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Chemical speciation of PM and mass closure. David Green, Gary Fuller & Anja Tremper King’s College London. Contents. London sampling campaigns Methodology Use of uncertainty Results Source apportionment – London and Paris. Sampling campaigns. Summer campaign Aug-Oct 2008 - PowerPoint PPT Presentation
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Chemical speciation of PM and mass closure
David Green, Gary Fuller & Anja Tremper
King’s College London
2
ContentsLondon sampling campaigns
Methodology
Use of uncertainty
Results
Source apportionment – London and Paris
3
Sampling campaignsSummer campaign
• Aug-Oct 2008• Brent & Tower Hamlets
Winter 2008 campaign• Nov-Dec 2008• Camden, Brent & Tower
Hamlets
Further Camden campaigns
• May - June 2010• PM10 and PM2.5
• Summer 2010• Further PM10• Construction and another
roadside
Brent - Ikea
Tower Hamlets – Blackwall Tunnel
Camden – Swiss Cottage
4
Methodology
Pragmatic mass closure
2 Partisols• 1 Teflon – Mass, IC, ICP-MS• 1 Quartz – EC/OC
ERG mass closure
Existing TfL monitoring sites• TEOM / FDMS• Aethalometer (EC)
Sampled onto alternate filters on different days
• Mixed cellulose esters – ICP-MS• Quartz – EC/OC• Longer time period• Used one sampler
Existing Defra monitoring at North Ken and Marylebone Road for concentrations of regional pollutants when not measured directly
• IC and EC/OC• Nitrates, Sulphates, Chlorides, SOA
Aethalometer measurements for EC and POA using site specific empirical relationships
Results in time series composed of two datasets
5
Methodology
MassFDMS – direct massTEOM – used Volatile Correction Model (VCM)
6
Methodology Elemental CarbonDataset A
• Aethalometer using Xgenline empirical relationship
• Uncertainty included
Dataset B• Sunset
7
Methodology Primary Organic CarbonEC tracer measurement used to split SOA and POA
• Evidence of organic gas adsorption onto filters
• Intercept and slope derived using min 5% of EC/OC ratios
Factor for organic mass of 1.4 used (Japar, 1984) from direct measurements of diesel emissions
8
Methodology Secondary Organic CarbonEC tracer measurement used to split SOA and POA
• SOA = OC - (EC/OC)prim x EC• Evidence of organic gas adsorption onto
filters• Intercept and slope derived using min 5% of
EC/OC ratios• Factor for organic mass of 2.1 used (Turpin
and Lim, 2001), recommended for non-urban aerosol
Good agreement between sites• Dataset A mean of available measurements
in London direct• Dataset B Sunset analysis• Variation included in uncertainty calculation
9
Methodology Nitrates, sulphates & chloridesMeasurements from mean of Marylebone and North Kensington usedFactors applied to account for cationsNitrate can be ammonium or sodium
• Masses similar (18 or 23)• Harrison (2003) found 60% NH4NO3
• Applied a factor of 1.32 (60% NH4NO3 and 40% NaNO3)
Sulphate• Applied factor of 1.19
Chloride• Applied factor of 1.65
10
Methodology WaterUsed Aerosol Inorganic Model (AIM)
• Used nitrate and sulphate measurements as inputs
• Used FDMS sampling conditions of 30% RH and 30ºC
11
Methodology Iron Rich DustSplit into Minerals, Iron Oxide and MetalsMeasured wide range of metals (Fe, Ca, Al, Ba, Cu, Mo, Mn, Ni, Pb, Sb, Sr, V and Zn)Used Al as a tracer for feldspars (e.g. KAlSi3O8)
• Applied factor of 8.4• Included uncertainty in this factor
Ca used as a tracer for calcite and gypsum
• Applied factor of 3.8• Included uncertainty in this factor
These grouped together as mineralsFe used as a tracer for an iron oxide (FeO, Fe2O3 or Fe3O4)
• Applied factor of 1.37• Included uncertainty in this factor
Other metals included as ‘raw’ massOn days when ICP-MS not undertaken (dataset B) difference between PM10 mass and available components used to assess this
12
Alternate filters
Component Dataset A Dataset B
