Surface reactivity of the Rhône suspended matter and relation with trace element sorption

The reactivity of the Rhône estuarine suspended matter is investigated through three operational parameters: the heat of immersion in water (HI), the ammonium saturation index (ASI) and the specific surface area (SSA). The two former parameters are highly correlated for samples collected both in surface river water and in its plume water and in a deeper nepheloid layer. Using both ASI and HI theoretical contributions of each main individual suspended matter component, it is shown that actual and calculated HI values are in agreement, whereas measured ASI values are significantly lower than those calculated. Surface normalization of these reactive properties is discussed on the basis of the SSA measured by the (BET) N2 adsorption. This evaluation, on freeze-dried suspended matter, appears to underestimate the actual particulate reactive surface area in the natural environment; indeed, it is shown that the ammonium ion surfacial density obtained from ASI and SSA data is unrealistically high.To verify that HI and ASI may be considered as criteria for the surface potential reactivity of particles, it has been attempted to relate these parameters and the extent of sorption of radioactive tracer, which is either discharged in the Rhone river or introduced in a batch experiment. Relationships between both ASI and HI and the content of ⁵⁴Mn, ⁶⁰Co, ⁶⁵Zn, ¹⁰⁹Cd and ¹³⁷Cs, which are established for some of them, suggest that HI and ASI are useful indicators of particulate affinity for certain metals.     

Understanding shallow gas occurrences in the Gulf of Lions

New coring data have been acquired along the western Gulf of Lions showing anomalous concentrations of methane (up to 95,700 ppm) off the Rhône prodelta and the head of the southern canyons Lacaze-Duthiers and Cap de Creus. Sediment cores were acquired with box and kasten cores during 2004–2005 on several EuroSTRATAFORM cruises. Anomalous methane concentrations are discussed and integrated with organic carbon data. Sampled sites include locations where previous surveys identified acoustic anomalies in high-resolution seismic profiles, which may be related to the presence of gas. Interpretation of the collected data has enabled us to discuss the nature of shallow gas along the Gulf of Lions, and its association with recent sedimentary dynamics. The Rhône prodelta flood deposits deliver significant amounts of terrigenous organic matter that can be rapidly buried, effectively removing this organic matter from aerobic oxidation and biological uptake, and leading to the potential for methanogenesis with burial. Away from the flood-related sediments off the Rhône delta, the organic matter is being reworked and remineralized on its way along the western coast of the Gulf of Lions, with the result that the recent deposits in the canyon contain little reactive carbon. In the southernmost canyons, Lacaze-Duthiers and Cap de Creus, the gas analyses show relatively little shallow gas in the core samples. Samples with anomalous gas (up to 5,000 ppm methane) are limited to local areas where the samples also show higher amounts of organic matter. The anomalous samples at the head of the southern canyons may be related to methanogenesis of recent drape or of older sidewall canyon infills.     

Benthic remineralization at the land–ocean interface: A case study of the Rhône River (NW Mediterranean Sea)

Biogeochemical processes in sediments under the influence of the Rhône River plume were studied using both in situ microelectrodes and ex situ sediment core incubations. Organic carbon (OC) and total nitrogen (TN) content as well as stable carbon isotopic composition of OC (δ¹³C_OC) were analysed in 19 surface sediments to determine the distribution and sources of organic matter in the Rhône delta system. Large spatial variations were observed in both the total O₂ uptake (5.2 to 29.3 mmol m⁻² d⁻¹) and NH₄⁺ release (−0.1 to −3.5 mmol m⁻² d⁻¹) rates at the sediment–water interface. The highest fluxes were measured near the Rhône River mouth where sedimentary OC and TN contents reached 1.81% and 0.23% respectively. Values of δ¹³C_OC ranged from −26.83‰ to −23.88‰ with a significant seawards enrichment tracing the dispersal of terrestrial organic matter on the continental shelf. The amount of terrestrial-derived OC reaches 85% in sediments close to the Rhône mouth decreasing down to 25% in continental shelf sediments. On the prodelta, high terrestrial OC accumulation rates support high oxygen uptake rates and thus indicating that a significant fraction of terrestrial OC is remineralized. A particulate organic carbon (POC) mass balance indicates that only 3% of the deposited POC is remineralized in prodelta sediments while 96% is recycled on the continental shelf. It was calculated that a large proportion of the Rhône POC input is either buried (52%) or remineralized (8%), mostly on the prodelta area. The remaining fraction (40%) is either mineralized in the water or exported outside the Rhône delta system in dissolved or particulate forms.     

