Aaron Perry - SARP Presentation

A Comparison of Instruments
Using Common Gases

Aaron T. Perry
Cornell University
Student Airborne Research Program
Outline
•  Gases Analyzed
•  Overview of Instruments
•  Flight Tracks
•  Methane Analysis
•  A look at PICARRO data
•  Carbon Dioxide Analysis
•  Sources of Error
•  Effect of Water Vapor on the Whole Air Sampler
•  Conclusions
•  Acknowledgements/References/Questions
Gases Analyzed
Carbon Dioxide [CO2] Methane [CH4]
•  Prominent Greenhouse gas •  Another important Greenhouse
•  Released from plant and animal
respiration as well as fossil fuel gas.
burning. •  Created near the Earth’s surface
•  Taken up by plants for by microbes and animals.
photosynthesis.
•  Detected by WAS, PICARRO, and •  Detected by WAS and PICARRO
AVOCET
Whole Air Sampler and
Analytical Systems for Methane
and Carbon Dioxide
Air samples are taken in canisters

onboard the aircraft using the Whole Air
Sampler and later analyzed in the lab.
Methane analysis is performed by

injecting 5mL of sample into a Flame
Ionization Detector. This method is
accurate to 1%.
Carbon Dioxide analysis is performed

using a Thermal Conductivity detector,
and is accurate to 5%
During both analysis’ standards are run

every 8 samples that have calibrated
From top left going clockwise: against a National Bureaus of Standards
students taking samples on the whole
air sampler, unloading canisters from standard.
the DC-8, a student copying down
Methane readouts
PICARRO
Newer instrument on the DC-8,

operated by Randy Kawa on SARP
flights.
Piccaro is an in-situ LiDAR that uses

Cavity Ring Down Spectroscopy to
analyze Carbon Dioxide, Methane and
Water Vapor in real time.
Precise to less than 50 ppbv for Carbon

Dioxide, and 0.7 ppbv for Methane.
PICARRO CRDS Analyzer for CO2/CH4/H2O in air
Source: PICARRO website
AVOCET
Sensitive instrument used to measure

Carbon Dioxide in real time.
Operated by Stephanie Vay on the SARP

flights, and currently being used on the
ASCENDS mission.
Takes in air samples and runs them

through a modified non-dispersive
infrared gas analyzer.
Calibrations are frequently run in-flight

by running standards through the
system periodically.
Stephanie Vay showing a SARP student AVOCET data on board
the DC-8
Flight Tracks
Methane Comparison
SARP Flight 1 – CH4 Data
2.40
Methane in ppmv
2.30
2.20
2.10
2.00
WAS
1.90
1.80 avg_PICARRO
1.70
18:43:12 19:55:12 21:07:12 22:19:12 23:31:12
Universal Coordinated Time Date: June 29, 2010
SARP Flight 2 – CH4 Data

2.40
Methane in ppmv
2.30
2.20
2.10
2.00
WAS
1.90
1.80 avg_PICARRO
1.70
19:55:12 20:24:00 20:52:48 21:21:36 21:50:24 22:19:12 22:48:00 23:16:48 23:45:36
Universal Coordinated Time Date: July 1, 2010
‘avg’ means an averaging program was used on the data before analysis.
Methane Comparison - Statistics
•  Correlation = 0.932
•  Mean Difference = 0.00734 ppmv
•  PICARRO consistently had higher Methane

readings than WAS, but by a very small amount.
Benefits of using a higher resolution
dataset.
PICARRO Methane data
2.7
2.5
2.3
2.1
PICCARO
1.9
1.7
1.5
18:14:24 19:26:24 20:38:24 21:50:24 23:02:24 0:14:24
WAS Methane data

2.70
2.50
2.30
2.10
WAS
1.90
1.70
1.50
18:14:24 19:26:24 20:38:24 21:50:24 23:02:24 0:14:24
Carbon Dioxide Comparison – Flight 1
SARP Flight 1 – CO2 Data
410.000
405.000
400.000
Carbon Dioxide in ppmv
395.000
390.000
WAS Cans
385.000 Avg PICARRO
Avg AVOCET
380.000
375.000
370.000
365.000
18:43:12 19:55:12 21:07:12 22:19:12 23:31:12
Carbon Dioxide Comparison - Statistics
•  Mean differences between the

Correlations
datasets.
WAS PICARRO ▫  PICARRO – WAS
  9.2 ppmv
PICARRO 0.863
▫  AVOCET – WAS
  10.8 ppmv
AVOCET 0.862 0.997
▫  AVOCET – PICARRO
  1.548 ppmv
Who is right?
•  Mauna Loa Observatory
monthly average for June 2010
▫  392.04 ppm
•  WAS
▫  381 ppm
•  PICARRO
▫  390 ppm
•  AVOCET
Mauna Loa Observatory ▫  391.7 ppm
Why is there error in the readings from
the Whole Air Sampler?
•  Water is added to the canisters
to minimize the amount of
material that sticks to the
inside of the canister.
•  Normally when the CH4 and
CO2 samples are run the
canisters are placed in dry ice
to condense and freeze out all
the water.
•  Due to time constrains and
simplicity this part of the
analysis procedure was
Air sampling canister omitted.
Potential effects of water vapor on
CH4 and CO2
Where es is the saturation vapor pressure

[units: Pa] and T is in ˚C
Room temperature in the lab is about 20˚C
Canisters had about 50 psi of pressure = 3.45*10^5 Pa

Potential effects of water vapor on
CH4 and CO2
Potential Error due to water vapor = 0.68%
•  Corrected mean Carbon Dioxide value:

