Dissolved and particulate trace metal geochemistry in the scheldt estuary,S. W. Netherlands (water column and sediments)

The geochemistry of dissolved and particulate trace metals has been studied in the water column and the sediments of the Scheldt estuary between 1987 and 1990. A strong seasonal influence on the behaviour of dissolved Cd, Cu and Zn is observed, related to the redox conditions in the upper estuary and phytoplankton activity in the lower estuary (which are both seasonally dependent variables). The dissolved trace metal concentrations in the fresh water end-member are remarkably low during spring and summer, due to metal sulphide precipitation in the anoxic Scheldt river. However, the dissolved concentrations increase rapidly with increasing salinity, due to oxidation of metal sulphides that are present in the suspended matter, accompanied by (e.g. chloro-)complexation of the released metals. Readsorption of Cd and Zn occurs in the lower estuary during the spring phytoplankton bloom. During winter, when the Scheldt river is not completely anoxic, much higher dissolved trace metal concentrations are observed in the fresh water end-member since metal sulphide precipitation in the water column is precluded. Rapid trace metal removal is observed in the low salinity, high turbidity zone, due to adsorption onto suspended matter and freshly precipitated iron and manganese oxyhydroxides. Upon further mixing, desorption is apparent, due to a similar oxidation-complexation mechanism as observed during spring and summer. Pore water infusion may also contribute to the enrichment of dissolved Cd, Cu and Zn in the mid-estuarine region. The trace metal contents of the suspended matter and the sediments show a continuous decrease with increasing salinity. This behaviour is to a very large extent due to physical mixing of contaminated fluvial particulates and relatively unpolluted marine particulates. Desorption of Cd, Cu and Zn can be identified but is of minor importance compared to the conservative mixing process. The distribution of dissolved Cd, Cu and Zn in the pore waters of the mid-estuarine region reflects the impact of early diagenetic processes. Trace metal peaks are observed near the sediment-water interface, and at greater depth in the manganese and iron reduction zones. These peaks are attributed to oxidation of reduced trace metal compounds (e.g. sulphides) and reduction of the (iron and manganese) oxide carrier phases, respectively. At greater depth, the dissolved trace metal concentrations are much lower due to metal sulphide precipitation in the sulphate reduction zone. Analysis of a large sediment dataset indicates severe trace metal pollution of the Scheldt estuary at the end of the fifties. A major reduction of the pollution by As, Cr, Hg, Pb, and Zn has occurred in the seventies, and of Cd and Cu in the eighties. The Ni pollution has increased over the time period considered. In spite of this improvement, the present-day pollution status of the Scheldt estuary is still reason for concern.     

Nitrification, denitrification, and nitrate ammonification in sediments of two coastal lagoons in Southern France

Summary Seasonal and diurnal variations in sediment-water fluxes of O₂, NO ₃ ^– , and NH ₄ ⁺ as well as rates of nitrification, denitrification, and nitrate ammonification were determined in two different coastal lagoons of southern France: The seagrass (Zostera noltii) dominated tidal Bassin d'Arcachon and the dystrophic Etang du Prévost. Overall, denitrification rates in both Bassin d'Arcachon (<0.4 mmol m^–2 d^–1) and Etang du Prévost (<1 mmol m^–2 d^–1) were low. This was mainly caused by a combination of low NO ₃ ^– concentrations in the water column and a low nitrification activity within the sediment. In both Bassin d'Arcachon and Etang du Prévost, rates of nitrate ammonification were quantitatively as important as denitrification.Denitrification played a minor role as a nitrogen sink in both systems. In the tidal influenced Bassin d'Arcachon, Z. noltii was quantitatively more important than denitrification as a nitrogen sink due to the high assimilation rates of the plants. Throughout the year, Z. noltii stabilized the mudflats of the bay by its well- developed root matrix and controlled the nitrogen cycle due to its high uptake rates. In contrast, the lack of rooted macrophytes, and dominance of floating macroalgae, made nitrogen cycling in Etang du Prévost more unstable and unpredictable. Inhibition of nitrification and denitrification during the dystrophic crisis in the summer time increased the inorganic nitrogen flux from the sediment to the water column and thus increased the degree of benthic-pelagic coupling within this bay. During winter, however, benthic microalgae colonizing the sediment surface changed the sediment in the lagoon from being a nitrogen source to the over lying water to being a sink due to their high assimilation rates. It is likely, however, that this assimilated nitrogen is liberated to the water column at the onset of summer thereby fueling the extensive growth of the floating macroalgae, Ulva sp. The combination of a high nitrogen coupling between sediment and water column, little water exchange and low denitrification rates resulted in an unstable system with fast growing algal species such as phytoplankton and floating algae.     

