Activity Concentrations and Fluxes of Radiocesium in the Southern Baltic Sea

The activity concentrations of dissolved¹³⁷Cs have been determined in the water column and¹³⁷Cs and¹³⁴Cs in the sediments and the sediment porewaters of the southern Baltic Sea. The mean activity concentration of dissolved¹³⁷Cs in the Gdansk Deep declined from 109 Bq m⁻³in June 1986 to 61 Bq m⁻³in 1999. In sediments, the activity concentrations of¹³⁷Cs (33-231 Bq kg⁻¹) were highest in muds and the activity concentrations of¹³⁴Cs were about 6% of the total Cs activity. The Chernobyl contribution to¹³⁷Cs activity was between 43% and 77%. The porewater activity concentrations of¹³⁷Cs in muddy sediments were in the range 71 to 3900 Bq m⁻³and were higher than those in the overlying seawater. The diffusive flux of dissolved¹³⁷Cs from the muddy sediments was estimated in the range 5 to 480 Bq m⁻²year⁻¹. The flux of¹³⁷Cs from sediment porewaters of the southern Baltic Sea was about 45% of the total, including fluxes of¹³⁷Cs from wet and dry atmospheric deposition and the fluvial inputs. The results were used to elucidate the rate of recovery of the sediments and the waters of the southern Baltic from Chernobyl-derived¹³⁷Cs.     

Ammonia Nitrogen at the Water–Sediment Interface in Puck Bay (Baltic Sea)

The magnitude of the exchange flux at the water–sediment interface was determined on the basis of the ammonia concentration gradient at the near-bottom water–interstitial interface and Fick's first law. It was established that in Puck Bay, ammonia almost always passes from the sediment to water. Ammonia flux varied from 5 to 1434 μmol NH₄-N m⁻² day⁻¹. In total,c. 138·2 tonneammonia year⁻¹pass from sediments of Internal Puck Bay to near-bottom water, the equivalent value for External Puck Bay being 686·9 tonne year⁻¹. In total, about 825 tonne ammonia year⁻¹passes from the sediment to near-bottom water of Puck Bay. In interstitial waters, ammonia occurred in concentrations varying over a wide range (3–1084 μmol NH₄-N dm⁻³).The basic factors affecting the magnitude of ammonia concentration in interstitial waters included: oxidation of organic matter, type of sediment, and inflow of fresh underground waters to the region examined.This paper involves preliminary studies only and constitutes a continuation of the studies on ionic macrocomponents and phosphorus in interstitial waters of Puck Bay undertaken previously.     

Factors affecting spatial and temporal variability in material exchange between the Southern Everglades wetlands and Florida Bay (USA)

Physical and biological processes controlling spatial and temporal variations in material concentration and exchange between the Southern Everglades wetlands and Florida Bay were studied for 2.5 years in three of the five major creek systems draining the watershed. Daily total nitrogen (TN), and total phosphorus (TP) fluxes were measured for 2 years in Taylor River, and ten 10-day intensive studies were conducted in this creek to estimate the seasonal flux of dissolved inorganic nitrogen (N), phosphorus (P), total organic carbon (TOC), and suspended matter. Four 10-day studies were conducted simultaneously in Taylor, McCormick, and Trout Creeks to study the spatial variation in concentration and flux. The annual fluxes of TOC, TN, and TP from the Southern Everglades were estimated from regression equations. The Southern Everglades watershed, a 460-km² area that includes Taylor Slough and the area south of the C-111 canal, exported 7.1 g C m⁻², 0.46 g N m⁻², and 0.007 g P m⁻², annually. Everglades P flux is three to four orders of magnitude lower than published flux estimates from wetlands influenced by terrigenous sedimentary inputs. These low P flux values reflect both the inherently low P content of Everglades surface water and the efficiency of Everglades carbonate sediments and biota in conserving and recycling this limiting nutrient. The seasonal variation of freshwater input to the watershed was responsible for major temporal variations in N, P, and C export to Florida Bay; approximately 99% of the export occurred during the rainy season. Wind-driven forcing was most important during the later stages of the dry season when low freshwater head coincided with southerly winds, resulting in a net import of water and materials into the wetlands. We also observed an east to west decrease in TN:TP ratio from 212:1 to 127:1. Major spatial gradients in N:P ratios and nutrient concentration and flux among the creek were consistent with the westward decrease in surface water runoff from the P-limited Everglades and increased advection of relatively P-rich Gulf of Mexico (GOM) waters into Florida Bay. Comparison of measured nutrient flux from Everglades surface water inputs from this study with published estimates of other sources of nutrients to Florida Bay (i.e. atmospheric deposition, anthropogenic inputs from the Florida Keys, advection from the GOM) show that Everglades runoff represents only 2% of N inputs and 0.5% of P input to Florida Bay.     

