update of improve carbon analysis
TRANSCRIPT
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Update of IMPROVE Carbon Analysis
Presented at: 2015 IMPROVE Steering Committee Meeting
Grand Canyon, AZ
November 3, 2015
Judith C. Chow ([email protected]) John G. Watson Xiaoliang Wang Dana L. Trimble Steven D. Kohl
Desert Research Institute, Reno, NV
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Objectives
• Report status of IMPROVE carbon analyses
• Update on Model 2001 hardware improvements
• Discuss plans for transition to DRI Model 2015
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Carbon Laboratory Operations (July 2014 to June 2015 samples)
• Received ~1,700 samples per month (varied from 1,200 to 2,000 for samples received each month)
• Maintained 24 hours per day/5-7 days per week operation with 6 staff
• Analyzed ~21,600 IMPROVE samples (869 to 3,000 per month)
• Averaged ~4,247 samples per month in the queue (2,290 to 7,400)
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IMPROVE_A Carbon Analyses (July 2014 to June 2015 samples)
Sampling Period Samples Received
Analysis Completion Date
7/1/14-12/31/14 9,966 May 2015
1/1/15-6/30/15 10,400 Est. November 2015
a Chow et al. (2007) JAWMA
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IMPROVE carbon reporting time fluctuates between 150 and 200 days (increased frequency of instrument failures)
Batches received outside of the original sample month group
Special studies with fast turn-around
batches expedited to report a full month
Date Received
Cale
ndar
Day
s fro
m S
ampl
e Re
ceip
t to
Dat
e Re
port
ed
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Traceable O2 in pure He remains below 30 ppm (O2 performance test limit is 100 ppm)
OC4
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Thrice per week sucrose performance tests are within 5% tolerance
(Between 7/1/2014 and 6/30/2015, acceptance testing limits are ± 10%) Acceptable Limit (5%=between 17.1 and 18.9 µg C ) Revised Acceptable Limit (10%=Between 16.2 and 19.8 µ C) +10%
+5%
-5%
-10%
Date of Sucrose Analysis
Aver
age
Carb
on M
easu
rem
ent (μC
)
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Current boards in Model 2001 became obsolete (working with Chinese firm to reverse
engineer the boards) • Stepper Drive Control ● Signal Control • Optical Shutter (Chopper) (Working after DRI modifications)
• Power Distribution (needs modification)
Original New
Missing cable fastener
Cable fastener was upside down
New Power Board Original Power Board
J2 contains 6 pins instead of 4 J2 contains 4 pins
Molex pins do not fit current Molex sockets due to pin dividers .
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DRI Model 2015 has been designed, tested, and commercialized
(Magee Scientific, Berkeley, CA, USA)
Oxidation Oven(MnO2)C→CO2
NDIR CO2 Detector
Carrier/ReactionGases
10%
O2 i
n H
e
100%
He
5% C
H4 in
He
CalibrationGas
Oven
Filter LoadingPush Rod
UV-VIS-NIRLight Source(λ=405-980 nm)
ReflectanceDetector
TransmittanceDetector
OpticalFibers
Filter Filter Holder
Thermocouple
Oxidation ReactorC→CO2
FIDMethanatorCO2→CH4
From Oven
DRI Model 2001 Carbon Analyzer
MFC MFC MFC
Vent
6-Port Injection
Valve Loop
MFM
10% O2 in He (OC Stage)100% He (EC Stage)
MFC Mass Flow Controller
MFM Mass Flow Meter
3-Way Solenoid Valve
Manual Ball Valve
Symbols:
Com
pres
sed
Air
MFCMakeup Air
Soda LimeCO2 Scrubber
Filter
2% O2 in He (EC Stage) 100% He (OC Stage)
DRI Model 2015 configuration
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60-70% lower MDLs† are achieved
† Minimum Detectable Limits
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MDLs are similar among the 7 wavelengths
OC
(μg/
cm2 )
EC (μ
g/cm
2 )
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Began replicate analysis between Models 2001 and 2015 during Fall 2014
(equivalence in carbon found for >350 samples) Model 2015 vs. Model 2001
(2/8/2015-7/29/2015)
Model 2001 vs. Model 2001 (2/8/2015-7/29/2015)
y = 1.00x + 0.22 R² = 1.00 n = 779
0200400600800
10001200
0 200 400 600 800 1000 1200
Mod
el 2
001
(µg/
filte
r)
Model 2001 (µg/filter)
OC y = 0.94x + 0.23 R² = 0.97 n = 779
020406080
100120
0 20 40 60 80 100 120Mod
el 2
001
(µg/
filte
r)
Model 2001 (µg/filter)
