Production of methyl bromide and methyl chloride in laboratory cultures of marine phytoplankton II

Methyl halides (monohalomethanes), especially methyl bromide, are known to contribute significantly to ozone destruction in the stratosphere. Budgets of natural and anthropogenic methyl bromide suggest that marine organisms may be the source of a significant proportion of the total global production. Since phytoplankton are abundant in surface waters, they are obvious candidates. Cultures of nine phytoplankton species were grown in CO2-enriched, nitrate-limited medium in sealed glass vessels. Species tested include Chaetoceros calcitrans, Isochrysis sp., Porphyridium sp., Synechococcus sp., Phaeodactylum tricornutum, Tetraselmis sp., Prorocentrum sp., Emiliania huxleyi and Phaeocystis sp. Methyl bromide (CH3Br) and methyl chloride (CH3Cl) concentrations were determined by bubbling the cultures with high-purity air, cryotrapping the effluent and analyzing it on a gas chromatograph with an electron capture detector. The Phaeocystis sp. samples were monitored with GCMS. Cell population, bacterial population, Chl a, pH, and nitrate concentration were monitored for periods of at least two weeks. CH3Cl was produced by all cultures. CH3Br was absent in Tetraselmis sp. and Isochrysis sp. cultures, but present in all the others. Methyl iodide (CH3I) was present in most cultures but could not be quantified due to analytical limitations. CH3I and CH3Br production was fastest in stationary phase and continued long after cell division had ceased. Axeic cultures of Phaeocystis sp. achieved almost identical production rates of CH3Cl and CH3Br as xenic cultures of the same species. Species from tropical waters had faster CH3Cl and CH3Br production rates than temperate species. Scaling the observed production rates using global standing stock estimates for Chl a and particulate nitrogen indicate that phytoplankton can account for only a fraction of the CH3Cl and CH3Br believed to be produced in the ocean. Calculations based on the estimated global biomass of Phaeocystis sp. and E. huxleyi blooms show that their contribution is insignificantly small.