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Dimethyl Sulfide - Summary
Several years ago, Charlson et al. (1987) discussed the plausibility of a multi-stage negative feedback process, whereby warming-induced increases in the emission of dimethyl sulfide (DMS) from the world's oceans tend to counteract any initial impetus for warming.  The basic tenant of their hypothesis was that the global radiation balance is significantly influenced by the albedo of marine stratus clouds (the greater the cloud albedo, the less the input of solar radiation to the earth's surface).  The albedo of these clouds, in turn, is known to be a function of cloud droplet concentration (the more and smaller the cloud droplets, the greater the cloud albedo and the reflection of solar radiation), which is dependent upon the availability of cloud condensation nuclei on which the droplets form (the more cloud condensation nuclei, the more and smaller the cloud droplets).  And in completing the negative feedback loop, Charlson et al. noted that the cloud condensation nuclei concentration often depends upon the flux of biologically-produced DMS from the world's oceans (the higher the sea surface temperature, the greater the sea-to-air flux of DMS).

Since the publication of Charlson et al.'s initial hypothesis, much empirical evidence has been gathered in support of its several tenants.  A recent review, for example, states that "major links in the feedback chain proposed by Charlson et al. (1987) have a sound physical basis," and that there is "compelling observational evidence to suggest that DMS and its atmospheric products participate significantly in processes of climate regulation and reactive atmospheric chemistry in the remote marine boundary layer of the Southern Hemisphere" (Ayers and Gillett, 2000).

But just how strong is the negative feedback phenomenon proposed by Charlson et al.?  Is it powerful enough to counter the threat of greenhouse gas-induced global warming?  According to the findings of Sciare et al. (2000), it may well be able to do just that, for in examining ten years of DMS data from Amsterdam Island in the southern Indian Ocean, these researchers found that a sea surface temperature increase of only 1°C was sufficient to increase the atmospheric DMS concentration by as much as 50%.  This finding suggests that the degree of warming typically predicted to accompany a doubling of the air's CO2 content would increase the atmosphere's DMS concentration by a factor of three or more, providing what they call a "very important" negative feedback that could potentially offset the original impetus for warming.

Other research has shown that this same chain of events can be set in motion by means of phenomena not discussed in Charlson et al.'s original hypothesis.  Simo and Pedros-Alio (1999), for example, discovered that the depth of the surface mixing-layer has a substantial influence on DMS yield in the short term, via a number of photo-induced (and thereby mixing-depth mediated) influences on several complex physiological phenomena, as do longer-term seasonal variations in vertical mixing, via their influence on seasonal planktonic succession scenarios and food-web structure.

More directly supportive of Charlson et al.'s hypothesis was the study of Kouvarakis and Mihalopoulos (2002), who measured seasonal variations of gaseous DMS and its oxidation products - non-sea-salt sulfate (nss-SO42-) and methanesulfonic acid (MSA) - at a remote coastal location in the Eastern Mediterranean Sea from May 1997 through October 1999, as well as the diurnal variation of DMS during two intensive measurement campaigns conducted in September 1997.  In the seasonal investigation, DMS concentrations tracked sea surface temperature (SST) almost perfectly, going from a low of 0.87 nmol m-3 in the winter to a high of 3.74 nmol m-3 in the summer.  Such was also the case in the diurnal studies: DMS concentrations were lowest when it was coldest (just before sunrise), rose rapidly as it warmed thereafter to about 1100, after which they dipped slightly and then experienced a further rise to the time of maximum temperature at 2000, whereupon a decline in both temperature and DMS concentration set in that continued until just before sunrise.  Consequently, because concentrations of DMS and its oxidation products (MSA and nss-SO42-) rise dramatically in response to both diurnal and seasonal increases in SST, there is every reason to believe that the same negative feedback phenomenon would operate in the case of the long-term warming that could arise from increasing greenhouse gas concentrations, and that it could substantially mute the climatic impacts of those gases.

Also of note in this regard, Baboukas et al. (2002) report the results of nine years of measurements of methanesulfonate (MS-), an exclusive oxidation product of DMS, in rainwater at Amsterdam Island.  Their data, too, revealed "a well distinguished seasonal variation with higher values in summer, in line with the seasonal variation of its gaseous precursor (DMS)," which, in their words, "further confirms the findings of Sciare et al. (2000)."  In addition, the MS- anomalies in the rainwater were found to be closely related to SST anomalies; and Baboukas et al. say that this observation provides even more support for "the existence of a positive ocean-atmosphere feedback on the biogenic sulfur cycle above the Austral Ocean, one of the most important DMS sources of the world."

In a newer study of this phenomenon, Toole and Siegel (2004) note that it has been shown to operate as described above in the 15% of the world's oceans "consisting primarily of high latitude, continental shelf, and equatorial upwelling regions," where DMS may be accurately predicted as a function of the ratio of the amount of surface chlorophyll derived from satellite observations to the depth of the climatological mixed layer, which they refer to as the "bloom-forced regime."  For the other 85% of the world's marine waters, they demonstrate that modeled surface DMS concentrations are independent of chlorophyll and are a function of the mixed layer depth alone, which they call the "stress-forced regime."  So how does the warming-induced DMS negative feedback cycle operate in these waters?

