Current estimates of global halocarbon emissions highlight the tropical coastal environment as an important source of very short-lived (VSL) biogenic halocarbons to the troposphere and stratosphere, ...due to a combination of assumed high primary productivity in tropical coastal waters and the prevalence of deep convective transport, potentially capable of rapidly lifting surface emissions to the upper troposphere/lower stratosphere. However, despite this perceived importance, direct measurements of tropical coastal biogenic halocarbon emissions, notably from macroalgae (seaweeds), have not been made. In light of this, we provide the first dedicated study of halocarbon production by a range of 15 common tropical macroalgal species and compare these results to those from previous studies of polar and temperate macroalgae. Variation between species was substantial; CHBr3 production rates, measured at the end of a 24 h incubation, varied from 1.4 to 1129 pmol g FW−1 h−1 (FW = fresh weight of sample). We used our laboratory-determined emission rates to estimate emissions of CHBr3 and CH2Br2 (the two dominant VSL precursors of stratospheric bromine) from the coastlines of Malaysia and elsewhere in South East Asia (SEA). We compare these values to previous top-down model estimates of emissions from these regions and, by using several emission scenarios, we calculate an annual CHBr3 emission of 40 (6–224 Mmol Br−1 yr), a value that is lower than previous estimates. The contribution of tropical aquaculture to current emission budgets is also considered. Whilst the current aquaculture contribution to halocarbon emissions in this regional is small, the potential exists for substantial increases in aquaculture to make a significant contribution to regional halocarbon budgets.
Automated in situ gas chromatograph/mass spectrometer (GC/MS) measurements of a range of predominantly biogenic alkyl halides in air, including CHBr3, CHBr2Cl, CH3Br, C2H5Br, CH3I, C2H5I, CH2ICl, ...CH2I2, and the hitherto unreported CH2IBr were made at Mace Head during a 3‐week period in May 1997. C3H7I and CH3CHICH3 were monitored but not detected. Positive correlations were observed between the polyhalomethane pairs CHBr3/CHBr2Cl and CHBr3/CH2IBr and between the monohalomethane pair CH3I/C2H5I, which are interpreted in terms of common or linked marine sources. During periods when air masses were affected by emissions from local seaweed beds, the concentrations of CHBr3, CH2ICl, and CH2IBr not only showed remarkable correlation but also maximized at low water. These are the first field observations to provide evidence for a link between the tidal cycle, polyhalomethanes in air, and potential marine production. The calculated total flux of iodine atoms into the boundary layer at Mace Head from organic gaseous precursors was dominated by photolytic destruction of CH2I2. Photolysis of CH3I contributed less than 3%. The calculated peak flux of iodine atoms during the campaign coincided with the highest measured levels of iodine oxide radicals, as determined using Differential Optical Absorption Spectrometry (DOAS).
Exposure of intertidal macroalgae during low tide has been linked to the emission of a variety of atmospherically-important trace gases into the coastal atmosphere. In recent years, several studies ...have investigated the role of inorganic iodine and organoiodides as antioxidants and their emission during exposure to combat oxidative stress, yet the role of organic bromine species during desiccation is less well understood. In this study the emission of dibromomethane (CH2Br2) and bromoform (CHBr3) during exposure and desiccation of two common temperate macroalgae, Fucus vesiculosus and Ulva intestinalis, is reported. Determination of the impact exposure may have on algal physiological processes is difficult as intertidal species are adapted to desiccation and may undergo varying degrees of desiccation before their physiology is affected. For this reason we include comparisons between photosynthetic capacity (Fv/Fm) and halocarbon emissions during a desiccation time series. In addition, the role of rewetting with freshwater to simulate exposure to rain was also investigated. Our results show that an immediate flux of bromocarbons occurs upon exposure, followed by a decline in bromocarbon emissions. We suggest that this immediate bromocarbon pulse may be linked to volatilisation or emissions of existing bromocarbon stores from the algal surface rather than the production of bromocarbons as an antioxidant response.
Chlorine Isotope Fractionation in the Stratosphere Laube, J.C; Kaiser, J; Sturges, W.T ...
Science (American Association for the Advancement of Science),
09/2010, Volume:
329, Issue:
5996
Journal Article
Peer reviewed
Open access
Chlorinated organic compounds are important contributors to the anthropogenic enhancement of stratospheric ozone depletion. We report measurements of stratospheric isotope fractionation in such a ...compound. Stratospheric and tropospheric difluorodichloromethane (CF₂Cl₂) were found to have the largest relative ³⁷Cl/³⁵Cl isotope ratio difference ever measured for a natural compound. The increase of the relative isotope ratio difference with altitude was tightly correlated to the corresponding decrease in the CF₂Cl₂ mixing ratio. The observed relationship has a high potential to provide new insights into atmospheric chemistry and transport processes.
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