Gill Malin

In situ evaluation of air-sea gas exchange parameterizations using novel conservative and volatile tracers

Measurements of air-sea gas exchange rates are reported from two deliberate tracer experiments in the southern North Sea during February 1992 and 1993. A conservative tracer, spores of the bacterium Bacillus globigii var. Niger, was used for the first time in an in situ air-sea gas exchange experiment. This nonvolatile tracer is used to correct for dispersive dilution of the volatile tracers and allows three estimations of the transfer velocity for the same time period. The first estimation of the power dependence of gas transfer on molecular diffusivity in the marine environment is reported. This allows the impact of bubbles on estimates of the transfer velocity derived from changes in the helium/sulphur hexafluoride ratio to be assessed. Data from earlier dual tracer experiments are reinterpreted, and findings suggest that results from all dual tracer experiments are mutually consistent. The complete data set is used to test published parameterizations of gas transfer with wind speed. A gas ex- change relationship that shows a dependence on wind speed intermediate between those ofLiss and Merlivat [1986] and Wanninkhof [1992] is found to be optimal. The dual tracer data are shown to be reasonably consistent with global estimates of gas exchange based on the uptake of natural and bomb-derived radiocarbon. The degree of scatter in the data when plotted against wind speed suggests that parameters not scaling with wind speed are also influencing gas exchange rates.

A global database of sea surface dimethylsulfide (DMS) measurements and a procedure to predict sea surface DMS as a function of latitude, longitude, and month

A database of 15,617 point measurements of dimethylsulfide (DMS) in surface waters along with lesser amounts of data for aqueous and particulate dimethylsulfoniopropionate concentration, chlorophyll concentration, sea surface salinity and temperature, and wind speed has been assembled. The database was processed to create a series of climatological annual and monthly 1°×1° latitude-longitude squares of data. The results were compared to published fields of geophysical and biological parameters. No significant correlation was found between DMS and these parameters, and no simple algorithm could be found to create monthly fields of sea surface DMS concentration based on these parameters. Instead, an annual map of sea surface DMS was produced using an algorithm similar to that employed by Conkright et al. [1994]. In this approach, a first-guess field of DMS sea surface concentration measurements is created and then a correction to this field is generated based on actual measurements. Monthly sea surface grids of DMS were obtained using a similar scheme, but the sparsity of DMS measurements made the method difficult to implement. A scheme was used which projected actual data into months of the year where no data were otherwise present.

The Response of Diatom Central Carbon Metabolism to Nitrogen Starvation Is Different from That of Green Algae and Higher Plants

The availability of nitrogen varies greatly in the ocean and limits primary productivity over large areas. Diatoms, a group of phytoplankton that are responsible for about 20% of global carbon fixation, respond rapidly to influxes of nitrate and are highly successful in upwelling regions. Although recent diatom genome projects have highlighted clues to the success of this group, very little is known about their adaptive response to changing environmental conditions. Here, we compare the proteome of the marine diatom Thalassiosira pseudonana (CCMP 1335) at the onset of nitrogen starvation with that of nitrogen-replete cells using two-dimensional gel electrophoresis. In total, 3,310 protein spots were distinguishable, and we identified 42 proteins increasing and 23 decreasing in abundance (greater than 1.5-fold change; P < 0.005). Proteins involved in the metabolism of nitrogen, amino acids, proteins, and carbohydrates, photosynthesis, and chlorophyll biosynthesis were represented. Comparison of our proteomics data with the transcriptome response of this species under similar growth conditions showed good correlation and provided insight into different levels of response. The T. pseudonana response to nitrogen starvation was also compared with that of the higher plant Arabidopsis (Arabidopsis thaliana), the green alga Chlamydomonas reinhardtii, and the cyanobacterium Prochlorococcus marinus. We have found that the response of diatom carbon metabolism to nitrogen starvation is different from that of other photosynthetic eukaryotes and bears closer resemblance to the response of cyanobacteria.

