Lucinda J. Spokes

Factors controlling the solubility of aerosol trace metals in the atmosphere and on mixing into seawater

Previous work has shown that the type and pH history of an aerosol governs trace metal solubility in rainwater. This study concentrates on the crustal elements Al, Fe and Mn and identifies additional processes which affect dissolution not only in the atmosphere but also on mixing into seawater. Aerosol dissolution experiments (at aerosol concentrations of about 30 mg 1−1) show manganese exhibiting high solubility at the low pH values typical of clouds (54±2.5% at pH 2, with results expressed in mole percent units) with 85% of this increase occurring within 6 hours of acidification. The percentage dissolution decreases to 50% at pH values representative of rainwater (pH 5.5) and to 26±4% at pH 8, typical of seawater. No such dramatic solution phase removal occurs at pH 8 in the presence of inorganic anions (to a final solubility of 44±2%). Thus the extent of manganese dissolution depends strongly on whether aerosols are cycled through acidic environments and on subsequent inorganic complexation once rainwater mixes into sea. Aluminium shows highest dissolution (7.1±0.6%) at low pH with 78% of this increase occurring within 6 hours of acidification. Rapid solution phase removal occurs on increasing the pH to that representative of rainwater (to 0.9±0.4% with 87% of this decrease occurring within 15 min). As a consequence of acid cycling and aluminiums amphoteric nature, solubility is enhanced at seawater pH (2.3±0.3%) over that in rain. Iron shows a strong pH-solubility relationship with highest solubility at low pH (4.7±0.2%), 70% of this value being reached within 6 hours of acidification, and decreasing rapidly to 0.17% as pH is raised to 8. Addition of inorganic anions at pH 8 to simulate mixing into seawater causes a further decrease in solubility, perhaps due to anion induced colloid destabilisation. Photochemical reduction also effects solubility under low pH conditions with Fe(II) comprising 1% of the total iron in the Saharan Aerosol used and 8.4% in an Urban material at a pH of ≈ 2. This element shows rapid solution phase removal with increasing particulate load which is tentatively rationalised in terms of a simple Kd approach.

Nitrogen deposition to the eastern Atlantic Ocean: The importance of south-easterly flow

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 (μ1 ¼m diameter) ammonium nitrate aerosol. In the coastal zone, nitric acid reacts with coarse mode seasalt aerosols to form coarse 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.

Comparisons of aerosol nitrogen isotopic composition at two polluted coastal sites

Abstract 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.

Photochemically induced redox reactions in seawater, I. Cations

Abstract Experiments have been conducted to determine whether the speciation of the manganese and iron redox couples can be influenced by light and organic matter in seawater. The results indicate that photochemically induced reduction of Mn(IV) to Mn(II) occurs through the mediation of humic acids. The rate of the reaction is dependent on many variables, some of which are identified here. Stirring plays an important role in the reductive dissolution process, the effect of which is dependent on the organic loading. It is suggested that this results from an adsorptive competition between organic matter and photoproduced reductants such as H 2 O 2 . Photochemically induced reduction reaction, at least in part, controls the speciation and thus biological availability of manganese in surface seawater. The results obtained from studies of the iron redox system show generally poor reproducibility and no conclusive evidence for photochemically induced reduction of Fe(III) under seawater conditions. These results are perhaps understandable given the fast reoxidation reactions by hydrogen peroxide and oxygen at seawater pH and the use of membrane filtration to separate soluble and insoluble iron. Reproducible results are obtained in stirred seawater and show a gradual decrease in levels of 0.2 μm filterable iron over time. The light replicates show a slower rate of iron loss from solution than in the dark. The possible implications of these results for iron bioavailability in seawater are discussed.

Photochemically induced redox reactions in seawater, II. Nitrogen and iodine

Abstract Experiments have been conducted to determine whether the speciation of the nitrate-nitrite and iodate-iodide redox couples is influenced by light and organic matter in both deionised and sea waters. The results obtained indicate that photochemical production of nitrite occurs and that the rate of this reaction is dependent on the concentration of organic matter present in the system. The findings suggest that nitrate undergoes not only direct photochemical reaction, acting itself as a primary chromophore, but also a photochemically induced reduction through organic matter. This reaction is, however, unlikely to influence productivity to any great extent as most phytoplankton can use both species as nutrients. It may, however, be a source of the highly reactive hydroxyl radical and of NO which has the potential to degas to the atmosphere and there help to regulate ozone concentration. Experiments conducted on the iodine redox system similarly indicate that photochemically induced production of iodide occurs. The results show that the reaction is not biologically mediated and that the presence of organic matter is essential for iodide photoproduction. At the concentrations of added iodate used in the experiments no direct 1:1 relationship between iodate and iodide is seen. It is suggested that, under these conditions, organic matter is not only essential for the photochemical production of iodide but that it is also the limiting species for the reduction reaction.

