Atmospheric transport of trace elements and nutrients to the oceans.

This paper reviews atmospheric inputs of trace elements and nutrients to the oceans in the context of the GEOTRACES programme and provides new data from two Atlantic GEOTRACES cruises. We consider the deposition of nitrogen to the oceans, which is now dominated by anthropogenic emissions, the deposition of mineral dust and related trace elements, and the deposition of other trace elements which have a mixture of anthropogenic and dust sources. We then consider the solubility (as a surrogate for bioavailability) of the various elements. We consider briefly the sources, atmospheric transport and transformations of these elements and how this results in strong spatial deposition gradients. Solubility of the trace elements also varies systematically between elements, reflecting their sources and cycling, and for some trace elements there are also systematic gradients in solubility related to dust loading. Together, these effects create strong spatial gradients in the inputs of bioavailable trace elements to the oceans, and we are only just beginning to understand how these affect ocean biogeochemistry.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Coastal Zone Ecosystem Services: from science to values and decision making; a case study.

This research is concerned with the following environmental research questions: socio-ecological system complexity, especially when valuing ecosystem services; ecosystems stock and services flow sustainability and valuation; the incorporation of scale issues when valuing ecosystem services; and the integration of knowledge from diverse disciplines for governance and decision making. In this case study, we focused on ecosystem services that can be jointly supplied but independently valued in economic terms: healthy climate (via carbon sequestration and storage), food (via fisheries production in nursery grounds), and nature recreation (nature watching and enjoyment). We also explored the issue of ecosystem stock and services flow, and we provide recommendations on how to value stock and flows of ecosystem services via accounting and economic values respectively. We considered broadly comparable estuarine systems located on the English North Sea coast: the Blackwater estuary and the Humber estuary. In the past, these two estuaries have undergone major land-claim. Managed realignment is a policy through which previously claimed intertidal habitats are recreated allowing the enhancement of the ecosystem services provided by saltmarshes. In this context, we investigated ecosystem service values, through biophysical estimates and welfare value estimates. Using an optimistic (extended conservation of coastal ecosystems) and a pessimistic (loss of coastal ecosystems because of, for example, European policy reversal) scenario, we find that context dependency, and hence value transfer possibilities, vary among ecosystem services and benefits. As a result, careful consideration in the use and application of value transfer, both in biophysical estimates and welfare value estimates, is advocated to supply reliable information for policy making.

The cycling of organic nitrogen through the atmosphere.

Atmospheric organic nitrogen (ON) appears to be a ubiquitous but poorly understood component of the atmospheric nitrogen deposition flux. Here, we focus on the ON components that dominate deposition and do not consider reactive atmospheric gases containing ON such as peroxyacyl nitrates that are important in atmospheric nitrogen transport, but are probably not particularly important in deposition. We first review the approaches to the analysis and characterization of atmospheric ON. We then briefly summarize the available data on the concentrations of ON in both aerosols and rainwater from around the world, and the limited information available on its chemical characterization. This evidence clearly shows that atmospheric aerosol and rainwater ON is a complex mixture of material from multiple sources. This synthesis of available information is then used to try and identify some of the important sources of this material, in particular, if it is of predominantly natural or anthropogenic origin. Finally, we suggest that the flux of ON is about 25 per cent of the total nitrogen deposition flux.

Climate change and coupling of macronutrient cycles along the atmospheric, terrestrial, freshwater and estuarine continuum.

This paper provides an introduction to the Special Issue on "Climate Change and Coupling of Macronutrient Cycles along the Atmospheric, Terrestrial, Freshwater and Estuarine Continuum", dedicated to Colin Neal on his retirement. It is not intended to be a review of this vast subject, but an attempt to synthesize some of the major findings from the 22 contributions to the Special Issue in the context of what is already known. The major research challenges involved in understanding coupled macronutrient cycles in these environmental media are highlighted, and the difficulties of making credible predictions of the effects of climate change are discussed. Of particular concern is the possibility of interactions which will enhance greenhouse gas concentrations and provide positive feedback to global warming.

Nitrous oxide and methane fluxes vs. carbon, nitrogen and phosphorous burial in new intertidal and saltmarsh sediments.