Benthic Nutrient Recycling in Port Phillip Bay, Australia

Benthic chamber measurements of the reactants and products involved with biogenic matter remineralization (oxygen, ammonium, nitrate, nitrite, phosphate, silicate, TCO₂and alkalinity) were used to define solute exchange rates between the sediment and overlying water column of Port Phillip Bay, Australia. Measurements at various sites throughout the bay, conducted during the summers of 1994 and 1995, indicate that the variability in flux values within a site is comparable to year-to-year variability (±50%). Four regions of the bay were distinguished by sediment properties and the northern region was identified as having 3–30 times greater nutrient regeneration rates than the other regions. Benthic recycling accounted for 63 and 72% of the annualized N and P input, respectively, to the entire bay as determined by summing benthic, dissolved riverine, atmospheric and dissolved effluent sources. However, bay-wide sedimentary denitrification accounted for a loss of 63% of the potentially recyclable N. This fraction is higher than many other coastal regions with comparable carbon loading. Denitrification efficiency is apparently not enhanced by benthic productivity nor by bio-irrigation. The rate of bio-irrigation is negatively correlated with denitrification efficiency. Bio-irrigation was studied using radon-222 and CsCl spike injection chamber measurements. Radon fluxes from sediments in Port Phillip Bay were enhanced over the diffusive flux by 3–16 times. The modelled rate of loss of Cs from chamber water was positively correlated with radon flux enhancement results. Both methods identify regions within Port Phillip Bay that have particularly high rates of non-diffusive pore-water overlying water solute exchange.     

Imbalance in the carbonate budget of surficial sediments in the North Atlantic Ocean: variations over the last millenium?

Fluxes contributing to the particulate carbonate system in deep-sea sediments were investigated at the BENGAL site in the Porcupine Abyssal Plain (Northeast Atlantic). Deposition fluxes were estimated using sediment traps at a nominal depth of 3000 m and amounted to 0.37±0.1 mmol C m⁻² d⁻¹. Dissolution of carbonate was determined using flux of total alkalinity from in situ benthic chambers, is 0.4±0.1 mmol C m⁻² d⁻¹. Burial of carbonate was calculated from data on the carbonate content of the sediment and sedimentation rates from a model age based on ¹⁴C dating on foraminifera (0.66±0.1 mmol C m⁻² d⁻¹). Burial plus dissolution was three times larger than particle deposition flux which indicates that steady-state is not achieved in these sediments. Mass balances for other components (BSi, ²¹⁰Pb), and calculations of the focusing factor using ²³⁰Th, show that lateral inputs play only a minor role in this imbalance. Decadal variations of annual particle fluxes are also within the uncertainty of our average. Long-term change in dissolution may contribute to the imbalance, but can not be the main reason because burial alone is greater than the input flux. The observed imbalance is thus the consequence of a large change of carbonate input flux which has occured in the recent past. A box model is used to check the response time of the solid carbonate system in these sediments and the time to reach a new steady-state is in the order of 3 kyr. Thus it is likely that the system has been perturbed recently and that large dissolution and burial rates reflect the previously larger particulate carbonate deposition rates. We estimate that particulate carbonate fluxes have certainly decreased by a factor of at least 3 and that this change has occurred during the last few centuries.     

