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 25 km. 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 9 km 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.     

Enhanced regeneration of phosphorus during formation of the most recent eastern Mediterranean sapropel (S1)

Phosphorus regeneration and burial fluxes during and after formation of the most recent sapropel S1 were determined for two deep-basin, low-sedimentation sites in the eastern Mediterranean Sea. Organic C/P ratios and burial fluxes indicate enhanced regeneration of P relative to C during deposition of sapropel S1. This is largely due to the enhanced release of P from organic matter during sulfate reduction. Release of P from Fe-bound P also increased, but this was only a relatively minor source of dissolved P. Pore-water HPO₄²⁻ concentrations remained too low for carbonate fluorapatite formation. An increased burial of biogenic Ca-P (i.e., fish debris) was observed for one site. Estimated benthic fluxes of P during sapropel formation were elevated relative to the present day (∼900 to 2800 vs. ∼70 to 120 μmol m⁻² yr⁻¹). The present-day sedimentary P cycle in the deep-basin sediments is characterized by two major zones of reaction: (1) the zone near the sediment-water interface where substantial release of HPO₄²⁻ from organic matter takes place, and (2) the oxidation front at the top of the S1 where upward-diffusing HPO₄²⁻ from below the sapropel is sorbed to Fe-oxides. The efficiency of aerobic organisms in retaining P is reflected in the low organic C/P ratios in the oxidized part of the sapropel. Burial efficiencies for reactive P were significantly lower during S1 times compared with the present day (∼7 to 15% vs. 64 to 77%). Budget calculations for the eastern Mediterranean Sea demonstrate that the weakening of the antiestuarine circulation and the enhanced regeneration of P both contributed to a significant increase in deep-water HPO₄²⁻ concentrations during sapropel S1 times. Provided that sufficient vertical mixing occurred, enhanced regeneration of P at the seafloor may have played a key role in maintaining increased productivity during sapropel S1 formation.     

Thermobarometry of mafic igneous rocks based on clinopyroxene-liquid equilibria, 0–30 kbar

 Models for estimating the pressure and temperature of igneous rocks from co-existing clino-pyroxene and liquid compositions are calibrated from existing data and from new data obtained from experiments performed on several mafic bulk compositions (from 8–30 kbar and 1100–1475° C). The resulting geothermobarometers involve thermodynamic expressions that relate temperature and pressure to equilibrium constants. Specifically, the jadeite (Jd; NaAlSi₂O₆)–diopside/hedenbergite (DiHd; Ca(Mg, Fe) Si₂O₆) exchange equilibrium between clinopyroxene and liquid is temperature sensitive. When compositional corrections are made to the calibrated equilibrium constant the resulting geothermometer is (i) 10⁴ T=6.73−0.26^* ln [Jd^px*Ca^liq*Fm^liqDiHd^px*Na^liq*Al^liq] −0.86^* ln [Mg^liqMg^liq+Fe^liq]+0.52^*ln [Ca^liq] an expression which estimates temperature to ±27 K. Compared to (i), the equilibrium constant for jadeite formation is more sensitive to pressure resulting in a thermobarometer (ii) P=−54.3+299^* T10⁴+36.4^* T10⁴ ln [Jd^px[Si^liq]^2*Na^liq*Al^liq] +367^*[Na^liq*Al^liq] which estimates pressure to ± 1.4 kbar. Pressure is in kbar, T is in Kelvin. Quantities such as Na^liq represent the cation fraction of the given oxide (NaO_0.5) in the liquid and Fm=MgO+FeO. The mole fractions of Jd and diopside+hedenbergite (DiHd) components are calculated from a normative scheme which assigns the lesser of Na or octahedral Al to form Jd; any excess Al^VI forms Calcium Tschermak’s component (CaTs; CaAlAlSiO₆); Ca remaining after forming CaTs and CaTiAl₂O₆ is taken as DiHd. Experimental data not included in the regressions were used to test models (i) and (ii). Error on predictions of T using model (i) is ±40 K. A pressure-dependent form of (i) reduces this error to ±30 K. Using model (ii) to predict pressures, the error on mean values of 10 isobaric data sets (0–25 kbar, 118 data) is ±0.3 kbar. Calculating thermodynamic properties from regression coefficients in (ii) gives V^Jd _f of 23.4 ±1.3 cm³/mol, close to the value anticipated from bar molar volume data (23.5 cm³/mol). Applied to clinopyroxene phenocrysts from Mauna Kea, Hawaii lavas, the expressions estimate equilibration depths as great as 40 km. This result indicates that transport was sufficiently rapid that at least some phenocrysts had insufficient time to re-equilibrate at lower pressures. Received: 16 May 1994/Accepted: 15 June 1995     