Behaviour of selected PCBs,PAHs and γ-HCH in the Scheldt estuary,S.W. Netherlands

The behaviour of some organic micropollutants in the abiotic compartments water, particulate matter and bottom sediments of the Scheldt estuary, S.W. Netherlands, was studied between 1986 and 1989. Special attention was given to two individual PolyChlorinated Biphenyl congeners (PCB 52 and PCB 153), two Polycyclic Aromatic Hydrocarbons (PAHs) fluoranthene and benzo(a)pyrene and γ-HCH. Dissolved PCBs and γ-HCH behave conservatively during estuarine mixing. The concentration of γ-HCH in the fresh-water is extremely high in spring compared to the other seasons. Dissolved fluoranthene does not behave conservatively. The concentration of dissolved fluoranthene in the freshwater endmember shows a seasonal dependence with highest concentrations in winter and lowest in summer. Benzo(a)pyrene could hardly be detected in the dissolved phase with the methods used. PCBs and PAHs in particulate matter and sediments behave essentially conservatively as a result of the mixing of riverine particulates with high, and marine particulates with low organic micropollutant contents. Particulate fluoranthene is removed at low salinities under (nearly) anoxic conditions probably by microbial degradation. The rivers Scheldt and Rupel appear to be the major sources for the compounds studied. However, in particular the organic micropollutant contents of the sediments indicate that important emissions along the estuary were or are still present. Measurements of individual PCBs and PAHs in the <63 μm fraction of a dated sediment core from a salt marsh in the eastern part of the Scheldt estuary show that the recent input of PCBs and PAHs into the estuaryis probably 2–3 times lower than the maximum input in the mid-1960s. The PCB profile shows postdepositional congener-selective mobilization caused by advective transport. The PAH assemblage is remarkably uniform in the sediment core. The PAH ratios indicate that combustion of coal is the main source of PAHs in the Scheldt estuary.     

Nitrogen dynamics in the Westerschelde estuary (SW Netherlands) estimated by means of the ecosystem model MOSES

A tentative nitrogen budget for the Westerschelde (SW Netherlands) is constructed by means of a simulation model with thirteen spatial compartments. Biochemical and chemical processes in the water column are dynamically modeled; fluxes of dissolved constituents across the water-bottom interface are expressed by means of diagenetic equations.The model is calibrated on a large amount of observed variables in the estuary (1980–1986) with relatively fine temporal and spatial detail. Additional constraints are imposed by the stoichiometric coupling of carbon, nitrogen and oxygen flows and the required conservation of mass. The model is able to reproduce rather well the observed distributions of nitrate, ammonium, oxygen and Kjeldahl nitrogen both in time and space. Also, model output of biochemical oxygen demand and total organic carbon falls within observed ranges.By far the most pervasive process in the nitrogen cycle of the estuary is nitrification which mainly takes place in the water column of the upper estuarine part. On average about three times as much nitrate is leaving the estuary at the sea side compared to what enters from the river and from waste discharges. Ammonium on the other hand is consumed much faster (nitrification) than it is regenerated and only about one third of the total import leaves the estuary at the sea side. The budget for detrital nitrogen reveals import from the river, from wastes and from the sea. Phytoplankton uptake of inorganic nitrogen is negligible in the model.About 21% of total nitrogen, 33% of inorganic nitrogen, is removed from the estuary (mainly to the atmosphere through denitrification) and the load of nitrogen net exported to the sea amounts to about 51 000 tonnes per year. Total denitrification in our model is lower than what was estimated in the literature from the late seventies, where a nitrogen removal up to 40–50% of the total inorganic load was reported. Part of the differences could be methodological, but inspection of the nutrient profiles that led to these conclusions show them to be different to the ones used in our study. The oxygen deficient zone has moved upstream since the late seventies, entrailing the zone of denitrification into the riverine part of the Schelde. The nitrification process now starts immediately upon entering the estuary.     