Wintertime nutrients in the North Atlantic—new approaches and implications for new production estimates

Observations of wintertime nutrient concentrations in surface waters are scarce in the temperate and subarctic North Atlantic Ocean. Three new methods of their estimation from spring or early summer observations are described and evaluated. The methods make use of a priori knowledge of the vertical distribution of oxygen saturation and empirical relationships between nutrient concentrations and oxygen saturation. A south–north increase in surface water winter nutrient concentration is observed. Winter nitrate concentrations range from very low levels of about 0.5 μmol dm⁻³ at 33°N to about 13.5 μmol dm⁻³ at 60°N. Previous estimates of winter nitrate concentrations have been overestimates by up to 50%. At the Biotrans Site (47°N, 20°W), a typical station in the temperate Northeast Atlantic, a mean winter nitrate concentration of 8 μmol dm⁻³ is estimated, compared to recently published values between 11 and 12.5 μmol dm⁻³. It is shown that most of the difference is due to a contribution of remineralised nitrate that had not been recognized in previous winter nutrient estimates. Mesoscale variation of wintertime nitrate concentrations at Biotrans are moderate (less than ±15% of the regional mean value of about 8 μmol dm⁻³). Interannual variation of the regional mean is small, too. In the available dataset, there was only 1 year with a significantly lower regional mean winter nitrate concentration (7 μmol dm⁻³), presumably due to restricted deep mixing during an atypically warm winter. The significance of winter nitrate estimates for the assessment of spring-bloom new production and the interpretation of bloom dynamics is evaluated. Applying estimates of wintertime nitrate concentrations of this study, it is found that pre-bloom new production (0.275 mol N m⁻²) at Biotrans almost equals spring-bloom new production (0.3 mol N m⁻²). Using previous estimates of wintertime nitrate yields unrealistically high estimates of pre-bloom new production (1.21–1.79 mol N m⁻²) which are inconsistent with observed levels of primary production and the seasonal development of biomass.     

Dissolved silica concentrations and reactions in pore waters from continental slope sediments offshore from Cape Hatteras, North Carolina, USA

The pore water concentrations of dissolved silica in sediment cores from the continental slope offshore from Cape Hatteras, North Carolina, varied from 150 to almost 700 μ,M with depth in the top 40 cm of sediment. Sediment cores from 630 to 2010 m depth had very similar profiles of dissolved silica in their pore waters, even though these cores came from regions greatly different in slope, topography, sedimentation rate, and abundance of benthic macrofauna. Cores from 474 to 525 m were more variable, both with respect to pore water dissolved silica profiles, and with respect to sediment texture. Experiments indicate that both the rate of dissolution of silica and the saturation concentration decrease as sediment depth below the sediment-seawater interface increases. These data are consistent with depletion of a reactive silica phase in surface sediment, which may be radiolarian tests, or the alteration of biogenic silica to a less reactive form over time. Experimental results suggest that the pore water dissolved silica concentration in sediments below the top few centimeters may be higher than the sediments could now achieve. The flux of dissolved silica out of these sediments is estimated to be 15 μmoles cm⁻² yr⁻¹.     

Microbial biogeochemistry and bioturbation in the sediments of Great Bay, New Hampshire

The influence of bioturbation on certain aspects of the biogeochemistry of sulfur and iron was examined in shallow-water sediments of Great Bay Estuary, New Hampshire. A bioturbated (JEL) and non-bioturbated (SQUAM) site were compared. Annual sulfate reduction measured with ³⁵S, was 4·5 times more rapid at JEL. A significant portion of this difference was attributed to rapid rates which occurred throughout the upper 12 cm of sediment at JEL due to infaunal reworking activities. Sulfate reduction decreased rapidly with depth at SQUAM. FeS in the upper 2 cm at JEL increased in concentration from 3 to 45 μmol ml⁻¹ from early May to late July while only increasing from 3 to 8 μmol ml⁻¹ at SQUAM. Infaunal irrigation and reworking activities caused rapid and continous subsurface cycling of iron and sulfur at JEL. This maintained dissolved iron concentrations at 160–170 μM throughout the summer despite rapid sulfide production. Therefore, dissolved sulfide never accumulated in JEL pore waters. Although dissolved organic carbon (DOC) was generated during sulfate reduction, bioturbation during summer caused a net removal of DOC from JEL pore waters. Sulfate reduction rates, decomposition stoichiometry and nutrient concentrations were used to calculate turnover times of nutrients in pore waters. Nutrient turnover varied temporally and increased three-to five-fold during bioturbation. A secondary maximum in the abundance of recoverable sulfate-reducing bacteria occurred at 10 cm in JEL sediments only during periods of active bioturbation, demonstrating the influence of macrofaunal activities on bacterial distributions.     