Monitoring of the chemical pollution of the river Rhône through measurement of DNA damage and cytochrome P4501a induction in chub (Leuciscus cephalus)

The in vivo response of freshwater fish exposed to pollutants was assessed using two biomarkers, 7-ethoxyresorufin-O-deethylase (EROD) induction and DNA single strand breaks. Chub (Leuciscus cephalus) were caught in spring and in fall at various locations in the river Rhône watershed. EROD activity was measured in the liver while DNA damage was evaluated in chub erythrocytes using the recently developed Comet assay. Chemical contamination was evaluated both in fish muscle (PCBs) and in sediment (PCBs, PAHs, heavy metals) collected at each sampling station. Sex of individuals was shown to influence the level of EROD activity but not the level of DNA damage. The EROD activity as well as the DNA damage were found to be higher in the mostly contaminated stations compared to the reference one. This study shows that multibiomarker-based approach provides complementary informations about early effects in feral fish exposed to complex chemical pollution and highlights the interest of the Comet assay in genotoxicity assessment.     

Seasonal comparison of the diets of juvenile European anchovy Engraulis encrasicolus and sardine Sardina pilchardus in the Gulf of Lions

Anchovy and sardine in the Mediterranean are known to share the same habitat and, consequently, to interact with one another. These two sympatric pelagic species are planktivorous and consume a wide range of planktonic prey items during all their developmental stages, potentially overlapping their ecological niches, although the feeding interactions between these species have been poorly investigated. Here we compare the dietary habits of the juvenile phases of anchovy and sardine during different seasons in the northwestern Mediterranean Sea, through analysis of their stomach contents and of their feeding-related anatomical characteristics. In this study we show that juveniles of anchovy and sardine do not compete for food, and we describe significant dietary differences between anchovy and sardine due to their different alimentary tract morphology.     

Sea-floor sediment distribution in the Gulf of Mexico

Carbonate content, smear-slide analysis and diffuse reflectance spectrophotometry were utilized to determine modern sediment composition and distribution throughout the Gulf of Mexico. In all, 186 core top and grab samples distributed throughout the Gulf were analyzed. Reflectance spectra were taken from thick smear slides from the near ultraviolet, through the visible, and into the near infrared. The first derivatives of the percent reflectance data were subjected to factor analysis producing factors that grouped covarying first-derivative wavelengths. Factors were interpreted by comparison to first-derivative curves for known sediment components and minerals. Interpretation was aided by the mapping of both calcium carbonate content and smear-slide sediment classes. The most easily interpreted factor solution was produced by analyzing only the visible region of the spectrum and extracting seven factors which explained 98% of the cumulative variance. These factors, in order of their relative importance, are interpreted as (1) marl and calcareous clay, (2) glauconite, (3) kaolinite, (4) organic matter, (5) phosphorite, (6) hematite, and (7) goethite. Some factor maps are consistent with known sources of fluvial sediment input; for example, kaolinite is deposited off rivers draining the southeastern US. Other factor maps are related to the origin of the material in the factor, glauconite, for example, being confined to low sedimentation regions of the outer shelf. The most unusual observation concerns the distribution of hematite, which appears to be transported from the rivers of south Texas, primarily the Rio Grande, across the shelf then eastward downslope along the base of the Sigsbee Escarpment. This eastward transport seems to be explainable only by transport in bottom currents flowing along the base of the Sigsbee Escarpment.     

Evaluation of a dynamically downscaled atmospheric reanalyse in the prospect of forcing long term simulations of the ocean circulation in the Gulf of Lions

The paper evaluates atmospheric reanalysis as possible forcing of model simulations of the ocean circulation inter-annual variability in the Gulf of Lions in the Western Mediterranean Sea between 1990 and 2000. The sensitivity of the coastal atmospheric patterns to the model resolution is investigated using the REMO regional climate model (18 km, 1 h), and the recent global atmospheric reanalysis ERA40 (125 km, 6 h). At scales from a few years to a few days, both atmospheric data sets exhibit a very similar weather, and agreement between REMO and ERA40 is especially good on the seasonal cycle and at the daily variability scale. At smaller scales, REMO reproduces more realistic spatio-temporal patterns in the ocean forcing: specific wind systems, particular atmospheric behaviour on the shelf, diurnal cycle, sea-breeze. Ocean twin experiments (1990–1993) clearly underline REMO skills to drive dominant oceanic processes in this microtidal area. Finer wind patterns induce a more realistic circulation and hydrology of the shelf water: unique shelf circulation, upwelling, temperature and salinity exchanges at the shelf break. The hourly sampling of REMO introduces a diurnal forcing which enhances the behaviour of the ocean mixed layer. In addition, the more numerous wind extremes modify the exchanges at the shelf break: favouring the export of dense shelf water, enhancing the mesoscale variability and the interactions of the along slope current with the bathymetry.     