Denitrification,Nitrificastion and Nitrogen Fixation in Sublittoral Sediments of the South China Sea

Measurements of denitrification, nitrification and nitrogen fixation rates were made alongside with measuring of chemical and physical properties in sublittoral sediments of the South China Sea near the coast of Vietnam. Studied sediments were suboxic (Eh was positive as a rule), had 0.18–1.5 % of organic carbon, 0.004–0.135 % of total nitrogen and 3-12 % of total iron. The numbers of denitrifying and nitrate-reducing bacteria were as high as millions and hundreds of millions cells per gram wet weight of sediment matter, respectively. The processes of nitrification and denitrification were not spearated spacely. The nitrification was measured in both superficial layer and in a 10-cm sediment column. There were indirect evidences suggesting possibility of anaerobic ammonium oxidation. Denitrification was detectable in the sediments from two sites of sampling; maximal value was 86.2 μmoles N m⁻²h⁻¹. The denitrification potential determined at 1 mM nitrate decreased regularly from the upper to lower layers. Its values in the different sediments ranged from 134 to 532 μmoles N m⁻²h⁻¹. Nitrogen fixation (from 4.8 to 86μmoles N m⁻²h⁻¹) was close to that found in similar sediments in temperate waters in summer, and was not a significant source of nitrogen. It was comparable with diffusion of ammonium from sedimnts.     

Nitrogen Behaviour and Nitrous Oxide Emission in the Tidal Seine River Estuary (France) as Influenced by Human Activities in the Upstream Watershed

The Seine River estuary (France) is the receptacle of a drainage basin characterised by high population density, heavy industrial activity and intensive agriculture. Whereas nitrate concentrations are high due to diffuse sources in the upstream drainage basin, ammonium mainly originates from the effluents of the Achères wastewater treatment plant (WWTP) downstream from Paris and its suburbs (6.5 million equivalent-inhabitants). Ammonium is mostly nitrified in the tidal freshwater estuary and nitrification causes a strong summer oxygen deficit. Average longitudinal summer profiles of oxygen and nitrogen concentrations for two periods, between 1993–1997 and 1998–2003 in dry hydrological conditions (excluding the wet years 2000 and 2001) clearly reflect the changes due to the improved treatment of wastewater from Paris and its suburbs. On the basis of daily water flux data and twice monthly nitrogen measurements at the boundaries of the upstream freshwater estuarine section (108 km), we calculated nitrification and denitrification fluxes, whose annual averages were 43 and 71 × 10³ kg N d⁻¹ respectively from 1993 to 2003, with summer values (July–September) representing 73 and 57% of the annual fluxes, respectively. The degree of denitrification in the upper estuary appears to be closely related to the nitrification, itself more loosely related to the amount of reduced nitrogen (Kjeldahl) brought by the treated effluents from the Achères WWTP. We estimated the total N₂O emissions to about 40 kg N d⁻¹ (25–60 kg N d⁻¹) in the same sector.     

Experimental measurement of sediment nitrification and denitrification in Hamilton Harbour,Canada

This research examines the role of sediment nitrification and denitrification in the nitrogen cycle of Hamilton Harbour. The Harbour is subject to large ammonia and carbon loadings from a waste-water treatment plant and from steel industries. Spring ammonia concentrations rapidly decrease from 4.5 to 0.5 mg 1⁻¹, while spring nitrate concentrations increase from 1 to 2 mg l⁻¹, by mid-summer. A three-layer sediment model was developed. The first layer is aerobic; in it, oxidation of organics and nitrification occurs. The second layer is for denitrification, and the third layer is for anaerobic processes. Ammonia sources for nitrification include diffusion from the water column, sources associated with the oxidation of organics, sources from denitrification and from anaerobic processes. Diffusion of oxygen, ammonia and nitrate across the sediment-water interface occurs. Temperature effects are modelled using the Arrhenius concept. A combination of zero-order kinetics for nitrate or ammonia consumption with diffusion results in a half-order reaction, with respect to the water column loss rate to sediments. From experimental measurement, the rate of nitrification is 200 mg N 1⁻¹ sediment per day, while that of denitrification is 85 mg N 1–1 sediment per day at 20 °C. The Arrhenius activation energy is estimated as 15 000 cal/ mole-K and 17 000 cal/ mole-K for nitrification and denitrification, respectively, between 10 °C and 20 °C. Calculations of the flux of ammonia with the sediments, using the biofilm model, compare favourably with experimental observations. The ammonia flux from the water column is estimated to account for 20% of the observed decrease in water column stocks of ammonia, while the nitrate flux from the water column is estimated to account for 25% of the total nitrogen produced by the sediments.     