Atmospheric inputs of trace metals to the northeast Atlantic Ocean: The importance of southeasterly flow

The study of aerosols and rainwater presented here demonstrates that episodic atmospheric deposition events associated with southeasterly flow are quantitatively significant for large areas of the North Atlantic Ocean. This paper considers aluminium and manganese, with predominantly crustal sources, and lead and zinc, which are mobilised into the atmosphere primarily through anthropogenic activity. High levels of all trace metals are associated with southeasterly flow from Europe as the air passes over heavily populated and industrialised regions before reaching the northeast Atlantic Ocean. Fluxes calculated using the 1% HNO3 acid soluble metal concentration show that, although the climatological norm for this area is westerly flow, short-lived southeasterly transport events dominate the input of trace metals to this ocean region. This material may be toxic to phytoplankton or may be represent a new source of nutrients to the biological community. A significant decrease in atmospheric lead levels in polluted air is seen between June 1996 and May 1997, reflecting the decrease in use of leaded fuels in Europe. Comparing atmospheric flux values to sediment trap metal fluxes shows that the atmosphere represents the dominant source of zinc to the deep ocean, whereas an additional, non-atmospheric, manganese source this required, perhaps from mobilisation of sedimentary material from the continental shelf or long range advection of manganese rich Saharan material.

The role of organic matter in controlling copper speciation in precipitation

Abstract 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.

Atmospheric input of nitrogen into the North Sea: ANICE project overview.

The aim of the atmospheric nitrogen inputs into the coastal ecosystem (ANICE) project is to improve transport-chemistry models that estimate nitrogen deposition to the sea. To achieve this, experimental and modelling work is being conducted which aims to improve understanding of the processes involved in the chemical transformation, transport and deposition of atmospheric nitrogen compounds. Of particular emphasis within ANICE is the influence of coastal zone processes. Both short episodes with high deposition and chronic nitrogen inputs are considered in the project. The improved transport-chemistry models will be used to assess the atmospheric inputs of nitrogen compounds into the European regional seas (the North Sea is studied as a prototype) and evaluate the impact of various emission reduction strategies on the atmospheric nitrogen loads. Assessment of the impact of atmospheric nitrogen on coastal ecosystems will be based on comparisons of phytoplankton nitrogen requirements, other external nitrogen inputs to the ANICE area of interest and the direct nitrogen fluxes provided by ANICE. Selected results from both the experimental and modelling components are presented here. The experimental results show the large spatial and temporal variability in the concentrations of gaseous nitrogen compounds, and their influences on fluxes. Model calculations show the strong variation of both concentrations and gradients of nitric acid at fetches of up to 25km. Aerosol concentrations also show high temporal variability and experimental evidence for the reaction between nitric acid and sea salt aerosol is provided by size-segregated aerosol composition measured at both sides of the North Sea. In several occasions throughout the experimental period, air mass back trajectory analysis showed connected flow between the two sampling sites (the Weybourne Atmospheric Observatory on the North Norfolk coast of the UK and Meetpost Noordwijk, a research tower at 9km off the Dutch coast). Results from the METRAS/SEMA mesoscale chemistry transport model system for one of these cases are presented. Measurements of aerosol and rain chemical composition, using equipment mounted on a commercial ferry, show variations in composition across the North Sea. These measurements have been compared to results obtained with the transport-chemistry model ACDEP which calculates the atmospheric inputs into the whole North Sea area. Finally, the results will be made available for the assessment of the impact of atmospheric nitrogen on coastal ecosystems.

Deposition of nitrogen into the North Sea

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.

Intercomparison of elemental concentrations in total and size-fractionated aerosol samples collected during the mace head experiment, April 1991

Abstract 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.