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The discovery of atmospheric micro(nano)plastic transport and ocean-atmosphere exchange points to a highly complex marine plastic cycle, with negative implications for human and ecosystem health. Yet, observations are currently limited. In this Perspective, we quantify the processes and fluxes of the marine-atmospheric micro(nano)plastic cycle, with the aim of highlighting the remaining unknowns in atmospheric micro(nano)plastic transport. Between 0.013 and 25 million metric tons per year of micro(nano)plastics are potentially being transported within the marine atmosphere and deposited in the oceans. However, the high uncertainty in these marine-atmospheric fluxes is related to data limitations and a lack of study intercomparability. To address the uncertainties and remaining knowledge gaps in the marine-atmospheric micro(nano)plastic cycle, we propose a future global marine-atmospheric micro(nano)plastic observation strategy, incorporating novel sampling methods and the creation of a comparable, harmonized and global data set. Together with long-term observations and intensive investigations, this strategy will help to define the trends in marine-atmospheric pollution and any responses to future policy and management actions. Atmospheric transport of microplastics could be a major source of plastic pollution to the ocean, yet observations currently remain limited. This Perspective quantifies the known budgets of the marine-atmospheric micro(nano)plastic cycle and proposes a future global observation strategy.

To mark the publication of the special collection in honor of Robert (Bob) A. Duce in the Journal of the Atmospheric Sciences, we have summarized his most important contributions to the subject of biogeochemical coupling between the atmosphere and ocean. Here we have divided these contributions into four themes—deposition from the atmosphere and its effects on the oceans, volatile elements emitted from the oceans, sea surface biology and aerosol formation, and marine aerosols and clouds. It is our intent that this summary along with the papers in this special collection provide an overview of the enormous contributions that Bob Duce has made to the subject during his distinguished scientific career.

Changing atmospheric acidity alters the delivery of nutrients to the ocean and affects marine productivity and ecology., Anthropogenic emissions to the atmosphere have increased the flux of nutrients, especially nitrogen, to the ocean, but they have also altered the acidity of aerosol, cloud water, and precipitation over much of the marine atmosphere. For nitrogen, acidity-driven changes in chemical speciation result in altered partitioning between the gas and particulate phases that subsequently affect long-range transport. Other important nutrients, notably iron and phosphorus, are affected, because their soluble fractions increase upon exposure to acidic environments during atmospheric transport. These changes affect the magnitude, distribution, and deposition mode of individual nutrients supplied to the ocean, the extent to which nutrient deposition interacts with the sea surface microlayer during its passage into bulk seawater, and the relative abundances of soluble nutrients in atmospheric deposition. Atmospheric acidity change therefore affects ecosystem composition, in addition to overall marine productivity, and these effects will continue to evolve with changing anthropogenic emissions in the future.

An ocean iodine cycling model is presented, which predicts upper ocean iodine speciation. The model comprises a three-layer advective and diffusive ocean circulation model of the upper ocean, and an iodine cycling model embedded within this circulation. The two primary reservoirs of iodine are represented, iodide and iodate. Iodate is reduced to iodide in the mixed layer in association with primary production, linked by an iodine to carbon (I:C) ratio. A satisfactory model fit with observations cannot be obtained with a globally constant I:C ratio, and the best fit is obtained when the I:C ratio is dependent on sea surface temperature, increasing at low temperatures. Comparisons with observed iodide distributions show that the best model fit is obtained when oxidation of iodide back to iodate is associated with mixed layer nitrification. Sensitivity tests, where model parameters and processes are perturbed, reveal that primary productivity, mixed layer depth, oxidation, advection, surface fresh water flux and the I:C ratio all have a role in determining surface iodide concentrations, and the timescale of iodide in the mixed layer is sufficiently long for non-local processes to be important. Comparisons of the modelled iodide surface field with parameterisations by other authors shows good agreement in regions where observations exist, but significant differences in regions without observations. This raises the question of whether the existing parameterisations are capturing the full range of processes involved in determining surface iodide, and shows the urgent need for observations in regions where there are currently none.

Air pollution creates high Fe solubility in pyrogenic aerosols, raising the flux of biologically essential Fe to the oceans., Atmospheric deposition is a source of potentially bioavailable iron (Fe) and thus can partially control biological productivity in large parts of the ocean. However, the explanation of observed high aerosol Fe solubility compared to that in soil particles is still controversial, as several hypotheses have been proposed to explain this observation. Here, a statistical analysis of aerosol Fe solubility estimated from four models and observations compiled from multiple field campaigns suggests that pyrogenic aerosols are the main sources of aerosols with high Fe solubility at low concentration. Additionally, we find that field data over the Southern Ocean display a much wider range in aerosol Fe solubility compared to the models, which indicate an underestimation of labile Fe concentrations by a factor of 15. These findings suggest that pyrogenic Fe-containing aerosols are important sources of atmospheric bioavailable Fe to the open ocean and crucial for predicting anthropogenic perturbations to marine productivity.

We report a new synthesis of best estimates of the inputs of fixed nitrogen to the world ocean via atmospheric deposition and compare this to fluvial inputs and dinitrogen fixation. We evaluate the scale of human perturbation of these fluxes. Fluvial inputs dominate inputs to the continental shelf, and we estimate that about 75% of this fluvial nitrogen escapes from the shelf to the open ocean. Biological dinitrogen fixation is the main external source of nitrogen to the open ocean, i.e., beyond the continental shelf. Atmospheric deposition is the primary mechanism by which land-based nitrogen inputs, and hence human perturbations of the nitrogen cycle, reach the open ocean. We estimate that anthropogenic inputs are currently leading to an increase in overall ocean carbon sequestration of ~0.4% (equivalent to an uptake of 0.15 Pg C yr−1 and less than the Duce et al. (2008) estimate). The resulting reduction in climate change forcing from this ocean CO2 uptake is offset to a small extent by an increase in ocean N2O emissions. We identify four important feedbacks in the ocean atmosphere nitrogen system that need to be better quantified to improve our understanding of the perturbation of ocean biogeochemistry by atmospheric nitrogen inputs. These feedbacks are recycling of (1) ammonia and (2) organic nitrogen from the ocean to the atmosphere and back, (3) the suppression of nitrogen fixation by increased nitrogen concentrations in surface waters from atmospheric deposition, and (4) increased loss of nitrogen from the ocean by denitrification due to increased productivity stimulated by atmospheric inputs.

