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Excessive inputs of phosphorus (P) to aquatic environments can lead to eutrophication. Adsorption of phosphate on Fe oxides is one of the main process that can limit P availability. Oxidized forms of Mn have also been suggested to play a role in P trapping. However, although a considerable number of studies have shown the relationships between the geochemistry of Fe and that of phosphates, few studies have attempted to show the direct links between Mn and P. In the present study, we studied the adsorption of phosphate on synthetized Mn(III) and Mn(IV) oxides placed under natural conditions. The aim was to compare the role of Fe and Mn oxides in phosphate adsorption. Two muddy sediments were collected in a river bed at the edge of a large agricultural area. A sandy sediment was collected downstream. A muddy and a sandy sample were taken in a coastal environment. The experiments on phosphate adsorption by sediment and Mn oxides were carried out in slurries containing in situ waters spiked with 10 μM phosphate. Control experiments without Mn-oxide addition showed that the natural sediments tested still had the capacity to adsorb phosphate, in particular due to the presence of reactive Fe(III) oxides, extractable by an ascorbate solution. The addition of Mn(III) and Mn(IV) oxides in much larger quantities than the initial quantity of Fe oxides had little impact on the rate of phosphate adsorption. For both Mn(III) and Mn(IV) oxides, the Mn/P ratio between added particulate Mn and adsorbed P was very high, with values between 260 and 1000. The Fe/P ratio of the iron oxides contained in the slurries was between 6 and 20. On average, the P adsorption capacity of the Fe oxides was 50 times greater than that of the Mn oxides. Manganese oxides are generally less abundant than iron oxides in natural environments. Mn oxides therefore play a minor role in P sequestration compared with Fe oxides. Even if there are environments where Mn oxides can concentrate, the reduction of Mn oxides and subsequent liberation of adsorbed P does not represent a major risk for eutrophication of aquatic ecosystems. • Experiments on PO 4 adsorption on Mn(III,IV) oxides added to natural freshwater and coastal sediments. • Small amount of iron oxide has a much greater phosphate adsorption capacity than a large amount of Mn-ox. • Sequestering a given quantity of phosphate would require on average 50 times more Mn oxides than Fe oxides. [ABSTRACT FROM AUTHOR]

High-energy tidal beaches are exposed to strong physical forcings. The submarine groundwater discharge (SGD) that occurs in intertidal sandy sediments includes both terrestrial, fresh groundwater flow and seawater recirculation, and plays a significant role in regulating biogeochemical cycles in some coastal zones. In this transition zone between land and sea, complex biogeochemical reactions alter the chemical composition of pore waters that discharge to the coastal ocean. Recent studies highlight that SGD can be a significant source of carbon to the coastal ocean but very few have investigated SGD in high-energy environments. We have characterized the dissolved carbon dynamics in such a high-energy environment (Truc Vert Beach, SW France) through pore-water sampling in key compartments of the SGD system. Dissolved organic carbon (DOC), pH, total alkalinity (TA), and the isotopic composition of dissolved inorganic carbon (δ13C-DIC) were measured in pore waters sampled at regular intervals between 2011 and 2014 in the intertidal zone of the beach, the mixing zone of the subterranean estuary (STE), and the freshwater aquifer upstream from the beach. Results reveal that SGD exports dissolved carbon mostly as DIC to the Aquitaine coast, some of which originates from the aerobic respiration of marine organic matter within the beach aquifer. This is highlighted by the reverse spatial trend of DOC, which is consumed, and DIC, which is produced. Saline pore waters expelled from the beach through tidally-driven recirculation of seawater provide about 4400 tons of carbon per year to the coastal zone of the 240-km long Aquitaine sandy coast. Terrestrial groundwater, characterized by high pCO 2 values, is also a significant contributor to the DIC flux to the coastal ocean (16,200 tons per year). This flux is abated by CO 2 evasion in the upper beach, at the onset of the salinity gradient in the STE, and within the surficial freshwater aquifer along the forest-beach transect below the coastal foredune. Accordingly, the DIC:TA ratio evolves to below 1, suggesting that this SGD increases the buffer capacity of coastal seawater against acidification. This study demonstrates that high-energy beaches are active vectors of DIC from the land to the coastal ocean as well as significant sources of CO 2 to the atmosphere, and must therefore be taken into consideration in SGD carbon budgets. [ABSTRACT FROM AUTHOR]

Mercury (Hg) and methyl mercury (MeHg) concentrations have never been measured in sediments of coastal lakes of Aquitaine, although high concentrations of Hg have been measured in fish. Our objective was to characterize benthic biogeochemical processes and the distribution of Hg in lake sediments and to connect these results with fish contamination. For this, we mapped and characterized sediments. We measured sediment Hg and MeHg content, and biogeochemical parameters. We identified organic deposits in deep areas, and sandy sediments in shallow areas. Sediments were anoxic below the sediment–water interface. The average Hg concentration in organic sediment was 213 μg kg−1 dry weight. Sandy sediments had an average Hg concentration of 4 μg kg−1 dw. We measured concentrations below 6 μg kg−1 dw in sediments from streams that drain the catchment. Similar concentrations in the four lakes suggest that the source of total Hg was not a point source in a given lake. The highest MeHg concentrations were found in the upper centimetres of organic sediments, where sulphate reduction occurred. MeHg represented 2.53% of total Hg for Lake Carcans-Hourtin, less in other lakes. The proportion of MeHg in sediment followed lake water sulphate concentrations. High sulphate concentrations resulted from agricultural activity in the Lake Carcans-Hourtin catchment. Our results corroborate the hypothesis that Hg methylation is linked to sulphate-reducing activity. High fluxes of sulphate from a drainage basin may induce large proportions of potentially bioavailable MeHg in lake sediment, even in non-polluted areas. The Hg methylation activity in the sediment reflected the exposure of predatory fish to MeHg. Image 1 • Hg and methyl mercury (MeHg) in sediments from 4 great lakes of the Aquitaine coast. • Hg concentrations follows organic matter content and are similar in the 4 lakes. • MeHg concentration differs between lakes and is related to sulphate concentration. • Sulphate originates from agricultural activities. • Fish contamination follows sediment MeHg and water sulphate gradient. [ABSTRACT FROM AUTHOR]

Abstract During land-aquatic transfer, carbon (C) and inorganic nutrients (IN) are transformed in soils, groundwater, and at the groundwater-surface water interface as well as in stream channels and stream sediments. However, processes and factors controlling these transfers and transformations are not well constrained, particularly with respect to land use effect. We compared C and IN concentrations in shallow groundwater and first-order streams of a sandy lowland catchment dominated by two types of land use: pine forest and maize cropland. Contrary to forest groundwater, crop groundwater exhibited oxic conditions all-year round as a result of higher evapotranspiration and better lateral drainage that decreased the water table below the organic-rich soil horizon, prevented the leaching of soil-generated dissolved organic carbon (DOC) in groundwater, and thus limited consumption of dissolved oxygen (O 2). In crop groundwater, oxic conditions inhibited denitrification and methanogenesis resulting in high nitrate (NO 3 −; on average 1140 ± 485 μmol L−1) and low methane (CH 4 ; 40 ± 25 nmol L−1) concentrations. Conversely, anoxic conditions in forest groundwater led to lower NO 3 − (25 ± 40 μmol L−1) and higher CH 4 (1770 ± 1830 nmol L−1) concentrations. The partial pressure of carbon dioxide (pCO 2 ; 30,650 ± 11,590 ppmv) in crop groundwater was significantly lower than in forest groundwater (50,630 ± 26,070 ppmv), and was apparently caused by the deeper water table delaying downward diffusion of soil CO 2 to the water table. In contrast, pCO 2 was not significantly different in crop (4480 ± 2680 ppmv) and forest (4900 ± 4500 ppmv) streams, suggesting faster degassing in forest streams resulting from greater water turbulence. Although NO 3 −concentrations indicated that denitrification occurred in riparian-forest groundwater, crop streams nevertheless exhibited important signs of spring and summer eutrophication such as the development of macrophytes. Stream eutrophication favored development of anaerobic conditions in crop stream sediments, as evidenced by increased ammonia (NH 4 +) and CH 4 in stream waters and concomitant decreased in NO 3 − concentrations as a result of sediment denitrification. In crop streams, dredging and erosion of streambed sediments during winter sustained high concentration of particulate organic C, NH 4 + and CH 4. In forest streams, dissolved iron (Fe2+), NH 4 + and CH 4 were negatively correlated with O 2 reflecting the gradual oxygenation of stream water and associated oxidations of Fe2+, NH 4 + and CH 4. The results overall showed that forest groundwater behaved as source of CO 2 and CH 4 to streams, the intensity depending on the hydrological connectivity among soils, groundwater, and streams. CH 4 production was prevented in cropland in soils and groundwater, however crop groundwater acted as a source of CO 2 to streams (but less so than forest groundwater). Conversely, in streams, pCO 2 was not significantly affected by land use while CH 4 production was enhanced by cropland. At the catchment scale, this study found substantial biogeochemical heterogeneity in C and IN concentrations between forest and crop waters, demonstrating the importance of including the full vegetation-groundwater-stream continuum when estimating land-water fluxes of C (and nitrogen) and attempting to understand their spatial and temporal dynamics. Graphical abstract Unlabelled Image Highlights • Forest groundwater was in anoxic conditions whereas crop groundwater was in oxic conditions. • Leaching of soil DOC occurred mostly in forest groundwater during high flow period. • CO 2 and CH 4 were higher in forest groundwater than in crop groundwater. • CH 4 was higher in crop streams compared to forest streams. • CO 2 was not different between crop streams and forest streams. [ABSTRACT FROM AUTHOR]

