purpose of the study
DESCRIPTION
Continuous Analysis of Fresno Aerosols by Size, Time, and Elemental Concentrations, March – December, 2001. Thomas A. Cahill, Steven S. Cliff, Michael Jimenez-Cruz, and 1 Kevin D. Perry, DELTA Group, University of California, Davis, http://delta.ucdavis.edu and - PowerPoint PPT PresentationTRANSCRIPT
Continuous Analysis of Fresno Continuous Analysis of Fresno Aerosols by Size, Time, and Aerosols by Size, Time, and Elemental Concentrations,Elemental Concentrations,
March – December, 2001March – December, 2001
Thomas A. Cahill, Steven S. Cliff, Michael Thomas A. Cahill, Steven S. Cliff, Michael Jimenez-Cruz, and Jimenez-Cruz, and 11Kevin D. Perry, Kevin D. Perry,
DELTA Group, University of California, Davis, DELTA Group, University of California, Davis, http://delta.ucdavis.eduhttp://delta.ucdavis.edu and and
11Dept. of Meteorology. University of UtahDept. of Meteorology. University of Utah
Purpose of the StudyPurpose of the StudyFresno, California, has one of the highest
childhood asthma rates in California.
Fresno also is in violation of state and federal air quality criteria –
Ozone, PM10 in summer
PM10 and PM2.5 in winter
To what degree does Fresno air pollution impact the short term childhood asthma rate?
0
0.5
1
1.5
2
2.5
Valu
es
Rela
tive t
o B
utt
e a
nd
Sh
asta
Ischemic Heart Mortality Annual PM10 Childhhod Asthma
Health and Aerosols in the Central Valley of CaliforniaData Relative to Shasta and Butte counties
Get a wide variety of aerosol transition metals as a function of size and time to support short term medical data for the Fresno
Asthmatic Children’s Environment Study (FACES)
Original design: PM10 and PM2.5, day – night, 2 stage DRUMNot possible: Mis-sizing by too few cut points (coarse); Too much loading (accumulation mode); loss of sub-0.25 μm particles
Final design:8 size modes 10.0 μm to 0.09 μm
Why? EPA/IMPROVE 8 DRUM QA; very fine modes;
3 hr time resolutionWhy? Identification of sharp metal concentration episodes
Consequence: Needed to examine over 1500 time periods, 12,000 samples,
and yielding over 1/3 million S-XRF elemental values; but … $$$
Design of the StudyDesign of the Study
6 6 6 6 6 7 7 7 7 7 7 8 8 8 8 8
June, 2002 July, 2002 August, 2002
0
5
10
15
20
25
30
35
Mic
rog
ram
s/m
3
PM 2.5 mass PM 2.5 mass (sum of species)
Fine aerosols at the Sequoia NP IMPROVE site
Oregon forest fires
6 6 6 6 6 7 7 7 7 7 7 8 8 8 8 8
June, 2002 July, 2002 August, 2002
0
5
10
15
20
25
Mic
rog
ram
s/m
3
Elemental carbonSoil
Organic aerosolsAmmonium nitrate
Ammonium sulfate
Fine aerosols at the Sequoia NP IMPROVE site
Oregon forest fires
11 11 11 12 12 12 12 12 1 1 1 1 1 2 2 2
November, 2002 December, 2002 January, 2003 February, 2003
0
5
10
15
20
25
30
Mic
rogr
ams/
m3
Elemental carbon
Soil
Organic aerosols
Ammonium nitrate
Ammonium sulfate
Fine aerosols at the Sequoia NP IMPROVE site
511
1723
295
1117
2329
410
1622
284
1016
2228
September October November December
0
10
20
30
40
Mic
rogra
m/m
3
SacramentoFresno
CorcoranBakersfield
Fog days at Fresno x 5, no rainRain prev 5 days, Fresno
24 hr Nitrate AerosolsFall, 2002
Wind Bay Area to Bakersfield
Wind Bakersfield to Bay Area
Rain 3 mm
Cold, down-slope
Hot, up-slope
Here there be cows
.
.
ImplementationImplementation• Sampling: a PM10 modified DELTA Group
slotted DRUM impactor, with size cuts at 10, 5, 2.5, 1.15, 0,.75, 0.56, 0.34, 0.26, and 0.09 μm aerodynamic diameter (Raabe-Marple values).
• Analysis: Synchrotron x-ray fluorescence (S-XRF) at the DELTA Group x-ray microprobe of the Advanced Light Source, Lawrence Berkeley National Laboratory.