The atmospheric deposition of both macronutrients and micronutrients plays an important role in driving primary productivity, particularly in the low-latitude ocean. We report aerosol major ion measurements for five ship-based sampling campaigns in the western Pacific from similar to 25 degrees N to 20 degrees S and compare the results with those from Atlantic meridional transects (similar to 50 degrees N to 50 degrees S) with aerosols collected and analyzed in the same laboratory, allowing full incomparability. We discuss sources of the main nutrient species (nitrogen (N), phosphorus (P), and iron (Fe)) in the aerosols and their stoichiometry. Striking north-south gradients are evident over both basins with the Northern Hemisphere more impacted by terrestrial dust sources and anthropogenic emissions and the North Atlantic apparently more impacted than the North Pacific. We estimate the atmospheric supply rates of these nutrients and the potential impact of the atmospheric deposition on the tropical western Pacific. Our results suggest that the atmospheric deposition is P deficient relative to the needs of the resident phytoplankton. These findings suggest that atmospheric supply of N, Fe, and P increases primary productivity utilizing some of the residual excess phosphorus (P*) in the surface waters to compensate for aerosol P deficiency. Regional primary productivity is further enhanced via the stimulation of nitrogen fixation fuelled by the residual atmospheric iron and P*. Our stoichiometric calculations reveal that a P* of 0.1 mu mol L-1 can offset the P deficiency in atmospheric supply for many months. This study suggests that atmospheric deposition may sustain similar to 10% of primary production in both the western tropical Pacific.

Dissolved iron (dFe) distributions and atmospheric and vertical subduction fluxes of dFe were determined in the upper water column for two meridional transects of the Atlantic Ocean. The data demonstrate the disparity between the iron biogeochemistry of the North and South Atlantic Ocean and show well-defined gradients of size fractionated iron species in surface waters between geographic provinces. The highest dFe and lowest mixed layer residence times (0.4–2.5 years) were found in the northern tropical and subtropical regions. In contrast, the South Atlantic Gyre had lower dFe concentrations ( 5 years), presumably due to lower atmospheric inputs and more efficient biological recycling of iron in this region. Vertical input fluxes of dFe to surface waters ranged from 20 to 170 nmol m–2 d–1 in the North Atlantic and tropical provinces, whereas average fluxes of 6–13 nmol m–2 d–1 were estimated for the South Atlantic. Our estimates showed that the variable dFe distribution over the surface Atlantic ( 50% of total vertical Fe flux to surface waters) rather than upwelling or vertical mixing. This demonstrates the strength of the connection between land-derived atmospheric Fe fluxes and the biological cycling of carbon and nitrogen in the Atlantic Ocean.

Atmospheric inputs of mineral dust supply iron and other trace metals to the remote ocean and can influence the marine carbon cycle due to iron's role as a potentially limiting micronutrient. Dust generation, transport, and deposition are highly heterogeneous, and there are very few remote marine locations where dust concentrations and chemistry (e.g., iron solubility) are routinely monitored. Here we use aerosol and rainwater samples collected during 10 large-scale research cruises to estimate the atmospheric input of iron, aluminum, and manganese to four broad regions of the Atlantic Ocean over two 3month periods for the years 2001-2005. We estimate total inputs of these metals to our study regions to be 4.2, 17, and 0.27Gmol in April-June and 4.9, 14, and 0.19Gmol in September-November, respectively. Inputs were highest in regions of high rainfall (the intertropical convergence zone and South Atlantic storm track), and rainfall contributed higher proportions of total input to wetter regions. By combining input estimates for total and soluble metals for these time periods, we calculated overall percentage solubilities for each metal that account for the contributions from both wet and dry depositions and the relative contributions from different aerosol types. Calculated solubilities were in the range 2.4%-9.1% for iron, 6.1%-15% for aluminum, and 54%-73% for manganese. We discuss sources of uncertainty in our estimates and compare our results to some recent estimates of atmospheric iron input to the Atlantic.

The results of fine mode ( 2 or methane sulphonic acid (MSA). Using our estimates of marine biogenic sulphate and measurements of MSA concentrations we confirm that the ratio of MSA/sulphate from DMS oxidation increases systematically from low to high latitudes, consistent with the laboratory measurements, inferences from field studies and modelling predictions of others.

We report aerosol ammonium 15 N signatures for samples collected from research cruises on the South Atlantic and Caribbean using a new high sensitivity method. We confirm a pattern of isotopic signals from generally light (δ 15 N −5 to −10‰), for aerosols with very low ( −3 ) ammonium concentrations from the remote high latitude ocean, to generally heavier values (δ 15 N +5 to +10‰), for aerosols collected in temperate and tropical latitudes and with higher ammonium concentrations (>2 nmol m −3 ). We discuss whether this reflects a mixing of aerosols from two end-members (polluted continental and remote marine emissions), or isotopic fractionation during aerosol transport.

