update of improve carbon analysis
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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 (judith.chow@dri.edu) John G. Watson Xiaoliang Wang Dana L. Trimble Steven D. Kohl
Desert Research Institute, Reno, NV
Objectives
• Report status of IMPROVE carbon analyses
• Update on Model 2001 hardware improvements
• Discuss plans for transition to DRI Model 2015
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)
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
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
Traceable O2 in pure He remains below 30 ppm (O2 performance test limit is 100 ppm)
OC4
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
)
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 .
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
60-70% lower MDLs† are achieved
† Minimum Detectable Limits
MDLs are similar among the 7 wavelengths
OC
(μg/
cm2 )
EC (μ
g/cm
2 )
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
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
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
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
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)
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
• 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
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.
• 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)
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