove
2.0
10
1.5
K+ (wt% PM10)
K (wt% PM2.5)
Fireplace
1.0
0.5
0.0
8
6
4
2
0
Maritime pine Golden wattle
30
K (wt% PM10)
25
Pellet stove
20
15
10
5
0
Pellets Pellets Pellets Pellets Olive Pit Shell of Almond
type I type II type III type IV
Pine
Shell
Nuts
Eucalypt
Cork oak
Proportion 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
PM10 mass fractions of trace elements (wt.%)
6
7
Pb
5.29
6
5
Zn
5.98
5
4
4
2.91
3
3.56
3.26
3
1.70
2
2
1
0.81
1
0.169
0.027
0.005
0.05
0.011
0.134
0.064
0
0
Pellets
type I
Pellets
type II
Pellets
type III
Pellets
type I
Pellets Olive pit Shell of Almond
type IV
pine nuts shell
Pellets
type III
0.09
Fe
6
Pellets
type II
As
0.079
0.08
5.10
5
Pellets Olive pit Shell of Almond
type IV
pine nuts shell
0.07
0.06
4
0.05
3
0.04
0.030
0.03
1.70
2
0.022
0.02
1
0.128
0.054
Pellets
type I
Pellets
type II
0.012
0.248
0.01
bdl
0
Pellets
type III
Pellets Olive pit Shell of Almond
type IV
pine nuts
shell
0.001
0.001
bdl
bdl
0
Pellets
type I
Pellets
type II
Pellets
type III
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.
Pellets Olive pit Shell of Almond
type IV
pine nuts shell
19
Other organic tracers
Average OC-normalised concentrations of some tracers (mg/g OC)
Tracers
Equipment
Vanillic acid
Syringic acid
Stigmasterol
Retene
Softwood
Hardwood
Fireplace
2.01
1.58
Traditional woodstove
8.26
2.73
Eco-labelled stove
15.0
7.79
Fireplace
0.07
7.77
Traditional woodstove
0.18
6.59
Eco-labelled stove
1.75
29.9
Fireplace
---
0.61
Traditional woodstove
---
0.28
Eco-labelled stove
---
0.43
Fireplace
3.99
0.11
Traditional woodstove
9.75
0.19
Eco-labelled stove
14.3
0.15
Conclusions (1)
 www.airuse.eu provides updated and speciated EFs (including
condensables), for several domestic heating appliances and fuel
types (softwood, hardwood, pellets, alternative agrofuels)
 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.
 Chemically treated material should not be allowed in any
quality class of pellets; all pellets sold at the market must have
quality certification.
21
Conclusions (2)
 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.
 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).
 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.
22
Thank you very much for your attention
[email protected]
[email protected]
Other organic tracers
Average OC-normalised concentrations of RESIN ACIDS (mg/g OC)
RESIN ACIDS
Equipment
Pimaric acid
Isopimaric acid
Abietic acid
Dehydroabietic acid
Softwood
Hardwood
Fireplace
218
6.90
Traditional woodstove
146
10.2
Eco-labelled stove
4.70
---
Fireplace
24.0
0.87
Traditional woodstove
17.8
2.01
Eco-labelled stove
31.2
0.32
Fireplace
19.2
0.40
Traditional woodstove
12.0
3.34
Eco-labelled stove
1.50
0.30
Fireplace
187
8.84
Traditional woodstove
119
7.17
Eco-labelled stove
5.44
0.12
Other organic tracers – automatically fed appliance
25
Pellets type I
Pellets type II
Pellets type III
20
µg compound mg-1 OC
Pellets type IV
Olive pit
Shell of pine nuts
15
Almond shell
10
5
0
Vanillin
Vanillic acid
Syringic acid
Coniferyl
alcohol
Isopimaric acid Dehydroabietic
acid
Abietic acid
25