This review considers the ways in which atmospheric organic nitrogen has been measured and linked to potential sources. Organic N exists in gas, particle and dissolved phases and represents a large (ca. 30%) fraction of total airborne nitrogen, but with large variability in time and space. Although some components (e.g. amines) have been the subject of several studies, little information is available for the many other components of organic N that have been identified in individual measurements. Measurements of organic N in precipitation have been made for many decades, but both sampling and chemical analytical methods have changed, resulting in data that are not directly comparable. Nevertheless, it is clear that organic N is ubiquitous and chemically complex. We discuss some of the issues which have inhibited the widespread adoption of organic N as a routine analyte in atmospheric sampling, and identify current best practice. Correlation analysis is the most widely used technique for attributing likely sources, examining the co-variation in time and/or space of organic N with other components of precipitation or particulate matter, yet the shortcomings of such simple approaches are rarely recognised. Novel measurement techniques which can identify, if not yet quantify, many of the components of particulate or dissolved organic N greatly enhance the data richness, thereby permitting powerful statistical analyses of co-variation such as factor analysis, to be employed. However, these techniques also have their limitations, and whilst specific questions about the origin and fate of particular components of atmospheric organic N may now be addressed, attempts to quantify and attribute the whole suite of materials that comprise atmospheric organic N to their sources is still a distant goal. Recommendations are made as to the steps that need to be taken if a consistent and systematic approach in identifying and quantifying atmospheric organic N is to progress. Only once sources have been recognised can any necessary control measures to mitigate adverse effects of atmospheric organic N on human health or ecosystem function be determined.

Atmospheric deposition contributes potentially significant amounts of the nutrients iron, nitrogen, and phosphorus (via mineral dust and anthropogenic aerosols) to the oligotrophic tropical North Atlantic Ocean. Transport pathways, deposition processes, and source strengths contributing to this atmospheric flux are all highly variable in space and time. Atmospheric sampling was conducted during 28 research cruises through the eastern tropical North Atlantic (ETNA) over a 12-yr period, and a substantial dataset of measured concentrations of nutrients and trace metals in aerosol and rainfall over the region was acquired. This database was used to quantify (on a spatial and seasonal basis) the atmospheric input of ammonium, nitrate, soluble phosphorus, and soluble and total iron, aluminum, and manganese to the ETNA. The magnitude of atmospheric input varies strongly across the region, with high rainfall rates associated with the intertropical convergence zone contributing to high wet deposition fluxes in the south, particularly for soluble species. Dry deposition fluxes of species associated with mineral dust exhibited strong seasonality, with the highest fluxes associated with wintertime low-level transport of Saharan dust. Overall (wet plus dry) atmospheric inputs of soluble and total trace metals were used to estimate their soluble fractions. These also varied with season and were generally lower in the dry north than in the wet south. The ratio of ammonium plus nitrate to soluble iron in deposition to the ETNA was lower than the N:Fe requirement for algal growth in all cases, indicating the importance of the atmosphere as a source of excess iron.

Atmospheric concentrations of trace metals over the oceans are investigated through analysis of aerosol samples collected during cruises from the UK to the Falkland Islands and from South Africa to Australia. The readily soluble concentrations of Cu (4–256 pmol m−3), Ni (0.1–54 pmol m−3), Ba (0.2–60 pmol m−3), Zn (6–316 pmol m−3), Cd (0.01–0.29 pmol m−3) and Pb (0.4–22 pmol m−3) were measured in the aerosols, along with total concentrations of crustal elements (Fe, Al and Mn) to evaluate the crustal contributions. Air mass back trajectories suggested most of the aerosol samples had spent several days over the ocean prior to collection. The highest metal concentrations were observed in aerosols close to South Africa, Australia and major cities in South America, although these concentrations were lower than had been reported previously in the literature. Apart from Ba, which had a major crustal source, the trace metals were enriched relative to crustal sources in most samples, including some collected thousands of kilometers from emission sources. The mean trace metal concentrations in the remote Indian Ocean were lower than those measured in the Atlantic Ocean. Even lower concentrations are reported in the literature for the remote Pacific Ocean. In contrast to previous studies, no clear north–south gradient is observed in the concentrations of the trace metals in the aerosols. Lead isotope measurements were also carried out on aerosol samples using a multicollector inductively coupled plasma mass spectrometer to assist in source apportionment. Clear differences were noted in the isotope ratios collected on either side of the Indian Ocean with Australian lead ore dominating over much of the eastern and mid-southern Indian Ocean. Samples collected over the western Indian Ocean and Atlantic Ocean under South African influence had lead isotopes quite different from those seen in South African cities in the past, and are closer in ratio to the coal signature of the region.

A new method is presented to analyse the isotopic abundance of organic matter in aerosols. The method involves water extraction of aerosol filters, elution through an ion retardation resin to remove inorganic components and lyophilising the eluent to concentrate the fraction prior to isotopic analysis. Results of analyses of a series of aerosol samples collected in the UK, for the fraction of organic matter passing through the resin, are presented. Carbon and nitrogen isotopic abundances ranged from −23.0‰ to −35.5‰ (versus PDB) and −14.6‰ to +12.5‰ (versus AIR), respectively.

Despite over a century of published reports of dissolved organic nitrogen (DON) in precipitation, its implications are still being appraised. The number of studies focusing on atmospheric organic nitrogen deposition has increased steadily in recent years, but comparatively little has been done to draw together this disparate knowledge. This is partly a consequence of valid concerns about the comparability of analysis and sampling methodologies. Given the current global trends in anthropogenic nitrogen fixation, an improved qualitative and quantitative understanding of the organic nitrogen component is needed to complement the well-established knowledge base pertaining to nitrate and ammonium deposition. This global review confirms the quantitative importance of bulk DON in precipitation. This cumulative data set also helps to resolve some of the uncertainty that arises from the generally locally and temporally limited scale of the individual studies. Because of analytical and procedural changes in recent decades, assessments are made of the comparability of the data sets; caution is needed in comparisons of individual studies, but the overall trends in the compiled set are more robust. Despite the large number of reports considered, evidence for long-term temporal changes in rainwater organic nitrogen concentrations is ambiguous. With regard to sources, it is likely that some of the organic material observed is not locally generated, but undergoes extensive or long-range atmospheric transport. The compiled data set shows a land-to-sea gradient in organic nitrogen concentration. Possible precursors, reported data on the most likely component groups, and potential source mechanisms are also outlined.