• Quality Control: – Routine re-analysis of previously analyzed samples,– Comparison with side by side Dichot samplers,– Re-analysis of ARB Dichot samples,– Comparisons with IMPROVE PIXE, XRF.
DELTA Group slotted 8 DRUM DELTA Group slotted 8 DRUM ImpactorImpactor
• 8 size ranges:• 10.0 to 5.0 μm (std PM10 inlet)• 5.0 to 2.5 μm• 2.5 to 1.15 μm• 1.15 to 0.75 μm• 0.75 to 0.56 μm• 0.56 to 0.34 μm• 0.34 to 0.26 μm• 0.26 to 0.09 μm
• 16.7 l/min, critical orifice control, ¼ hp pump
• 10.0 x 168 mm Mylar strips• For 42 day run, 4 mm/day, S-XRF beam 0.5 mm, = 3 hr.• Field portable
• 10 kg, 43 cm × 22 cm × 13 cm
43
cm
Stage 8 of DRUM , 0.26 > DStage 8 of DRUM , 0.26 > Dpp > 0.09 > 0.09 µm µm
diameter, showing strong diurnal pattern; diameter, showing strong diurnal pattern; the deposit shown covers 3 weeks.the deposit shown covers 3 weeks.
DELTA Group Synchrotron-XRF DELTA Group Synchrotron-XRF Facility at the LBNL Advanced Light Facility at the LBNL Advanced Light
SourceSource
For scale? (At least it’s not duct tape.)
Typical S-XRF Spectrum Typical S-XRF Spectrum Raw data, Teflon substrate with no blank subtractionRaw data, Teflon substrate with no blank subtraction
Energy (keV)4 8 12 160
1
10
100
1000
10,000
100,000
Cou
nts
Na 150
100
14
Si 6 23 3S 4 20 3V 1 6 0.1Ni 0.9 0.9 0.2As 1.7 0.5 0.1Sr 2.3 1.3 0.3Cd 7.6 NA NABa 84 NA 1.0Pb 4 2 0.6
RT
I X
RF
IMPR
OV
E
S-X
RF
MDL values(ng/cm2)
Nic
kel
Pot
assi
um
Van
adiu
mM
anga
nes
e Iron
Cop
per Zin
c
Bro
min
eR
ub
idiu
mFlu
orin
e
Su
lfu
r
Ars
enic
an
d L
ead
Cal
ciu
m
Str
onti
um
0 5 10 15 20 25
ARB Dichot ng/m3
0
5
10
15
20
25
AR
B R
AA
S n
g/m
3Fresno FACES Filter Intercomparison
ARB Dichot vs ARB RAASZinc
0 5 10 15 20 25
DELTA Group S-XRF ng/m3
0
5
10
15
20
25
AR
B D
ich
ot,
AR
B R
AA
S n
g/m
3
ARB Dichot ARB RAAS
DELTA S-XRF vs ARB Dichot and ARB RAAS FiltersZinc
All filters S-XRF
vs ARB XRF
1.02 0.11
vs ARB RAAS
1.29 0.58
ARB XRF vs ARB RAAS
1.29 0.63
DRUM S-XRF vs ARB XRF and ARB RAASDRUM S-XRF vs ARB XRF and ARB RAASnote: it takes 24 6 hr 6 size cuts S-XRF measurements to note: it takes 24 6 hr 6 size cuts S-XRF measurements to
match a single 24 hr PMmatch a single 24 hr PM2.52.5 filter filter
PM-2.5 Zn Concentration vs. Date (6-hour data)
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
3/10/01 3/20/01 3/30/01 4/9/01 4/19/01
ng/
m^
3
DRUM -Zn RAAS-Zn Dichot-Zn
The DRUM sees more soil, almost all The DRUM sees more soil, almost all lying between 2.5 and 1.15 lying between 2.5 and 1.15 µmµm
0 100 200 300 400 500 600
FRM - SASS ng/m3
0
100
200
300
400
500
600
700
Dic
hot, D
RU
M n
g/m
3
Dichot DRUM
Silicon Dichot vs FRM
11
11
22
22
33
33
44
44
45
55
56
66
67
77
77
88
88
99
99
910
1010
1011
1111
1112
1212
1212
Month of the year, 2001
0
20
40
60
80
100
120
Mic
rorg
am
s/m
3
PM2.5 Mass, 2001
Aerosols at the Fresno 1st Street Supersite
EPA 24 hr standard
EPA annual standard
1014
1923
2731
48
1216
2024
293
711
1519
2327
15
913
1721
2529
37
11
March April May June July, 2001
0
1000
2000
3000
4000
5000
6000
7000
8000
Na
no
gra
m/m
3
PM10 PM2.5
Silicon Aerosols at Fresno during the FACES StudyDRUM Impactor, S-XRF Analysis Data, 6 hr resolution
1216
2024
281
59
1317
2125
292
610
1418
2226
304
812
1620
2428
15
913
1721
2428
26
1014
18
July August September October November December, 2001
0
1000
2000
3000
4000
5000
6000
7000
8000
Na
no