Remineralization and accumulation of organic carbon and nitrogen in marine sediments of eutrophic bays: the case of the Bay of Concepcion, Chile

The Bay of Concepcion (36°40′S; 73°02′W) is a semi-enclosed and shallow embayment in which biogeochemical processes are seasonally coupled to coastal upwelling during the austral spring and summer. The nutrient cycle in the bay is complex due to the combined effects of a pronounced O₂ minimum layer and high nutrient concentrations both originating from subsurface equatorial water during coastal upwelling and a rapid rate of sediment nutrient recycling. The sediments are characterized by a high content of organic matter mainly due to the extremely high rates of phytoplankton production and deposition. During the upwelling period, a black flocculent layer frequently covers the sediment–water interface in the inner part of the bay where an extensive mat of Beggiatoa spp. develops. Three approaches are used to analyse the extent to which the benthic system recycles or retains nutrients at two stations, located at the centre (station C, St. C) and mouth (station B, St. B) of the bay for a 1-year period (March 1996–1997): (1) estimation of C and N remineralization rates based on SO₄²⁻ reduction measurements, (2) calculation of C and N turnover rates using a diagenetic model applied to total organic carbon and total nitrogen vertical distributions and, (3) construction of C and N budgets from direct measurements of sedimentation (from a sediment trap) and estimates of the C and N burial rates. Depth-integrated SO₄²⁻ reduction rates varied between 3.4 (winter) and 25.5 (summer) mmol m⁻² d⁻¹. Estimated C and N oxidation rates ranged between 7.9 and 87.8 mol C m⁻² yr⁻¹ and between 0.9 and 6.9 mol N m⁻² yr⁻¹, respectively. Each approach yielded minor differences in the C and N remineralization rates (and also minor differences between both studied stations), except when the kinetic model was applied to C and N distribution without including the presence of the flocculent layer. The rates of carbon oxidation and sulphate reduction were considerably higher than in other coastal sediments with similar depositional regime. The C and N burial rates were 2.23 and 0.21 (St. C) and 1.30 and 0.09 (St. B) mol m⁻² yr⁻¹, respectively. The C/N ratio of the buried fraction was ca. 10.6 at St. C and 14.4 at St. B. Because the observed differences in burial rates could not be ascribed to distinctive depositional (both stations have similar sediment accumulation rates) and oceanographic (similar O₂ concentration and hydrography) conditions, differences may be due to in part spatial heterogeneity in the supply of organic matter. The degree of preservation of organic matter as plankton detritus and nitrogen accumulating bacterial biomass associated with Beggiatoa spp. at St. C may also be involved.     

Evaluation of atmospheric transport as a nonpoint source of polycyclic aromatic hydrocarbons in marine sediments of the Eastern Mediterranean

Coastal marine sediment, air and seawater samples were collected at six sampling stations in the Eastern Mediterranean Sea distant from pollutant point sources. All sediment samples were analyzed to determine polycyclic aromatic hydrocarbon (PAH), black carbon (BC) and organic carbon (OC) contents. The PAH contents of gaseous and seawater samples of the study were determined in order to evaluate the role of air–sea exchange as PAH nonpoint source to the marine sediments. The average concentration of the total PAHs (∑PAHs) in the sediments varied from 2.2 to 1056.2 ng g⁻¹ dry weight. The average BC and OC contents varied from 0.3 to 5.6 and from 2.9 to 21.4 mg g⁻¹ dry weight, respectively. ∑PAH concentration in the marine atmosphere varied from 20.0 to 83.2 ng m⁻³. Air–water exchange flux (F_A–W) estimation has indicated air transport as a significant source of PAHs to pristine marine sediments of Eastern Mediterranean. In addition, the significant correlation between the PAHs and the organic and soot carbon content further suggests the importance of atmospheric input of PAHs to the sediments.     