Abstract In coastal environments, oscillating redox conditions represent a functional state affecting organic matter mineralization. Such transient diagenetic processes remain difficult to study in situ, and we therefore designed a specific reactor to provide experimental results that are environmentally relevant in this context. Here, we present the results of two independent experiments carried out with sediment having contrasting Fe, Mn contents, collected from a coastal tidal lagoon (the Arcachon bay) and a mesotidal estuary (Adour river). Sediment and overlying water were mixed to form slurries that were submitted to redox oscillations to assess the diagenetic mechanisms that affect N, P, Fe, Mn, and S. Changing from anoxic to oxic conditions, we observed a rapid oxidation of dissolved Fe(II) and dissolved inorganic phosphorus (DIP) was apparently trapped by the newly formed Fe-oxyhydroxides (Fe-ox). DIP was totally titrated in the coastal lagoon sediment, but not in estuarine sediment, where the initial amount of Fe available was lower. In both experiments, Mn(II) was only slowly oxidized during the oxidation events and a major part of Mn(II) was adsorbed on new Fe-ox. In coastal lagoon sediment, ammonium remained constant in oxic conditions while nitrate was produced from organic-N mineralization. On the contrary, in estuarine sediment, ammonium was quantitatively oxidized to nitrate. When the conditions became anoxic again, direct reduction of nitrate to ammonium occurred in coastal lagoon sediment. Anaerobic production of nitrate occurred in estuarine sediment, probably because Mn-oxides (Mn-ox), which had a high concentration, acted as an oxidant for ammonium. Consequently, nitrate production prevented Fe(II) accumulation. The Mn-N-Fe coupling outlined here is an apparent indirect oxidation of Fe(II) by Mn-ox through anaerobic nitrification (with Mn-ox) and denitrification (with Fe-ox). This coupling also implied P availability because of the strong control of P by Fe. These experimental results show that nutrient dynamics in oscillatory redox environments such as the estuarine turbidity zone, bioturbated sediment, or tidal permeable sediments highly depends on Mn-and Fe-ox availability. Highlights • We designed a reactor to simulate oscillating redox conditions. • Two sediments with different Mn oxide content submitted to redox oscillations. • Nutrient dynamics depends on reactive Fe and Mn content. • We outline a Mn-N-Fe coupling, which also imply P availability. • Anaerobic nitrification with Mn-ox and denitrification with Fe-ox. [ABSTRACT FROM AUTHOR]

Abstract Manganese (Mn) is a major redox reactive element in marine sediments and it plays an important role in the biogeochemical cycles of carbon, nitrogen, phosphorus, or trace metals. Mn cycle in marine sediments is characterized by an alternation of oxidation and reduction processes depending on physicochemical and biological conditions: assessing the quantification and the speciation of Mn is thus an essential issue to understand redox reaction-transport processes in sedimentary deposits. Solid Mn phases can be determined through chemical extractions techniques that permits selective leaching of operationally defined Mn fractions. Mn oxides and oxyhydroxides are extracted with an ascorbate leaching solution, while the whole Mn (oxyhydr-)oxides and Mn associated to carbonates is extracted with HCl. An existing spectrophotometric method allows to quantify Mn dissolved in (sea) water. We present here a modified version, which permits to measure Mn in acidified matrices, including ascorbate and HCl solutions. A metallic substitution occurs between a Cd-TCPP complex and Mn at pH 7.5–8.0, with imidazole as catalyst. We propose here to use a NaHCO 3 solution to dilute the samples in order to be in the necessary pH range to perform the metal substitution. Using this method, Mn(II,III) concentrations were determined in standard solutions with a precision of 3% within a concentration range of 0.5–80 μM. The procedure was successfully applied to determine Mn in acidified pore waters and in ascorbate and HCl sequential extractions from muddy sediments of the Bay of Biscay. Spectrophotometric results agreed closely with results from atomic absorption spectrometry, validating the proposed method. Graphical abstract fx1 Highlights • A spectrophotometric method was adapted to measure dissolved Mn in acidified matrices. • The method is accurate for acidified pore waters and sequential leaching solutions. • The method is accurate within a range of 0.5–100 μM with a precision of 3%. [ABSTRACT FROM AUTHOR]

Benthic fluxes of biogenic compounds play a major role in the biogeochemistry of shallow aquatic environments. Quantifying these fluxes at the scale of a lagoon is a challenge, especially when sediments are heterogeneous and fluxes at the sediment-water interface combine diffusive and advective transport processes. Diagenetic processes and associated benthic fluxes were quantified across different seasons in a lagoon of the French Mediterranean coast (La Palme lagoon) from vertical profiles of pore water and sedimentary solid fraction carried out at many representative stations of the lagoon. The northwestern part of the lagoon is covered with fine-grained sediment with low permeability and the rest of the lagoon contains permeable sandy sediment. We obtained vertical profiles with centimetre-scale resolution of water content, salinity, and major particulate and dissolved biogenic compounds of C, N, P, Si, S, Fe and Mn. This study allowed us to refine the sedimentary mapping of the lagoon, to specify the spatio-temporal evolution of biogeochemical processes, and to determine more precisely the part of the diffusive fluxes of nutrient compared to advective fluxes. Comparison of the vertical profiles with a molecular diffusion transport model shows that molecular diffusion is the dominant process in fine-grained sediments, while sandy sediments are dominated by advection due to circulation of lagoon water in shallow sediments. Benthic respiration renders fine-grained and sandy sediments anoxic from the first few mm below the sediment-water interface, particularly due to the availability of labile organic matter. Benthic dissolved inorganic nitrogen fluxes are of the same order of magnitude in both sediment types, despite the different flux mechanisms. This suggests that the intensity of organic matter mineralization processes is the same in fine and sandy sediments. Benthic phosphate fluxes are greater in sandy than in fine sediments because phosphorus is more efficiently retained in the solid fraction of fine sediments. Thus, sandy sediments play a dominant role in the pelagic-benthic coupling of the lagoon. • Benthic biogeochemical processes and fluxes were estimated in sediments of the La Palme lagoon. • Molecular diffusion in fine-grained sediments and in sands have been calculated. • Additional advective fluxes due to seawater recirculation in sandy sediment have been assessed. • Benthic fluxes of NH4, Si, and Fe from sands and from fine-grained sediments are equivalent. • Benthic fluxes of P to the water column are higher for sands than for fine-grained sediments. [ABSTRACT FROM AUTHOR]

We collected samples from sea water, runnel water, beach pore waters, water from the unconfined surficial aquifer discharging at the beach face, groundwater, and rainwater from the Aquitanian coast in order to determine the flux of dissolved inorganic nitrogen (DIN), phosphorus and silica from terrestrial submarine groundwater discharge (SGD). The flux of fresh groundwater was obtained from a water balance calculation based on precipitation and evapotranspiration and assessment of the coastal watershed from hydrograph separation. Waters with intermediate salinities between sea water and freshwaters are found all along the 240-km-long coast, indicating that SGD is ubiquitous. The estimated fresh water flux is 2.25 m 3 d − 1 m − 1 longshore. Terrestrial SGD provides a DIN flux of 9·10 6 mol each year to the adjacent coastal zone. This flux is about four times lower than the release of DIN due to tidally driven saline SGD. The freshwater DIN flux is low because the upland land use consists almost exclusively of pine forest. Dissolved organic nitrogen represents more than 60% of the total dissolved nitrogen flux. Dissolved iron, phosphorus and silica have much higher concentrations in the anoxic forest aquifer than in the fresh-water end-member of the subterranean estuary sampled in the upper beach aquifer. This suggests that the salinity gradient of the estuary does not correspond to a redox gradient. The redox front between anoxic groundwater and fresh oxic waters occurs below the soil-depleted foredune/yellow dune. Anoxic P- and Si-rich waters seep directly on the beach face only in the north Gironde, where the foredunes are eroded. This study reveals the role of the sandy foredune aquifer in biogeochemical fluxes from SGD, which is to dilute and oxidize waters from the unconfined surficial upland aquifer. [ABSTRACT FROM AUTHOR]

We have studied the heterogeneity of vertical profiles of biogeochemical components obtained from sediment core slicing. Sediment cores were collected in the intertidal zone of the Arcachon Bay and on the continental slope of the Bay of Biscay, at 550 and 1000 m depth. At each station of the Arcachon Bay, five 1 m-side zones were delimited at low tide. In each square, 3 cores were collected. Spatial heterogeneity on the continental slope was obtained from the study of 3 cores of multi-corer while 2 or 3 multi-corer deployments were used during the same oceanographic cruise. Similarity between profiles was determined to estimate the spatial heterogeneity at different scales. In the Arcachon Bay, results showed a spatial heterogeneity at a decimetre scale on apparently homogeneous areas. Despite the spatial variability, all the replicated profiles in Arcachon Bay sediments had similar trends, suggesting homogeneous benthic properties. However, a sampling with replicate cores handling is required for seasonal monitoring or study of biogeochemical mechanisms in coastal environments. We observe that the spatial variability on the continental margin of the Bay of Biscay is lower than in coastal environment of the Arcachon Bay. Heterogeneity is equivalent at a decimetre scale and at a hundred meters scale, which is the precision of the sampling positioning due to the drift of the boat and the tilt of the corer cable. In addition, our 10-year-long database for the Bay of Biscay showed that differences in the shape of profiles obtained in sediment cores collected at the same stations throughout this long period may not be interpreted in terms of evolution with time, because the observed variability is as high as the spatial heterogeneity. [ABSTRACT FROM AUTHOR]

