Search

Atmospheric fixed-nitrogen deposition can contribute to eutrophication in coastal and estuarine waters. Stable nitrogen isotope data can provide important information regarding the sources and processing of atmospheric fixed-nitrogen species and is thus important in controlling eutrophication. Size-segregated aerosol samples were collected from two coastal sites: Weybourne, England and Mace Head, Ireland and also aboard the RRS Challenger in the Eastern Atlantic Ocean. Aerosol concentrations of ammonium and nitrate were determined prior to δ 15 N isotopic analysis. The isotopic enrichment factor, e , was calculated for both the species by subtracting the respective δ 15 N values of the coarse-mode fraction (>1 μm diameter) from those of the fine-mode fraction ( 4 NO 3 followed by scavenging of the HNO 3 produced appears to be significantly more important than in samples of onshore, marine dominated air. In contrast, ammonium appears to be transferred to the coarse mode during offshore flow largely via the dissolution and coagulation of aerosol ammonium, nitrate and sulphate-containing species. During onshore flow, the uptake of gaseous NH 3 , arising from the continued dissociation of NH 4 NO 3 , seems to become increasingly important.

Direct atmospheric fixed-nitrogen deposition can contribute to eutrophication in coastal and estuarine waters and can be enhanced by heterogeneous reactions between gaseous atmospheric nitrogen species and aerosol sea salt, which increase deposition rates. Size-segregated aerosol samples were collected from two coastal sites: Weybourne, England and Mace Head, Ireland. Major-ion aerosol concentrations were determined and temporal patterns were interpreted with the use of air-mass back trajectories. Low levels of terrestrially derived material were seen during periods of clean, onshore flow, with respective concentration ranges for nitrate and ammonium of 0.47–220 and below detection limit to 340 nmol m −3 . Corresponding levels of marine derived material during these periods were high, with sodium concentrations ranging from 39 to 1400 nmol m −3 . Highest levels of terrestrially derived material were seen during polluted, offshore flow, where the air had passed recently over strong source regions of the UK and northern Europe, with concentration ranges of nitrate and ammonium of 5.6–790 and 9.7–1000 nmol m −3 , respectively. During polluted flow ∼40–60% of the nitrate was found in the coarse mode (>1 μm diameter) and under clean marine conditions almost 100% conversion was seen. In addition, our data suggests strong evidence for dissolution/coagulation processes that also shift nitrate to the coarse mode. Furthermore, such processes are thought also to give rise to the size-shifting of aerosol ammonium, since significant coarse-mode fractions of this species (∼19–45%) were seen at both sites. A comparison of the relative importance of nitrate and ammonium in the overall dry deposition of inorganic fixed-nitrogen at each site indicates that at Weybourne the mass-weighted dry deposition velocity of the latter is around double that seen at Mace Head with its resultant contribution to the overall inorganic nitrogen dry flux exceeding that of nitrate.

Atmospheric fixed-nitrogen deposition can contribute to eutrophication in coastal and estuarine waters. Stable nitrogen isotope data can provide important information regarding the sources and processing of atmospheric fixed-nitrogen species and is thus important in controlling eutrophication. Size-segregated aerosol samples were collected from two coastal sites: Weybourne, England and Mace Head, Ireland and also aboard the RRS Challenger in the Eastern Atlantic Ocean. Aerosol concentrations of ammonium and nitrate were determined prior to δ15N isotopic analysis. For both species a significant difference in mean isotopic composition was seen between samples from Weybourne ( +6±6‰ for ammonium and +7±6‰ for nitrate) and Mace Head and RRS Challenger campaigns ( −9±8‰ for ammonium and −1±3‰ for nitrate). At each site a strong dependence of isotopic composition on the geographical origin of the sampled air mass was also observed. For aerosol ammonium, marine and terrestrially dominated samples were found to be isotopically distinct, perhaps reflecting the presence of oceanic sources of ammonia in addition to anthropogenic or natural terrestrial sources. Further distinctions were made within terrestrially dominated samples, possibly indicative of different types of animal husbandry regimes or other forms of anthropogenic activity. For aerosol nitrate, there was found to be generally less variation between samples at each site, although at Weybourne a significant difference was observed between the mean isotopic composition of samples originating from the northern UK ( +15±3‰ ) and that of those originating from the southern UK (+10±3‰) , suggesting that aerosol δ15N data might possibly facilitate source apportionment between NOx emissions from power stations and those from vehicle exhausts. The nitrate data also appeared to show seasonality with higher concentrations and lower δ15N values seen in the summer.