Carbon (C), nitrogen (N) and phosphorous (P) burial rates were determined within natural saltmarsh (NSM) and 'managed realignment' (MR) sediments of the Blackwater estuary, UK. Methane (CH(4)) and nitrous oxide (N(2)O) fluxes were measured along with their ability to offset a portion of the C burial to give net C sequestration. C and N densities (Cρ and Nρ) of NSM sediments (0.022 and 0.0019 g cm(-3)) are comparable to other UK NSM sediments. Less vegetationally developed MR sediments have lower Cρ and Nρ (0.012 and 0.0011 g cm(-3)) while the more vegetationally developed sites possess higher Cρ and Nρ (0.023 and 0.0030 g cm(-3)) than NSM. Both NSM and MR areas were small CH(4) (0.10-0.40 g m(-2)yr(-1)) and N(2)O (0.03-0.37 g m(-2) yr(-1)) sources. Due to their large Global Warming Potentials, even these relatively small greenhouse gas (GHG) fluxes reduced the net C sequestration within MR marshes by as much as 49%, but by only 2% from NSM. Potential MR areas within the Blackwater estuary (29.5 km(2) saltmarsh and 23.7 km(2) intertidal mudflat) could bury 5478 t C yr(-1) and 695.5 t N yr(-1), with a further 476t N yr(-1) denitrified. The saltmarsh MR would also sequester 139.4 t Pyr(-1). GHG fluxes would reduce the C burial benefit by 24% giving a C sequestration rate of 4174 t Cyr(-1). Similar areas within the Humber estuary (74.95 km(2)) could bury 3597 t Cyr(-1) and 180 t N yr(-1), with a further 442 t Nyr(-1) denitrified. GHG fluxes would reduce the C burial benefit by 31% giving a C sequestration rate of 2492 t C yr(-1). Overall, MR sites provide sustainable coastal defence options with significant biogeochemical value and, despite being net sources of CH(4) and N(2)O, can sequester C and reduce estuarine nutrient loads.

Impacts of atmospheric anthropogenic nitrogen on the open ocean.

Increasing quantities of atmospheric anthropogenic fixed nitrogen entering the open ocean could account for up to about a third of the ocean's external (nonrecycled) nitrogen supply and up to approximately 3% of the annual new marine biological production, approximately 0.3 petagram of carbon per year. This input could account for the production of up to approximately 1.6 teragrams of nitrous oxide (N2O) per year. Although approximately 10% of the ocean's drawdown of atmospheric anthropogenic carbon dioxide may result from this atmospheric nitrogen fertilization, leading to a decrease in radiative forcing, up to about two-thirds of this amount may be offset by the increase in N2O emissions. The effects of increasing atmospheric nitrogen deposition are expected to continue to grow in the future.

Mesoscale iron enrichment experiments 1993-2005: synthesis and future directions.

Since the mid-1980s, our understanding of nutrient limitation of oceanic primary production has radically changed. Mesoscale iron addition experiments (FeAXs) have unequivocally shown that iron supply limits production in one-third of the world ocean, where surface macronutrient concentrations are perennially high. The findings of these 12 FeAXs also reveal that iron supply exerts controls on the dynamics of plankton blooms, which in turn affect the biogeochemical cycles of carbon, nitrogen, silicon, and sulfur and ultimately influence the Earth climate system. However, extrapolation of the key results of FeAXs to regional and seasonal scales in some cases is limited because of differing modes of iron supply in FeAXs and in the modern and paleo-oceans. New research directions include quantification of the coupling of oceanic iron and carbon biogeochemistry.

Biogeochemical value of managed realignment, Humber estuary, UK.

We outline a plausible, albeit extreme, managed realignment scenario ('Extended Deep Green' scenario) for a large UK estuary to demonstrate the maximum possible biogeochemical effects and economic outcomes of estuarine management decisions. Our interdisciplinary approach aims to better inform the policy process, by combining biogeochemical and socioeconomic components of managed realignment schemes. Adding 7494 ha of new intertidal area to the UK Humber estuary through managed realignment leads to the annual accumulation of a 1.2 x 10(5) t of 'new' sediment and increases the current annual sink of organic C and N, and particle reactive P in the estuary by 150%, 83% and 50%, respectively. The increase in intertidal area should also increase denitrification. However, this positive outcome is offset by the negative effect of enhanced greenhouse gas emissions in new marshes in the low salinity region of the estuary. Short-term microbial reactions decrease the potential benefits of CO(2) sequestration through gross organic carbon burial by at least 50%. Net carbon storage is thus most effective where oxidation and denitrification reactions are reduced. In the Humber this translates to wet, saline marshes at the seaward end of estuaries. Cost-benefit analysis (CBA) was used to determine the economic efficiency of the Extended Deep Green managed realignment. When compared to a 'Hold-the-Line' future scenario, i.e. the present state/extent of sea defences in the estuary, the CBA shows that managed realignment is cost effective when viewed on >25 year timescales. This is because capital costs are incurred in the first years, whereas the benefits from habitat creation, carbon sequestration and reduced maintenance costs build up over time. Over 50- and 100-year timescales, the Extended Deep Green managed realignment scenario is superior in efficiency terms. The increased sediment accumulation is also likely to enhance storage of contaminant metals. In the case of Cu, a metal that currently causes significant water quality issues, Cu removal due to burial of suspended sediment in realigned areas translates to a value of approximately pounds sterling 1000 a(-1) (avoided clean up costs). Although this is not formally included in the CBA it illustrates another likely positive economic outcome of managed realignment. Although we focus on the Humber, the history of reclamation and its biogeochemistry is common to many estuaries in northern Europe.

