ALBERT

Description: Emissions of dimethylsulfide (DMS) from the polar oceans play a key role in atmospheric processes and climate. Therefore, it is important to increase our understanding of how DMS production in these regions may respond to climate change. The polar oceans are particularly vulnerable to ocean acidification (OA). However, our understanding of the polar DMS response is limited to two studies conducted in Arctic waters, where in both cases DMS concentrations decreased with increasing acidity. Here, we report on our findings from seven summertime shipboard microcosm experiments undertaken in a variety of locations in the Arctic Ocean and Southern Ocean. These experiments reveal no significant effects of short-term OA on the net production of DMS by planktonic communities. This is in contrast to similar experiments from temperate north-western European shelf waters where surface ocean communities responded to OA with significant increases in dissolved DMS concentrations. A meta-analysis of the findings from both temperate and polar waters (n=18 experiments) reveals clear regional differences in the DMS response to OA. Based on our findings, we hypothesize that the differences in DMS response between temperate and polar waters reflect the natural variability in carbonate chemistry to which the respective communities of each region may already be adapted. If so, future temperate oceans could be more sensitive to OA, resulting in an increase in DMS emissions to the atmosphere, whilst perhaps surprisingly DMS emissions from the polar oceans may remain relatively unchanged. By demonstrating that DMS emissions from geographically distinct regions may vary in their response to OA, our results may facilitate a better understanding of Earth's future climate. Our study suggests that the way in which processes that generate DMS respond to OA may be regionally distinct, and this should be taken into account in predicting future DMS emissions and their influence on Earth's climate.

Description: This paper describes a Near Surface Ocean Profiler, which has been designed to precisely measure vertical gradients in the top 10 m of the ocean. Variations in the depth of seawater collection are minimised when using the profiler compared to conventional CTD/rosette deployments. The profiler consists of a remotely operated winch mounted on a tethered yet free floating buoy, which is used to raise and lower a small frame housing sensors and inlet tubing. Seawater at the inlet depth is pumped back to the ship for analysis. The profiler can be used to make continuous vertical profiles or to target a series of discrete depths. The profiler has been successfully deployed during wind speeds up to 10 m s−1 and significant wave heights up to 2 m. We demonstrate the potential of the profiler by presenting measured vertical profiles of the trace gases carbon dioxide and dimethylsulfide. Trace gas measurements use an efficient microporous membrane equilibrator to minimise the system response time. The example profiles show vertical gradients in the upper 5 m for temperature, carbon dioxide and dimethylsulfide of 0.15 °C, 4 μatm and 0.4 nM respectively.

Description: 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 the Plymouth Sound. New International Maritime Organization (IMO) regulation came into force in January 2015 to reduce sulfur emissions tenfold in Sulfur Emission Control Areas such as the English Channel. Our observations suggest a three-fold reduction from 2014 to 2015 in ship-emitted SO2 from that direction. Apparent fuel sulfur content calculated from coincidental SO2 and carbon dioxide (CO2) peaks from local ship plum es show a high level of compliance to the IMO regulation (〉 95 %) in both years. Dimethylsulfide (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 ~ 1/3 in 2014 to ~ 1/2 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.

Description: The Baltic Sea is a unique environment as the largest body of brackish water in the world. Acidification of the surface oceans due to absorption of anthropogenic CO2 emissions is an additional stressor facing the pelagic community of the already challenging Baltic Sea. To investigate its impact on trace gas biogeochemistry, a large-scale mesocosm experiment was performed off Tvärminne Research Station, Finland, in summer 2012. During the second half of the experiment, dimethylsulfide (DMS) concentrations in the highest-fCO2 mesocosms (1075–1333 µatm) were 34 % lower than at ambient CO2 (350 µatm). However, the net production (as measured by concentration change) of seven halocarbons analysed was not significantly affected by even the highest CO2 levels after 5 weeks' exposure. Methyl iodide (CH3I) and diiodomethane (CH2I2) showed 15 and 57 % increases in mean mesocosm concentration (3.8 ± 0.6 increasing to 4.3 ± 0.4 pmol L−1 and 87.4 ± 14.9 increasing to 134.4 ± 24.1 pmol L−1 respectively) during Phase II of the experiment, which were unrelated to CO2 and corresponded to 30 % lower Chl a concentrations compared to Phase I. No other iodocarbons increased or showed a peak, with mean chloroiodomethane (CH2ClI) concentrations measured at 5.3 (±0.9) pmol L−1 and iodoethane (C2H5I) at 0.5 (±0.1) pmol L−1. Of the concentrations of bromoform (CHBr3; mean 88.1 ± 13.2 pmol L−1), dibromomethane (CH2Br2; mean 5.3 ± 0.8 pmol L−1), and dibromochloromethane (CHBr2Cl, mean 3.0 ± 0.5 pmol L−1), only CH2Br2 showed a decrease of 17 % between Phases I and II, with CHBr3 and CHBr2Cl showing similar mean concentrations in both phases. Outside the mesocosms, an upwelling event was responsible for bringing colder, high-CO2, low-pH water to the surface starting on day t16 of the experiment; this variable CO2 system with frequent upwelling events implies that the community of the Baltic Sea is acclimated to regular significant declines in pH caused by up to 800 µatm fCO2. After this upwelling, DMS concentrations declined, but halocarbon concentrations remained similar or increased compared to measurements prior to the change in conditions. Based on our findings, with future acidification of Baltic Sea waters, biogenic halocarbon emissions are likely to remain at similar values to today; however, emissions of biogenic sulfur could significantly decrease in this region.