Converting measured concentrations into fluxes and using estimates of biological productivity in the coastal waters of the eastern Atlantic Ocean enables us to determine the role of the atmosphere as a source of biologically essential species, including nitrate and ammonium, to the marine biota. To understand the effects of the atmosphere as a source of nitrogen capable of promoting new production, we need to know both the seasonality of the input as well as the effects of extreme high deposition events which, while small in overall annual budget terms, maybe able to extend, or even promote, phytoplankton growth under nutrient depleted summer conditions. Aerosols and rainwater were collected at both Mace Head and at sea aboard RRS Challenger. Temporal patterns have been interpreted using airmass back trajectories which give the predicted air path prior to arrival at the sampling site. Low levels of both nitrate and ammonium are seen associated with marine westerly flow across the Atlantic and northerly air originating in the Arctic region. As expected, marine derived sodium, chloride, magnesium and seasalt sulphate are high during these periods. High concentration nitrate and ammonium events are seen associated with south-easterly flow where the airmass passes over the UK and northern Europe prior to arrival on the west coast of Ireland. In the polluted atmosphere, nitrate exists as nitric acid and as fine mode (1 μm diameter) sodium nitrate: HNO3 (g) + NaCl(s) → NaNO3(s) + HCl(g). This seasalt displacement reaction not only enhances dry nitrate deposition through more efficient gravitational settling of large particles, but also increases the efficiency of precipitational scavenging via inertial impaction. By looking at the size distribution of nitrate, we can see evidence for the seasalt displacement reaction. Under the polluted south-easterly flow, ∼40−60% of the nitrate occurs in the coarse mode fraction. Under clean marine conditions, the seasalt displacement reaction results in almost complete conversion of nitrate from the fine to the coarse aerosol mode. By converting measured wet and dry nitrate, ammonium and organic nitrogen concentrations into fluxes and comparing the data with estimates of biological productivity in the surface waters, our data suggest that ∼30% of new production in eastern Atlantic surface waters off Ireland can be supported by atmospheric inputs in May 1997 and that most of the input occurs during short lived, high-concentration, south-easterly transport events.DOI: 10.1034/j.1600-0889.2000.00062.x

Organic complexation has been suggested to be an important mechanism by which the biogeochemistry of transition metals is altered in natural waters. We have conducted complexing ligand titrations on rainwater, collected during the winter and spring from a semi-urban U.K. location, using cathodic stripping voltammetry with tropolone as the added ligand. The results show that organic ligands capable of binding copper are present in all the precipitation samples measured. As a consequence of the method used, only those copper-natural ligand complexes with conditional stability constants (1 : 1 stoichiometry-log K CuL ′) between 11 and 14 have been identified. Within this stability region, ligand concentrations vary from 10.2 to 34.5 nM, very similar to the total copper levels which range between 10.2 and 33.2 nM. While total copper has a concentration of the order of 10 −8 M, free Cu 2+ ions exist at levels of just 10 −11 −10 −12 M, showing that copper is largely complexed in the rainwater samples measured. The existence of such low free ion concentrations must be considered when assessing the catalytic role of rain and aerosol trace metals in atmospheric reactions and determining the impact of atmospheric inputs on surface water biogeochemistry. Conditional stability constants increase with the detection window used (from log K CuL ′) = 11.4 at a detection window centred at log α CuAL = 2.68 to log K CuL ′) = 12.57 at log α CuAL = 4.47). As the method is specific to a limited range of conditional stabilities, dependent on the strength and amount of competitive ligand used, this concentration dependence suggests the presence of a wider range of natural ligands than those identified here. The source of the organic complexant in precipitation is unclear. We postulate, based on stable isotope measurements made on rains collected at the same location (Cornell et al. , 1995), that the organic ligands are likely to be terrestrial in origin.

THE concentrations of bioavailable iron in the surface waters of some ocean regions may indirectly modulate climate by controlling phytoplankton productivity and thus the amounts of carbon dioxide1 and dimethyl sulphide (DMS) that are exchanged with the atmosphere. Oxidation of DMS is involved in the formation of atmospheric sulphate particles, which can exert a climate cooling effect2 directly (by scattering and absorbing solar radiation), and indirectly (by affecting cloudiness and hence global albedo). But direct evidence supporting the hypothesis that DMS production in the ocean is affected by iron availability is lacking. Here we report changes in the concentrations of DMS in response to in situ iron-enrichment during two ecosystem-scale experiments designed to investigate the biological and chemical effects of iron fertilization of under-productive surface ocean waters3,4. The first such experiment revealed a limited overall biological response3 and no significant changes in DMS concentrations, although the concentrations of its biochemical precursor doubled5. The second experiment, designed to better mimic the natural process of iron enrichment, elicited a much stronger biological response4, and DMS concentrations increased by a factor of 3.5. This result provides direct support for an important link in the iron–DMS–climate hypothesis.