EC y = 0.99x + 0.47 R² = 1.00 n = 779
0200400600800
10001200
0 200 400 600 800 1000 1200M
odel
200
1 (µ
g/fil
ter)
Model 2001 (µg/filter)
TC
y = 1.03x - 3.41 R² = 0.96 n = 354
0
50
100
150
200
0 50 100 150 200Mod
el 2
015
(µg/
filte
r)
Model 2001 (µg/filter)
TC y = 1.05x - 0.72 R² = 0.95 n = 354
0102030405060
0 20 40 60Mod
el 2
015
(µg/
filte
r)
Model 2001 (µg/filter)
EC y = 1.02x - 2.43 R² = 0.95 n = 354
0
50
100
150
200
0 50 100 150 200Mod
el 2
015
(µg/
filte
r)
Model 2001 (µg/filter)
OC
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IMPROVE_A NIOSH STN EUSAAR_2
Atmosphere
Temp (°C)
Residence Time (tr, sec)
Temp (°C)
Residence Time (tr, sec)
Temp (°C)
Residence Time (tr, sec)
Temp (°C)
Residence Time (tr, sec)
OC1 Inert (He) 140 80-580 250 150 310 60 200 120 OC2 Inert 280 80-580 500 150 480 60 300 150 OC3 Inert 480 80-580 650 150 615 60 450 180 OC4 Inert 580 80-580 850 160 900 90 650 180 Cooling N/A 45 45 45 EC1 Oxidizing
(2% O2 in He) 580 80-580 650 150 600 45 500 120
EC2 Oxidizing 740 80-580 750 150 675 45 550 120 EC3 Oxidizing 840 80-580 850 150 750 45 700 70 EC4 Oxidizing N/A N/A 825 45 850 80 EC5 Oxidizing N/A N/A 920 120 N/A
All temperature and optical (R or T) protocols can be implemented
Common analysis protocols are pre-programmed
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Comparable TC is found using different thermal/optical protocols, but
OC and EC are different DRI Model 2015 TC Comparison
NIOSH: y=(1.00±0.04)x + (1.42±1.00), r2=0.99 STN: y=(1.07±0.07)x + (1.43±1.39), r2=0.99 EUSAAR_2: y=(1.10±0.07)x + (-0.40±1.38), r2=0.99
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For wood smoke dominated samplesa
EC405 (i.e., ECR and ECT at 405 nm) exceeds EC635
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0
200
400
600
800
1000
1200
0 500 1000 1500 2000
Ref
lect
ance
(R) a
nd T
rans
mitt
ance
(T)
Tem
pera
ture
(°C
) and
evo
lved
car
bon
(ng
C)
Time since analysis start (seconds)
Sample Temperature Evolved CarbonR635 T635R405 T405
98% He/2% O2100% He
ECR635
ECT635
OC1
CH4CAL
OC3
OC2
OC4
EC1
EC2EC3
ECT405
ECR405
a IMPROVE samples from Buffalo Pass, CO, USA, using multiwavelength IMPROVE_A protocol
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Introduction of BrC in DRI Model 2015 requires redefinition of LACλ
• EC633 = LAC633 (IMPROVE_A protocol in Model 2001) • EC405 = BrC405 + BC405 (For each wavelength in DRI Model 2015)
EC445 = BrC445 + BC445
EC532 = BrC532 + BC 532 EC635 = BrC635 + BC635
EC780 = BrC780 + BC780
EC808 = BrC808 + BC808
EC980 = BrC980 + BC980
(LACλ = BCλ + BrCλ)
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Continue software development to separate brown from black carbon (λ-AAE* assumption does not
necessarily provide a good fit to the measurements)
Wavelength (nm)
400 500 600 700 800 900 1000
b ATN(,
mM
-1)
0
10
20
30
40
50
bATN (Total) by UV-VIS Spectrometer
bATN (Total) by DRI Model 2015 TOT
Power law fit to bATN (Total) bATN (Total)=4.4×105/1.614
bATN (BC)=7.4×103/
bATN (BrC)=bATN (Total)-bATN (BC)
Power law fit to bATN (BrC) bATN (BrC)=5×1030/11.6
(IMPROVE Buffalo Pass, CO, samples influenced by forest fire smoke)
* AAE = Absorption Ångström Exponent
ATNT(λ) = ln (𝐹𝐹𝐹𝐹λ,𝐹𝐹
𝐹𝐹𝐹𝐹λ,𝐼𝐼)
bATN(λ,Mm-1) = ATN(λ) x AreaVolume
bATN(λ) ∝ λ-AAE Law
b ATN
(λ, M
m-1
)
Law
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• Start replicates on available Model 2015 units (3 units by December 2015 – total of 6-8 units by Spring 2016)
• Working with U.C. Davis team to begin 7 λ data reporting for samples collected after January 1, 2016 (~May 2016)
Transition Plan
445 445
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DRI publications and reports using the IMPROVE protocol (2014 and 2015, n=17)
• Blanchard, C.L., Chow, J.C., Edgerton, E.S., Watson, J.G., Hidy, G.M., Shaw, S., 2014. Organic aerosols in the southeastern United States: Speciated particulate carbon measurements from the SEARCH network, 2006 to 2010. Atmos. Environ 95, 327-333.
• Chakrabarty, R.K., Pervez, S., Chow, J.C., Dewangan, S., Robles, J.A., Tian, G.X., Watson, J.G., 2014. Funeral pyres in south Asia: Large-scale brown carbon emissions and associated warming. Environmental Science & Technology Letters 1, 44-48.
