Variability in surface ocean DMS and isoprene in the eastern Atlantic Ocean
Christa A. Marandino1 (cmarandino@ifm-geomar.de), Cathleen Zindler1, Hermann W. Bange1, Eric S. Saltzman2, and Douglas W. R. Wallace1
1IFM-GEOMAR, Duesternbrooker Weg 20, 24105 Kiel, Germany
2UCI, Irvine, CA, 92697 USA
Introduction
• Surface seawater DMS, DMSP and isoprene were measured in the eastern Atlantic Ocean, November 2008
• DMS, formed out of the algae metabolite DMSP, is an important precursor of remote marine aerosols
• Isoprene, known to be emitted from terrestrial vegetation, forms secondary organic aerosols
• Isoprene can also be produced in the ocean (e.g. Shaw et al., 2003), but the role of phytoplankton in the production of marine isoprene and its influence on atmospheric aerosol development has not been widely studied
• Continuous measurements were performed for DMS and isoprene with an atmospheric pressure chemical ionization mass spectrometer (AP-CIMS)
• Discrete measurements were performed for DMS and DMSP using a purge and trap gas chromatograph (GC)-flame-photometric detector (FPD) system
Conclusion
• DMS measurements from AP-CIMS and GC-FPD in agreement regarding
DMS concentration trends over the cruise track
• There appears to be a systematic difference in the concentrations
measured using the two methods. We are currently examining the possible reasons and hope to do more standard and instrument comparisons in the upcoming year.
• Future laboratory tests should be performed to reduce the uncertainties
for isoprene measurements
• It is not readily apparent how the biological controls on DMS and
isoprene concentrations differ in the surface ocean. Pigments, bacterial DNA, and bacterial productivity data from the cruise will be available in the next months.
• Comparison of this data with aerosol load and chemical speciation will
be attempted.
50°N 40°N
30°N 20°N 10°N 0°N 10°S 20°S 30°S 40°S
30°W 20°W 10°W 0°W 10°E 20°E 30°W 20°W 10°W 0°W 10°E 20°E
50°N 40°N
30°N 20°N 10°N 0°N 10°S 20°S 30°S 40°S
DMS, DMSP and Isoprene Measurements
Equilibrator Ion source Collision chamber and high vacuum region Atmospheric Pressure Chemical Ionization Mass Spectrometer
He stream
water sample purge
unit
purge gas flame
photometric detector (FPD)
gas chromatograph (GC) water trap
(K2CO3) Preconcen- tration unit
purging injection on the GC
coo- lerhea-
ter
Purge and trap system + gas chromatograph (GC) and flame photometric detector (FPD)
Purge and trap GC-FPD
AP-CIMS
• DMS and isoprene were analyzed by equilibrating clean air with flowing seawater across a porous Teflon membrane
• DMS (m/z 63) and isoprene (m/z 69) are ionized at atmospheric pressure via proton transfer from water vapor, mass filtered via single quadrupole mass spectrometry, and detected with an electron multiplier
Purge and Trap System + GC-FPD
• DMS was transferred into gas phase by purging filtrated seawater samples, preconcentrated in liquid nitrogen, injected on the GC column ,and detected with the FPD
• DMSP was converted into DMS under alkaline conditions and analyzed in the same manner as DMS
Chlorophyll a
concentration in the sea surface in the eastern Atlantic ocean in the fourth week of November 2008 Phytoplankton blooms occurred along the north west and south west coast of AfricaCruise track
ofANTXXV/1 on the R/V Polarstern from Bremerhaven, Germany to Cape Town, South Africa from 31th October to 2nd December 2008
Calcite
concentration in the sea surface in the eastern Atlantic ocean in the fourth week of November 2008 Elevated calcite concen- trations indicate a phyto- plankton bloom dominated by coccolithophoridsIntercomparison of DMS measurement methods
Acknowledgements:
Thanks to the Captain and Crew of the R/V Polarstern, Cyril McCormick, the Saltzman
Lab at UCI, and Prof. Dr. Arne Körtzinger
1x10-2 1x10-1 1x100 1x101 mg m-3
1x10-4 1x10-3 1x10-2 1x10-1 mol m-3
DMS and Isoprene: Different Biological Controls?
• Both instruments showed the same trend in DMS concentrations along the cruise track
• DMS concentrations measured by AP-CIMS were systematically higher than the FPD system
• Possible explanations:
• Increased room temperature increased the sensitivity of the FPD
• Changes in the FPD gas mixture caused a shift toward higher sensitivity
• Calibration errors for either instrument
• Positive interferences at m/z 63 w/ AP-CIMS
• It does not appear that there was DMSP to DMS conversion in the AP-CIMS
• DMSP variability accounts for about 28% of the DMS variability
• Isoprene H at 25°C in seawater – no temperature dependent values
• Isoprene is very insoluble, can cause stripping in the equilibrator (data here corrected )
• Clear difference in DMS and isoprene distributions, although both appear to be influenced by the presence of coccolithophorids (indicated by calcite) especially between 10°S and 30°S
• elevated DMS and DMSP concentrations coincided with increasing calcite between 10°S and 30°S > coccolithophorid bloom is the main producer of DMSP and DMS
• at 15°N strong increase in calcite but only weak increase in DMS and DMSP and no influence on the isoprene concentration > possibly the age of the algae bloom determines the production rate of these compounds
• Isoprene is clearly influenced by phytoplankton blooms, however, the main producers are unclear
• Pigment, bacterial productivity & bacterial group type data needed to understand biological controls
References:
MODIS data from http://oceancolor.gsfc.nasa.gov/cgi/l3?per=DAY Shaw et al. (2003), Marine Chemistry, 80, 227– 245