Ocean-atmosphere trace gas exchange

The oceans contribute significantly to the global emissions of a number of atmospherically important volatile gases, notably those containing sulfur, nitrogen and halogens. Such gases play critical roles not only in global biogeochemical cycling but also in a wide range of atmospheric processes including marine aerosol formation and modification, tropospheric ozone formation and destruction, photooxidant cycling and stratospheric ozone loss. A number of marine emissions are greenhouse gases, others influence the Earth's radiative budget indirectly through aerosol formation and/or by modifying oxidant levels and thus changing the atmospheric lifetime of gases such as methane. In this article we review current literature concerning the physical, chemical and biological controls on the sea-air emissions of a wide range of gases including dimethyl sulphide (DMS), halocarbons, nitrogen-containing gases including ammonia (NH3), amines (including dimethylamine, DMA, and diethylamine, DEA), alkyl nitrates (RONO2) and nitrous oxide (N2O), non-methane hydrocarbons (NMHC) including isoprene and oxygenated (O)VOCs, methane (CH4) and carbon monoxide (CO). Where possible we review the current global emission budgets of these gases as well as known mechanisms for their formation and loss in the surface ocean.

Nitrogen uptake of phytoplankton assemblages under contrasting upwelling and downwelling conditions: The Ría de Vigo, NW Iberia

Regenerated production (including organic nitrogen) is shown here to be important in the Ria de Vigo (Galicia, NW Iberia) in supporting both harmful algal bloom communities during the downwelling season, but also (to a lesser extent) diatom communities during stratified periods of weak to moderate upwelling. The Galician Rias, situated in the Iberian upwelling system, are regularly affected by blooms of toxic dinoflagellates, which pose serious threats to the local mussel farming industry. These tend to occur towards the end of summer, during the transition from upwelling to downwelling favourable seasons, when cold bottom shelf waters in the rias are replaced by warm surface shelf waters. Nitrate, ammonium and urea uptake rates were measured in the Ria de Vigo during a downwelling event in September 2006 and during an upwelling event in June 2007. In September the ria was well mixed, with a downwelling front observed towards the middle of the ria and relatively high nutrient concentrations (1.0-2.6 mu mol L-1 nitrate; 1.0-5.6 mu mol L-1 ammonium; 0.1-0.8 mu mol L-1 phosphate; 2.0-9.0 mu mol L-1 silicic acid) were present throughout the water column. Ammonium represented more than 80% of the nitrogenous nutrients, and the phytoplankton assemblage was dominated by dinoflagellates and small flagellates. In June the water column was stratified, with nutrient-rich, upwelled water below the thermocline and warm, nutrient-depleted water in the surface. At this time, nitrate represented more than 80% of the nitrogenous nutrients, and a mixed diatom assemblage was present. Primary phytoplankton production during both events was mainly sustained by regenerated nitrogen, with ammonium uptake rates of 0.035-0.063 mu mol N L-1 h(-1) in September and 0.078-0.188 mu mol N L-1 h(-1) in June. Although f-ratios were generally low (<0.2) in both June and September, a maximum of 0.61 was reached in June due to higher nitrate uptake (0.225 mu mol N L-1 h(-1)). Total nitrogen uptake was also higher during the upwelling event (0.153-0.366 in June and 0.053-0.096 mu mol N L-1 h(-1) in September). Nitrogen uptake kinetics demonstrated a strong preference for ammonium and urea over nitrate in June.

Effects of formalin preservation on stable carbon and nitrogen isotope signatures in Calanoid copepods: implications for the use of Continuous Plankton Recorder Survey samples in stable isotope analyses