• Chen, L.-W.A., Chow, J.C., Wang, X.L., Robles, J.A., Sumlin, B.J., Lowenthal, D.H., Watson, J.G., 2015a. Multi-wavelength optical measurement to enhance thermal/optical analysis for carbonaceous aerosol. Atmos. Meas. Tech 8, 451-461.
• Chen, L.-W.A., Han, Y.M., Chow, J.C., Watson, J.G., Cao, J.J., 2015b. Black carbon in urban dust and surface soil particles: Refining optical measurement for environmental pollution survey. J. Aerosol Sci, submitted.
• Cheng, Y., Lee, S.C., Gu, Z.L., Ho, K.F., Zhang, Y.W., Huang, Y., Chow, J.C., Watson, J.G., Cao, J.J., Zhang, R.J., 2015. PM2.5 and PM10-2.5 chemical composition and source apportionment near a Hong Kong roadway. Particuology 18, 96-104.
• Cheng, Z., Wang, S.X., Fu, X., Watson, J.G., Jiang, J.K., Fu, Q.Y., Chen, C.H., Xu, B.Y., Yu, J.S., Chow, J.C., Hao, J.M., 2014. Impact of biomass burning on haze pollution in the Yangtze River Delta, China: A case study of summer in 2011. Atmos. Chem. Phys 14, 4573-4585.
• Chow, J.C., Wang, X.L., Sumlin, B.J., Gronstal, S.B., Chen, L.-W.A., Trimble, D.L., Kohl, S.D., Mayorgal, S.R., Riggio, G.M., Hurbain, P.R., Johnson, M., Zimmermann, R., Watson, J.G., 2015a. Optical calibration and equivalence of a multiwavelength thermal/optical carbon analyzer. AAQR 15, 1145-1159.
• Chow, J.C., Yang, X.F., Wang, X.L., Kohl, S.D., Watson, J.G., 2015b. Characterization of ambient PM10 bioaerosols in a California agricultural town. AAQR 15, 1433-1447.
• Diab, J., Streibel, T., Cavalli, F., Lee.S.C., Saathoff, H., Mamakos, T., Chow, J.C., Chen, L.-W.A., Watson, J.G., Sippula, O., Zimmermann, R., 2015. Hyphenation of a EC/OC thermal-optical carbon analyzer to photo ionization time-of-flight mass spectrometry: A new off-line aerosol mass spectrometric approach for characterization of primary and secondary particulate matter. Atmos. Meas. Tech, 3337-3353.
• Eklund, A.G., Chow, J.C., Greenbaum, D.S., Hidy, G.M., Kleinman, M.T., Watson, J.G., Wyzga, R.E., 2014. Public health and components of particulate matter: The changing assessment of black carbon-Critical review discussion. JAWMA 64, 1221-1231.
• Gargava, P., Chow, J.C., Watson, J.G., Lowenthal, D.H., 2014. Speciated PM10 emission inventory for Delhi, India. AAQR 14, 1515-1526.
• Hand, J.L., Schichtel, B.A., Malm, W.C., Copeland, S., Molenar, J.V., Frank, N.H., Pitchford, M.L., 2014a. Widespread reductions in haze across the United States from the early 1990s through 2011. Atmos. Environ 94, 671-679.
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• Hand, J.L., Schichtel, B.A., Malm, W.C., Pitchford, M.L., Frank, N.H., 2014b. Spatial and seasonal patterns in urban influence on regional concentrations of speciated aerosols across the United States. J. Geophys. Res. Atmos 119, 12832-12849.
• Lowenthal, D.H., Zielinska, B., Samburova, V., Collins, D., Taylor, N., Kumar, N., 2015. Evaluation of assumptions for estimating chemical light extinction at US national parks. JAWMA 65, 249-260.
• Orasche, J., Seidel, T., Hartmann, H., Schnelle-Kreis, J., Chow, J.C., Ruppert, H., Zimmermann, R., 2012. Comparison of emissions from wood combustion. Part 1: Emission factors and characteristics from different small-scale residential heating appliances considering particulate matter and polycyclic aromatic hydrocarbon (PAH)-related toxicological potential of particle-bound organic species. Energy & Fuels 26, 6695-6704.
• Pervez, S., Chakrabarty, R.K., Dewangan, S., Watson, J.G., Chow, J.C., Matawle, J.L., Pervez, Y., 2015. Cultural and ritual burning emission factors and activity levels in India. AAQR 15, 72-80.
• Schwander, S., Okello, C.D., Freers, J., Chow, J.C., Watson, J.G., M., C., Q.Y., M., 2014. Particulate matter air pollution in Mpererwe District, Kampala, Uganda - A pilot study. Journal of Environmental and Public Health 2014, 1-7.
• Tang, D.L., Li, T.Y., Chow, J.C., Kulkarni, S.U., Watson, J.G., Ho, S.S.H., Quan, Z.Y., Qu, L.R., Perera, F., 2014. Air pollution effects on fetal and child development: A cohort comparison in China. Environ. Poll 185, 90-96.
DRI publications and reports using the IMPROVE protocol (2014 and 2015, continued)