The ocean is increasingly seen as a vital component of the climate system. It exchanges with the atmosphere large quantities of heat, water, gases, particles and momentum. It is an important part of the global redistribution of heat from tropics to polar regions keeping our planet habitable, particularly equatorward of about 30°. In this article we review recent work examining the role of the oceans in climate, focusing on research in the Third Assessment Report of the IPCC and later. We discuss the general nature of oceanic climate variability and the large role played by stochastic variability in the interaction of the atmosphere and ocean. We consider the growing evidence for biogeochemical interaction of climatic significance between ocean and atmosphere. Air–sea exchange of several radiatively important gases, in particular CO2, is a major mechanism for altering their atmospheric concentrations. Some more reactive gases, such as dimethyl sulphide, can alter cloud formation and hence albedo. Particulates containing iron and originating over land can alter ocean primary productivity and hence feedbacks to other biogeochemical exchanges. We show that not only the tropical Pacific Ocean basin can exhibit coupled ocean–atmosphere interaction, but also the tropical Atlantic and Indian Oceans. Longer lived interactions in the North Pacific and Southern Ocean (the circumpolar wave) are also reviewed. The role of the thermohaline circulation in long-term and abrupt climatic change is examined, with the freshwater budget of the ocean being a key factor for the degree, and longevity, of change. The potential for the Mediterranean outflow to contribute to abrupt change is raised. We end by examining the probability of thermohaline changes in a future of global warming. Copyright © 2003 Royal Meteorological Society

Emissions from the Black Triangle Region were considered to be the major source of air pollution problems in Europe during the 1990s. This discussion reviews the changes in emissions and pollution concentrations in the Krusne Hory Region (Czech Republic) in the winter half of the year during most of the past decade, and describes the relationships with meteorology. Sulfur dioxide (SO2) is used as the example pollutant. The results show a decrease in pollution concentrations since 1996, as air pollution control and management strategies for important point sources take effect. The winter of 1995–1996 was especially harsh in the number of pollution episodes. Correlations between SO2 and meteorological parameters are inconsistent. Wind direction provides the best relationship at monitoring stations along the Krusne Hory Plateau, with wind speed and temperature more variable depending on month and location. For the valley stations, higher SO2 concentrations are strongly related to colder temperatures, higher relative humidities, and lower wind speeds. A case study during the winter of 1995–1996 (November 9–15) illustrated the importance of synoptic high pressure and a low-level inversion in minimizing plume dispersion from point sources. Specific sources of SO2 affecting each station could thus be identified.

The concentration and speciation of iodine have been determined in wet and dry deposition at a coastal site over a 15-month period. Deposition fluxes in rain (2.7 μmol m−2 yr−1) and aerosol (3.6–6.5 μmol m−2 yr−1) are the major routes for removal of iodine from the marine atmosphere onto the Earth's surface, with only a minor contribution from direct deposition of methyl iodide (0.003–0.17 μmol m−2 yr−1). Iodate (IO3−) is often considered to be the only species of iodine that is permanently removed to the aerosol phase, and IO3− may therefore be expected to be the dominant form of iodine in precipitation. However, iodide (I−) was found to constitute a significant fraction (5–100%) of iodine in both rain and aerosol. This implies that the rates of iodate formation and iodide volatilization (through reaction with hypohalous acids) are relatively slow. A third pool of aerosol iodine (nonvolatile organic compounds) may also contribute to removal of iodine from the atmosphere in dry or wet deposition.

Water-soluble organic nitrogen (ON) is an important component of fixed nitrogen in clean marine aerosol and rainwater collected at a site on the windward coast of Oahu, Hawaii. Aerosol material associated with the predominant trade winds carries 3.3 ± 2.0 nmol ON m-3, which makes up roughly one third of the total nitrogen in aerosol (11 ± 4 nmol N m-3). The inorganic nitrogen (65% as nitrate) is predominantly found in coarse-mode aerosol, consistent with displacement reactions of sea-salt chloride. In contrast, most of the ON is found in fine particle (submicrometer) aerosol, and may be associated with gas-to-particle conversions and with long-range transport in the atmosphere. At times, aerosol ON also appears to have a local, anthropogenic source, and when meteorological conditions are favorable, large pulses of ON from these local sources can dominate the total fixed nitrogen in the sampled aerosol (30-50 nmol ON m-3, contributing about 80% of the total aerosol nitrogen). About one fifth of rainwater dissolved nitrogen at this site is organic nitrogen. The average rainwater concentration of dissolved ON was 2.8 µmol N L-1, and of inorganic nitrogen (nitrate plus ammonium) was 15 µmol N L-1. In both rainwater and aerosol, urea was a major component of the ON, contributing about half of the ON and about 15% of total nitrogen. This quantitative importance of urea as a component of ON has not previously been seen in continental locations.

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.

A number of atmospherically important trace gases (dimethyl sulphide (DMS), methyl iodide (CH3I), and nonmethane hydrocarbons (NMHCs)) were measured simultaneously in the eastern Atlantic Ocean during May 1997. This investigation was part of the U.K. Atmospheric Chemistry Studies in the Oceanic Environment (ACSOE) Community Research Program and covered a 200 by 200 nautical mile (1 nautical mile is 1.852 km) area to the west of the Mace Head Atmospheric Research Station on the coast of Ireland. Different spatial and temporal patterns were observed for each of the gases, showing that distinct sources dominate their production in this region: specific species of phytoplankton (DMS), macroalgae (CH3I), total phytoplankton biomass (isoprene), and photochemistry (ethene). Sea-to-air fluxes of the gases are calculated for near and offshore domains, and their temporal variations are discussed. A simple photochemical box model has been used to assess the contributions of the gas fluxes to the levels of the gases observed at Mace Head, Results show that the area studied may constitute a substantial source of DMS, a weak source of CH 3 I, a small source of ethene at night, and an insignificant source of isoprene to atmospheric levels of these gases measured at Mace Head in western Ireland.

