Quan%fying

Sulfur-Containing
Compounds Over the Santa
Barbara Channel
Julia Black1, Don Blake2, Stacey Hughes2, Rafe Day2
1Scripps College, Keck Science Department

2University of California Irvine, Department of Chemistry

Introduc%on
Sulfur is abundant in
seawater
Ocean surface waters are
supersaturated with sulfur
containing compounds

Brhl, C. et al. Atmos. Chem. Phys., 12, (2012).

Introduc%on Carbonyl Sulde (OCS)

OCS is the most abundant sulfur gas in
the atmosphere
Atmospheric life%me of 2 years
Global mixing ra%o of 500 pptv
Mixing ra%o over Santa Barbara: 587 pptv
Sources:

Ocean surface layer

Volcanic erup%ons
Biomass Burning
Terrestrial microorganisms
Derived from atmospheric oxida%on of
dimethyl sulde (DMS) and carbon
disulde (CS2)

Blake, N.J., et al. J. Geophys. Res., 113, (2008).

Brhl, C. et al. Atmos. Chem. Phys., 12, (2012).

Introduc%on Dimethyl Sulde (DMS)

DMS is the most abundant biological
sulfur compound in the atmosphere
Atmospheric life%me of day to 2 days
Mixing ra%o over Santa Barbara: 1.5 pptv
Sources:

Ocean surface layer

Biogenic produc%on by marine algae
Biological ac%vity from phytoplankton
Marshes

Brhl, C. et al. Atmos. Chem. Phys., 12, (2012).

Keller, M.D. et al. American Chem. Society. Ch.11

Introduc%on Carbon Disulde

The ocean is a major source of CS2

Atmospheric life%me of 7-12 days
Mixing ra%o over Santa Barbara: 2.3 pptv
Sources:

Ocean surface layer

Volcanic erup%ons
Microbial processes
Photochemical reac%ons in seawater
Phytoplankton ac%vity
Produces short-lived SO2 and long-lived
OCS

Brhl, C. et al. J Geophys. Res., 120, (2015).

Khalil, M.A.K., and R.A. Rasmussen. Atmos. Environ., 18, (1984).

Stratosphere

Mo%va%on

Insola%on

Troposphere

SO2

SO2

Blake, N.J., et al. J. Geophys. Res., 113, (2008).

Atmospheric oxida%on

OCS
DMS
CS2

Julia Black

Summary of Main Compounds

Berresheim, H. et al. Comp. Chem. and Climate of Atmos., (1995).

Brhl, C. et al. J Geophys. Res., 120, (2015).
Khalil, M.A.K., and R.A. Rasmussen. Atmos. Environ., 18, (1984).

Methods
5 surface samples collected
by Oceans group in Santa
Barbara Channel
Samples taken on the DC-8
over channel between 200
and 11,000 feet
Samples analyzed using gas
chromatography
Compared concentra%ons of
carbonyl sulde (OCS),
dimethyl sulde (DMS),
carbon disulde (CS2),
bromoform (CHBr3), and
methyl iodide (CH3I)

Flight Path

Santa Barbara Channel

Latitude

Whole Air Samples Taken Over Santa Barbara Channel

Longitude
Established that the boundary layer was 1,500 ft for the 2nd flight
Everything above 1,500 ft was homogenous

Latitude

Whole Air Samples Taken Over Santa Barbara Channel

Longitude
All surface samples have OCS concentrations greater than 650 pptv
Background concentration: 590 pptv

Latitude

Whole Air Samples Taken Over Santa Barbara Channel

Longitude
50 1,500 ft samples with concentrations less than 650 pptv

Latitude

Whole Air Samples Taken Over Santa Barbara Channel

Longitude
1,500 11,000 ft samples mostly with concentrations less than 650 pptv

Samples Affected by Elevated Acetonitrile Concentrations

Latitude

(PTRMS Data)

Longitude
OCS and acetonitrile can both be sourced from biomass burning
Eliminated any points that were potentially biomass sourced during the flight

Carbonyl Sulfide Concentration Over the Santa Barbara Channel

If ocean-sourced, increased pptv at surface
2 year lifetime, similar concentrations in troposphere

OCS (pptv)

Expectations:

Reality:

Elevated at surface!

Dimethyl Sulfide Concentration Over the Santa Barbara Channel

Short lifetime, quick dilution with altitude

DMS (pptv)

Expectations:

Reality:

Similar to expectation

Carbon Disulfide Concentration Over the Santa Barbara Channel

Longer lifetime than DMS
Dilution with increasing altitude

CS2 (pptv)

Expectations:

Reality:

Similar to expectation, some variability with higher altitude

Bromoform Concentration Over the Santa Barbara Channel

Dilution with increasing altitude

CHBr3 (pptv)

Expectations:

Reality:

Expected profile of a marine influenced compound

Methyl Iodide Concentration Over the Santa Barbara Channel

Dilution with increasing altitude

CH3I (pptv)

Expectations:

Reality:

Expected profile of a marine influenced compound

OCS (pptv)

Conclusions
The ocean is an important source of OCS
If we want to understand OCS emissions, we
have to collect more than just samples from the
plane

Surface samples are needed to prole OCS

Future SARP missions:
Marine boundary layer
In situ ocean can sampling

Acknowledgements

Dr. Donny Boy

Stacey Hughes
Rafe Day
WAS Group
Oceans Group
Dr. Emily Schaller
SARPians
KORUS-AQ

Rowland-Blake Lab
oSimone Meinardi
oBarbara Barlega
oGloria Liu
oBrent Love
oCam
NSERC
UND

Ques%ons?

References
Berresheim, H. et al. Comp. Chem. and
Climate of Atmos., (1995).
Blake, N.J., et al. J. Geophys. Res., 113, (2008).
Brhl, C. et al. Atmos. Chem. Phys., 12, (2012).
Brhl, C. et al. J Geophys. Res., 120, (2015).
Khalil, M.A.K., and R.A. Rasmussen. Atmos.
Environ., 18, (1984).
Turco, R.P. Nature, 283, (1980).