Recent sediments, sediment accumulation and carbon burial at Goban Spur, N.W. European Continental Margin (47–50°N)

To quantify recent sediment accumulation, carbon fluxes and cycling, three N.W. European Continental Margin transects on Goban Spur and Meriadzek Terrace were extensively studied by repeated box- and multicore sampling of bottom sediments. The recent sediment distribution and characteristics appear directly related to the near-bed hydrodynamic regime on the margin, which at the upper slope break on the Goban Spur results in along-slope and periodic off-slope directed transport of particles, possibly by entrainment of particles in a detached bottom or intermediate nepheloid layer. From the shelf to the abyssal plain the surface sediments on the Goban Spur change from terrigenous sandy shelf sediments into clayey silts. ²¹⁰Pb activity decreases exponentially down core, reaching a stable background value at 10 cm (shallower stations) to 5 cm (deeper stations) sediment depth. ²¹⁰Pb profiles of repeatedly sampled stations indicate negligible annual variability of mixing and flux. The ²¹⁰Pb_xs flux to the sediment shows a decreasing trend with increasing water depth. Below about 2000 m the average ²¹⁰Pb_xs flux is about 0.3 dpm cm⁻² y⁻¹, a third of the fluxes measured on the shelf and upper slope stations. Sediment mixing rates (D_b) correlate with macro- and meiofaunal density changes and are within the normal oceanic ranges. Lower mixing rates on the lower slope likely reflect lower organic carbon fluxes there. Mass accumulation rates on Meriadzek Terrace are at maximum 80 g m⁻² y⁻¹, almost twice as high as at Goban Spur stations of comparable depth. A minimum accumulation rate of 16.6 g m⁻² y⁻¹ is found at the Goban Spur upper slope break. Organic carbon burial rates are low compared to other margins and range from a lowest value of 0.05 g m⁻² y⁻¹ at the upper slope break to 0.11 g m⁻² y⁻¹ downslope. A maximum organic carbon burial rate of 0.41 g m⁻² y⁻¹ is found on Meriadzek Terrace. Carbonate burial rates increase along the northern transect from the shelf (13 g m⁻² y⁻¹) via a low (9.3 g m⁻² y⁻¹) on the upper slope break to the deep sea (30.7 g m⁻² y⁻¹). Carbonate burial is highest on Meriadzek Terrace (44.5 g m⁻² y⁻¹). The N.W. European Margin at Goban Spur and Meriadzek Terrace cannot be considered a major carbon depocenter.     

Nutrient enrichment and phytoplankton response in an Adriatic karstic estuary

Nutrients, chlorophyll a, primary production (¹⁴C), and standard oceanographic parameters were measured seasonally from 1983 to 1988 along the axis of a karstic estuary of the central Adriatic Sea (the Krka River estuary). Because of anthropogenic phosphorus discharges, the surface-layer orthophosphate concentrations (up to 1.7 mmol m⁻³), phytoplankton biomass (chlorophyll a up to 23 mg m⁻³) and primary production (up to 108 mg C m⁻³ h⁻¹) were significantly higher in ibenik Bay (lower estuary) than in the other estuarine subregions, and the coastal sea in particular. In contrast, nitrate and orthosilicate (up to 59 and 65 mmol m⁻³, respectively) distributions during autumn and winter were ascribed to dilution of Krka River nutrients along the estuary. As a consequence, the surface-layer inorganic N/P ratio was extremely high in the upper estuary (averages up to 180), but this ratio was reduced up to three times in ibenik Bay and the coastal sea. In spring and summer, nitrate and orthosilicate, but not orthophosphate, were almost exhausted from the water because of biological utilization. In the saline layer below the halocline (depth 2–5 m) oxygen saturation varied over a large range, particularly in the upper estuary (16–176%), and nutrient concentration ratios differed from those in the surface layer. A nutrient regeneration stoichiometric model was derived, based on a linear regression analysis: AOU:Si:N:P = 276:16:6:0.4. Anthropogenic nutrient inputs should be urgently reduced to re-establish a natural nutrient environment.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Benthic denitrification and nitrogen cycling at the slope and rise of the N.W. European Continental Margin (Goban Spur)