Iodine has been determined in aerosol samples collected at a coastal site in southeast England using instrumental neutron activation analysis (INAA) and by an electrochemical technique, after aqueous extraction. Size distribution and enrichment factor data for the samples are consistent with a non-sea-salt source of iodine, presumably gas-to-particle conversion of volatile iodocarbons. On average, only ∼70% of INAA (i.e. total) iodine could be released from the aerosols as inorganic iodine by aqueous extraction at 95°C. Extraction at a more environmentally realistic temperature (20°C) decreased this yield to ∼25%. Through the use of high-energy UV light, which is known to destroy organic matter, the yield of aqueous extractable iodine at the lower temperature was increased for some samples. Thus, it appears likely that iodine is present in aerosol in varying proportions as soluble inorganic iodine, soluble organic iodine and insoluble, or unextractable, iodine. The different characteristics of these fractions are likely to have significant impacts on the cycling and reactivity of iodine in the atmosphere.

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

Two well established methods that are widely applied in the determination of marine dissolved organic nitrogen (DON) have been investigated in their application to the determination of rainwater DON and the water-soluble organic nitrogen component of atmospheric aerosol. Empirical observation highlighted some difficulties in the analysis of DON in these non-marine matrices, so some practical suggestions for the extension of the oxidative methods to atmospheric samples are proposed. Ten rain samples, 20 aqueous aerosol extracts, and a suite of commercially obtained organic nitrogen compounds were both chemically oxidised by persulfate and oxidised by exposure to high-intensity ultraviolet light. The total dissolved nitrogen concentration of the rains in this study ranged from 4 to 35 μM nitrogen. The aerosol extracts were diluted to a pre-oxidation concentration range of 12–65 μM N for oxidation and analysis. Both UV and persulfate methods require the aqueous extract of the aerosol organic nitrogen to be diluted approximately to rainwater concentrations for optimal oxidation efficiency, since sub-optimal recoveries and high analytical variability arise at high concentration. Some potential causes of analytical interference at higher concentration are discussed. This study shows that total dissolved nitrogen results obtained by the two methods are linearly correlated (with an R 2 of 0.87 for 30 samples) over the full range of natural rainwater concentrations, but results obtained using the persulfate oxidation are about 30% lower than those obtained by photo-oxidation.

The measurement of urea (CO(NH2)2) in rainwater samples from predominantly marine-influenced locations in Bermuda, and Ireland, and in rains and aqueous aerosol extracts from a rural site at UEA, Norwich indicates that urea is not generally a major contributor to atmospheric water-soluble organic nitrogen. At UEA, where anthropogenic and natural sources of urea are expected to be most intense, urea accounts for 40% of the DON measured in those samples. This may be a consequence of strong local sources, or it could possibly result from the partial breakdown of other DON compounds to urea during sample transport and storage. However, the similarity in urea concentrations observed in Pacific samples in this present study and in a previous one ( Timperley et al., 1985 , Canadian Journal of Fisheries and Aquatic Science 42, 1171–1177) suggests that this may reflect a difference in rain chemistry between Atlantic and Pacific rains, perhaps resulting from differences in levels of agricultural urea usage between Asia and the rest of the world.

The record of atmospheric dust deposition as recorded by a deep sea sediment trap in the Sargasso Sea is presented. The record is shown to be consistent with the limited available data on directly measured atmospheric dust loadings. The seasonality of the sediment trap dust flux is different from that of the atmospheric deposition as a result of seasonal biological cycles in the surface water. On the longer term the sediment trap dust flux undergoes quite large variations in the annual average flux from 3.6 to 9.4 mg m−2 d−1. These variations are shown to reflect changes in atmospheric transport efficiency from source regions in North Africa rather than changes in the strength of the dust source in that region. The changes in the dust inputs to this area of the Sargasso Sea appear not to have changed the flux of carbon reaching the deep water, and the implications of this are discussed.

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.

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.

Chemical processes controlling the dissolved and particulate phase distribution of crustal (Al) and noncrustal metals (Pb, Cu, and Zn) appear to differ in marine precipitation sampled over the North Atlantic Ocean and Mediterranean Sea. Dissolved Al appears to be in equilibrium with a trivalent Al salt at rainwater pH 80% of the total Pb, Cu, and Zn concentrations are delivered to the surface oceans in the dissolved form. For a corresponding pH range, Al solubility varies from 60%. Over the wider observed pH range (of 3.5 to 6.9), the solubilities of Pb, Cu, Zn, and Al are highly variable. The use of mean trace metal solubilities for the assessment of dissolved atmospheric trace metal wet deposition fluxes, and their effects on surface ocean biogeochemistry should be constrained by taking into account rainwater pH in future estimates in global models.

The results of parallel aerosol and rain sampling programmes for trace and major ions at a coastal site in southeast England and on the southern North Sea are presented. The two data sets agree reasonably well, suggesting that extrapolation from coastal sites to adjacent marine areas does not introduce large errors. However, detailed consideration provides evidence of somewhat different scavenging processes at the two sites which can in part be rationalized in terms of different transport processes and atmospheric chemistry in marine and terrestrial settings.