We conducted six field campaigns to investigate the spatial and temporal evolution of pore water oxygen content on a high-energy sandy beach aquifer during several tidal cycles at different seasons. We buried autonomous probes in intertidal sands to record dissolved oxygen saturation, salinity, temperature and water head at a 2–10 min frequency. Oxygen concentrations display significant changes both with time (tide and seasons) and space (cross-shore and vertical variations). Seawater circulation in tidal sands forms a saline pore water circulation cell with oxygen-saturated pore water in the zone of seawater recharge. Oxygen-depleted pore water in the lower beach is the result of in situ respiration processes that occur during seawater circulation. Oxygen depletion varies throughout the year and anoxic conditions are reached at the end of spring, as planktonic organic matter becomes abundant in seawater and more organic matter is therefore supplied to pore water. On a shorter time scale (weeks to minutes), oxygen variations are driven directly by physical forcing. Tidal amplitude affects the extent of the saltwater circulation cell and the associated location of the recharging and discharging zones of the beach. The evolution of the water table level during the tidal cycle influences the circulation of pore water in the sand and ultimately, the timing of oxygen variations during flood and ebb. This first in situ study in a high-energy sandy beach shows that the dynamics of pore water oxygen are governed by biogeochemical processes at the seasonal scale and by physical forcing at the time scale of minutes to a few days. [ABSTRACT FROM AUTHOR]

Abstract: Wave and tide dominated beaches are composed of medium to coarse sandy sediments depleted in organic matter. In these sediments, the availability of organic matter limits benthic heterotrophic respiration processes. This study shows that oxygen consumption linked with nutrient recycling occurs in sands and that the intensity of this process follows a seasonal pattern. Furthermore, substantial seawater exchange occurs through intertidal sandy sediments during each tide. During floods, seawater penetrates sandy sediments, filling the pore spaces with dissolved oxygen and marine organic matter. Water expelled from the sediment during ebb is depleted in oxygen and enriched in nitrate. In order to quantify the extent of respiration processes, we collected pore waters at low tide on tidal cross-shore transects on the Truc Vert beach (France) every two weeks over 20months. Temperature, salinity and oxygen saturation were recorded in situ and nutrient concentrations were determined from collected samples. The seasonal monitoring showed that aerobic respiration occurred in sands. Organic matter supplied by the seawater entering the pore spaces during floods was trapped long enough to be mineralized. An efficient recycling of nutrients was thus found to occur in tidal sandy beaches. The intensity of the respiration processes varied seasonally. The strongest oxygen depletions occurred in spring, when planktonic organic matter was abundant, as well as in summer when we observed occasional denitrification. Nitrate concentration of recycled seeping seawater reached values up to 40μM. According to our calculations, the 240-km-long Aquitanian beach recycles 3500t of carbon and releases 600t of N-nitrate to the adjacent coastal zone each year. Since phosphorus is readily adsorbed on particles, the N:P ratio of recycled nutrients released to the seawater was much higher than the Redfield ratio. [Copyright &y& Elsevier]

Abstract: This work studied the impact of a small estuary (a 4 km-long estuary, at the interface between the Leyre River and the Arcachon lagoon, SW France) with a short flushing time on continental nutrient loads to a coastal lagoon. While large estuaries are known to modify the nutrient load of rivers to the coast, the impact on continental fluxes of a short salinity gradient from small coastal rivers is rarely studied. A survey of nutrient and dissolved organic matter concentration, particulate phosphorus speciation and particulate organic matter (POM) concentration and characteristics (C:N ratio and particulate organic carbon δ13C) showed that the estuarine behaviour varied throughout the year. The autochthonous primary production was a sink of dissolved N, P and Si in spring. During this period, the continental load of dissolved nitrogen was reduced by about 1/3 and phosphorus was totally consumed by estuarine processes. Nutrient recycling occurred in summer with ammonium production although this source was low in comparison with continental fluxes of nitrogen. The phosphorus concentration was dominated by the iron oxides-bound fraction. Contrary to large estuaries, the desorption of particulate phosphorus was not a source of dissolved phosphorus. Our results showed that estuarine processes impacted the net nutrient fluxes during productive periods, although estuarine residence time was very short. Passive transport with conservative mixing of nutrient was observed in autumn and winter. The non-conservative behaviour of small estuaries must be taken into account for nutrient mass balance calculation in lagoon. [Copyright &y& Elsevier]

We have studied 15 catchments supplying freshwater to a French Atlantic coastal lagoon, where increase in nitrogen loads due to agriculture is supposed to have destabilized the ecosystem in the last decades. The catchment is a lowland composed of Pleistocene sands with an average slope of 0.25%. To study the nutrient export in relation to land-use surface waters were sampled bi-weekly between October 2006 and January 2009 and land-use was established by plane photographs and Geographic Information System (GIS). Cultivated pine forests represent more than 80% of the total surface and 7% of the catchment area has been deforested recently. Significant areas of some catchments are used for maize crop. Housing is confined to the coastal zone. Maize and forest crop give a robust signature in terms of nitrate export. In view of modeling the nutrient fluxes, we have established the mean export rate for every land-use: forested parcels, deforested parcels, cultivated surfaces, and housing areas export 45, 93, 2850, and 61 kg N-nitrate km year, respectively. Exports of ammonium, dissolved organic N (DON), and dissolved inorganic P (DIP) could not be related to land use. The mean export is 13, 100, and 0.57 kg km year for N-ammonium, DON, and DIP, respectively. The modeling of nitrogen flux is in good agreement with our measures for the largest catchment, which supplies about 90% of the total continental DIN flux. However, small catchments are more dynamic due to hydrological conditions and the model is less accurate. This work has permitted to complete and unify scattered studies about nutrient cycling in this area. Thus we have established and compared the nitrogen budget of cornfields and cultivated pine forest. We have emphasized that (i) fertilizer use should be reduced in cornfields because they stock between 200 and 6400 kg DIN km year, and (ii) the nitrogen budget in pine forest mostly depends on tree harvesting and symbiotic N-fixation, which is poorly constrained. Export of N by rivers represents a small contribution to the N budget of soils. [ABSTRACT FROM AUTHOR]

Abstract: The Arcachon lagoon is a 156 km2 temperate mesotidal lagoon dominated by tidal flats (66% of the surface area). The methane (CH4) sources, sinks and fluxes were estimated from water and pore water concentrations, from chamber flux measurements at the sediment–air (low tide), sediment–water and water–air (high tide) interfaces, and from potential oxidation and production rate measurements in sediments. CH4 concentrations in waters were maximal (500–1000 nmol l−1) in river waters and in tidal creeks at low tide, and minimal in the lagoon at high tide (<50 nmol l−1). The major CH4 sources are continental waters and the tidal pumping of sediment pore waters at low tide. Methanogenesis occurred in the tidal flat sediments, in which pore water concentrations were relatively high (2.5–8.0 μmol l−1). Nevertheless, the sediment was a minor CH4 source for the water column and the atmosphere because of a high degree of anaerobic and aerobic CH4 oxidation in sediments. Atmospheric CH4 fluxes at high and low tide were low compared to freshwater wetlands. Temperate tidal lagoons appear to be very minor contributor of CH4 to global atmosphere and to open ocean. [Copyright &y& Elsevier]

Abstract: Groundwaters impacted by mature landfill leachate are generally enriched in ammonium. In order to assess the dynamics of ammonium exchanges between leachates and the water system inside a sandy permeable catchment we measured ammonium, nitrate and chloride concentrations in the stream and in sediment pore waters of the streambed of a landfill impacted aquifer. Geophysical investigation methods complemented the biogeochemical survey. The studied zone is a 23km² catchment located in a coastal lagoon area sensitive to eutrophication risk. Ammonium concentrations in the river were up to 800µmoll− 1 during low water period in summer. Three surveys of the river chemistry showed a regular increase in ammonium, nitrate and chloride concentrations along a 1km section of the watercourse, downstream the landfill, implying that the leachate plume exfiltrates along this section. Sediment cores collected within this section showed all an increase in ammonium concentrations with depth in pore waters as a consequence of the landfill leachate dispersion, as attested by a simultaneous increase in chloride concentrations. Nitrate enrichment in the river water was due to nitrification of ammonium at the interface between groundwater and streamwater. The apparent nitrification rate obtained was within values reported for turbid estuaries, although the river contained very little suspended particulate matter. Actually, pore water chemistry suggests that nitrification occurred for the most part in subsurface permeable sediments, rather than in stream water. The overall topographic, hydrological, geochemical, and geoelectrical data set permit to estimate the extension of the chloride and ammonium plume. The estimation of the apparent ammonium plume velocity is 23myear− 1 whereas the chloride plume velocity should be 50myear− 1. The river is the outlet of the impacted groundwaters. Considering that the input of ammonium from the landfill is balanced by the present day output via the river, the residence time of ammonium in the aquifer is between 7 and 18years. [Copyright &y& Elsevier]