Influence of hydrological connectivity of riverine wetlands on nitrogen removal via denitrification

Wetland ecosystems in agricultural areas often become progressively more isolated from main water bodies. Stagnation favors the accumulation of organic matter as the supply of electron acceptors with water renewal is limited. In this context it is expected that nitrogen recycling prevails over nitrogen dissipation. To test this hypothesis, denitrification rates, fluxes of dissolved oxygen (SOD), inorganic carbon (DIC) and nitrogen and sediment features were measured in winter and summer 2007 on 22 shallow riverine wetlands in the Po River Plain (Northern Italy). Fluxes were determined from incubations of intact cores by measurement of concentration changes or isotope pairing in the case of denitrification. Sampled sites were eutrophic to hypertrophic; 10 were connected and 12 were isolated from the adjacent rivers, resulting in large differences in nitrate concentrations in the water column (from <5 to 1,133 μM). Benthic metabolism and denitrification rates were investigated by two overarching factors: season and hydrological connectivity. SOD and DIC fluxes resulted in respiratory quotients greater than one at most sampling sites. Sediment respiration was coupled to both ammonium efflux, which increased from winter to summer, and nitrate consumption, with higher rates in river-connected wetlands. Denitrification rates measured in river-connected wetlands (35–1,888 μmol N m^?2 h^?1) were up to two orders of magnitude higher than rates measured in isolated wetlands (2–231 μmol N m^?2 h^?1), suggesting a strong regulation of the process by nitrate availability. These rates were also significantly higher in summer (9–1,888 μmol N m^?2 h^?1) than in winter (2–365 μmol N m^?2 h^?1). Denitrification supported by water column nitrate (D_W) accounted for 60–100% of total denitrification (Dtot); denitrification coupled to nitrification (D_N) was probably controlled by limited oxygen availability within sediments. Denitrification efficiency, calculated as the ratio between N removal via denitrification and N regeneration, and the relative role of denitrification for organic matter oxidation, were high in connected wetlands but not in isolated sites. This study confirms the importance of restoring hydraulic connectivity of riverine wetlands for the maintenance of important biogeochemical functions such as nitrogen removal via denitrification.     

Inorganic nitrogen dynamics in the River Seine downstream from Paris (France)

The River Seine, below Paris, receives the effluents from a large sewage treatment plant, increasing the ammonium concentration up to 6 mgN.1⁻ in late summer. Careful measurement of ammonium, nitrate and organic nitrogen during the downriver travel of the water masses over 100 km below the outfall, along with direct determination of nitrification and benthic fluxes, allowed to establish a budget of nitrogen transport and transformations in this reach of the river. Nitrification is shown to start after a distinct period of several days required for the growth of a significant nitrifying bacterial population. Denitrification is active in the upper layer of bottom sediments but absent from the water column. Comparison of our data with those published for the period 1973–1976 shows that the nitrate load carried by the river has increased not only because of higher runoff of agricultural nitrate in the upstream part of the watershed, but also as a result of the severe reduction in the rate of denitrification processes, owing to the restoration of better oxygen conditions.     

Vertical Patterns of Nitrogen Transformations during Infiltration in Two Wetland Soils

The (sup15)N isotope dilution and pairing methods were applied to investigate the vertical distribution of nitrogen transformations during infiltration in one peaty soil and one sandy soil. Water containing (sup15)N-nitrate (99.9%; 200 (mu)M) as the only nitrogen fraction was infiltrated through cores containing homogenized soil, with lengths varying from 5.5 to 38 cm. Oxygen and nitrogen dynamics were investigated by measuring inflowing and outflowing water. The experimental design allowed determinations of vertical profiles of aerobic respiration, nitrification, and coupled and uncoupled denitrification and ammonification. In the sandy soil, all oxygen was consumed in the upper 14 cm and nitrate was subsequently consumed and removed, up to a maximum of 70% in the longest core (28 cm). In the peaty soil, oxygen was consumed in the upper 7.5 cm and all nitrate was denitrified in the top 20 cm. In both soils, nitrogen removal by denitrification was counteracted by the release of ammonium and dissolved organic nitrogen. In the sandy soil, net nitrogen removal occurred in cores of 14 cm and longer; in the longest core, 40% was removed. In the peaty soil, release was equal to removal in the top 14 cm but release exceeded removal in the deeper layers, leading to a 100% increase of total nitrogen in the effluent water from the longest core (38 cm).     