For oligotrophic regimes, Toole and Siegel find that "DMS biological production rates are negatively or insignificantly correlated with phytoplankton and bacterial indices for abundance and productivity while more than 82% of the variability is explained by UVR(325) [ultraviolet radiation at 325 nm]."  This relationship, in their words, is "consistent with recent laboratory results (e.g., Sunda et al., 2002)," who demonstrated that intracellular DMS concentration and its biological precursors (particulate and dissolved dimethylsulfoniopropionate) "dramatically increase under conditions of acute oxidative stress such as exposure to high levels of UVR," which "are a function of mixed layer depth."

These results -- which Toole and Siegel confirmed via an analysis of the Dacey et al. (1998) 1992-1994 organic sulfur time-series that was sampled in concert with the U.S. JGOFS Bermuda Atlantic Time-Series Study (Steinberg et al., 2001) -- suggest, in their words, "the potential of a global change-DMS-climate feedback."  Specifically, they say that "UVR doses will increase as a result of observed decreases in stratospheric ozone and the shoaling of ocean mixed layers as a result of global warming (e.g., Boyd and Doney, 2002)," and that "in response, open-ocean phytoplankton communities should increase their DMS production and ventilation to the atmosphere, increasing cloud condensing nuclei, and potentially playing out a coupled global change-DMS-climate feedback."

This second DMS-induced negative-feedback cycle, which operates over 85% of the world's marine waters and complements the first DMS-induced negative-feedback cycle, which operates over the other 15%, is but another manifestation of the wonderful capacity of earth's biosphere to regulate its affairs in such a way as to maintain climatic conditions over the vast majority of the planet's surface within bounds conducive to the continued existence of life, in all its variety and richness.  In addition, it has been suggested that a DMS-induced negative climate feedback phenomenon also operates over the terrestrial surface of the globe, where the volatilization of reduced sulfur gases from soils may be just as important as marine DMS emissions in enhancing cloud albedo (Idso, 1990).  On the basis of experiments that showed soil DMS emissions to be positively correlated with soil organic matter content, for example, and noting that additions of organic matter to a soil tend to increase the amount of sulfur gases emitted therefrom, Idso (1990) hypothesized that because atmospheric CO2 is an effective aerial fertilizer, augmenting its atmospheric concentration and thereby increasing vegetative inputs of organic matter to earth's soils should also produce an impetus for cooling, even in the absence of surface warming.

Nevertheless, and in spite of the overwhelming empirical evidence for both land- and ocean-based DMS-driven negative feedbacks to global warming, the effects of these processes have not been fully incorporated into today's state-of-the-art climate models.  Hence, the warming they predict in response to future anthropogenic CO2 emissions must be considerably larger than what could actually occur in the real world.  In fact, it is very possible these biologically-driven phenomena could totally compensate for the warming influence of all greenhouse gas emissions experienced to date, as well as all those that are anticipated to occur in the future.

References
Ayers, G.P. and Gillett, R.W.  2000.  DMS and its oxidation products in the remote marine atmosphere: implications for climate and atmospheric chemistry.  Journal of Sea Research 43: 275-286.

Baboukas, E., Sciare, J. and Mihalopoulos, N.  2002.  Interannual variability of methanesulfonate in rainwater at Amsterdam Island (Southern Indian Ocean).  Atmospheric Environment 36: 5131-5139.

Boyd, P.W. and Doney, S.C.  2002.  Modeling regional responses by marine pelagic ecosystems to global climate change.  Geophysical Research Letters 29: 10.1029/2001GL014130

Charlson, R.J., Lovelock, J.E., Andrea, M.O. and Warren, S.G.  1987.  Oceanic phytoplankton, atmospheric sulfur, cloud albedo and climate.  Nature 326: 655-661.

Dacey, J.W.H., Howse, F.A., Michaels, A.F. and Wakeham, S.G.  1998.  Temporal variability of dimethylsulfide and dimethylsulfoniopropionate in the Sagasso Sea.  Deep Sea Research 45: 2085-2104.

Idso, S.B.  1990.  A role for soil microbes in moderating the carbon dioxide greenhouse effect?  Soil Science 149: 179-180.

Kouvarakis, G. and Mihalopoulos, N.  2002.  Seasonal variation of dimethylsulfide in the gas phase and of methanesulfonate and non-sea-salt sulfate in the aerosols phase in the Eastern Mediterranean atmosphere.  Atmospheric Environment 36: 929-938.

Sciare, J., Mihalopoulos, N. and Dentener, F.J.  2000.  Interannual variability of atmospheric dimethylsulfide in the southern Indian Ocean.  Journal of Geophysical Research 105: 26,369-26,377.

Simo, R. and Pedros-Alio, C.  1999.  Role of vertical mixing in controlling the oceanic production of dimethyl sulphide.  Nature 402: 396-399.

Steinberg, D.K., Carlson, C.A., Bates, N.R., Johnson, R.J., Michaels, A.F. and Knap, A.H.  2001.  Overview of the US JGOFS Bermuda Atlantic Time-series Study (BATS): a decade-scale look at ocean biology and biogeochemistry.  Deep Sea Research Part II: Topical Studies in Oceanography 48: 1405-1447.

Sunda, W., Kieber, D.J., Kiene, R.P. and Huntsman, S.  2002.  An antioxidant function for DMSP and DMS in marine algae.  Nature 418: 317-320.

Toole, D.A. and Siegel, D.A.  2004.  Light-driven cycling of dimethylsulfide (DMS) in the Sargasso Sea: Closing the loop.  Geophysical Research Letters 31: 10.1029/2004GL019581.