Abstract: The relationship between particulate organic carbon (POC) concentrations measured in modern sediment and fluxes of exported POC to the sediment surface needs to be understood in order to use POC content as a proxy of paleo-environmental conditions. The objective of our study was to compare POC concentrations, POC mineralization rates calculated from O2 consumption and POC burial rates. Benthic O2 distributions were determined in 58 fine-grained sediment cores collected at different periods at 14 stations in the southeastern part of the Bay of Biscay with depths ranging from 140 to 2800m. Depth-dependent volume-specific oxygen consumption rates were used to assess rates of aerobic oxidation of organic matter (OM), assuming that O2 consumption solely was related to heterotrophic activity at the sediment–water interface. Heterogeneity of benthic O2 fluxes denoted changes in time and space of fresh organic material sedimentation. The most labile fraction of exported POC engendered a steep decrease in concentration in the upper 5mm of vertical O2 profiles. The rupture in the gradient of O2 microprofile may be related to the bioturbation-induced mixing depth of fast-decaying carbon. Average diffusive O2 fluxes showed that this fast-decaying OM flux was much higher than buried POC, although diffusive O2 fluxes underestimated the total sediment oxygen demand, and thus the fast-decaying OM flux to the sediment surface. Sedimentary POC burial was calculated from sediment mass accumulation rate and the organic carbon content measured at the top of the sediment. The proportion of buried POC relative to total exported POC ranged at the most between 50% and 10%, depending on station location. Therefore, for a narrow geographic area like the Bay of Biscay, burial efficiency of POC was variable. A fraction of buried POC consisted of slow-decaying OM that was mineralized within the upper decimetres of sediment through oxic and anoxic processes. This fraction was deduced from the decrease with depth in POC concentration. At sites located below 500m water depth, where the fast-decaying carbon did not reach the anoxic sediment, the slow-decaying pool may control the O2 penetration depth. Only refractory organic material was fossilized in sedimentary records at locations where labile OM did not reach the anoxic portion of the sediment. [Copyright &y& Elsevier]

Abstract: Sandy sediments of continental shelves and most beaches are often thought of as geochemical deserts because they are usually poor in organic matter and other reactive substances. The present study focuses on analyses of dissolved biogenic compounds of surface seawater and pore waters of Aquitanian coastal beach sediments. To quantitatively assess the biogeochemical reactions, we collected pore waters at low tide on tidal cross-shore transects unaffected by freshwater inputs. We recorded temperature, salinity, oxygen saturation state, and nutrient concentrations. These parameters were compared to the values recorded in the seawater entering the interstitial environment during floods. Cross-shore topography and position of piezometric level at low tide were obtained from kinematics GPS records. Residence time of pore waters was estimated by a tracer approach, using dissolved silica concentration and kinetics estimate of quartz dissolution with seawater. Kinetics parameters were based on dissolved silica concentration monitoring during 20-day incubations of sediment with seawater. We found that seawater that entered the sediment during flood tides remained up to seven tidal cycles within the interstitial environment. Oxygen saturation of seawater was close to 100%, whereas it was as low as 80% in pore waters. Concentrations of dissolved nutrients were higher in pore waters than in seawater. These results suggest that aerobic respiration occurred in the sands. We propose that mineralised organic matter originated from planktonic material that infiltrated the sediment with water during flood tides. Therefore, the sandy tidal sediment of the Aquitanian coast is a biogeochemical reactor that promotes or accelerates remineralisation of coastal pelagic primary production. Mass balance calculations suggest that this single process supplies about 37kmol of nitrate and 1.9kmol of dissolved inorganic phosphorus (DIP) to the 250-km long Aquitanian coast during each semi-diurnal tidal cycle. It represents about 1.5% of nitrate and 5% of DIP supplied by the nearest estuary. [Copyright &y& Elsevier]

Manganese is a major redox reactive element of benthic metabolism. We have built a database of existing knowledge on the benthic geochemistry of Mn in the Bay of Biscay, in order to comprehensively assess the behaviour of Mn in a variety of environments during early diagenesis. The database contains vertical profiles of particulate and dissolved Mn species of 59 cores collected during 17 cruises between 1997 and 2006 at nine stations positioned between 140 and 4,800 m water depths. At all studied stations, Mn species follow the conventional distribution, where Mn(III,IV) species are enriched in the oxic layer, and dissolved Mn is present in the anoxic sediments. A minor part of Mn-oxides originates from sedimenting particles. The major part is of diagenetic origin, and derives from the oxidation of upward-diffusing dissolved Mn(II). Mn-oxide inventories are higher at the deeper stations than at the shallower ones. This difference cannot be attributed to different sources of sedimenting particles, but it must depend on sedimentation rate and diagenetic processes. At depth, dissolved Mn(II) concentrations are constant. This probably reflects equilibrium with an authigenic Mn(II) phase, which is the ultimate phase into which Mn is fossilized. The Mn content of deeper anoxic sediments is similarly low in all the cores studied, associated with corresponding trends of Mn content in sedimenting particles of the Bay of Biscay. Bioturbation, rather than redox oscillations, can convey Mn(III,IV) species downwards into the anoxic sediments where they are reduced, associated with a peak of dissolved Mn. Because dissolved Mn(II) is re-oxidized when it diffuses towards the oxic layer, the inventory of the diagenetic Mn(III,IV) phase remains at steady state, especially at stations where the oxic layer is thick. It then becomes possible to calculate the residence time of diagenetic Mn(III,IV) particles within the oxic layer, using the upward-directed flux of pore water Mn(II). By applying this residence time to the accumulation of sediments within the oxic layer, we obtain the sediment mass accumulation rate. The values calculated for the sediments of the Bay of Biscay fit well with accumulation rates obtained from radionuclides or sediment traps. The method has also been validated with data collected in other marine sedimentary environments. [ABSTRACT FROM AUTHOR]

Abstract: Hydrographic structure of the water column, dissolved nutrient concentrations and the distribution of suspended particulate matter were recorded from CDT measurements and Niskin bottles sampling on the continental slope of the Bay of Biscay and on the axis of Capbreton canyon. Ascorbate extraction was applied here for the first time on marine suspended particles to determine the content of reactive Fe- and Mn-oxides, and P associated with Fe-oxides. Hydrographic structure of the south-eastern part of the Bay of Biscay did not change during the last three decades. Particulate organic carbon (POC) contents dropped strongly with depth, showing that organic matter mineralization was efficient in the water column. Organic matter mineralized in the water column had a Redfield N:P ratio. POC percent of particles collected at depth were higher during a bloom period, suggesting that some new organic matter reached the bottom. Contents of Fe and Mn extracted with the ascorbate leaching solution showed that suspended particles originated from the Gironde estuary, one of the major sources of particles in the Bay of Biscay. Intermediate and deeper nepheloid layers occurred in the Capbreton canyon. Particles of nepheloid layers were enriched in Mn- and Fe-oxides because they originated from resuspension of surface sediment. [Copyright &y& Elsevier]

Abstract: The hypothesis of nutrient-rich pore-waters seeping at low tide through sediments to channel waters, which drain tidal flats during ebb, was evaluated in the Arcachon lagoon. The back of the bay is affected by freshwater inputs and underground freshwater discharges. The upper part of tidal flat consists of permeable sandy sediments, which are covered by a muddy sediment layer on the lower part. Permeable sediments outcrop in the bed of channel web. Surface water chemistry and early diagenesis processes in sediment were estimated by collecting channel web waters and cores on a tidal flat and in channels at different seasons and time scales. Waters from tidal creeks are under-oxygenated, and enriched in reduced solutes. Muddy sediments showed evidences of strong organic matter mineralization and bioturbation. Underlying permeable sandy sediments revealed as well evidences of an enrichment of inorganic nutrients, and dilution with fresh continental groundwater. During ebb, tidal creek waters stem from mudflats by seeping of anoxic pore-waters, and from permeable sediments by advection of reduced waters. A rough estimation shows that the yearly contribution of this tidal pump of pore-waters for dissolved inorganic phosphorus (DIP) and ammonia inputs is of the same order of magnitude than river inputs for the studied part of the bay. Extrapolated to the whole Arcachon lagoon, pore-water discharge at low tide supplies to water column at least 556 kmol yr−1 and 18300 kmol yr−1 of DIP and NH4 +, respectively. Tidal drainage at low tide represents therefore a minimal contribution of recycled nutrient of 55% for DIP and 15% for dissolved inorganic nitrogen to the lagoon. [Copyright &y& Elsevier]

Abstract: We describe the depth distribution of phosphorus in relation to the distribution of major redox species (dissolved O2, NO3 −, NH4 +, Mn, and Fe, and particulate S, organic C, reactive Mn- and Fe-oxides) in modern sediments of two stations in the Thau Lagoon. Sediments close to the oyster bank zone are enriched in organic carbon and are highly bioturbated, while those outside the bank are less bioturbated and organic carbon levels are lower. In all sites, early diagenesis follows the well-accepted depth sequence of redox reactions of organic matter mineralization. The upper sediments of the station enriched in organic carbon contain high amounts of reactive particulate organic phosphorus that arrives at the sediment surface through biodeposition. Only a part of this phosphorus is released to the bottom water after mineralization, since more than 50% of total P is buried as an authigenic phosphate mineral. In the middle of the lagoon, outside the oyster bank zone, organic matter seems to be much more refractory, but the distribution of the major redox compounds indicates that this organic matter is partially mineralized. A portion of the phosphate and ammonium released during mineralization does not escape the sediment, since the concentration gradient is close to zero between 1 and 25cm depth below the sediment–water interface. Pore water N and P are likely fixed by biological uptake. The characterisation and magnitude of this process require further study. [Copyright &y& Elsevier]