The winter and summer partitioning of dissolved nitrogen and phosphorus. Observations across the Irish Sea during 1997 and 1998

Winter and summer water column profiles from a transect co-inciding with the 54° N parallel across the Irish Sea were examined for relationships between the fractions of total dissolved nitrogen and phosphorus. Inorganic nitrogen and phosphorus gave the expected seasonal variation. As inorganic nitrogen concentrations decreased during the summer, dissolved organic nitrogen concentrations increased. Dissolved organic phosphorus showed little seasonal variation and formed a smaller fraction of the total dissolved pool compared to nitrogen. Winter inorganic nitrogen and phosphorus salinity relationships were conservative: winter organic nitrogen and phosphorus salinity relationships were not conservative. In the winter, dissolved organic nitrogen and phosphorus formed a significant fraction of the total dissolved pool.     

Seasonal oxygen,nitrogen and phosphorus benthic cycling along an impacted Baltic Sea estuary: regulation and spatial patterns

The regulatory roles of temperature, eutrophication and oxygen availability on benthic nitrogen (N) cycling and the stoichiometry of regenerated nitrogen and phosphorus (P) were explored along a Baltic Sea estuary affected by treated sewage discharge. Rates of sediment denitrification, anammox, dissimilatory nitrate reduction to ammonium (DNRA), nutrient exchange, oxygen (O₂) uptake and penetration were measured seasonally. Sediments not affected by the nutrient plume released by the sewage treatment plant (STP) showed a strong seasonality in rates of O₂ uptake and coupled nitrification–denitrification, with anammox never accounting for more than 20 % of the total dinitrogen (N₂) production. N cycling in sediments close to the STP was highly dependent on oxygen availability, which masked temperature-related effects. These sediments switched from low N loss and high ammonium (NH₄ ⁺) efflux under hypoxic conditions in the fall, to a major N loss system in the winter when the sediment surface was oxidized. In the fall DNRA outcompeted denitrification as the main nitrate (NO₃ ^?) reduction pathway, resulting in N recycling and potential spreading of eutrophication. A comparison with historical records of nutrient discharge and denitrification indicated that the total N loss in the estuary has been tightly coupled to the total amount of nutrient discharge from the STP. Changes in dissolved inorganic nitrogen (DIN) released from the STP agreed well with variations in sedimentary N₂ removal. This indicates that denitrification and anammox efficiently counterbalance N loading in the estuary across the range of historical and present-day anthropogenic nutrient discharge. Overall low N/P ratios of the regenerated nutrient fluxes impose strong N limitation for the pelagic system and generate a high potential for nuisance cyanobacterial blooms.     

Assessing Nitrification and Denitrification in the Seine River and Estuary Using Chemical and Isotopic Techniques

Downstream from metropolitan Paris (France), a large amount of ammonium is discharged into the Seine River by the effluents of the wastewater treatment plant at Achères. To assess the extent of nitrification and denitrification in the water column, concentrations and isotopic compositions of ammonium (δ¹⁵N–NH₄⁺) and nitrate (δ¹⁵N–NO₃⁻, δ¹⁸O–NO₃⁻) were measured during summer low-flow conditions along the lower Seine and its estuary. The results indicated that most of the ammonium released from the wastewater treatment plant is nitrified in the lower Seine River and its upper estuary, but there was no evidence for water-column denitrification. In the lower part of the estuary, however, concentration and isotopic data for nitrate were not consistent with simple mixing between riverine and marine nitrate. A significant departure of the nitrate isotopic composition from what would be expected from simple mixing of freshwater and marine nitrates suggested coupled nitrification and denitrification in the water, in spite of the apparent conservative behavior of nitrate. Denitrification rates of approximately 0.02 mg N/L/h were estimated for this part of the estuary.     