EC Aethalometer
Sunset
POA Aethalometer
Sunset
SOA Regional Sunset
Nitrates Regional IC
Sulphates Regional IC
Chlorides Regional IC
Water AIM AIMMinerals / unidentified
ICP-MS Difference
A
B
13
Site Variability
14
Daily Variability
15
Uncertainty analysis
Guide to uncertainty in measurement methodology (GUM)
Simple…
Measurement equation• TEOMVCM = TEOM – (ƒVCM x FDMS purge) – FDMS purge
Uncertainty equation• UVCM = 2 x √(uTEOM)2 + (uƒVCM x FDMS purge)2 + (ƒVCM x uFDMS purge)2
Complex…
Total Mass• uTotalMassA = 2x √(uECa
2 + uPOAMa2 + uSOAMregional
2 + uNO3total2 + uSO4total2 + uCltotal
2 + uWater2 + uMinerals2 + uIronOxide2 + uMetals2)
16
Validation against PM10Tower Hamlets
4Brent 4Camden 1
y = 0.91 (±0.05) x+ 2.19 (±1.91)
r2 =0.84
y = 1.11 (±0.07) x+ -3.88 (±2.26)
r2 =0.82
y = 0.87 (±0.11) x+ 6.9 (±3.22)
r2 =0.58
17
Analysis outputs - Comparison to source apportionment
18
Dataset Date
PM10
(µg
m-3)
EC (µ
g m
-3)
POA
M (µ
g m
-3)
SOA
M (µ
g m
-3)
Nitr
ate
(µg
m-3
)
Sulp
hate
(µg
m-3
)
Chl
orid
e (µ
g m
-3)
Wat
er (µ
g m
-3)
Min
eral
s (µ
g m
-3)
Iron
Oxi
de (µ
g m
-3)
Oth
er m
etal
s (µ
g m
-3)
Uni
dent
ified
(µg
m-3
)
Tota
l (µg
m-3)
Epis
ode
driv
er(s
)
Bre
nt
Dat
aset
A
04/11/08 56.3 12.3 3.9 5.5 16.7 11.6 5.4 0.0 7.3 2.6 0.3 -9.4 65.7 S
20/09/08 52.0 13.6 4.3 3.8 9.0 3.0 2.5 2.0 9.9 3.7 0.4 -0.3 52.3 PSM
26/09/08 51.0 12.3 3.9 5.9 9.7 5.5 4.3 1.4 9.1 3.5 0.4 -4.9 55.9 SM
16/12/08 50.1 10.1 3.2 6.0 5.0 2.3 1.7 1.0 2.2 2.4 0.2 16.0 34.1 N
Mean 29.4 6.7 2.1 3.2 4.2 2.4 3.4 0.7 3.9 1.9 0.2 0.7 28.7
Bre
nt
Dat
aset
B
30/08/08 57.5 6.0 1.9 6.5 18.8 8.2 3.1 3.9 - - - 9.1 48.4 S
17/09/08 53.3 11.2 3.5 3.4 9.0 2.9 3.1 2.0 - - - 18.1 35.1 M
27/09/08 58.7 10.1 3.2 8.3 16.2 6.0 1.8 3.5 - - - 9.5 49.1 S
07/12/08 56.8 14.2 4.5 10.0 12.0 2.0 4.9 3.1 - - - 6.1 50.7 PS
Mean 28.1 6.7 2.1 3.0 4.5 2.3 3.5 0.9 - - - 5.1 23.0
Tow
er H
amle
ts
Dat
aset
A
31/08/08 61.5 6.1 4.6 7.1 26.6 6.5 4.7 6.5 2.3 1.6 0.2 -4.7 66.2 S
22/09/08 65.4 8.2 6.2 2.7 5.3 2.3 3.0 1.1 12.2 3.3 0.4 20.6 44.8 N
04/11/08 57.1 4.6 3.5 5.5 16.7 11.6 5.4 0.0 9.2 1.7 0.4 -1.5 58.6 S
06/11/08 69.5 9.7 7.3 7.9 6.2 5.2 1.0 0.0 18.8 4.0 0.6 8.8 60.7 SM
10/12/08 64.6 6.9 5.2 6.5 5.7 1.1 4.0 1.5 18.7 4.4 0.4 10.2 54.3 M
16/12/08 58.6 8.5 6.5 6.0 5.0 2.3 1.7 1.0 9.9 3.5 0.4 13.8 44.8 N
Mean 33.1 5.2 3.9 3.4 4.4 2.2 3.5 0.8 6.5 2.3 0.3 0.7 32.5
Tow
er H
amle
ts
Dat
aset
B
30/08/08 54.0 1.8 1.3 7.3 18.8 8.2 3.1 3.9 - - - 9.5 54.0 S
19/09/08 53.7 6.9 5.2 6.6 6.8 2.8 3.6 1.4 - - - 20.3 53.7 N
05/11/08 69.2 7.9 6.0 9.3 5.5 5.8 0.7 0.0 - - - 34.1 69.2 SM
07/12/08 56.1 8.2 6.2 13.8 12.0 2.0 4.9 3.1 - - - 5.9 56.1 S
11/12/08 60.2 9.8 7.4 6.5 11.4 2.1 5.3 2.9 - - - 14.8 60.2 S
17/12/08 52.3 8.3 6.2 7.7 3.3 1.3 4.3 0.7 - - - 20.5 52.3 S
Mean 34.2 4.9 3.7 3.5 4.7 2.2 3.4 0.9 - - - 10.8 34.2
19
Next steps and improvements…
Organic absorption onto quartz filters• Quartz back quartz study to assess adsorption in next 2 months
Efficiency of aqua regia digest for extracting Al• HF digest
ICP-MS for Ca and Al• Comparisons with ICP-AES
Al as a tracer for Si• XRF analysis
How representative is one location to another• More direct measurements
20
Acknowledgements
London Borough of Camden
Transport for London
Source apportionment of PM10 in London and Paris-intial results
Gary Fuller and Anna Font Font King’s College
LondonMarch 2010
Centre for Environment and Health
22
Relationship between annual mean PM10 and NOX in London Fuller et al., (2002), Fuller and Green (2006)
23
Relationship between annual mean PM10 and NOX in Paris
24
Primary PM10 : NOX ratio London and ParisProgressive Euro classes preferentially abate PM10 over NOX then grad should
be decreasing!Effects of London specific PM measures?
25
Non-primary PM10 London and ParisNon primary PM10 converging
Paris did not experience 2006 elevation seen in London