The flux of bioavailable Fe from mineral dust to the surface ocean is controlled not only by the processes in the atmosphere but also by the nature and source of the dust. In this study, we investigated how the nature of Fe minerals in the dust affects its potential Fe solubility (Fe-psol) employing traditional and modern geochemical, mineralogical, and microscopic techniques. The chemical and mineralogical compositions, particularly Fe mineralogy, in soil samples as dust precursors collected from North African dust source regions were determined. The Fe-psol was measured after 3 days of contact with sulfuric acid at pH 2 to simulate acid processes in the atmosphere. Fe-psol of the soil dust samples were compared with calculated predictions of Fe-psol based on the amount of individual Fe-bearing minerals present in the samples and Fe solubilities of corresponding standard minerals. The calculated Fe-psol deviated significantly from the measured Fe-psol of the soil dust samples. We attributed this to the variability in properties of Fe minerals (e. g., size of Fe oxides and heterogeneity of chemical compositions of clay minerals) in soil dusts in comparison to the standard minerals. There were, however, clear relationships between the degree of chemical weathering of North African soils and Fe-psol. The Parker index and ratio of ascorbate plus dithionite Fe to total Fe ((FeA+FeD)/FeT) are positively and negatively correlated with Fe-psol, respectively. In addition, the ratio of FeA/(FeA+FeD), which decreases with aging of the Fe oxides, was found to be positively correlated with Fe-psol in the soil dusts. Overall, our results indicate that there is a significant regional variability in the chemical and Fe mineralogical compositions of dusts across North African sources, as a result of the differences in chemical weathering and aging of Fe oxides. Furthermore, the indices for these weathering processes can provide an estimate of the fraction of Fe which can be solubilized if acid processed in the atmosphere.

Observations show that the fractional solubility of Fe (FS-Fe, percentage of dissolved to total Fe) in dust aerosol increases considerably from 0.1 % in regions of high dust mass concentration to 80 % in remote regions where concentrations are low. Here, we combined laboratory geochemical measurements with global aerosol model simulations to test the hypothesis that the increase in FS-Fe is due to physical size sorting during transport. We determined the FS-Fe and fractional solubility of Al (FS-Al) in size-fractionated dust generated from two representative soil samples collected from known Saharan dust source regions using a customized dust re-suspension and collection system. The results show that the FS-Fe is size-dependent and ranges from 0.1–0.3 % in the coarse size fractions (>1 μm) to ~0.2–0.8 % in the fine size fractions (100 μg m−3) to ~0.2 % at low concentrations (–3) due to physical size sorting (i.e., particle gravitational settling). These values are one to two orders of magnitude smaller than those observed on cruises across the tropical and sub-tropical North Atlantic Ocean under an important pathway of Saharan dust plumes for similar dust mass concentrations. Even when the FS-Fe of sub-micrometer size fractions (0.18–0.32 μm, 0.32–0.56 μm, and 0.56–1.0 μm) in the model is increased by a factor of 10 over the measured values, the calculated FS-Fe of the dust is still more than an order of magnitude lower than that measured in the field. Therefore, the physical sorting of dust particles alone is unlikely to be an important factor in the observed inverse relationship between the FS-Fe and FS-Al and the atmospheric mineral dust mass concentrations. The results suggest that processes such as chemical reactions and/or mixing with combustion particles are the main mechanisms to cause the increased FS-Fe in long-range transported dust aerosols.

We investigated the iron (Fe) dissolution kinetics of African (Tibesti) and Asian (Beijing) dust samples at acidic pH with the aim of reproducing the low pH conditions in atmospheric aerosols. The Beijing dust and three size fractions of the Tibesti dust (20; 10; and 2.5) were dissolved at pH 1, 2 and/or 3 for up to 1000 h. In the first 10 min, all dust samples underwent an extremely fast Fe solubilisation. Subsequently, the Fe dissolution proceeded at a much slower rate before reaching a stable dissolution plateau. The time-dependant Fe dissolution datasets were best described by a model comprising three acid-extractable Fe pools each dissolving according to first-order kinetics. The dissolution rate constant k (h−1) of each pool was independent of the source (Saharan or Asian) and the size (PM20, PM10 or PM2.5) of the dust but highly dependent on pH. The "fast" Fe pool had a k (25 h−1 at pH = 1) of a similar magnitude to "dry" ferrihydrite nanoparticles and/or poorly crystalline Fe(III) oxyhydroxide, while the "intermediate" and "slow" Fe pools had k values respectively 50–60 times and 3000–4000 times smaller than the "fast" pool. The "slow" Fe pool was likely to consist of both crystalline Fe oxide phases (i.e., goethite and/or hematite) and Fe contained in the clay minerals. The initial mass of the "fast", "intermediate" and "slow" Fe pools represented respectively about 0.5–2%, 1–3% and 15–40% of the total Fe in the dust samples. Furthermore, we showed that in systems with low dust/liquid ratios, Fe can be dissolved from all three pools, whereas at high dust/liquid ratios (e.g., in aerosols), sufficient Fe may be solubilised from the "fast" phase to dominate the Fe dissolved and to suppress the dissolution of Fe from the other Fe pools. These data demonstrated that dust/liquid ratio and pH are fundamental parameters controlling Fe dissolution kinetics in the dust. In order to reduce errors in atmospheric and climate models, these fundamental controlling factors need to be included.

A worldwide compilation of atmospheric total phosphorus (TP) and phosphate (PO4) concentration and deposition flux observations are combined with transport model simulations to derive the global distribution of concentrations and deposition fluxes of TP and PO4. Our results suggest that mineral aerosols are the dominant source of TP on a global scale (82%), with primary biogenic particles (12%) and combustion sources (5%) important in nondusty regions. Globally averaged anthropogenic inputs are estimated to be similar to 5 and 15% for TP and PO4, respectively, and may contribute as much as 50% to the deposition over the oligotrophic ocean where productivity may be phosphorus-limited. There is a net loss of TP from many (but not all) land ecosystems and a net gain of TP by the oceans (560 Gg P a(-1)). More measurements of atmospheric TP and PO4 will assist in reducing uncertainties in our understanding of the role that atmospheric phosphorus may play in global biogeochemistry.