The rate of benthic denitrification in slope and rise sediments of a transect across the N.W. European Continental Margin (Goban Spur) was evaluated from 31 pore water nitrate profiles obtained during six cruises between May and October. All profiles had well separated zones of nitrification and denitrification. High near-surface nitrate concentrations prevented the influx of nitrate from the bottom water. The denitrification rates obtained from steady-state-modelling ranged from 0.13 to 2.56 μmol N cm⁻² y⁻¹ and showed an exponential increase both with decreasing water depth and with increasing rate of organic carbon degradation. Denitrification rates in a nearby canyon, which did not follow these relationships, were estimated to be much higher as a result of erosion and redistribution of organic matter. Denitrification at the Goban Spur slope and rise is much lower than previously reported for similar environments in the Pacific resulting predominantly from the different oxygen and nitrate concentrations in the bottom water. A weighted average for the whole slope and rise sediment system shows that 17% of the particulate organic nitrogen input (8.93 μmol N cm⁻² y⁻¹) is denitrified and only 1% is buried, the rest being released as nitrate. Although being ten times higher compared with basin sediments, denitrification on the slope and rise is several times lower than on the adjacent shelf.     

Chlorinated hydrocarbons in the open mediterranean ecosystem and implications for mass balance calculations

Studies on the biogeochemical cycling of organic contaminants in the Mediterranean have demonstrated the importance of polychlorinated biphenyls (PCBs) as relatively stable markers of recent anthropogenic influence in ocean systems. This paper presents results of hydrocarbon analyses of deep water profiles, sediments and their associated surface flocculent layers, and zooplankton samples collected in the western basin. Seawater concentrations were higher than those previously reported for the eastern basin and were consistent with the presence of industrial sources in the northwestern segment. In the water column, the percent of PCBs associated with filterable particles was related to the ambient concentrations of total suspended matter, distance from coastal input sources and on depth. The occurrence of deep water residues primarily in the dissolved phase and observations of subsurface maxima in seawater concentrations during a season of high surface productivity were consistent with the predictions of vertical transport models based on residues associated with sinking particles and equilibrium partitioning. Flocculent layers at the sea/sediment interface contained two and three orders of magnitude, respectively, more PCBs and petroleum hydrocarbons (PHCs) than their associated surface sediments. The flocculent particles also contained several biogenic hydrocarbons presumably originating from plankton and relatively soluble and labile contaminants such as hexachlorohexane isomers (HCH) and hexachlorobenzene (HCB), thus confirming that the majority of the flux of hydrocarbons to sediments is carried on rapidly settling large particles. By combining the sediment and flocculents data with published sedimentation rates for the deep basins of the Mediterranean, a yearly flux rate of PCBs to the open sea sediments was estimated as 13 μg m⁻² yr⁻¹ or less than half of the rate measured in a coastal sediment trap experiment. Analytical results are placed in the context of other distribution data for PCBs and long-term flux studies to construct a partial mass balance budget for this semi-enclosed sea. The computed coastal inventory showed that about 35% remains suspended in the water column while the majority of residues are deposited in coastal sediments. However in the open sea, the deep water column may contain up to 70% of the total inventory and may be a continually increasing reservoir of stable organic contaminants reaching the ocean. The budget shows that priority for improved research and monitoring efforts in ocean systems should be given to continued advancement in techniques for the precise measurement of deep water concentrations and for measuring current atmospheric inputs and sedimentation rates in order to develop more accurate ocean flux models.     