Preserved and archived organic material offers huge potential for the conduct of retrospective and long-term historical ecosystem reconstructions using stable isotope analyses, but because of isotopic exchange with preservatives the obtained values require validation. The Continuous Plankton Recorder (CPR) Survey is the most extensive long-term monitoring program for plankton communities worldwide and has utilised ships of opportunity to collect samples since 1931. To keep the samples intact for subsequent analysis, they are collected and preserved in formalin; however, previous studies have found that this may alter stable carbon and nitrogen isotope ratios in zooplankton. A maximum ~0.9‰ increase of δ15N and a time dependent maximum ~1.0‰ decrease of δ13C were observed when the copepod, Calanus helgolandicus, was experimentally exposed to two formalin preservatives for 12 months. Applying specific correction factors to δ15N and δ13C values for similarly preserved Calanoid species collected by the CPR Survey within 12 months of analysis may be appropriate to enable their use in stable isotope studies. The isotope values of samples stored frozen did not differ significantly from those of controls. Although the impact of formalin preservation was relatively small in this and other studies of marine zooplankton, changes in isotope signatures are not consistent across taxa, especially for δ15N, indicating that species-specific studies may be required. Copyright © 2011 John Wiley & Sons, Ltd.

Air-Sea Exchange of Marine Trace Gases

Many of the reactive trace gases detected in the atmosphere are both emitted from and deposited to the global oceans via exchange across the air–sea interface. The resistance to transfer through both air and water phases is highly sensitive to physical drivers (waves, bubbles, films, etc.), which can either enhance or suppress the rate of diffusion. In addition to outlining the fundamental processes controlling the air–sea gas exchange, the authors discuss these drivers, describe the existing parameterizations used to predict transfer velocities, and summarize the novel techniques for measuring in situ exchange rates. They review trace gases that influence climate via radiative forcing (greenhouse gases), those that can alter the oxidative capacity of the atmosphere (nitrogen- and sulfur-containing gases), and those that impact ozone levels (organohalogens), both in the troposphere and stratosphere. They review the known biological and chemical routes of production and destruction within the water column for these gases, whether the ocean acts as a source or sink, and whether temporal and spatial variations in saturation anomalies are observed. A current estimate of the marine contribution to the total atmospheric flux of these gases, which often highlights the significance of the oceans in biogeochemical cycling of trace gases, is provided, and how air–sea gas fluxes may change in the future is briefly assessed.

Biogeochemical cycling of dissolved zinc along the GEOTRACES South Atlantic transect GA10 at 40°S

The biogeochemical cycle of zinc (Zn) in the South Atlantic, at 40°S, was investigated as part of the UK GEOTRACES program. To date there is little understanding of the supply of Zn, an essential requirement for phytoplankton growth, to this highly productive region. Vertical Zn profiles displayed nutrient-like distributions with distinct gradients associated with the watermasses present. Surface Zn concentrations are among the lowest reported for theworld’s oceans (<50 pM). A strong Zn-Si linear relationshipwas observed (Zn (nM)= 0.065 Si (μM), r2=0.97, n = 460). Our results suggest that the use of a global Zn-Si relationship would lead to an underestimation of dissolved Zn in deeper waters of the South Atlantic. By utilizing Si* and a new tracer Zn* our data indicate that the preferential removal of Zn in the Southern Ocean prevented a direct return path for dissolved Zn to the surface waters of the South Atlantic at 40°S and potentially the thermocline waters of the South Atlantic subtropical gyre. The importance of Zn for phytoplankton growth was evaluated using the Zn-soluble reactive phosphorus (SRP) relationship. We hypothesize that the low Zn concentrations in the South Atlantic may select for phytoplankton cells with a lower Zn requirement. In addition, a much deeper kink at ~ 500m in the Zn:SRP ratio was observed compared to other oceanic regions.

Impact of zooplankton food selectivity on plankton dynamics and nutrient cycling

Within models, zooplankton grazing is typically defined as being dependent on total prey concentration, with feeding selectivity expressed only as a function of prey size. This behavior ignores taxonomic preferences shown by the preda- tors and the capacity of some zooplankton to actively select or reject individual prey items from mixtures. We carried out two model experiments comparing impacts of zooplankton displaying passive and active selection, which resulted in contrasting dynamics for the pelagic system. Passive selection by the grazer resulted in a top down control on the prey with a fast turn-over of nutrients. Active selection, on the other hand led to a bottom-up control, with slower nutrient turnover constraining primary production by changing the system toward export of particulate matter. Our results suggest that selective feeding behavior is an important trait, and should be considered alongside size and taxonomy when studying the role of zooplankton impact in the ecosystem.