[1] Simultaneous measurements of NH3 in the atmosphere and NH4+ in the ocean are presented from fieldwork spanning 10 years and 110 degrees of latitude, including the first such simultaneous measurements in the remote marine environment at >55°N. At high latitudes, fluxes were almost exclusively from air to sea, in contradiction with previous lower-latitude studies, which have suggested that the open oceans are predominantly sources of ammonia to the atmosphere. Sensitivity analysis demonstrates that the direction and magnitude of the ocean-atmosphere NH3 exchange is highly dependent on water temperature. This temperature effect is sufficiently strong to outweigh the effects of variability in concentrations in seawater and atmosphere in many parts of the (open) ocean. This is highlighted in data from the Atlantic oligotrophic gyres, where fluxes were found to be predominantly out of the ocean despite extremely low dissolved ammonium concentrations in surface waters.

Phosphorus (P) availability constrains both carbon uptake and loss in some of the world's most productive ecosystems. In some of these regions, atmospheric aerosols appear to be an important, if not dominant, source of new P inputs. For example, previous work suggests that mineral aerosols from North Africa bring significant amounts of new phosphorus to the P-impoverished soils of the Amazon Basin. Here we use recent observations and atmospheric transport modeling to show that the Amazon Basin itself appears to be losing atmospheric phosphorus to neighboring regions as a consequence of biomass burning emissions, anthropogenic sources of mineral aerosols and primary biogenic particles. Observations suggest that biomass burning emissions and human disturbance are responsible for ∼23% of the phosphorus flux in the Amazon. Although biomass burning and disturbance may bring new phosphorus into nondisturbed regions, as a whole the Amazon appears to be losing phosphorus through the atmosphere. Phosphorus lost via atmospheric transport from the Amazon is deposited in the adjacent oceans and in other regions downwind. These results suggest that land use change within the Amazon may substantially increase phosphorus availability to the remaining undisturbed forests, and that this fertilization mechanism could potentially contribute to recent changes in carbon uptake measured in undisturbed stands, as well as fertilizing downwind ocean regions.

[1] Since iron is an important micronutrient, deposition of iron in mineral aerosols can impact the carbon cycle and atmospheric CO2. This paper reviews our current understanding of the global dust cycle and identifies future research needs. The global distribution of desert dust is estimated from a combination of observations of dust from in situ concentration, optical depth, and deposition data; observations from satellite; and global atmospheric models. The anthropogenically influenced portion of atmospheric desert dust flux is thought to be smaller than the natural portion, but is difficult to quantify due to the poorly understood response of desert dust to changes in climate, land use, and water use. The iron content of aerosols is thought to vary by a factor of 2, while the uncertainty in dust deposition is at least a factor of 10 in some regions due to the high spatial and temporal variability and limited observations. Importantly, we have a limited understanding of the processes by which relatively insoluble soil iron (typically ∼0.5% is soluble) becomes more soluble (1–80%) during atmospheric transport, but these processes could be impacted by anthropogenic emissions of sulfur or organic acids. In order to understand how humans will impact future iron deposition to the oceans, we need to improve our understanding of: iron deposition to remote oceans, iron chemistry in aerosols, how desert dust sources will respond to climate change, and how humans will impact the transport of bioavailable fraction of iron to the oceans.

The complexation of copper was studied in rainwater collected in Norwich, UK, and during Atlantic and Indian Ocean cruises. The complexation was measured with Chelex resin, Sep-Pak columns and adsorptive cathodic stripping voltammetry with tropolone as a competing ligand. Strong organic complexation was observed in semi-urban and marine rain samples with conditional stability constants between 1011 and 1014. Model solutions of copper and humic matter found organic complexes of a similar strength to those observed in the rain samples suggesting humic material as a potential ligand. A large proportion of the copper in the rains was associated with strong organic complexes over the pH range 4-8 in both filtered and unfiltered rain samples suggesting organic complexation is an important process both in the atmosphere and on arrival to oceans. © 2005 Elsevier Ltd. All rights reserved.

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.

The Atmospheric Nitrogen Inputs into the Costal Ecosystem (ANICE) project was initiated to improve the accuracy and performance of model tools used to estimate the atmospheric nitrogen deposition to the sea. The experimental work includes the use of a ferry for long-term measurements of gaseous species, aerosols and rain water during one year, and two intensive field campaigns. During the first ANICE intensity experiment, situations were encountered in which the air flow connected the different stations. Differences in nitrate and ammonium concentrations between the various stations were analyzed in terms of the processes determining the concentrations of these species and to quantify their variations with fetch.

