Seminar

Calibrated in situ measurement of UT/LS water vapor using chemical ionization mass spectrometry

DSRC entrance

Troy Thornberry, NOAA ESRL CSD & CU CIRES

Wednesday, November 16, 2011, 3:30 pm Mountain Time
DSRC 2A305

Abstract

Over the past several decades there has been considerable disagreement among in situ water vapor measurements by different instruments at the low part per million (ppm) mixing ratios found in the upper troposphere and lower stratosphere (UT/LS). These discrepancies contribute to uncertainty in our understanding of the microphysics related to cirrus cloud particle nucleation and growth and affect our ability to determine the effect of climate changes on the radiatively important feedback from UT/LS water vapor. To address the discrepancies observed in measured UT/LS water vapor, a new chemical ionization mass spectrometer (CIMS) instrument has been developed for the fast, precise, and accurate measurement of water vapor at low mixing ratios. The instrument utilizes a radioactive source to ionize a flow of sample air drawn into the instrument. A cascade of ion-molecule reactions results in the production of protonated water ions proportional to the water vapor mixing ratio that are then detected by the mass spectrometer. The multi-step nature of the ionization mechanism results in a non-linear sensitivity to water vapor, necessitating calibration across the full range of values to be measured. To accomplish this calibration, we have developed a novel calibration scheme using catalytic oxidation of hydrogen to produce well-defined water vapor mixing ratios that can be introduced into the instrument inlet during flight.

The water vapor CIMS instrument was deployed for the first time aboard the NASA WB-57 high altitude research aircraft during the Mid-latitude Airborne Cirrus Properties Experiment (MACPEX) mission in March and April 2011. The sensitivity of the instrument to water vapor was calibrated every ~45 minutes in flight from < 1 to 150 ppm. Analysis of in-flight data demonstrates a typical sensitivity of 2000 Hz/ppm at 4.5 ppm with a signal to noise ratio (2 σ) > 50 for a 1 second measurement.

The instrument and its calibration system performed successfully in 7 flights during the MACPEX mission, sampling water vapor mixing ratios as low as ~4 ppm in stratospheric air. A comparison of the new measurement with other water vapor measurements made on board the aircraft and coincident water vapor balloon sonde and satellite remote sensing measurements is expected to help resolve the long-standing differences in low water measurements in the lower stratosphere.

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