MEAD: an interdisciplinary study of the marine effects of atmospheric deposition in the Kattegat.

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.

Global iron connections between desert dust, ocean biogeochemistry, and climate.

The environmental conditions of Earth, including the climate, are determined by physical, chemical, biological, and human interactions that transform and transport materials and energy. This is the "Earth system": a highly complex entity characterized by multiple nonlinear responses and thresholds, with linkages between disparate components. One important part of this system is the iron cycle, in which iron-containing soil dust is transported from land through the atmosphere to the oceans, affecting ocean biogeochemistry and hence having feedback effects on climate and dust production. Here we review the key components of this cycle, identifying critical uncertainties and priorities for future research.

The Humber catchment and its coastal area: from UK to European perspectives.

The present water quality of the Humber rivers and coastal zone depends on a complex interplay of factors, including physical ones, such as the underlying geology, which influences soil type, climatic ones, such as the rainfall, which influences runoff, socio-economic ones, which influence present-day human activities in the catchment, and the legacy of former activities, such as contaminated sediments from mining. All of these factors affect the fluxes of nutrients and other contaminants to the rivers and coastal zone. The Water Framework Directive (WFD) requires the production of a river basin management plan intended to lead to the achievement of good chemical and ecological status for all water bodies in the catchment over the next two decades. This paper provides an overview of the current environmental and socio-economic state of the Humber catchment and coastal zone, and broadly examines how socio-economic drivers affect the fluxes of nutrients and contaminants to the coastal zone, using the driver-pressure-state-impact-response (DPSIR) approach. This is followed by an overview of future research, describing the use of scenarios to simulate future fluxes and provide a consistent framework to evaluate potential policies to improve water quality in the estuary. The Humber catchment is one of eight case studies within a European research project, EUROCAT (EVK1-CT-2000-00044), which aims to achieve integrated catchment and coastal zone management by analysing the response of the coastal sea to changes in fluxes of nutrients and contaminants from the catchments. For the Humber case study, the research focuses on the fluxes of two nutrient elements, N and P, and four metal contaminants, As, Cu, Pb and Zn. The project requires the integration of scientific and socio-economic approaches, bringing together quantitative environmental data garnered for individual river catchments and coastal zones in previous research programmes, and local and regional socio-economic data, to aid decision-makers in their search for integrated and sustainable coastal zone management strategies.

Organic nitrogen in precipitation: real problem or sampling artefact?

Published observations of organic nitrogen (N) compounds in precipitation go back almost a century. Several different methods have been used to measure both the total and ionic concentrations of N. There is therefore some uncertainty as to whether reported "organic N" is real, or simply the result of uncertainties in chemical analyses or inadequate sampling methods. We found that the materials from which the collector was made (polypropylene, steel, or glass) had no significant effect on the composition of dissolved organic N (DON). The use of a biocide was found to be very important during sampling and storage of samples before analysis. We set up a network of seven collectors across the U.K., from the Cairngorms to Dorset, all operating to the same protocol, and including a biocide. Samples were analysed centrally, using proven methods. Over 6 months, organic N contributed about 20% to the total N in U.K. precipitation, but with a large variation across the country. This means that current estimates of wet deposited N to the U.K., which are based only on the ammonium and nitrate concentrations, are too small. Organic N is not an artefact, but a real problem that needs to be addressed.

Multi-element geochemical analysis of snow samples: Use of discriminant analysis in interpreting the results.

This paper records the concentrations of major and trace elements determined from snow samples collected during a comprehensive survey undertaken in the Scottish Highlands during the winter and spring period of 1987. The configuration of calculated back-trajectories allowed the samples to be categorized into one of five geographical sectors. Discriminant analysis was used to check the validity of these calculations, to isolate potentially deviant samples, and to predict the possible source of one sample whose back-trajectory could not be computed with confidence. Limitations of the statistical method are discussed, but we conclude that the technique justifies more use by environmental scientists involved in the evaluation of data.

Biological control of the removal of abiogenic particles from the surface ocean.

Concurrent measurements of particle concentrations in the near-surface water and of particle fluxes in the deep water of the Sargasso Sea show a close coupling between the two for biogenic components. The concentrations of suspended matter appear to follow an annual cycle similar to that of primary production and deepwater particle flux. Although the concentration of particulate aluminum in the surface water appears to vary randomly with respect to that cycle, the removal of aluminum to deep water is intimately linked to the rapid downward transport of organic matter.