Description: Emissions of dimethylsulfide (DMS) from the polar oceans play a key role in atmospheric processes and climate. Therefore, it is important we increase our understanding of how DMS production in these regions may respond to environmental change. The polar oceans are particularly vulnerable to ocean acidification (OA). However, our understanding of the polar DMS response is limited to two studies conducted in Arctic waters, where in both cases DMS concentrations decreased with increasing acidity. Here, we report on our findings from seven summertime shipboard microcosm experiments undertaken in a variety of locations in the Arctic Ocean and Southern Ocean. These experiments reveal no significant effects of short term OA on the net production of DMS by planktonic communities. This is in contrast to identical experiments from temperate NW European shelf waters where surface ocean communities responded to OA with significant increases in dissolved DMS concentrations. A meta-analysis of the findings from both temperate and polar waters (n = 18 experiments) reveals clear regional differences in the DMS response to OA. We suggest that these regional differences in DMS response reflect the natural variability in carbonate chemistry to which the respective communities may already be adapted. Future temperate oceans could be more sensitive to OA resulting in a change in DMS emissions to the atmosphere, whilst perhaps surprisingly DMS emissions from the polar oceans may remain relatively unchanged. By demonstrating that DMS emissions from geographically distinct regions may vary in response to OA, our results may facilitate a better understanding of Earth's future climate. Our study suggests that the way in which processes that generate DMS respond to OA may be regionally distinct and this should be taken into account in predicting future DMS emissions and their influence on Earth's climate.

Description: This paper describes a near-surface ocean profiler, which has been designed to precisely measure vertical gradients in the top 10 m of the ocean. Variations in the depth of seawater collection are minimized when using the profiler compared to conventional CTD/rosette deployments. The profiler consists of a remotely operated winch mounted on a tethered yet free-floating buoy, which is used to raise and lower a small frame housing sensors and inlet tubing. Seawater at the inlet depth is pumped back to the ship for analysis. The profiler can be used to make continuous vertical profiles or to target a series of discrete depths. The profiler has been successfully deployed during wind speeds up to 10 m s−1 and significant wave heights up to 2 m. We demonstrate the potential of the profiler by presenting measured vertical profiles of the trace gases carbon dioxide and dimethylsulfide. Trace gas measurements use an efficient microporous membrane equilibrator to minimize the system response time. The example profiles show vertical gradients in the upper 5 m for temperature, carbon dioxide and dimethylsulfide of 0.15 °C, 4 µatm and 0.4 nM respectively.

Description: We present air–sea fluxes of carbon dioxide (CO2), methane (CH4), momentum, and sensible heat measured by the eddy covariance method from the recently established Penlee Point Atmospheric Observatory (PPAO) on the south-west coast of the United Kingdom. Measurements from the south-westerly direction (open water sector) were made at three different sampling heights (approximately 15, 18, and 27 m above mean sea level, a.m.s.l.), each from a different period during 2014–2015. At sampling heights  ≥  18 m a.m.s.l., measured fluxes of momentum and sensible heat demonstrate reasonable ( ≤  ±20 % in the mean) agreement with transfer rates over the open ocean. This confirms the suitability of PPAO for air–sea exchange measurements in shelf regions. Covariance air–sea CO2 fluxes demonstrate high temporal variability. Air-to-sea transport of CO2 declined from spring to summer in both years, coinciding with the breakdown of the spring phytoplankton bloom. We report, to the best of our knowledge, the first successful eddy covariance measurements of CH4 emissions from a marine environment. Higher sea-to-air CH4 fluxes were observed during rising tides (20 ± 3; 38 ± 3; 29 ± 6 µmole m−2 d−1 at 15, 18, 27 m a.m.s.l.) than during falling tides (14 ± 2; 22 ± 2; 21 ± 5 µmole m−2 d−1), consistent with an elevated CH4 source from an estuarine outflow driven by local tidal circulation. These fluxes are a few times higher than the predicted CH4 emissions over the open ocean and are significantly lower than estimates from other aquatic CH4 hotspots (e.g. polar regions, freshwater). Finally, we found the detection limit of the air–sea CH4 flux by eddy covariance to be 20 µmole m−2 d−1 over hourly timescales (4 µmole m−2 d−1 over 24 h).

Description: 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.