Over the past decade it has become apparent that the atmosphere is a significant pathway for the transport of many natural and pollutant materials from the continents to the ocean. The atmospheric input of many of these species can have an impact (either positive or negative) on biological processes in the sea and on marine chemical cycling. For example, there is now evidence that the atmosphere may be an important transport path for such essential nutrients as iron and nitrogen in some regions. In this report we assess current data in this area, develop global scale estimates of the atmospheric fluxes of trace elements, mineral aerosol, nitrogen species, and synthetic organic compounds to the ocean; and compare the atmospheric input rates of these substances to their input via rivers. Trace elements considered were Pb, Cd, Zn, Cu, Ni, As, Hg, Sn, Al, Fe, Si, and P. Oxidized and reduced forms of nitrogen were considered, including nitrate and ammonium ions and the gaseous species NO, NO2, HNO3, and NH3. Synthetic organic compounds considered included polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs), DDTs, chlordane, dieldrin, and hexachlorobenzenes (HCBs). Making this assessment was difficult because there are very few actual measurements of deposition rates of these substances to the ocean. However, there are considerably more data on the atmospheric concentrations of these species in aerosol and gaseous form. Mean concentration data for 10° × 10° ocean areas were determined from the available concentration data or from extrapolation of these data into other regions. These concentration distributions were then combined with appropriate exchange coefficients and precipitation fields to obtain the global wet and dry deposition fluxes. Careful consideration was given to atmospheric transport processes as well as to removal mechanisms and the physical and physicochemical properties of aerosols and gases. Only annual values were calculated. On a global scale atmospheric inputs are generally equal to or greater than riverine inputs, and for most species atmospheric input to the ocean is significantly greater in the northern hemisphere than in the southern hemisphere. For dissolved trace metals in seawater, global atmospheric input dominates riverine input for Pb, Cd, and Zn, and the two transport paths are roughly equal for Cu, Ni, As, and Fe. Fluxes and basin-wide deposition of trace metals are generally a factor of 5-10 higher in the North Atlantic and North Pacific regions than in the South Atlantic and South Pacific. Global input of oxidized and reduced nitrogen species are roughly equal to each other, although the major fraction of oxidized nitrogen enters the ocean in the northern hemisphere, primarily as a result of pollution sources. Reduced nitrogen species are much more uniformly distributed, suggesting that the ocean itself may be a significant source. The global atmospheric input of such synthetic organic species as HCH,PCBs, DDT, and HCB completely dominates their input via rivers.

The results of measurements of sea-to-air fluxes of methyl iodide and air-to-sea wet depositional fluxes of iodide and iodate over the southern North Sea are reported. The estimated average annual flux of methyl iodide out of the southern North Sea is 8 × 10 5 moles yr −1 while the iodine deposition flux, based on average rainwater concentrations, is 6 × 10 5 moles yr −1 . Both emission fluxes of methyl iodide and deposition fluxes of total iodine show a modest seasonality with minimum fluxes in winter. The average concentration of iodine in the rainwater samples ( n = 40) over a one year period was 6.8 + 7.5 nm for total iodine, 3.1 + 2.7 nm for iodate and 3.7 + 6.6 nm for iodide. There is no evidence of seasonality in the iodide/iodate ratio in rainwater over the year. DOI: 10.1034/j.1600-0889.1996.00010.x

An assessment of atmospheric inputs of nitrogen to the southern North Sea (south of 56°N) has been made following a series of research cruises between August 1988 and October 1989, during which wet and dry sampling for aerosol and gaseous species was undertaken. Wet and dry deposition appear to contribute approximately equally to total deposition, yielding fluxes of 126 × 10 3 t N a -1 and 102 × 10 3 t N a -1 , respectively. A tentative assessment for the northern North Sea has been made based on extrapolation from data generated here and from coastal sites. When combined with fluxes calculated for the southern area, the total atmospheric deposition of nitrogen to the whole North Sea is estimated to be 412 × 10 3 t a -1 . In terms of gross nitrogen inputs to the North Sea, the contribution from the atmosphere is relatively minor, the budget being dominated by the influence of the North Atlantic inflow. However, it does represent at least 26% of the terrestrial input. Furthermore, the effects of both seasonality in inputs and remoteness from estuarine influence suggest that during the growing season, when primary production in the North Sea is often nutrient limited, the atmosphere may provide the dominant source of nitrogen in stratified areas away from the coast, and at a time when the long-term trend in European emissions of NH 3 and NO x to the atmosphere is upward. DOI: 10.1034/j.1600-0889.1993.00005.x

Trace metal distributions in ocean waters are dominated by internal recycling processes. However, fluxes out of the water column must balance inputs if steady state is to be maintained. We use deep-sea particle fluxes at 3200 m in the Sargasso Sea as measured by sediment traps to define the flux to the sediments beneath the Sargasso Sea and compare this flux to the atmospheric input for a group of trace metals. Despite the uncertainties associated with the comparison, several important features are revealed. For elements predominantly associated with crustal particles (Al, Mn, Fe, and V), lateral advection provides a significant part of the deep-sea particle flux. For Cd, Cu, Ni, Pb, and Zn this lateral component is minor, and atmospheric inputs to the Sargasso Sea exceed deep-sea particle fluxes. These excesses appear to be consistent with calculations of the export of these metals from the Sargasso Sea arising from ocean boundary scavenging (Pb) and release from decomposing organic matter in the southward flowing North Atlantic Deep Water (Cd, Cu, Ni, and Zn). In the atmospheric deposition itself, wet deposition exceeds dry deposition for Cd, Cu, Mn, Ni, Pb, and Zn, while wet and dry deposition are of similar magnitudes for V, Fe, and Al.

Organic nitrogen (N) is an important component of the atmospheric deposition of reactive N, but its sources are essentially unknown. Assessing whether this dissolved organic N (DON) is of natural, anthropogenic or mixed origin is critically important in attempting to determine the scale of human perturbation of the global N cycle. Here we report evidence for atmospheric organic N deposition and its anthropogenic sources in China. Precipitation samples were collected and analyzed from 15 rural, Suburban and urban sites during 2005 and 2006. The average deposition of DON was 8.6 kg ha(-1) yr(-1) with a volume-weighted concentration of 111 mu mol L-1, which was much higher than in other regions of the world. The contribution of DON to total dissolved N (TDN) was approximately 30% on average, agreeing well with other reported data in the literature. Parallel collections of wet-only and bulk deposition showed wet deposition to be 68% on average, indicating a significant dry deposition component. Combining data from the Chinese sites with those from elsewhere in the world, significant (p < 0.0001) correlations between DON and NH4-N, TDN and TDN suggest that atmospheric organic N originates from similar sources to dissolved inorganic N (DIN) (NH4-N and NO3-N), which are largely attributed to anthropogenic emissions from both agricultural and industrial sources.