gra
m/m
3
PM10 PM2.5
DRUM Impactor, S-XRF Analysis Data, 3 hr resolution
1014
1923
2731
48
1216
2024
293
711
1519
2327
15
913
1721
2529
37
11
March April May June July, 2001
0
500
1000
1500
2000
2500
Na
no
gra
m/m
3
PM10 PM2.5
Potassium Aerosols at Fresno during the FACES StudyDRUM Impactor, S-XRF Analysis Data, 6 hr resolution
1216
2024
281
59
1317
2125
292
610
1418
2226
304
812
1620
2428
15
913
1721
2428
26
1014
18
July August September October November December, 2001
0
500
1000
1500
2000
2500
Na
no
gra
m/m
3
PM10 PM2.5
DRUM Impactor, S-XRF Analysis Data, 3 hr resolution
Fireworks
1014
1923
2731
48
1216
2024
293
711
1519
2327
15
913
1721
2529
37
11
March April May June July, 2001
0
10
20
30N
an
og
ram
/m3
PM10 PM2.5
Strontium Aerosols at Fresno during the FACES StudyDRUM Impactor, S-XRF Analysis Data, 6 hr resolution
1216
2024
281
59
1317
2125
292
610
1418
2226
304
812
1620
2428
15
913
1721
2428
26
1014
18
July August September October November December, 2001
0
5
10
15
20
25
30
35
Na
no
gra
m/m
3
PM10 PM2.5
DRUM Impactor, S-XRF Analysis Data, 3 hr resolution
Fireworks
1014
1923
2731
48
1216
2024
293
711
1519
2327
15
913
1721
2529
37
11
March April May June July, 2001
0
50
100
150
Na
no
gra
m/m
3
PM10 PM2.5
Copper Aerosols at Fresno during the FACES StudyDRUM Impactor, S-XRF Analysis Data, 6 hr resolution
1216
2024
281
59
1317
2125
292
610
1418
2226
304
812
1620
2428
15
913
1721
2428
26
1014
18
July August September October November December, 2001
0
100
200
300
400
500
600
700
Na
no
gra
m/m
3
PM10 PM2.5
DRUM Impactor, S-XRF Analysis Data, 3 hr resolution
1012
1417
1921
2325
2729
312
46
810
1214
1618
2022
2426
291
35
7911
1315
1719
2123
2527
291
35
7911
1315
1719
2123
2527
291
35
7911
March April May June July, 2001
0
500
1000
1500
2000
Na
no
gra
ms/
m3
PM10 Chlorine Aerosols at Fresno during FACES
12141618202224262830
135791113151719212324262830
1357911131517192123252729
135791113151719212325272931
24681012141618202224262830
2468101214161820
July August September October November December, 2001
0
500
1000
1500
2000
Na
no
gra
ms/
m3
PM10 Chlorine Aerosols at Fresno during FACES
1014
1923
2731
48
1216
2024
293
711
1519
2327
15
913
1721
2529
37
11
March April May June July, 2001
0
10
20
30
40
50
60
70
Na
no
gra
m/m
3
PM10 PM2.5
Zinc Aerosols at Fresno during the FACES StudyDRUM Impactor, S-XRF Analysis Data, 6 hr resolution
1216
2024
281
59
1317
2125
292
610
1418
2226
304
812
1620
2428
15
913
1721
2428
26
1014
18
July August September October November December, 2001
0
10
20
30
40
50
60
70
80
90
Na
no
gra
m/m
3
PM10 PM2.5
DRUM Impactor, S-XRF Analysis Data, 3 hr resolution
A few observationsA few observations
• Differences summer to winter were extreme• Rapid mass variations were seen over short time
periods (a few hours) in almost every coarse and fine aerosol component, major and minor
• Some transition metals reached high levels during these episodes
• Wide variations in particle size are seen over short periods of time
• A great deal of the soil mass at Fresno is respirable
1516
1718
1920
2122
2324
2526
2728
2930
12
34
56
78
910
1112
1314
1516
1718
1920
21
November December
0
50
100
150
200
250
300
Nan
ogra
ms/
m3
Phosphorus x 10 Sulfur Potassium Zinc x 10
Aerosols at the Fresno First Street Super-siteVery fine (0.26 > Dp > 0.09 micron) elemental concentrations for FACES, CARB