Nitrogen cycling in deep-sea sediments of the Porcupine Abyssal Plain, NE Atlantic

Rates of transformation, recycling and burial of nitrogen and their temporal and spatial variability were investigated in deep-sea sediments of the Porcupine Abyssal Plain (PAP), NE Atlantic during eight cruises from 1996 to 2000. Benthic fluxes of ammonium (NH₄) and nitrate (NO₃) were measured in situ using a benthic lander. Fluxes of dissolved organic nitrogen (DON) and denitrification rates were calculated from pore water profiles of DON and NO₃, respectively. Burial of nitrogen was calculated from down core profiles of nitrogen in the solid phase together with ¹⁴C-based sediment accumulation rates and dry bulk density. Average NH₄ and NO₃-effluxes were 7.4 ± 19 μmol m⁻² d⁻¹ (n = 7) and 52 ± 30 μmol m⁻² d⁻¹ (n = 14), respectively, during the period 1996–2000. During the same period, the DON-flux was 11 ± 5.6 μmol m⁻² d⁻¹ (n = 5) and the denitrification rate was 5.1 ± 3.0 μmol m⁻² d⁻¹ (n = 22). Temporal and spatial variations were only found in the benthic NO₃ fluxes. The average burial rate was 4.6 ± 0.9 μmol m⁻² d⁻¹. On average over the sampling period, the recycling efficiency of the PON input to the sediment was 94% and the burial efficiency hence 6%. The DON flux constituted 14% of the nitrogen recycled, and it was of similar magnitude as the sum of burial and denitrification. By assuming the PAP is representative of all deep-sea areas, rates of denitrification, burial and DON efflux were extrapolated to the total area of the deep-sea floor (>2000 m) and integrated values of denitrification and burial of 8 ± 5 and 7 ± 1 Tg N year⁻¹, respectively, were obtained. This value of total deep-sea sediment denitrification corresponds to 3–12% of the global ocean benthic denitrification. Burial in deep-sea sediments makes up at least 25% of the global ocean nitrogen burial. The integrated DON flux from the deep-sea floor is comparable in magnitude to a reported global riverine input of DON suggesting that deep-sea sediments constitute an important source of DON to the world ocean.     

Changes in sediment processes across the western Irish Sea front

Sediment characteristics, sediment respiration (oxygen uptake and sulphate reduction) and sediment–water nutrient exchange, in conjunction with water column structure and phytoplankton biomass were measured at five stations across the western Irish Sea front in August 2000. The transition from thermally stratified (surface to bottom temperature difference of 2.3 °C) to isothermal water (14.3 °C) occurred over a distance of 13 km. The influence of the front on phytoplankton biomass was limited to a small region of elevated near surface chlorophyll (2.23 mg m⁻³; 50% > biomass in mixed waters). The front clearly marked the boundary between depositional sediments (silt/clays) with elevated sediment pigment levels (≈60 mg m⁻²) on the western side, to pigment impoverished (<5 mg m⁻²) sand, through to coarse sand and shell fragments on the eastern side. Maximal rates of sedimentary respiration on the western stratified side of the front e.g. oxygen uptake S2 (852 μmol O₂ m⁻² h⁻¹) and sulphate reduction at S1 (149 μmol SO₄²⁻ m⁻² h⁻¹), coupled to significant efflux of nitrate and silicate at the western stations indicate closer benthic–pelagic coupling in the western Irish Sea. Whether this simply reflects the input of phytodetritus from the overlying water column or entrapment and settlement of pelagic production from other regions of the Irish Sea cannot yet be resolved.     