Emissions of marine biogenic sulfur to the atmosphere of northern Europe

Measurements of DMS and other reduced sulfur compounds in surface waters have been carried out from a helicopter in the seas surrounding Scandinavia. Average summer time concentrations of DMS ranged from 70 to 150 ngS L^-1. Simultaneous measurements of biological and physical parameters revealed no correlation between DMS and phytoplankton species, species assemblages, total phytoplankton biomass, chlorophyll a, temperature, and salinity. The only exception was a correlation between DMS concentration, Chrysochromulina spp. belonging to the Prymnesiophyceae, and salinity over a narrow range of salinity in the Baltic Sea.The flux of reduced sulfur to the atmosphere in July in this region is estimated to be 120–170 gS m^-2 d^-1 from the Baltic, 240–810 in the Kattegat/Skagerrak, and 120–690 in the North Sea. Annual fluxes are roughly 100 times higher than these daily fluxes. On an annual basis, biogenic sulfur emissions from the coastal seas are negligible (<1%) compared to the anthropogenic emissions in northern Europe. However, during the summer months, the biogenic sulfur emissions from the seas surrounding the Scandinavian peninsula are estimated to be as high as 20–70% of the anthropogenic emissions in Scandinavia. This makes it of interest to incorporate the biogenic emissions in calculations of long-range transport and deposition of sulfur within the region.Other volatile sulfur species, mainly methyl mercaptan, contribute about 10% of the total flux of reduced sulfur. Estimated fluxes of CS₂ to the atmosphere ranged from 1 gS m^-2 d^-1 in the Baltic Sea to 6 gS m^-2 d^-1 in the North Sea. No emissions for H₂S or COS were detected.     

Concentrations of Cd,Zn and Cu in sediments and brown shrimp (Crangon crangon L.) from the Severn Estuary and Bristol Channel,UK

Cd, Zn and Cu levels were determined in sediments and Crangon crangon from 9 sites in the Severn Estuary/Bristol Channel during winter 1999. Metal levels in both shrimp and sediments varied significantly between sites and were related to proximity of input and/or sediment type. In the upper Estuary, Cd levels in shrimp were 100x higher than other reported values whereas sediment Cd contamination was comparable. It is suggested that high Cd levels in shrimp are due to the high inputs and enhanced bioavailability of metal during winter.     

Structure of Haida Eddies and Their Transport of Nutrient from Coastal Margins into the NE Pacific Ocean

Anticyclonic mesoscale eddies form near shore each winter in the Gulf of Alaska. One site near the Queen Charlotte Islands is shown to produce eddies that transport from 3000 to 6000 km³ of coastal water up to 1000 km westward. Eddies carry shelf nutrients either into the high nutrient, low chlorophyll waters of the NE Pacific, or in a more southerly direction into seasonally nitrate depleted waters. A large eddy sampled in summer 1998 was found to have elevated particulate levels on its perimeter. Nitrate supplied to the euphotic zone by this eddy during its natal summer is estimated to be three times greater than the usual seasonal nutrient transport in the Gulf of Alaska. This revised version was published online in August 2006 with corrections to the Cover Date.     

Modern saltmarsh diatom distributions of the Outer Banks, North Carolina, and the development of a transfer function for high resolution reconstructions of sea level

We collected modern diatom samples from Currituck Barrier Island, Oregon Inlet and Pea Island marshes, Outer Banks, North Carolina, USA, which have different salinity regimes due to their varying distances from a major barrier island inlet. Multivariate analyses separate the saltmarsh diatom assemblages into distinct elevational zones, dominated by differing abundances of polyhalobous, mesohalobous and oligohalobous taxa, suggesting that the distribution of saltmarsh diatoms is a direct function of elevation, with the most important controlling factors being the duration and frequency of subaerial exposure.We developed the first diatom-based transfer function for the east coast of North America to reconstruct former sea levels based upon the relationship between diatom assemblage and elevation. Results imply that this is possible to a precision of ±0.08 m, superior to most similar studies from temperate, mid-latitude environments. The transfer function is used to construct a relative sea-level curve from fossil assemblages from Salvo, North Carolina. These results suggest a sea-level rise of 0.7 m over the last c. 150 years, at an average of c. 3.7 mm year⁻¹. This is consistent with existing sea-level data, and illustrates the utility of the transfer function approach.