During an intercomparison field experiment, organized at the Atlantic coast station of Mace Head, Ireland, in April 1991, aerosol samples were collected by four research groups. A variety of samplers was used, combining both high- and low-volume devices, with different types of collection substrates: Hi-Vol Whatman 41 filter holders, single Nuclepore filters and stacked filter units, as well as PIXE cascade impactors. The samples were analyzed by each participating group, using in-house analytical techniques and procedures. The intercomparison of the daily concentrations for 15 elements, measured by two or more participants, revealed a good agreement for the low-volume samplers for the majority of the elements, but also indicated some specific analytical problems, owing to the very low concentrations of the non-sea-salt elements at the sampling site. With the Hi-Vol Whatman 41 filter sampler, on the other hand, much higher results were obtained in particular for the sea-salt and crustal elements. The discrepancy was dependent upon the wind speed and was attributed to a higher collection efficiency of the Hi-Vol sampler for the very coarse particles, as compared to the low-volume devices under high wind speed conditions. The elemental mass size distribution, as derived from parallel cascade impactor samplings by two groups, showed discrepancies in the submicrometer aerosol fraction, which were tentatively attributed to differences in stage cut-off diameters and/or to bounce-off or splintering effects on the quartz impactor slides used by one of the groups. However, the atmospheric concentrations (sums over all stages) were rather similar in the parallel impactor samples and were only slightly lower than those derived from stacked filter unit samples taken in parallel.

[1] Ammonium salts represent a major component of fine mode marine aerosol that play an important role in climate regulation, atmospheric pH control and nutrient supply to the oceans. We report here the results of analyses of aerosol samples collected in remote areas of the Atlantic Ocean. We show the isotopic abundance of aerosol ammonium varies with concentration, with isotopically light ammonium (−5 to −8‰) associated with the lowest ammonium concentrations compared to isotopically heavy ammonium (+10‰) associated with higher ammonium concentrations. We interpret the light ammonium signature as arising from marine emissions of ammonia. These results provide further evidence for the existence of a marine ammonia source and offers a method to define the relative contribution of marine and terrestrial ammonium to aerosols in remote areas and thereby investigate the role of these emissions in climate regulation.

The flux of nitrogen species from the atmosphere into the ocean, with emphasis on coastal waters, was addressed during the ANICE project (Atmospheric Nitrogen Inputs into the Coastal Ecosystem). ANICE focused on quantifying the deposition of atmospheric inputs of inorganic nitrogen compounds (HNO3, NO3-, NH3 and NH4+) into the North Sea and the processes governing this deposition. The Southern North Sea was studied as a prototype. Because the physical and chemical processes are described, as opposed to empirical relations, the results can potentially be transferred to other regional seas like the Mediterranean, the North Atlantic continental shelf area and the Baltic. Two intensive field experiments were undertaken, centred around the offshore tower Meetpost Noordwijk and the Weybourne Atmospheric Observatory in East Anglia (UK). Long-term measurements were made on a ferry sailing between Hamburg and Harwich/Newcastle. These measurements provided data for sensitivity studies of a variety of problems associated with the coastal region that are not easily evaluated with larger scale models, to constrain models and to test model results. Concentrations of nitrogen compounds over the North Sea and the resulting deposition presented in this paper were obtained with the Lagrangian transport-chemistry model ACDEP. The average annual deposition in 1999 was 906kg Nkm-2. The results are compared with experimental data from the ferry. Effects of temporal and spatial variations are evaluated based on experimental results and small-scale model studies. In particular, effects of the aerosol size distribution on the nitrogen deposition are discussed. © 2003 Elsevier Ltd. All rights reserved.

Dissection of the basilar artery caused sudden coma and death in a 40-year-old man. Atypical clinical features were explained at necropsy. A ventral dissection of the artery within its outer layers resulted in destruction of the pontine tegmentum with sparing of the basis pontis. An unsuspected defect in the internal elastic lamina in the left internal carotid artery was also found suggesting a more generalised disorder of arterial walls. Basilar artery dissection should be considered in the diagnosis of coma in young people.