Abstract: Particulate rare earth elements (REEs) were measured in modern sediment from the Bay of Biscay. Vertical profiles of total and reactive (ascorbate reducible) REEs have been studied in four contrasted sites ranging at water depth from 150 to 2800 m. The focus is on the coupling between the diagenetic conditions and the behavior of particulate REE. Total REEs fraction appears to be affected by the presence of metal sulphides that may act as an important carrier phase for solid REEs. In sediments where sulphate reduction is weak, the transfer from an unknown previous phase, stable in oxic conditions, to another one associated with sulphides seems to be direct, without mobilization in porewaters. In sediments where greater sulphate reduction occurs, we note the formation of an additional “authigenic” phase. Consequently, a threshold level of dissolved sulphide is a prerequisite for the formation of an additional “authigenic” REEs fraction. No direct relationship between the REEasc profiles and authigenic metal oxides have been observed, indicating that authigenic Fe and Mn oxides do not act as an efficient traps in the sediment. Despite particulate REE are mobile in these sediments, no fractionation of the lanthanide series is observed in relation to the redox conditions. [Copyright &y& Elsevier]

Abstract: The restricted exchange of water with the Indian Ocean makes the Red Sea extremely sensitive to global oceanographic changes, such as sea-level variations linked with Quaternary climate change. The 120 m global sea level lowering during the last glacial maximum caused great reduction in water exchange with the open ocean. At that time, salinities reached 50‰, and were beyond the tolerance of planktonic foraminifera. Some topographic depressions located on the Red Sea axial zone are the centre of hydrothermal activity. They are filled with hot brines and contain metalliferous sediments. We studied three sediment cores in the axial part of the Red Sea, one from the metal-rich Suakin Deep depression, and two cores sampled outside any deep, at two different depths. The sediment of the core located in the anoxic brine-filled Suakin Deep contained no benthic foraminifera, indicating the deep was filled by a brine pool during the recovered period of marine isotopic stages 1, 2, and 3. The distribution of benthic foraminifera in the two other cores indicates that Red Sea waters were saltier during stage 2 and 3 than today, and that at 2000 m depth, Red Sea waters were anoxic during stage 2 and dysoxic during stage 3. Profiles of Fe, Mn, and Zn indicate that the sedimentary flux of metals was higher during stage 1 than during stage 2 in hydrothermal brine-filled deeps. In contrast, the sedimentary flux of metal in cores outside the anoxic depressions was higher during stage 2. The shape of the metal profiles can be attributed to hydrological changes that induced variations of redox conditions in water column during isotopic stage 1, 2, and 3. During interglacial periods, metals dissolved in anoxic brines precipitated at the redox boundary that corresponded to the brine–seawater interface, so that metals precipitated only in the deeps. During glacial period, the deep water was anoxic, and the redox boundary was located above the brine–seawater interface. Therefore, the hydrothermal metals could diffuse into the anoxic deep Red Sea water and be precipitated over a large area. This interpretation suggests that the observed variations of metal concentrations are not only related to fluctuations of the hydrothermal fluid discharge, but also to the varying redox conditions in the deep Red Sea water. [Copyright &y& Elsevier]

Abstract: Particulate manganese oxides take a significant part in benthic biogeochemical processes of modern marine sediments. Thermodynamics calculations tell us that the reactivity of the different Mn oxides is variable. We describe here a method adapted for marine sediments, which allowed us to extract Mn oxides and determine the mean oxidation state of particulate Mn. Mn oxides are known to be enriched in the oxic layer of marine sediments. We have observed on a continental slope sediment that the oxidation state of particulate Mn changed with depth, within the 8 cm thick oxic layer. Mn(III) oxyhydroxides dominated at the sediment–water interface, and at the bottom of the oxic layer. In between, Mn(IV) oxides were more abundant. Mn(III) oxides are metastable phases which results from the primary oxidation of Mn2+. Mn oxides of the bottom of the oxic layer are enriched in Mn(III) phases because they result from the current in situ oxidation/precipitation of dissolved Mn2+ at the oxic–anoxic interface. Mn(III) oxyhydroxides of the surface sediment originate from the precipitation of Mn shortly before settling, presumably in estuaries where redox oscillations are intense. By contrast, Mn(IV) oxides result from the aging of Mn(III) oxyhydroxides during sediment burial. We have tested the reactivity of different types of Mn oxides with ammonia in anoxic environment. The formation of nitrate was observed after 13 days of incubation in experimental units that contained Mn(III) oxyhydroxides, but not in the units that contained Mn(IV) oxides. Therefore, Mn(III) oxyhydroxides may play a major role in the oxidation of ammonia to nitrate in marine sediments. [Copyright &y& Elsevier]

In order to understand the relationship between authigenic precipitation of U, Mo, Cd, and the redox properties of the marine environment, we have studied the vertical distribution of these metals and of the major redox species (oxygen, nitrate, manganese, reactive iron, sulfate, carbon, and sulfur) in modern sediment. We have sampled four sites at 150 to 2800 m depth in the Bay of Biscay. At the shallowest station, where sediment is highly bioturbated, organic carbon levels are above 2% and particulate sulfides are abundant. At the deepest stations, sediment is much less bioturbated, and organic carbon levels are lower. At all sites, early diagenesis follows a well-established depth sequence of redox reactions, based on the bacterially mediated oxidation of organic matter. Manganese-oxides and authigenic U and Mo were extracted by an ascorbate solution. Molybdenum is associated with these oxides in the oxic part of cores. In the anoxic layer of the sediment, Mo precipitates as a detectable authigenic phase only when sulfide minerals are present, i.e. when sulfate reduction becomes important. In anoxic sediments, Cd enrichment is a good indicator of sulfide production from sulfate reduction even if the production is weak. Uranium precipitates at the depth of reactive iron (III) reduction. No relationship was observed between U and S. The U concentration at the depth of precipitation agrees with values calculated using estimated accumulation rates and a downward diffusive flux of dissolved U from the bottom seawater into the sediment. However, authigenic U concentrations continue to increase in the anoxic part of the cores. Therefore, it is difficult to establish a direct relationship between the process of U accumulation and the flux of Corg to the sediment. [Copyright &y& Elsevier]

Presents a study which investigated the deep basins filled by hot brines in the Red Sea. Temperature and salinity of the Saukin, Port Sudan, Chain B and Nereus deeps; Methods; Results; Evolution of brine properties from 1972 to 1992; Discussion; Conclusion.

Reports on the findings of the REDSED cruise held in September 1992 at the Atlantis II Deep area. Methodology of the investigation; New stratification in the hydrothermal brine system of the Red Sea.

The interconnection between biotic and abiotic pathways involving the nitrogen and iron biogeochemical cycles has recently gained interest. While lacustrine ecosystems are considered prone to the biotic nitrate reduction (denitrification), their potential for promoting the abiotic nitrite reduction (chemodenitrification) remains unclear. In the present study, batch incubations were performed to assess the potential for chemodenitrification and denitrification in the saline inland lake Gallocanta. Sulfidic conditions are found in top sediments of the system while below (5–9 cm), it presents low organic carbon and high sulfate and ferrous iron availability. Anoxic incubations of sediment (5–9 cm) and water from the lake with nitrite revealed potential for chemodenitrification, especially when external ferrous iron was added. The obtained isotopic fractionation values for nitrite (ɛ 15N NO2) were −6.8 and −12.3 ‰ and therefore, fell in the range of those previously reported for the nitrite reduction. The more pronounced ɛ 15N NO2 (−12.3 ‰) measured in the experiment containing additional ferrous iron was attributed to a higher contribution of the chemodenitrification over biotic denitrification. Incubations containing nitrate also confirmed the potential for denitrification under autotrophic conditions (low organic carbon, high ferrous iron). Higher reaction rate constants were found in the experiment containing 100 μM compared to 400 μM nitrate. The obtained ɛ 15N NO3 values (−8.5 and −15.1 ‰) during nitrate consumption fell in the range of those expected for the denitrification. A more pronounced ɛ 15N NO3 (−15.1 ‰) was determined in the experiment presenting a lower reaction rate constant (400 μM nitrate). Therefore, in Gallocanta lake, nitrite generated during nitrate reduction can be further reduced by both the abiotic and biotic pathways. These findings establish the significance of chemodenitrification in lacustrine systems and support further exploration in aquatic environments with different levels of C, N, S, and Fe. This might be especially useful in predicting nitrous oxide emissions in natural ecosystems. [Display omitted] • Ferrous iron in Gallocanta lake drives nitrate and nitrite reduction. • Chemodenitrification seems enhanced by the addition of external ferrous iron. • Chemodenitrification experiments leaded to ɛ 15N NO2 between −6.8 and −12.3 ‰. • Denitrification experiments leaded to ɛ 15N NO3 between −8.5 and −15.1 ‰. [ABSTRACT FROM AUTHOR]

To investigate bioturbation effects on cadmium (Cd) fluxes from overlying water to sediments, indoor microcosms were developed. The bioturbating organisms were freshwater tubificid worms. Three experimental conditions were studied during 56 d. The three conditions were contaminated water column ([Cd]: 20 µg/L) with or without worms and uncontaminated water column with worms. Cadmium vertical profiles were determined in the pore water and in the sediments, based on six layers (0-0.5, 0.5- 1, 1-2, 2-3, 3-5, 5-12 cm). Dissolved oxygen, manganese, sulfate, and particulate manganese were measured. Bioturbation was analyzed using conservative fluorescent particulate tracers. Bioturbation increased Cd flux into the sediments by close to a factor of two. Scavenging of Cd was more efficient in the bioturbated sediments because particles and adsorption sites for Cd were renewed at the sediment--water interface. Tubificids also increased the thickness of the Cd-enriched layer. Metals adsorbed on particles at the sediment surface were distributed by bioadvection, which predominated the mixing processes. Bioturbation also modified the vertical profiles of dissolved and particulate manganese and dissolved sulfate but not the profiles of dissolved oxygen. These results indicate that the advective transport of particles by bioturbation and their subsequent modification by redox reactions accelerates the trapping of metals in sediments. [ABSTRACT FROM AUTHOR]

