Short-lived trace gases and aerosol particles

Timothy H. Bertram, Steve Schill, and Matt Zoerb

Department of Chemistry
University of Wisconsin, Madison

Why I am here Summer of 1999

What we seek: Cause and Effect

Spurious Correlations

Ozone Concentration
on West Coast of U.S.

Causal Relationships in Earth System Science

Emission Rate of NOx in China

Chemical Engines in Atmospheric Chemistry

HOx OH + HO2

Net O3 Destruc,on

Chemical Engines in Atmospheric Chemistry

HOx OH + HO2
NOx NO + NO2

Catalytic O3 Production

Role of Short-lived Species in Atmospheric Chemistry

How do we measure these reactive VOC compounds in situ

New tools in Atmospheric Chemistry

Instrumental design needs for detection axis:

Selectivity, Autonomy, High Short & Long term Precision, Accuracy, Detection Threshold

How do we detect molecules?

How do we detect molecules?

How do we detect molecules?

How do we detect molecules?

Mass Spectrometry in Atmospheric Chemistry

Selective, Autonomous, Precise,

Accurate, Low Detection
Threshold

Step #1: Convert neutral analyte to an ion NOT TRIVIAL

Step #2: Detect ion with high sensi,vity ALSO NOT TRIVIAL

CI-TOF-MS: Hardware

Wide array of reagent ions:

CH3C(O)O- , CH3C(O)O- (CH3COOH)
I-, I- (H2O)n,
H+(H2O)n,

C6H6+
Reference: Bertram et al. Atmospheric Measurements and Technology 2011.

CI-TOF-MS: Hardware

Dimensions: Detec,on Axis (42 cm x 30 cm x 42 cm)

Weight: Detec,on Axis < 45 kg
Reference: Bertram et al. Atmospheric Measurements and Technology 2011.

Benzene Cation CITOFMS

+

C6 H 6 + M M + + C6 H 6

(C6 H 6 )+2 + M M C6 H 6 + + C6 H 6

Acetone+

DMS+

Benzene+
monoterpenes
isoprene-benzene+

REF: Bertram et al., (2011), AMT, Leibrock and Huey, (2000) GRL

Challenges of AircraY Chemical Ioniza,on Measurements

ConsideraEons for aircraF measurements:

1) Reac,on rates depend on number density of reactants
2) Temperature impacts pumping speed
3) Vibra,ons can impact turbo pump eciency
4) Not all reagent ion precursors are safe for use (e.g., nitric oxide)
The CI-TOFMS will not y on SARP the UCSD miniCIMS will

Ma` Zoerb

Instrument #1: UCSD miniCIMS

UCSD miniCIMS: Instrument in a box

UCSD miniCIMS: From CAD to metal

UCSD miniCIMS: Hardware

UCSD miniCIMS: In the rack

Why Measure Molecules Fast (>10Hz)

Vertical flux directly measured as the covariance of scalar, x and vertical wind, w or
<xw>.
Instrument Challenge: Need to measure [x] at concentrations < 50ppt at 10Hz.

Why Measure Molecules Fast: Reactions at Surfaces

30-50% of NOx emitted is estimated to be lost via nocturnal processing

The reaction of N2O5 at chloride containing interfaces serves as both an
efficient NOx recycling and halogen activation mechanism.
REF: Alexander et al., ACP 2009, Finlayson-Pitts et al., Nature 1987, Osthoff et al., Nature Geo, 2008, Thornton et al., Nature 2010.

Measurements of N2O5 Deposition to the Ocean

Nocturnally averaged exchange
velocity (flux divided by
concentration) of -1.66 0.60 (1)
cm s-1 (for wind speed of 9.07
1.29 ms-1)

OUT
IN

kdep (N2O5) = 0.17 1.7 x 10-4 s-1

for zi = 1000 100m
Reference: Kim , Farmer, Bertram, PNAS, 2014

Air Sea Gas Exchange

Air Sea Gas Exchange: Dimethyl Sulfide

What is the DMS emission rate?

Air Sea Gas Exchange: Dimethyl Sulfide

OK, great . but what about SARP?

OK, great . but what about SARP?

Sample Project from 2014 SARP

Comparing bulk aerosol proles in the mixed layer in coastal Los
Angeles and the Inland Empire

Taia Wu, Senior Thesis
Scripps College

Sample Project from 2014 SARP

Conclusions

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