Novel biogenic iodine-containing trihalomethanes and other short-lived halocarbons in the coastal East Atlantic

Reactive halogen photochemistry and its impact on tropospheric oxidant levels have recently attracted intense research interest following the observation of the iodine oxide radical at midlatitudes. During September 1998, short-lived organoiodines including CH3I, C2H5I, CH2ICl, CH2IBr, CH2I2, and the hitherto undetected CHIBr2, as well as the organobromines CHBr3, CH2Br2, CHBr2Cl, CH3Br, and C2H5Br, were measured in air and seawater at and around Mace Head, on the west coast of Ireland. The release rates of organic bromines and iodines from seaweeds were determined from incubations of 10 species of brown, red, and green macroalgae collected in the intertidal or subtidal zones of the rocky shore. For all the brown algae studied, iodine was released mainly as CH2I2. However, for several seaweeds, the novel iodine-containing trihalomethanes CHIBr2 and CHI2Cl represented a significant fraction of the released organic iodine. The macroalgae incubation experiments as well as monitoring of the in situ concentrations in a rock pool indicated that natural halocarbon production by seaweeds was stimulated by incident light. The halocarbon fluxes derived from the seaweed incubations, coupled with published detailed biomass surveys, enabled coastal organohalogen seawater concentrations to be estimated. The CHBr3, CH2Br2, and CHBr2Cl concentrations calculated by this method compared well with coastal surface seawater measurements, implying that macroalgae were the major sources of the polybromomethanes. Measured CH3Br, CH3I, and CH2ICl levels were higher than calculated, which may be due to the existence of additional sources. CH3Br production by macroalgae accounted for less than 10% of measured levels in coastal waters. Short-lived iodocarbons such as CH2I2 and CHIBr2 were depleted in surface seawater compared to calculated levels, implying their photolytic loss within the upper water column.

Seasonal variation of dimethyl sulphide in the North Sea and an assessment of fluxes to the atmosphere

The distribution of DMS concentrations in surface waters of the southern North Sea is described for nine months (February–October) in 1989. Minimum concentrations in winter were 0.13 nM and the maximum, monthly mean concentration was 25 nM, in May, coincident with large blooms of Phaeocystis pouchetii, off the continental coast. Comparison with other North Sea data suggests that the interannual seasonal pattern of DMS concentrations is similar. Transfer velocities, for sea-to-air transfer of DMS are derived, comparing a number of methods, and some of the uncertainties in the flux calculation are discussed. Optimised flux data for the North Sea show a distinct annual cycle with monthly averages ranging from 0.2 to 16.4 μmol m−2 day−1 for February and June, respectively. Comparison with other data suggests that North Sea fluxes are very similar to other ocean areas in a similar latitude band and on an annual and seasonal basis. The potential impact of North Sea DMS fluxes on the European atmospheric sulphur budget is discussed.

Dimethyl sulphide and Phaeocystis: A review

Dimethyl sulphide (DMS) is the dominant sulphur gas found in surface marine waters and there is compelling evidence that it is formed biologically in these environments. In all areas so far investigated the oceans are found to be highly supersaturated (typically by two orders of magnitude) with respect to atmospheric levels of DMS, which indicates a net flux of the gas out of the oceans. In this paper, we first briefly review the environmental importance of the gas and particularly the role of its sea-to-air flux on atmospheric chemistry and physics. Then we discuss what is known of its mode of formation and cycling in seawater, before looking more specifically at the role and significance of Phaeocystis as a producer of DMS.

Trophic interactions in the sea: An ecological role for climate relevant volatiles?

When attacked by herbivores, land plants can produce a variety of volatile compounds that attract carnivorous mutualists. Plants and carnivores can benefit from this symbiotic relationship, because the induced defensive interaction increases foraging success of the carnivores, while reducing the grazing pressure exerted by the herbivores on the plants. Here, we examine whether aquatic phytoplankton use volatile chemical cues in analogous tritrophic interactions. Marine algae produce several classes of biogenic gases such as non‐methane hydrocarbons, organohalogens, ammonia and methylamines, and dimethylsulfide. The grazing‐induced release of marine biogenic volatiles is poorly understood, however, and its effect on the chemical ecology of plankton and the foraging behavior of predators is essentially unknown. We outline grazing‐induced defenses in algae and highlight the biogenic production of volatiles when phytoplankton are attacked by herbivores. The role of chemical signaling in marine ecology presents several possible avenues for future research, and we believe that progress in this area will result in better understanding of species competition, bloom development, and the structuring of food webs in the sea. This has further implications for biogeochemical cycles, because several key compounds are emitted that influence the chemistry of the atmosphere and global climate.