Gross Nitrogen Mineralization in Surface Sediments of the Yangtze Estuary

Nitrogen mineralization is a key biogeochemical process transforming organic nitrogen to inorganic nitrogen in estuarine and coastal sediments. Although sedimentary nitrogen mineralization is an important internal driver for aquatic eutrophication, few studies have investigated sedimentary nitrogen mineralization in these environments. Sediment-slurry incubation experiments combined with ¹⁵N isotope dilution technique were conducted to quantify the potential rates of nitrogen mineralization in surface sediments of the Yangtze Estuary. The gross nitrogen mineralization (GNM) rates ranged from 0.02 to 5.13 mg N kg^-1 d^-1 in surface sediments of the study area. The GNM rates were generally higher in summer than in winter, and the relative high rates were detected mainly at sites near the north branch and frontal edge of this estuary. The spatial and temporal distributions of GNM rates were observed to depend largely on temperature, salinity, sedimentary organic carbon and nitrogen contents, and extracellular enzyme (urease and L-glutaminase) activities. The total mineralized nitrogen in the sediments of the Yangtze Estuary was estimated to be about 6.17 × 10⁵ t N yr^-1, and approximately 37% of it was retained in the estuary. Assuming the retained mineralized nitrogen is totally released from the sediments into the water column, which contributed 12–15% of total dissolved inorganic nitrogen (DIN) sources in this study area. This result indicated that the mineralization process is a significant internal nitrogen source for the overlying water of the Yangtze Estuary, and thus may contribute to the estuarine and coastal eutrophication.     

海岸带地区的固氮、氨化、硝化与反硝化特征

海岸带是海洋环境中受人类活动影响最大、生物地球化学循环最为活跃的地区。这一地区氮的生物地球化学循环包括 :生物固氮、有机氮的氨化、氮的硝化、反硝化等 4个主要过程。概括性地介绍了有关这四个过程的发生机制、环境影响因素及研究方法等方面的研究动态、进展、存在的科学问题与今后的研究方向。过去十几年来 ,固氮主要集中在对束毛藻属的研究上 ,其间有两个重要发现 ,一是生物固氮在海洋氮循环中的作用远比人们以前的想象要重要得多 ;二是蓝细菌已经在海洋中存在了 2 0亿年 ,它们有可能调节大气中的 CO2 ,进而影响全球气候。由于有机物的结构千差万别 ,含氮有机物的氨化过程可能是一个简单的矿化反应 ,也有可能是一系列复杂的代谢过程 ,在水解酶的作用下含氮有机物降解为下一级化合物。硝化过程分两步进行 ,氨的硝化为反硝化细菌提供了重要的硝酸盐来源 ,通常采用同位素方法来研究硝化过程。发生在沉积物中的反硝化过程是氮循环的关键步骤 ,反硝化过程一方面减少了海水中初级生产者可利用的氮 ,另一方面产生了终结产物 N2 和 N2 O,而 N2 O是一种温室气体 ,可能影响全球气候变化     

Limitation of primary production by heterotrophic assimilation and transformation of inorganic nutrients

The planktonic environment is usually characterized by non-steady state conditions with events of phytoplankton blooms and sedimentation. Inorganic nutrients are stripped from the water column by sedimentation and end up in the sediments where they may be permanently deposited, or nitrogen may be liberated as nitrogen gas by denitrification. A major part of the denitrification activity is a coupled process of nitrification and denitrification which is dependent on a good supply of oxygen to the sediment. Urea may constitute a major part of the total outflux of dissolved N compounds from the sediment.     

Nitrogen cycle of Lake Vechten: concentration patterns and internal mass-balance

Concentration patterns of ammonia, nitrate and particulate- and dissolved organic nitrogen in Lake Vechten (The Netherlands) are given. The main processes playing a role in the lake's nitrogen cycle are inventorized. During spring and summer, the uptake of ammonia and nitrate by primary producers, accompanied by sedimentation of organic matter, result in significant nitrogen losses from the 0–6 m stratum. Ammonia accumulates during the stratification in the hypolimnion and after the autumn overturn is recirculated over the whole water column. In winter, release of ammonia from the sediments and nitrification further restore the lake's nutrient supply. The changes in nitrogen content of the different compartments are quantified, giving a basis for more detailed research.     

MMHg production and export from intertidal sediments to the water column of a tidal lagoon (Arcachon Bay,France)