The sulphur cycle has a key role on the fate of nutrients through its several interconnected reactions. Although sulphur cycling in aquatic ecosystems has been thoroughly studied since the early 70's, its characterisation in saline endorheic lakes still deserves further exploration. Gallocanta Lake (NE Spain) is an ephemeral saline inland lake whose main sulphate source is found on the lake bed minerals and leads to dissolved sulphate concentrations higher than those of seawater. An integrative study including geochemical and isotopic characterization of surface water, porewater and sediment has been performed to address how sulphur cycling is constrained by the geological background. In freshwater and marine environments, sulphate concentration decreases with depth are commonly associated with bacterial sulphate reduction (BSR). However, in Gallocanta Lake sulphate concentrations in porewater increase from 60 mM at the water–sediment interface to 230 mM at 25 cm depth. This extreme increase could be caused by dissolution of the sulphate rich mineral epsomite (MgSO4·7H2O). Sulphur isotopic data was used to validate this hypothesis and demonstrate the occurrence of BSR near the water–sediment interface. This dynamic prevents methane production and release from the anoxic sediment, which is advantageous in the current context of global warming. These results underline that geological context should be considered in future biogeochemical studies of inland lakes with higher potential availability of electron acceptors in the lake bed compared to the water column. [ABSTRACT FROM AUTHOR]

Inland aquifers are connected to the ocean through permeable coastal sediments. The mixing zone between sea water and fresh-groundwater forms a so-called subterranean estuary. The dynamics and the shape of this interface influence fluxes of fresh water to the coastal zone. On tidal sandy beaches, tide and waves actions lead to the formation of an intertidal saline circulation cell that complements the structure of the subterranean estuary between sea water and fresh water. The upper beach corresponds to the recharge zone, where large volumes sea water penetrate the sediment at high tide, whereas the lower beach corresponds to the discharge zone of older pore water that remains in the sand for several tidal cycles. The objective of our study was to characterize the shape and the evolution of this saline cell in a high-energy macro-tidal beach, the Truc Vert beach (SW France). In order to assess the distribution of saline, brackish and fresh water in this high-energy beach aquifer, we conducted electrical resistivity tomography (ERT) measurements from the lower beach face to the sand dune in winter 2012–2013. We also measured water table elevation and salinity in three piezometers situated at the base of the dune and in pore waters at low tide on tidal cross-shore transects. Results show that the intertidal saline plume can be identified and localized with the ERT method. The fresh-saline water interface is almost vertical in the upper beach. The saline circulation cell occupies the upper part of the tidal beach over a thickness of 5 m deep. Below this saline cell, a brackish water flows to the ocean: about 30% of fresh water was found in pore water in the lower part of the beach. Shifting of the vertical front between saline and fresh waters of about 2–5 m occurred during the spring–neap tidal cycle. This migration is small relative to the beach size, suggesting that the transition zone is relatively stable. The variations in salinity of the circulation cell suggest that the position of the saline plume is controlled by the spring tide level. Our results differ slightly from studies based on modelling and piezometric measurement made in less exposed micro-tidal sandy beaches. Our data would allow to better constrain numerical models that would enable to quantify water residence time and solute fluxes in subterranean estuaries of high-energy beaches. [ABSTRACT FROM AUTHOR]

Sandy beaches exposed to tide and waves are characterized by low abundance and diversity of benthic macrofauna, because of high-energy conditions. This is the reason why there are few studies on benthic communities living in such highly dynamic environments. It has been shown recently that tidal sandy beaches may act as biogeochemical reactors. Marine organic matter that is supplied in the sand during each flood tide is efficiently mineralized through aerobic respiration. In order to quantify the role of macrofauna in the whole beach benthic respiration, we studied the macrofauna and the pore water oxygen content of an exposed sandy beach (Truc Vert, SW of France) during four seasons in 2011. The results showed that macrofauna was characterised by a low number of species of specialized organisms such as the crustaceans Eurydice naylori and Gastrosaccus spp. and the polychaetes Ophelia bicornis and Scolelepis squamata . The distribution and abundance of macrofauna were clearly affected by exposure degree and emersion time. The combined monitoring of benthic macrofauna and pore waters chemistry allowed us to estimate (1) the macrofauna oxygen uptake, calculated with a standard allometric relationship using biomass data, and (2) the total benthic oxygen uptake, calculated from the oxygen deficit measured in pore waters. This revealed that benthic macrofauna respiration represented a variable but low (<10%) contribution to the total benthic oxygen consumption. This suggests that oxygen was mainly consumed by microbial respiration. [ABSTRACT FROM AUTHOR]

We used a diagenetic model to test the hypothesis that manganese-rich layers in gas hydrate-bearing Arctic Ocean sediments are reliable time markers for interglacial periods. In the model, diagenesis is fuelled by two sources of reactive carbon: particulate organic carbon settling to the sediment surface, and methane diffusing up from deep gas hydrate deposits. The model includes oxidation of organic carbon and soluble reduced manganese by oxygen supplied continuously from an invariant bottom-water oxygen reservoir; reduction of particulate manganese by hydrogen sulfide generated through anaerobic methane oxidation; transport of dissolved oxygen and manganese by diffusion; and advective transport of particulate components by burial. Particulate organic matter and particulate manganese are only supplied to the sediment during interglacials. Sulfate reduction is not modeled explicitly; instead, the effect of anaerobic methane oxidation on Mn reduction is simulated at the lower boundary of the model by prescribing that particulate manganese is reduced there to soluble Mn(II). The soluble reduced Mn then diffuses upward and is oxidatively precipitated to Mn(IV) by downward diffusing oxygen. The upward flux of soluble Mn(II) is thus a function of the rate at which particulate manganese is advected into the Mn-reduction layer at the bottom of the model; it is not synchronous with events at the sediment–water interface. Model runs reveal that, under idealized but realistic conditions for the Arctic Ocean, oxidation of upward-diffusing Mn(II) generates post-depositional manganese enrichments that cannot readily be distinguished from the manganese-rich sediment layers that accumulate during interglacials. This compromises the use of manganese-rich layers as proxies for interglacial periods. In contrast, manganese-rich layers may be used as first-order markers of interglacial periods in sediments where gas hydrates or other forms of reactive carbon are absent. [ABSTRACT FROM AUTHOR]

Abstract: Spatio-temporal changes in totally and enzymatically hydrolyzable amino acids (THAA and EHHA) and EHAA/THAA ratios of superficial sediments were assessed during 1997–1999 in three areas (i.e., the Gulf of Lions, the Bay of Biscay, and Central Chile) differing in their primary productivity. In all three areas, and even off Central Chile where a strong El Niño event took place during 1997–1998, spatial changes were always much greater than temporal ones. The factors affecting the spatial distributions of amino acid concentrations differed among areas. In the Gulf of Lions, sediment granulometry was apparently the most important driving force of THAA, EHAA, and EHAA/THAA, and there was no marked difference between stations located on the open slope and those in submarine canyons. Conversely, in the Bay of Biscay, there were clear differences between the stations located off Cap-Breton, on the open slope, and those in the Cap-Ferret canyon; the latter two featuring lower EHAA and THAA but higher EHAA/THAA. This pattern is likely to result from the predominance of different sources of organic matter and especially from the importance of continental inputs to the Cap-Breton canyon. Off Central Chile, amino acid concentrations and ratios were both maximal around 100m depth, probably reflecting the interaction between the primary productivity gradient and the presence of an oxygen minimum zone (OMZ) reducing the degradation of sedimentary organics. When comparing the average values collected in the three areas studied, THAA and EHAA were highest in Central Chile, intermediate in the Bay of Biscay and lowest in the Gulf of Lions. EHAA/THAA ratios were also highest in Central Chile but were lowest in the Bay of Biscay. Differences between the Gulf of Lions and the Bay of Biscay could have been affected by sampling design. In Central Chile, the use of labile organic carbon to total organic carbon (C-LOM/TOC) and EHAA/THAA as indices of organic matter lability led to very similar results. This was not the case in the Bay of Biscay. It is therefore argued that the use of C-LOM/TOC should be restricted to highly productive areas. [Copyright &y& Elsevier]

We have studied particulate and dissolved arsenic species in sediment and porewaters at sites in the Bay of Biscay, France, ranging in depths from 150 to 2,800 m. At all stations, major redox species (oxygen, nitrate, ammonia, total and reactive iron and manganese, sulphate and sulphur) reflect early diagenetic depth sequences of redox reactions comparable to other marine environments. Vertical distributions of dissolved and particulate As species and major redox species are related to changes in redox conditions and their major carrier phases, such as Fe and Mn-oxides. Arsenic diagenesis appears strongly dependent on Fe cycling. A subsurface maximum of dissolved As and surface enrichment of particulate As correspond to dissolution and precipitation of Fe (III) phases. Except for the shallowest and most bioturbated site, flux calculations show three different vertical diffusive As fluxes: two upwards and one downwards. Phase changes of recycled As result in local accumulations of reactive As at different redox fronts. Mass-balance calculations indicate that the upward As flux toward the oxidized layer can explain the enrichment of HCl extractable particulate As in this layer. A portion of the upward diffusing As can escape the sediment and may be fixed onto settling Fe-oxides by adsorption or co-precipitation and contribute to reactive particulate As input (i.e., As is recycled across the water sediment interface). [Copyright &y& Elsevier]