The ANICE (Atmospheric Nitrogen Inputs into the Coastal Ecosystem) project addressed the atmospheric deposition of nitrogen to the North Sea, with emphasis on coastal effects. ANlCE focused on quantifying the deposition of inorganic nitrogen compounds to the North Sea and the governing processes. An overview of the results from modelling and experimental efforts is presented. They serve to identify the role of the atmosphere as a source of biologically essential chemical species to the marine biota. Data from the Weybourne Atmospheric Observatory (UK) are used to evaluate the effect of short episodes with very high atmospheric nitrogen concentrations. One such episode resulted in an average deposition of 0.8 mmol N m-2 day-1, which has the potential to promote primary productivity of 5.3 mmol C m-2 day-1. This value is compared to long-term effects determined from model results. The total calculated atmospheric deposition to the North Sea in 1999 is 948 kg N km-1, i.e. 0.19 mmol N m-2 day -1 which has the potential to promote primary productivity of 1.2 mmol C m-2 day-1. Detailed results for August 1999 show strong gradients across the North Sea due to adjacent areas where emissions of NOx and NH3 are among the highest in Europe. The average atmospheric deposition to the southern part of the North Sea in August 1999 could potentially promote primary production of 2.0 mmol C m-2 day-1, i.e. ∼ 5.5% of the total production at this time of the year in this area of the North Sea. For the entire study area the atmospheric contribution to the primary production per m2 is about two-third of this value. Most of the deposition occurs during short periods with high atmospheric concentrations. This atmospheric nitrogen is almost entirely anthropogenic in origin and thus represents a human-induced perturbation of the ecosystem. © 2003 Elsevier Ltd. All rights reserved.

This paper summarises the results of the EU funded MEAD project, an interdisciplinary study of the effects of atmospheric nitrogen deposition on the Kattegat Sea between Denmark and Sweden. The study considers emissions of reactive nitrogen gases, their transport, transformations, deposition and effects on algal growth together with management options to reduce these effects. We conclude that atmospheric deposition is an important source of fixed nitrogen to the region particularly in summer, when nitrogen is the limiting nutrient for phytoplankton growth, and contributes to the overall eutrophication pressures in this region. However, we also conclude that it is unlikely that atmospheric deposition can, on its own, induce algal blooms in this region. A reduction of atmospheric nitrogen loads to this region will require strategies to reduce emissions of ammonia from local agriculture and Europe wide reductions in nitrous oxide emissions. 2005 Elsevier Ltd. All rights reserved.

Jickells, T.D. ... et. al.-- 34 pages, 6 tables, 10 figures We report the results of an experiment in the Northeast Atlantic in which sulphur hexafluoride (SF6) was released within an eddy and the behaviour of trace gases, nutrients and productivity followed within a Lagrangian framework over a period of 24 days. Measurements were also made in the air above the eddy in order to estimate air–sea exchange rates for some components. The physical, biological and biogeochemical properties of the eddy resemble those of other eddies studied in this area, suggesting that the results we report may be applicable beyond the specific eddy studied. During a period of low wind speed at the start of the experiment, we are able to quantitatively describe and balance the nutrient and carbon budgets for the eddy. We also report concentrations of various trace gases in the region which are similar to those observed in other studies and we estimate exchange rates for several trace gases. We show that the importance of gas exchange over other loss terms varies with time and also varies for the different gases. We show that the various trace gases considered (CO2, dimethyl sulphide (DMS), N2O, CH4, non-methane-hydrocarbons, methyl bromide, methyl iodide and volatile selenium species) are all influenced by physical and biological processes, but the overall distribution and temporal variability of individual gases are different to one another. A storm disrupted the stratification in the eddy during the experiment, resulting in enhanced nutrient supply to surface waters, enhanced gas exchange rates and a change in plankton community, which we quantify, although overall productivity was little changed. Emphasis is placed on the regularity of storms in the temperate ocean and the importance of these stochastic processes in such systems This is contribution no. ACP175 of the NERC ACSOE Thematic Programme. NERC grants GST/02/1276 supported the work of Jickells and Spokes, GST/02/1278 the work of Liss and Nightingale together with core funding to the Plymouth Marine Laboratory (PML) while the ACSOE core programme supported Broadgate and the shiptime costs, NERC grant GR9/3467 to G.S. supported Moncoiffé and Gilpin. Steinke was supported by NERC grant GR3/10956. The University of Newcastle upon Tyne Research Committee provided funding to support T. Frost. The work of Simó and Pedrós-Alió was supported by the Spanish McyT grant MAR97-1885-E