Hg cycling in biologically productive coastal areas is of special importance given the potential for bioaccumulation of monomethylmercury (MMHg) into aquatic organisms. Field experiments were performed during three different seasons in Arcachon Bay, a mesotidal lagoon (SW France), to assess the variability of the water column concentrations, sediment–water exchanges and potential formation and degradation of MMHg. The objectives were to evaluate the contribution of intertidal mudflats to MMHg production and the various pathways of Hg species export. Dissolved and bulk concentrations of Hg species in the water column downstream of tidal flats were measured throughout several tidal cycles. The Hg benthic fluxes at the sediment–water interface were determined by means of benthic chambers for three different stations. Hg methylation and demethylation potentials were determined in surficial sediments and the water column using isotopic tracers. The tidal surveys demonstrated that benthic remobilization of Hg occurs primarily in association with sediment erosion and advection during ebb tide. However, elevated dissolved Hg concentrations observed at low tide were found to be caused by a combination of pore-waters seeping, benthic fluxes and methylation in the water column. Benthic fluxes were more intense during late winter conditions (median MMHg and inorganic Hg (IHg) fluxes: 64 and 179 pmol m^?2 h^?1, respectively) and subsequently decreased in spring (median 0.7 and ?5 pmol m^?2 h^?1, respectively) and fall (median ?0.4 and ?1.3 pmol m^?2 h^?1, respectively). The trends in methylation and demethylation potentials were at the opposite of the fluxes, two times lower during winter than for spring or fall conditions. In this tidal environment, MMHg production in surface sediments and its subsequent release is estimated to be the major source of MMHg to the water column during winter and spring time. However, during the more productive summer period, the Hg methylation extent in the water column may be very significant and equivalent to the sediment contribution.     

Annual Pattern of Denitrification and Nitrate Ammonification in Estuarine Sediment

The seasonal variation and depth distribution of the capacity for denitrification and dissimilatory NO₃⁻ reduction to NH₄⁺ (NO₃⁻ ammonification) were studied in the upper 4 cm of the sediment of Norsminde Fjord estuary, Denmark. A combination of C₂H₂ inhibition and ¹⁵N isotope techniques was used in intact sediment cores in short-term incubations (maximum, 4 h). The denitrification capacity exhibited two maxima, one in the spring and one in the fall, whereas the capacity for NO₃⁻ ammonification was maximal in the late summer, when sediments were progressively reduced. The denitrification capacity was always highest in the uppermost 1 cm of the sediment and declined with depth. The NO₃⁻ ammonification was usually higher with depth, but the maximum activity in late summer was observed within the upper 1 cm. The capacity for NO₃⁻ incorporation into organic material was investigated on two occasions in intact sediment cores and accounted for less than 5% of the total NO₃⁻ reduction. Denitrification accounted for between 13 and 51% of the total NO₃⁻ reduction, and NH₄⁺ production accounted for between 4 and 21%, depending on initial rates during the time courses. Changes of the rates during the incubation were observed in the late summer, which reflected synthesis of denitrifying enzymes. This time lag was eliminated in experiments with mixed sediment because of preincubation with NO₃⁻ and alterations of the near-environmental conditions. The initial rates obtained in intact sediment cores therefore reflect the preexisting enzyme content of the sediment.     

Short-term influence of recolonisation by the polycheate worm [2pt] Nereis succinea on oxygen and nitrogen fluxes and [2pt] denitrification: a microcosm simulation

The short-term effects of sediment recolonisation by Nereis succinea on sediment-water column fluxes of oxygen and dissolved inorganic nitrogen, and rates of denitrification, were studied in microcosms of homogenised, sieved sediments. The added worms enhanced oxygen uptake by the sediments, due to the increased surface area provided by the burrow walls and the degree of stimulation was stable with time. Similarly, ammonium fluxes to the water column were stimulated by N. succinea, but declined over the 3 day incubation in all microcosms including the controls. Nitrate fluxes were generally greater in the faunated microcosms, but highly variable with time. Denitrification rates were positively stimulated by N. succinea populations, denitrification of water column nitrate was stimulated 10-fold in comparison to denitrification coupled to nitrification in the sediments. Rates of denitrification of water column nitrate were not significantly different from rates in undisturbed sediment cores with similar densities of N. succinea, whereas rates of coupled nitrification–denitrification were 3-fold lower in the experimental set-up. These results may reflect the relative growth rates of nitrifying and denitrifying bacteria, which allow more rapid colonisation of new burrow surfaces by denitrifier compared to nitrifier populations. The data indicate that recolonisation by burrowing macrofauna of the highly reduced sediments of the Sacca di Goro, Lagoon, Italy, following the annual dystrophic crisis, may play a significant role in the reoxidation and detoxification of the sediments. The increased rates of denitrification associated with the worm burrows, may promote nitrogen losses, but due to the low capacity of nitrifying bacteria to colonise the new burrow structures, these losses would be highly dependent upon water column nitrate concentrations.