scholarly journals Supplementary material to "Oceanic emissions of dimethyl sulfide and methanethiol and their contribution to sulfur dioxide production in the marine atmosphere"

Author(s):  
Gordon A. Novak ◽  
Delaney B. Kilgour ◽  
Christopher M. Jernigan ◽  
Michael P. Vermeuel ◽  
Timothy H. Bertram
2021 ◽  
Author(s):  
Gordon A. Novak ◽  
Delaney B. Kilgour ◽  
Christopher M. Jernigan ◽  
Michael P. Vermeuel ◽  
Timothy H. Bertram

Abstract. Oceanic emissions of dimethyl sulfide (CH3SCH3, DMS) have long been recognized to impact aerosol particle composition and size, the concentration of cloud condensation nuclei (CCN), and Earth’s radiation balance. The impact of oceanic emissions of methanethiol (CH3SH, MeSH), which is produced by the same oceanic precursor as DMS, on the volatile sulfur budget of the marine atmosphere is largely unconstrained. Here we present direct flux measurements of MeSH oceanic emissions using the eddy covariance (EC) method with a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToFMS) detector and compare them to simultaneous flux measurements of DMS emissions from a coastal ocean site. Campaign mean mixing ratios of DMS and MeSH were 72 ppt (28–90 ppt interquartile range) and 19.1 ppt (7.6–24.5 ppt interquartile range) respectively. Campaign mean (and interquartile range) emission fluxes of DMS (FDMS) and MeSH (FMeSH) were 1.13 (0.53–1.61) and 0.21 (0.10–0.31) ppt m s-1 respectively. Linear least squares regression of observed MeSH and DMS flux indicates the emissions are highly correlated with each other (R2 = 0.65) over the course of the campaign, consistent with a shared oceanic source. The campaign mean DMS to MeSH flux ratio (FDMS:FMeSH) was 5.5 ± 3.0 calculated from the ratio of 304 individual coincident measurements of FDMS and FMeSH. Measured FDMS:FMeSH was weakly correlated (R2 = 0.15) with ocean chlorophyll concentrations, with FDMS:FMeSH reaching a maximum of 10.8 ± 4.4 during a phytoplankton bloom period. No other volatile sulfur compounds were observed by PTR-ToFMS to have a resolvable emission flux above their flux limit of detection or to have a gas phase mixing ratio consistently above their limit of detection during the study period, suggesting DMS and MeSH are the dominant volatile organic sulfur compounds emitted from the ocean at this site. The impact of this MeSH emission source on atmospheric budgets of sulfur dioxide (SO2) was evaluated by implementing observed emissions into a coupled ocean-atmosphere chemical box model using a newly compiled MeSH oxidation mechanism. Model results suggest that MeSH emissions lead to afternoon instantaneous SO2 production of 2.5 ppt hr-1, which accounts for 30 % of the instantaneous SO2 production in the marine boundary layer at the mean measured FDMS and FMeSH. This contribution of MeSH to SO2 production is driven by a higher effective yield of SO2 from MeSH oxidation and the shorter oxidation lifetime of MeSH compared to DMS. This large additional source of marine SO2 has not been previously considered in global models of marine sulfur cycling. The field measurements and modeling results presented here demonstrate that MeSH is an important contributor to volatile sulfur budgets in the marine atmosphere, and must be measured along with DMS in order to constrain marine sulfur budgets. This large additional source of marine reduced sulfur from MeSH will contribute to particle formation and growth and CCN abundance in the marine atmosphere, with subsequent impacts on climate.


2021 ◽  
Vol 2 (1) ◽  
Author(s):  
Manon Rocco ◽  
Erin Dunne ◽  
Maija Peltola ◽  
Neill Barr ◽  
Jonathan Williams ◽  
...  

AbstractBenzene, toluene, ethylbenzene and xylenes can contribute to hydroxyl reactivity and secondary aerosol formation in the atmosphere. These aromatic hydrocarbons are typically classified as anthropogenic air pollutants, but there is growing evidence of biogenic sources, such as emissions from plants and phytoplankton. Here we use a series of shipborne measurements of the remote marine atmosphere, seawater mesocosm incubation experiments and phytoplankton laboratory cultures to investigate potential marine biogenic sources of these compounds in the oceanic atmosphere. Laboratory culture experiments confirmed marine phytoplankton are a source of benzene, toluene, ethylbenzene, xylenes and in mesocosm experiments their sea-air fluxes varied between seawater samples containing differing phytoplankton communities. These fluxes were of a similar magnitude or greater than the fluxes of dimethyl sulfide, which is considered to be the key reactive organic species in the marine atmosphere. Benzene, toluene, ethylbenzene, xylenes fluxes were observed to increase under elevated headspace ozone concentration in the mesocosm incubation experiments, indicating that phytoplankton produce these compounds in response to oxidative stress. Our findings suggest that biogenic sources of these gases may be sufficiently strong to influence atmospheric chemistry in some remote ocean regions.


2016 ◽  
Vol 16 (8) ◽  
pp. 4771-4783 ◽  
Author(s):  
Mingxi Yang ◽  
Thomas G. Bell ◽  
Frances E. Hopkins ◽  
Timothy J. Smyth

Abstract. Atmospheric sulfur dioxide (SO2) was measured continuously from the Penlee Point Atmospheric Observatory (PPAO) near Plymouth, United Kingdom, between May 2014 and November 2015. This coastal site is exposed to marine air across a wide wind sector. The predominant southwesterly winds carry relatively clean background Atlantic air. In contrast, air from the southeast is heavily influenced by exhaust plumes from ships in the English Channel as well as near Plymouth Sound. A new International Maritime Organization (IMO) regulation came into force in January 2015 to reduce the maximum allowed sulfur content in ships' fuel 10-fold in sulfur emission control areas such as the English Channel. Our observations suggest a 3-fold reduction in ship-emitted SO2 from 2014 to 2015. Apparent fuel sulfur content calculated from coincidental SO2 and carbon dioxide (CO2) peaks from local ship plumes show a high level of compliance to the IMO regulation (> 95 %) in both years (∼  70 % of ships in 2014 were already emitting at levels below the 2015 cap). Dimethyl sulfide (DMS) is an important source of atmospheric SO2 even in this semi-polluted region. The relative contribution of DMS oxidation to the SO2 burden over the English Channel increased from about one-third in 2014 to about one-half in 2015 due to the reduction in ship sulfur emissions. Our diel analysis suggests that SO2 is removed from the marine atmospheric boundary layer in about half a day, with dry deposition to the ocean accounting for a quarter of the total loss.


2021 ◽  
Author(s):  
Eleni Dovrou ◽  
Kelvin H. Bates ◽  
Jean C. Rivera-Rios ◽  
Joshua L. Cox ◽  
Joshua D. Shutter ◽  
...  

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