In situ Study of Bromide Tracer and Oxygen Flux in Coastal Sediments

Laboratory and in situ experiments were performed to assess the use of bromide as a tracer forin situ studies of benthic solute exchange. Bromide was used in the benthic chamber lander ‘ Elinor ’ for flux measurements in coastal sediments of the German Bight, Kiel Bight and Skagerrak (28–700 m water depth). Tracer and total oxygen uptake were monitored simultaneously in the same chamber incubation. Concurrently, in situ oxygen micro-profiles were recorded at the same locations by the profiling lander ‘ Profilur ’. Deployment in an anoxic silt (Kiel Bight) confirmed that in the absence of bioturbation and advection, tracer transport into the sediment was driven solely by molecular diffusion. This flux could be well described by a simple box model accounting for molecular diffusion only. In oxic sediments (German Bight and Skagerrak) enhanced exchange of bromide tracer due to bioirrigation parallelled enhanced oxygen uptake equivalent to a 4-fold molecular diffusive flux. Our experiments showed that incubations can be short. Depending on irrigation activity of the fauna, however, incubation length should exceed 3 h in order to provide a useful data base for flux calculations. The method demonstrating caveats is discussed and indicate possible improvements. The results show how the bromide tracer addition can be used as a tool for determining solute fluxes exceeding diffusive flux in benthic chamber incubations.     

Tidal time-scale variation in nutrient flux across the sediment–water interface of an estuarine tidal flat

We determined the range of the tidal variations in nutrient flux across the sediment–water interface and elucidated mechanisms of the flux variation in two estuarine intertidal flats (one sand, one mud) in northeastern Japan. Nutrient flux was measured using in situ light and dark chambers, which were incubated for 2 h, 2–6 times per day. Results showed that nutrient concentration in overlying water varied by tide and was also affected by sewage-treated water inflow. The nutrient fluxes responded quickly to the tidal variation in overlying water chemistry and the range of the variation in flux was as large as the seasonal-scale variation reported in previous studies. In the sand flat, salinity increase likely enhanced benthos respiration and led to increases in both O₂ consumption and PO₄³⁻ regeneration under low illumination, while benthic microalgae were likely to actively generate O₂, uptake PO₄³⁻ and suppress PO₄³⁻ release under high illumination (>900 μmol photons m⁻² s⁻¹). Also in the mud flat, PO₄³⁻ flux was related with O₂ flux, although the range of temporal variation in PO₄³⁻ flux was small. In both the flats, NH₄⁺ flux was always governed by NH₄⁺ concentration in the overlying water; either an increase in NH₄⁺ uptake or a decrease in NH₄⁺ release was observed as the NH₄⁺ concentration rose due to inflow of river water or input of sewage-treated water. Although NO₃⁻ tended to be released in both tidal flats when low NO₃⁻ concentration seawater dominated, their relationship was likely to be weakened under conditions of low oxygen consumption and suppressed denitrification. It is likely that tidal variation in nutrient flux is governed more by the nutrient concentration than other factors, such as benthic biological processes, particularly in the case where nutrient concentration in the overlying water is relatively high and with wide amplitude.     

Non-conservative Nutrient Fluxes from Budgets for the Irish Sea

Budgets for conservative tracers are used to determine the flow through the Irish Sea and combined with available data on nutrient distributions and inputs to estimate non-conservative nutrient fluxes. Steady state salinity and caesium-137 balances yield consistent estimates of the flow through the Irish Sea of Φ≈6×10⁴ m³s⁻¹. Using both tracers together with a mass balance allows the inclusion of separate diffusive flux terms and results in a diffusivity estimate ofK≈450 m²s⁻¹and a reduced flow of Φ≈4×10⁴ m³s⁻¹. These values are, however, sensitive to the gradients of salinity and caesium-137 concentration, which are not well defined by the observations.Following the LOICZ procedures, salinity and mass balances were combined with analogous statements for dissolved inorganic phosphorus (DIP) and dissolved inorganic nitrogen (DIN), in order to assess the non-conservative process rates. With regard to phosphorus it was found that the Irish Sea is close to balance with a slight net uptake of dissolved inorganic phosphorus, but the implied excess of uptake over release is not significant on account of uncertainties in the observations of boundary values and inputs. The DIN budget is subject to comparable uncertainties in the input data but does, however, indicate a significant imbalance with an average rate of denitrification of the order 0·3 mol N m⁻²y⁻¹.The implications of these budget results and their limitations are considered in relation to the application of the budgeting approach to areas with sparse data coverage. While the application of box model disciplines to conservative tracers can lead to satisfactory estimates of advective transport, the extension to non-conservative components requires extensive data to adequately specify the boundary values and input parameters averaged over the seasonal cycle.