A first appraisal of prognostic ocean DMS models and prospects for their use in climate models

Ocean dimethylsulfide (DMS) produced by marine biota is the largest natural source of atmospheric sulfur, playing a major role in the formation and evolution of aerosols, and consequently affecting climate. Several dynamic process-based DMS models have been developed over the last decade, and work is progressing integrating them into climate models. Here we report on the first international comparison exercise of both 1D and 3D prognostic ocean DMS models. Four global 3D models were compared to global sea surface chlorophyll and DMS concentrations. Three local 1D models were compared to three different oceanic stations (BATS, DYFAMED, OSP) where available time series data offer seasonal coverage of chlorophyll and DMS variability. Two other 1D models were run at one site only. The major point of divergence among models, both within 3D and 1D models, relates to their ability to reproduce the summer peak in surface DMS concentrations usually observed at low to mid- latitudes. This significantly affects estimates of global DMS emissions predicted by the models. The inability of most models to capture this summer DMS maximum appears to be constrained by the basic structure of prognostic DMS models: dynamics of DMS and dimethylsulfoniopropionate (DMSP), the precursor of DMS, are slaved to the parent ecosystem models. Only the models which include environmental effects on DMS fluxes independently of ecological dynamics can reproduce this summer mismatch between chlorophyll and DMS. A major conclusion of this exercise is that prognostic DMS models need to give more weight to the direct impact of environmental forcing (e.g., irradiance) on DMS dynamics to decouple them from ecological processes.

Determinations of dimethylsulphoniopropionate (DMSP) lyase activity using headspace analysis of dimethylsulphide (DMS)

Abstract The osmolyte dimethylsulphoniopropionate (DMSP) can be enzymatically cleaved to dimethylsulphide (DMS), acrylate and a proton. The enzyme involved in this reaction is dimethylpropiothetin dethiomethylase (DMSP lyase; enzyme classification number 4.4.1.3.). Although the importance of this reaction for the global sulphur cycle, the influence of DMS on atmospheric acidity and the possible effect on climate regulation have been widely recognised, our knowledge of DMSP lyases is limited to just a few studies. Activity measurements of DMSP lyases offer an important step towards a better understanding of the conditions under which DMS is produced. In the available published data somewhat similar methods have been used before, but a critical examination of the method limitations has not been reported. To encourage further research on this enzyme, we suggest and detail two protocols for measurements of DMSP lyase activity: An in vitro assay for crude cell extracts or purified enzyme and an in vivo method for whole cells, which we recently started to use. After addition of DMSP, samples incubated in a gas tight vial may produce DMS from enzymatic cleavage under suitable conditions, and a DMS production rate can be estimated from time-series measurements of DMS in the headspace of the vial. Headspace analysis of DMS is a useful and rapid technique to estimate and compare DMSP lyase activities from different sources. The relative rates of DMS production in the liquid and of the gas transfer between liquid and headspace, determine the rate of DMS production measured via headspace analysis. If DMS production in the liquid is higher than the rate of transfer, headspace measurements will not reflect the actual amount of DMS produced in the liquid. In this case, extracts have to be diluted to a level that ensures linearity between dilution factor and reduction of enzyme activity. Additionally, incubation volumes and vials should be selected to provide a high surface-to-volume ratio to ensure maximum flux of DMS from the aqueous phase into the headspace. The methods can be adapted to further investigate species- and strain-specific activities, biogeographical distribution, cellular location and biochemical properties of various DMSP lyases.

Vertical and temporal variability of DMSP lyase activity in a coccolithophorid bloom in the northern North Sea

The climatically relevant trace gas dimethyl sulphide (DMS) is produced within the microbial food-web from the algal metabolite dimethylsulphoniopropionate (DMSP). The presence of DMSP lyase isozymes is necessary for this process. Measurements of in vitro DMSP lyase activity (DLA) were conducted in the northern North Sea in June 1999 in order to investigate the vertical and temporal variability of activity in a Lagrangian time-series process study. DLA ranged from 4 to 207 nM h−1, with maximum values close to the surface and between 30 and 50 m depth. DLA increased towards the surface relative to chlorophyll a, as did the non-photosynthetic but photoprotective pigment diadinoxanthin, DMS and dissolved dimethylsulphoxide, a likely oxidation product of DMS. These observations support the hypothesis that DMSP lyases can be affected by irradiance levels, and that DMSP and its cleavage products could be involved in scavenging oxygen radicals; hence, they may function as antioxidants in marine algae. Linear regression analysis of our field data showed reduced biomass of some oligotrich and non-oligotrich ciliates at higher levels of DLA, a finding that could be supportive of a role for phytoplankton DMSP lyases in chemical defence.