Adele L. Chuck

Seasonal cycle of seawater bromoform and dibromomethane concentrations in a coastal bay on the western Antarctic Peninsula

Sea-to-air emissions of bromocarbon gases are known to play an important role in atmospheric ozone depletion. In this study, seawater concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) were measured regularly between February 2005 and March 2007 at the Rothera Oceanographic and Biological Time Series (RaTS) site located in Marguerite Bay on the Antarctic Peninsula. Strong seasonality in CHBr3 and CH2Br2 concentrations was observed. The highest bromocarbon concentrations (up to 276.4 +/- 13.0 pmol CHBr3 L-1 and 30.0 +/- 0.4 pmol CH2Br2 L-1) were found to coincide with the annual microalgal bloom during the austral summer, with lower concentrations (up to 39.5 pmol CHBr3 L-1 and 9.6 +/- 0.6 pmol CH2Br2 L-1) measured under the winter fast ice. The timing of the initial increase in bromocarbon concentrations was related to the sea-ice retreat and onset of the microalgal bloom. Observed seasonal variability in CH2Br2/CHBr3 suggests that this relationship may be of use in resolving bromocarbon source regions. Mainly positive saturation anomalies calculated for both the 2005/2006 and 2006/2007 summers suggest that the bay was a source of CHBr3 and CH2Br2 to the atmosphere. Estimates of bromocarbon sea-to-air flux rates from Marguerite Bay during ice-free periods are 84 (-13 to 275) CHBr3 nmol m(-2) d(-1) and 21 (2 to 70) nmol CH2Br2 m(-2) d(-1). If these flux rates are representative of the seasonal ice edge zone bloom which occurs each year over large areas of the Southern Ocean during the austral summer, sea-to-air bromocarbon emissions could have an important impact on the chemistry of the Antarctic atmosphere.

Air-sea gas exchange in Antarctic waters

The flux of gases between the atmosphere and the oceans can be calculated from the product of the concentration difference across the sea surface and a kinetic term, often called a transfer velocity. The transfer velocity is frequently parameterized in terms of wind speed, although the actual exchange process is also affected by waves, bubbles, wind fetch, and less certainly by surfactants and chemical reactivity. There is currently an uncertainty of about a factor of two in using the wind speed parameterization. In view of the windiness of the Southern Ocean, transfer velocities will often be high, although there are few published in situ measurements of transfer rates made in the region. Data for gas concentration fields in the Southern Ocean are generally sparse compared to other better studied oceanic areas. In this paper we discuss what is known for the region for carbon dioxide, including the oceanic sink for man-made inputs to the atmosphere; dimethyl sulphide, where there appears to be a substantial source, which has the potential for a significant climatic effect due to the low particulate loading in the region; and organo-halogen and alkyl nitrate gases, where marine emissions may play an important role in controlling the oxidation capacity of the Antarctic atmosphere.

Ocean fertilization with iron: effects on climate and air quality

It is well known that iron fertilization can increase primary production and hence CO2 drawdown over a significant fraction of the oceans. What is less well established is the extent to which this leads to long-term sequestration of carbon to the deep oceans, and to feedbacks to the atmosphere arising from increased biological activity. In this note results for changes in trace gas concentrations during an iron addition experiment in the Southern Ocean are presented. They demonstrate that a complex situation exists; some gases (DMS, CH3I, CHBr2Cl) show increases in concentration following fertilization with iron while others show no change (CH3ONO2, CH2ClI) or even a decrease (CHBr3). The concomitant effects on air—sea fluxes of these gases are potentially important for climate and atmospheric composition.

Methyl and ethyl nitrate saturation anomalies in the Southern Ocean (36–65°S, 30–70°W)

Environmental Context. The alkyl nitrates are a group of organic compounds that are known to be produced naturally in seawater. The sea-to-air flux of alkyl nitrates is believed to contribute significantly to the ‘odd nitrogen’ reservoir of the atmosphere and to play an important role in regulating tropospheric ozone levels in remote marine regions. Here we expand our knowledge of alkyl nitrate concentration distributions and saturation anomalies to Southern Ocean waters. Abstract. We report the first coupled atmosphere and seawater alkyl nitrate measurements for the Southern Ocean in the area bounded by 36–65°S, 30–70°W (November/December, 2004). Methyl and ethyl nitrate concentrations in seawater were 3.1–194.9 and 0.3–71.8 pmol L–1, respectively. Atmospheric mixing ratios ranged from 1.0 to 71.5 ppt for methyl nitrate and 0.6 to 16.6 ppt for ethyl nitrate. No correlations between alkyl nitrate distributions, and sea surface temperature, windspeed or chlorophyll a were observed. However, methyl and ethyl nitrate were well correlated in both the air and seawater, which suggests a common source. Calculations based on these observations estimate median saturation anomalies of –40% (–95 to 220%) for methyl nitrate and –11% (–98 to 174%) for ethyl nitrate. Positive saturation anomalies were spatially patchy, which suggests that some methyl and ethyl nitrate production was taking place in isolated areas of the study region. Overall our negative median saturation anomaly values suggest that during late austral spring (2004) the region of the Southern Ocean in which our measurements were made was not a net source of methyl or ethyl nitrate to the atmosphere. These results reinforce previous findings which suggest that whilst the equatorial ocean is a major source of methyl and ethyl nitrates to the atmosphere, higher latitude waters are generally at equilibrium or under-saturated. More measurements are required to assess how representative our results are of other areas of the Southern Ocean.