▫  383.6 ppm
  CO2 Analysis accurate to 5%
•  Corrected mean Methane value:
▫  1.875 ppm
  CH4 Analysis accurate to 1%
Flight 1 CO2 graph with corrected WAS
data
410
405
CO2 Concentration in ppm
400
395
WAS_Corrected
390 Avg PICARRO
Avg AVOCET
385
380
375
18:43:12 19:55:12 21:07:12 22:19:12 23:31:12
Conclusions – Whole Air Sampler
•  Provided >100 data points per
flight
•  Data points limited by the time

required to fill a canister
•  Very accurate with Methane

analysis, less with Carbon
Dioxide (but still within
specifications)
•  In addition to the common

gases shown it is also able to
analyze dozens more for each
Whole Air Sampler onboard the DC-8 data point.
Conclusions – PICARRO
•  Yielded ~12,000 data points
per flight.
•  Correlated very well with WAS

for Methane, and with
AVOCET for CO2
•  Provided much higher

resolution than WAS
PICARRO CRDS Analyzer for CO2/CH4/H2O in air
Source: PICARRO website
•  Limited to CO2, CH4, and
water vapor
Conclusions – AVOCET
•  Yielded ~19,000
AVOCET CO2 Data – Flight 1 data points per
415
flight
Carbon Dioxide in Micromoles per mole
410
•  Very high
405 resolution for
Carbon Dioxide
400
395
•  Correlated very
well with
390 PICARRO and
close with WAS
385
18:00:00 19:12:00 20:24:00 21:36:00 22:48:00 0:00:00
Universal Coordinated Time Date: June 29, 2010 •  Limited to CO2
Final thoughts
•  Petty, Grant W. "7.3.1 Vapor Pressure
References with Respect to Water." A First

Course in Atmospheric
Thermodynamics. 1st ed.
Madison: Sundog Pub, 2008.
181-83. Print.
•  Analytical Systems Used in Rowland/
Blake Lab Provided by Matt •  Picarro G1301 Carbon Dioxide,
Gartner Methane & Water Vapor Analyzer.
Sunnyvale, CA: PICARRO. PDF.
•  Dr. Pieter Tans, NOAA/ESRL
(www.esrl.noaa.gov/gmd/ccgg / •  Ross, Jim. DC-8. 2004. Photograph.
trends/), Mauna Loa CO2 Monthly NASA DC-8 Image Gallery.
Mean Data Web. 24 July 2010.
•  IMG_2517. Photograph. Mauna •  Vay, Stephanie A. AVOCET CO2 Data
Loa Observatory. NOAA/ from SARP 2010 Flights. June-
ESRL/GMD - Photo Gallery. 2 July 2010. Raw data. California.
July 2010. Web. 24 July 2010. •  Vay, Stephanie A. High-Resolution
<http://www.esrl.noaa.gov/g Measurements of Atmospheric
md/Photo_Gallery/Field_Site s/ CO2 from the DC-8 during
MLO/tn/IMG_2517.JPG.ht ml>. Operation ICE Bridge. Tech.
•  Kawa, S. R., J. B. Abshire, and H. Print.
Riris. Picarro Airborne In Situ •  Statistical Analysis done using
Analyzer ASCENDS-2010. June- Minitab 16
July 2010. Raw data. California. •  Maps created using ArcGIS
•  Facebook photo credits to Christy,
Heather, Ninoshka, Jane via
SARP 2010
Acknowledgements
•  Matt Gartner
•  Dr. Don Blake
•  Eric Buzay
•  Daniel Rothenberg
•  Dr. Rick Shetter and NSERC
•  Jane Peterson
•  Rafe Day
•  Rowland/Blake Research Group
•  SARP Air Group
•  DC-8 Crew
Questions?
Back-up Slides
Carbon Dioxide Comparison – Flight 2
SARP Flight 2 – CO2 Data
410.000
405.000
400.000
Carbon Dioxide in ppmv
395.000
390.000
WAS Cans
385.000
Avg PICARRO
Avg AVOCET
380.000
375.000
370.000
365.000
18:21:36 19:33:36 20:45:36 21:57:36 23:09:36
Universal Coordinated Time Date: July 1, 2010

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A Comparison of Instruments

Using Common Gases

Air samples are taken in canisters

Methane analysis is performed by

Carbon Dioxide analysis is performed

During both analysis’ standards are run

Newer instrument on the DC-8,

Piccaro is an in-situ LiDAR that uses

Precise to less than 50 ppbv for Carbon

Sensitive instrument used to measure

Operated by Stephanie Vay on the SARP

Takes in air samples and runs them

Calibrations are frequently run in-flight

SARP Flight 2 – CH4 Data

• Mean Difference = 0.00734 ppmv

• PICARRO consistently had higher Methane

WAS Methane data

• Mean differences between the

Where es is the saturation vapor pressure

Room temperature in the lab is about 20˚C

Canisters had about 50 psi of pressure = 3.45*10^5 Pa

Potential Error due to water vapor = 0.68%

• Corrected mean Carbon Dioxide value:

• Data points limited by the time

• Very accurate with Methane

• In addition to the common

• Correlated very well with WAS

• Provided much higher

References with Respect to Water." A First

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•  Mean Difference = 0.00734 ppmv

•  PICARRO consistently had higher Methane

•  Mean differences between the

•  Corrected mean Carbon Dioxide value:

•  Data points limited by the time

•  Very accurate with Methane

•  In addition to the common

•  Correlated very well with WAS

•  Provided much higher