We applied laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) as a new and precise technique for measuring trace elements in benthic foraminifera (Hoeglundina elegans). With this technique, trace element concentrations were accurately measured without the elaborate cleaning required in standard methods. Contaminated coatings are easily excluded during spatially resolved analysis. Application of this new technique allowed us to calibrate the trace elements incorporated in single tests of living (when sampled) benthic foraminifera to ambient seawater temperature (Mg and Sr) and redox conditions (Mn) for the first time. Incorporation of Ba showed a more complex pattern that cannot be explained by a direct correlation to water column concentration. [ABSTRACT FROM AUTHOR]

The subterranean flow of water through sand barriers between coastal lagoons and the sea, driven by a positive hydraulic gradient, is a net new pathway for solute transfer to the sea. On the sea side of sand barriers, seawater circulation in the swash‐zone generates a flux of recycled and new solutes. The significance and temporal variability of these vectors to the French Mediterranean Sea is unknown, despite lagoons constituting ~ 50% of the coastline. A one‐dimensional 224Raex/223Ra reactive‐transport model was used to quantify water flow between a coastal lagoon (La Palme) and the sea over a 6‐month period. Horizontal flow between the lagoon and sea decreased from ~ 85 cm d−1 during May 2017 (0.3 m3 d−1 m−1 of shoreline) to ~ 20 cm d−1 in July and was negligible in the summer months thereafter due to a decreasing hydraulic gradient. Seawater circulation in the swash‐zone varied from 10 to 52 cm d−1 (0.4–2.1 m3 d−1 m−1), driven by short‐term changes in the prevailing wind and wave regimes. Both flow paths supply minor dissolved silica fluxes on the order of ~ 3–10 mmol Si d−1 m−1. Lagoon–sea water exchange supplies a net dissolved inorganic carbon (DIC) flux (320–1100 mmol C d−1 m−1) two orders of magnitude greater than seawater circulation and may impact coastal ocean acidification. The subterranean flow of water through sand barriers represents a significant source of new DIC, and potentially other solutes, to the Mediterranean Sea during high lagoon water‐level periods and should be considered in seasonal element budgets. [ABSTRACT FROM AUTHOR]

Early diagenesis processes in the Bay of Biscay have been studied previously on short interface cores. In order to complete the data base and to characterize anoxic biogeochemical processes that affect Quaternary deposits, 1–3 m long gravity cores were collected at 150, 550, 1000 and 2000 m water depth on the continental slope of the south-eastern part of the Bay of Biscay. The aim of this work was to determine how a recorded signal could be changed in the several thousand-year situation of the Holocene period. For that, we determined radiocarbon and 210Pb dating, sedimentological characteristics, and the vertical distribution of particulate and pore water biogeochemical compounds. The sediment consists of a muddy facies deposited continuously during the Holocene. Results show that the distribution of redox sensitive compounds follows the well-established depth sequence of diagenetic reactions governed by the preferential use of the electron acceptor for the bacterially mediated oxidation of organic matter. Mineralization of organic matter occurs down to the bottom of the cores studied, indicating that Holocene sediment of the Bay of Biscay are in a transient state and they keep on being diagenetically transformed today. Effects of anoxic processes on buried sediments were estimated from fluxes induced by chemical gradients in pore waters. Anoxic processes consume up to 3.6 mg particulate organic carbon (POC) per g of dry sediment. They yield also precipitation of secondary calcium carbonate, which represent up to 5% of total buried carbonates. Early diagenetic reactions, which affect proxies commonly used in paleo-oceanography, such as POC, carbonates, phosphorus, or manganese, should be quantified in order to distinguish the part of a sedimentary record being the result of past environmental conditions from that due to post-depositional diagenetic processes. Diagenesis of Holocene deposits also contributes to a low, but significant fraction of N and P flux to the Bay of Biscay sea water. • Early diagenetic processes in 1–3 m-long cores from the Bay of Biscay. • Holocene sediment of the Bay of Biscay keep on being diagenetically transformed. • Post-depositional CaCO3 and organic C consumption affect paleo-oceanographic records. [ABSTRACT FROM AUTHOR]

The circulation of seawater through permeable coastal sediments is increasingly recognized as an important source of nutrients, including dissolved silica (DSi), to the coastal ocean. Here, we utilized a Ra isotope ( 223 Ra, 224 Ra ex , 228 Ra) mass balance to quantify DSi fluxes driven by water circulation to a small shallow coastal lagoon (La Palme; French Mediterranean) during June 2016, as compared to karstic groundwater spring inputs. The DSi flux driven by lagoon water circulation (derived from 224 Ra ex ) was approximately one order of magnitude greater (1900 ± 1700 mol d −1 ) than the DSi load of the karstic groundwater spring (250 ± 50 mol d −1 ) and greater than molecular diffusion (970 ± 750 mol d −1 ). Lagoon water circulation was a negligible source of 228 Ra, indicating that circulation-driven DSi inputs occur over a time-scale of days. Offshore transects were studied to quantify fluxes of marine-derived submarine groundwater discharge (SGD) from the permeable sandy coastline adjacent to the lagoon, into the Mediterranean Sea. Surface water transects revealed near-shore enrichments of Ra and DSi, attributed to wave-setup and water exchange through the permeable beach between the lagoon and the sea. Upscaling over the 9.5 km stretch of sandy beaches results in a marine SGD-driven DSi flux of 2.3 ± 1.3 × 10 4  mol d −1 , similar in magnitude to the Têt river during November 2016 (3.3 ± 2.4 × 10 4  mol d −1 ), the largest river in the region. A positive relationship between DSi and 224 Ra ex in lagoon water and seawater, but not 228 Ra, suggests that 224 Ra ex and DSi enrichments are derived from a similar source, the sediment (i.e. lithogenic particle dissolution), operating on short time-scales. A marine SGD-driven DSi flux to the Gulf of Lions (3.8 ± 2.2 × 10 5  mol d −1 ) is likely continuous over time. The relatively constant DSi inputs from water circulation for the shallow lagoons and beaches along the French Mediterranean Sea may sustain primary production in the coastal zone. In comparison, terrestrial groundwater and rivers supply temporally variable nutrient (N, P, Si) inputs via changes in regional precipitation, runoff and aquifer storage. [ABSTRACT FROM AUTHOR]

Isoetid macrophytes such as Lobelia dortmanna and Littorella uniflora are engineering species with an extensive root system and high radial oxygen loss. Despite several studies on these macrophytes, the effect of their oxygenation on methane dynamics has never been investigated. In this study, we hypothesise that isoetids promote dissolved inorganic carbon fixation and methane oxidation in sandy sediments. Our whole-ecosystem approach study lasted 2 years (2013-2014) on two oligo-mesotrophic shallow lakes. Benthic chamber incubations confirmed that, as a result of primary production and methanotrophy, isoetid lawns had consistently lower benthic carbon fluxes than bare sediments. On a daily basis, vegetated areas acted as a carbon sink (−0.7 ± 0.4 g C m days, as DIC + CH), whereas bare sediments acted as a net source (0.6 ± 0.5 g C m days, as DIC + CH). Photosynthetic quotients of <1 indicated that photosynthetically produced oxygen was not released into the water column, but accumulated in leaf lacunae or was transferred to the rhizosphere, that contributing to the alteration of net benthic fluxes at the sediment-water interface. This preliminary study highlights the necessity of further investigating the role that isoetids play in mitigating greenhouse gas emissions from temperate shallow lakes. [ABSTRACT FROM AUTHOR]

Microbial activity measurements and molecular approaches were combined to study temporal variation in nitrogen (N) removal mechanisms from muddy and sandy intertidal sediments (Arcachon Bay, France). Stable isotopes ( 15 NH 4 + / 15 NO 3 - ) were used to measure oxidation of NH 4 + to NO 3 − /NO 2 - and its subsequent reduction to N 2 via denitrification and/or anammox. We found that denitrification mainly fuelled N loss in both sediment types. However in sandy sediments, anammox accounted for relatively higher N 2 production (45%). Nitrification–denitrification (D n ) and nitrification–anammox coupling was observed particularly in muddy sediments. Temporal variations in prokaryotic abundance (Bacteria, Archaea) and of functional groups responsible for nitrification and denitrification were studied by qPCR and for anammoxifiers by cloning. Bacterial density in both sediment types varied between 10 7−8 equivalent cell per g −1 dry weight sediment and were overall more abundant in muddy sediments. Archaeal equivalent cell varied between 0.5 and 6.5% of the total prokaryotes, with extreme values observed in muddy sediment during October and January respectively. Denitrifiers were 1–2 orders higher than ammonium oxidizers and archeal nitrifiers appeared insignificant compared to betaproteobacterial counterpart. Furthermore, nitrifiers exhibited greater fluctuations in sandy sediments compared to muddy ones. Anammoxifiers were mainly restricted to the “ Candidatus Scalindua” group, and were detected in both sediment types and all sampling periods providing an indirect proof on the occurrence of anammox. In muddy sediments, N 2 production presented overall higher rate over sandy sediments and exhibited the same trend as nitrifier abundance. This finding suggests a central role of bacterially-mediated benthic nitrification in supporting dissimilatory processes through generation of NO 3 − /NO 2 and preventing eutrophication in this mesotidal lagoon. [ABSTRACT FROM AUTHOR]