S-XRF analyses via DELTA Group, UC Davis
Very fine aerosols characteristic of Very fine aerosols characteristic of diesels/smoking carsdiesels/smoking cars
1810
5.623.2
1.81
0.560.32
0.180.1
0.0560.032
0.0180.01
Coarse MOUDI Stage Diameter (micrometers) Ultra- Fine
-0.02
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
Mic
rog
ram
s/c
m2
Mass/200Sulfur
LeadZinc x 10
Calcium Phosphorus
For micrograms/m3, times 8.7DELTA Group, S-XRF, UC Davis
Diesel Particles by MOUDI Impactor and S-XRFSample Run # 4, CA Fuel; no grease
PM 2.5
PM 0.25 ?PM 10
Very fine zinc to diesel mass = 1800 1300
U. Minnesota/DRI/UC Davis Diesel U. Minnesota/DRI/UC Davis Diesel Sizing StudiesSizing Studies
1516
1718
1920
2122
2324
2526
2728
2930
12
34
56
78
910
1112
1314
1516
1718
1920
21
November December
0
50
100
150
200
250
300
Nan
ogra
ms/
m3
Phosphorus x 10 Sulfur Potassium Zinc x 10
Aerosols at the Fresno First Street Super-siteVery fine (0.26 > Dp > 0.09 micron) elemental concentrations for FACES, CARB
S-XRF analyses via DELTA Group, UC Davis
We see very fine aerosols characteristic We see very fine aerosols characteristic of diesels/smoking cars at Fresnoof diesels/smoking cars at Fresno
Predicted diesel vf/uf mass 11/25 – 12/17, 9 ± 6 µg/m3
1516
1718
1920
2122
2324
2526
2728
2930
12
34
56
78
910
1112
1314
1516
1718
1920
21
November December
0
5
10
15
20
Con
cent
ratio
ns/m
3
Mass by soft betas (ug/m3) Zinc by S-XRF (ng/m3)
Very fine (0.26 > Dp > 0.09) Aerosols at Fresno, CA
1516
1718
1920
2122
2324
2526
2728
2930
12
34
56
78
910
1112
1314
1516
1718
1920
21
November December
0
5
10
15
20
25
30
Mas
s ug
/m3
Mass measured Mass predicted based on U. Minn. diesels, CA fuel
Very fine (0.26 > Dp > 0.09) Aerosols at Fresno, CASupersite, First Street, > 1 km from nearest freeway
Nov 25 – Dec. 17, 0.26 to 0.09 μm, measured mass = 4.8 ± 1.0, predicted mass = 6.6 ± 4.8 μg/m3
For total vf mass, estimated via measured mass = 8.8 ± 2.0 μg/m3
Aerosol Information from Particle SizeAerosol Information from Particle Size
0.09 to 0.260.26 to 0.34
0.34 to 0.560.56 to 0.75
0.75 to 1.151.15 to 2.5
2.5 to 5.05.0 to 10.0
Particle aerodynamic diameter in micrometers
0
10
20
30
40
50
60
Nan
ogra
ms/
m3
Zinc x 10
Potassium
Copper x 10
Aerosol size distributions at the Fresno Super-siteNovember 15 - December 22, 2001
Soil, biomass, and diesel/smoking car elements derived elements
Fine particle PM2.5 cut
K soil
K biomass smoke
K diesel and smoking cars
Very fine aerosols
ConclusionsConclusions• Health data at high time resolution needs
matching aerosol data, not long term averages.• We find that there are sharp (order of
magnitude) excursions in transition metal mass of a few hours duration throughout the year.
• There are equally rapid changes in particle size.• Winter time exhibits a high level of very fine
particles associated with diesels and smoking cars even well away from major freeways.
• We have generated an extraordinarily detailed data set on Fresno aerosols of high quality and at a very modest cost.
AcknowledgementsAcknowledgements
• California Air Resources Board – Fresno FACES study
• National Renewable Energy Laboratory – DRI diesel tests
• Department of Energy - Lawrence Berkeley NL and the Advanced Light Source – S-XRF capabilities
• National Science Foundation – ACE-Asia DRUM samplers and development