Nutrient recycling is highly controlled by benthic macrophytes in shallow coastal zones. In seagrass bed, this recycling mainly occurs in sediment porewater, which is considered to be the main source of nutrients for plant growth. This work investigated the effect of a Zostera noltei meadow on the biogeochemistry of inorganic nutrients and carbon in vegetated sediments of the Arcachon Bay. We characterized the vertical distributions of dissolved inorganic C (DIC), NH 4 + , dissolved inorganic P (DIP) and redox-sensitive particulate inorganic P in bare sediments and in sediments heavily or sparsely colonised by Z . noltei . The obtained concentration profiles were used to calculate benthic production rates or particulate stocks. The porewater nutrient concentrations measured in vegetated sediments were depleted by a factor of 10–100 compared to bare sediments. The concentrations of NH 4 + , DIP and DIC exhibited a strong vertical zonation reflecting successive layers of intense production or consumption within the root zone often considered and sampled as a homogeneous zone. The deeper root zone showed higher consumption rates of dissolved inorganic nutrients compared to the upper root zone as young roots growing deeper in the sediment played a major role in nutrient plant uptake. A consumption of DIC was consistently recorded in the root zone. We hypothesized that this could result from a transport of CO 2 from roots to leaves supporting photosynthetic activity as suggested for freshwater plants. We pointed out to what extent the influence of seagrasses changed between sparse and dense meadows. This work emphasizes the high spatial variability in biogeochemical processes occurring at small scale within the root zone or between dense and sparse seagrass patches. Such a variability should be considered when dealing with the role of seagrass in biogeochemical cycles, especially in the context of global decline of seagrass. [ABSTRACT FROM AUTHOR]

Sediments are sinks for aquatic pollutants, and analyzing toxicity in such complex matrices is still challenging. To evaluate the toxicity of bioavailable pollutants accumulated in sediments from the Bizerte lagoon (Tunisia), a novel assay, the medaka embryo-larval assay by sediment contact, was applied. Japanese medaka ( Oryzias latipes) embryos were incubated in direct contact with sediment samples up to hatching. Lethal and sublethal adverse effects were recorded in embryos and larvae up to 20 d postfertilization. Results from medaka embryo-larval assay were compared with cytotoxicity (Microtox®), genotoxicity (SOS chromotest), and pollutant content of sediments. The results highlight differences in the contamination profile and toxicity pattern between the different studied sediments. A significant correlation was shown between medaka embryo-larval assay by sediment contact and SOS chromotest responses and concentrations of most organic pollutants studied. No correlation was shown between pollutant levels and Microtox. According to the number of sediment samples detected as toxic, medaka embryo-larval assay by sediment contact was more sensitive than Microtox, which in turn was more sensitive than the SOS chromotest; and medaka embryo-larval assay by sediment contact allowed sediment toxicity assessment of moderately polluted sediments without pollutant extraction and using an ecologically realistic exposure scenario. Although medaka embryo-larval assay by sediment contact should be tested on a larger sample set, the results show that it is sensitive and convenient enough to monitor the toxicity of natural sediments. Environ Toxicol Chem 2016;35:2270-2280. © 2016 SETAC [ABSTRACT FROM AUTHOR]

This study presents a new approach combining diffusive equilibrium in thin-film (DET) and spectrophotometric methods to determine the spatial variability of dissolved iron and dissolved reactive phosphorus (DRP) with a single gel probe. Its originality is (1) to postpone up to three months the colorimetric reaction of DET by freezing and (2) to measure simultaneously dissolved iron and DRP by hyperspectral imaging at a submillimeter resolution. After a few minutes at room temperature, the thawed gel is sandwiched between two monospecific reagent DET gels, leading to magenta and blue coloration for iron and phosphate, respectively. Spatial distribution of the resulting colors is obtained using a hyperspectral camera. Reflectance spectra analysis enables deconvolution of specific colorations by the unmixing method applied to the logarithmic reflectance, leading to an accurate quantification of iron and DRP. This method was applied in the Arcachon lagoon (France) on muddy sediments colonized by eelgrass (Zostera noltei) meadows. The 2D gel probes highlighted microstructures in the spatial distribution of dissolved iron and phosphorus, which are most likely associated with the occurrence of benthic fauna burrows and seagrass roots. [ABSTRACT FROM AUTHOR]

Benthic and planktic foraminiferal assemblages from two sediment cores (2,000 m depth, 44°33'N, 2°45'W) were analyzed to first compare modern and dead faunas and next to study changes in the hydrology of the southeastern Bay of Biscay (SE BoB) over the last 12.8 cal ka BP. Considering benthic ecosystem characteristics, the first part of the paleorecord (12.8-7.6 cal ka BP) is composed of laminated sediments that may have resulted from turbiditic overflow events, whereas occurrences of transported species (e.g. Nonionella sp., Cassidulina carinata) attest of continental influence at the core location. After 7.6 cal ka BP, the sediment becomes bioturbated concomitantly to the stabilization of the sea-level. The benthic foraminiferal fauna is largely dominated by Uvigerina peregrina suggesting a high seasonality with seasonal pulsed organic matter fluxes to the seafloor. On the other hand, the planktic foraminiferal composition indicates that surface water masses were under the influence of the polar front in the early record, which retreated at about 11.5 cal ka BP. The early Holocene is characterized by relatively warm and stratified water masses at 8.4-4.8 cal ka BP. The last 4.8 cal ka BP records a gradual sea surface water cooling trend and enhanced foraminiferal production from ~ 2.6 cal ka BP until present. The early (12.8-10.5 cal ka BP) and late (2.3-1.7 cal ka BP) Holocene are characterized by the presence of the planktic species Globigerinoides ruber probably caused by intrusions of the Iberian Poleward Current (IPC), and a negative state of the North Atlantic Oscillation (NAO). [ABSTRACT FROM AUTHOR]

Abstract: Sandy sediments of tidal beaches are poor in reactive substances because they are regularly flushed by significant flow caused by tidal forcing. This transport process may significantly affect the flux of reactive solutes to the ocean. A two dimensional model coupling the Richards equation that describes the flow in permeable sediments and the conservation equation of the silicic acid was developed to simulate the evolution of the silicic acid concentration into a variably saturated porous media submitted to tidal forcing. A detailed algorithm of drainage zone under tidal forcing and numerical methods needed to solve it are properly presented. Flux to the ocean has been estimated. The silicic acid concentration displays a permanent lens with low silicic acid concentration at the top of the tidal zone. This lens that results from the tidal forcing, presents weak variations of area during the tidal cycle. Silicic outflux to the ocean increases with increasing beach slope, hydraulic conductivity and tidal range. Simulations reveal that the total silicic acid flux to the ocean from the coastal marine sands can be considered as significant compared to the flux supplied by the rivers. These results may alter the previously published global budget of the silicic acid to the ocean. [Copyright &y& Elsevier]

Abstract: Nitrite and 29N2 productions in slurry incubations of anaerobically sediment after 15NO3 or 15NH4 labelling in the presence of Mn-oxides suggested that anaerobic Mn-oxides mediated nitrification coupled with denitrification in muddy intertidal sediments of Arcachon Bay (SW Atlantic French coast). From this sediment, bacterial strains were isolated and physiologically characterized in terms of Mn-oxides and nitrate reduction as well as potential anaerobic nitrification. One of the isolated strain, identified as Marinobacter daepoensis strain M4AY14, was a denitrifier. Nitrous oxide production by this strain was demonstrated in the absence of nitrate and with Mn-oxides and NH4 amendment, giving indirect proof of anaerobic nitrate or nitrite production. Anaerobic Mn-oxide-mediated nitrification was confirmed by 29N2 production in the presence of 15NO3 and 14NH4 under denitrifying conditions. Anaerobic nitrification by M4AY14 seemed to occur only in the absence of nitrate, or at nitrate levels lower than that of Mn-oxides. Most of the other isolates were affiliated with the Shewanella genus and were able to use both nitrate and Mn-oxides as electron acceptors. When both electron acceptors were present, whatever their concentrations, nitrate and Mn-oxide reduction co-occurred. These data indicate that bacterial Mn-oxide reduction could be an important process in marine sediments with low oxygen concentrations, and demonstrate for the first time the role of bacteria in anaerobic Mn-mediated nitrification. [Copyright &y& Elsevier]

Abstract: Despite their low water solubility, hydrophobic pollutants are widespread in the aquatic environment and could represent a threat for living organisms. EU regulations on chemicals require accurate and reliable data on chemical toxicity. Current normalised fish toxicity assays, in particular those advocated by OECD guidelines, do not allow reliable toxicity assessment of hydrophobic compounds due to their low water solubility. In order to accurately evaluate the toxicity of this kind of compounds, a new spiked sediment assay using embryos of the Japanese medaka was developed. It consists of directly exposing fertilised eggs, during their entire embryonic development, onto the reference sediment spiked with the test compound. A large set of lethal or sublethal effects in embryos and newly hatched larvae, including non-invasive endpoints is analysed in order to maximise the sensitivity of the test. The approach was validated using four model pollutants with different modes of action: DMBA, PCB126, PCB153 and 4-nonylphenol (NP). All compounds, except PCB153, induced a dose-dependent increase in toxic effects. In fact, lethal effects only occurred at the highest tested concentration. In contrast, sub-lethal effects including skeletal deformations, cardiac activity modulation, body length reduction and hatching delay were observed at low to moderate concentrations of DMBA and PCB126. NP induced subtle effects in embryos, altering cardiac activity and hatching success but only at high concentrations. Although a few more improvements would make it a fully standardised assay, this spiked sediment assay using medaka embryos proves to be sensitive enough to measure hydrophobic chemical toxicity using an environmentally realistic mode of exposure. [Copyright &y& Elsevier]