Some remarks on the study of subsidence of sedimentary basins Application to the Gulf of Lions margin (Western Mediterranean)

The study of basin subsidence is a helpful geological tool for understanding the tectonic and thermal evolution of sedimentary basins. Subsidence is clearly one major aspect of the geodynamics of ‘rifted’ basins. It is controlled by the inner lithospheric and crustal processes of mechanical, thermal and also tectonic origin. The load of sediments which fill the initial rift depression amplify these vertical movements, according to the laws of isostatic compensation.The purpose of the backstripping method is to separate these two components of subsidence. The subsidence due to both controlling factors (geodynamics and sediments loading), called total subsidence, can be estimated by a precise reconstruction of paleotopography in the basin during past sedimentation. This geohistorical reconstruction is based on observational data, mainly the chronostratigraphy of the sedimentary cover, lithologies and paleoenvironments, all data being constrained by the global geological context in the basin studied.The tectonic subsidence, which corresponds to the driving lithospheric phenomena, is computed according to a model of the response of lithosphere to sediment loading. Two models are considered, the Airy or local isostasy model and flexure models. In flexure models, the main difficulty is to estimate the history of the flexural rigidity of the lithosphere below continental margins and rifted basins. The influence of compensation models on subsidence history will be discussed.The present paper brings out some remarks on the use of backstripping techniques. In particular, the two-dimensional approach is emphasized because it gives better constraints on the geological validity of the paleotopographic reconstruction and the distribution of subsidence in space and time. Discussion is illustrated by the study of the young passive margin of Gulf of Lions, in the northwestern part of the Mediterranean Basin. The rifting was initiated during upper Oligocene and lasted until Aquitanian time. A seismic survey in the Gulf of Lions and on-shore geological studies of the bordering areas (Sardinia, Camargue) have shown that the postrift history mainly consists of a regional subsidence of the whole margin. The hypothesis of a thermal control of the postrift subsidence, as predicted by geodynamical models (McKenzie, 1978), will be discussed. The geohistorical reconstruction deals with two main problems. (1) Determination of paleobathymetry is not accurate enough from observation data. (2) A strong erosional event, known as the Messinian Event, is superimposed to the geodynamic evolution of the margin. Thus, the complete paleotopographic reconstruction will be based on observations and also geological hypotheses, mainly the likely continuity of the geological phenomena during the postrift history of the margin, since they are controlled by the thermal evolution at depth.     

Vertical distribution of the sound speed in the Gulf Stream system

Using archived historical data on the temperature/salinity distribution, this paper describes the structure of the mean seasonal and the actual field of the computed speed of sound in the Gulf Stream region. The formation of acoustic channels of large, medium, and small size is considered, depending on the vertical thermohaline structure of waters. The paper provides statistical characteristics of the sound speed field and acoustic channels of waters interacting in the Gulf Stream system. Translated by Vladimir A. Puchkin.     

Particulate manganese and iron in recent sediments of the Gulf of Lions continental margin (north-western Mediterranean Sea): deposition and diagenetic process

This study aims at apprehending the major forcing factors which govern the spatial and vertical Mn and Fe distributions in ten cores from the Gulf of Lions. Speciation by chemical leaching experiments helps understanding their chemical behaviour during the early diagenetic processes in a marine environment under strong continental influence.The distribution and chemical behaviour of Mn and Fe differ drastically. The strong dependence of Mn distribution on chemical conditions is expressed by a marked solid phase Mn enrichment in the oxic layers of sediment deposits. This enrichment increases with decreasing sedimentation rate (increasing water depth). It is illustrated by an enhanced portion of total Mn in the reducible phase and the precipitation of todorokite on calcareous supports in the upper part of the deepest cores. As a result, 65% of the margin total particulate Mn is thought to be stored in slope deposits in a relatively strongly held association. Conversely, the low chemical mobility of iron in the sedimentary column is indicated by uniform depth profiles and an exclusive location in the residual chemical phase in all the studied sites. The Fe distribution is largely controlled by the dispersion of particulate material on the margin from the Rhône River main source.A budget of Mn and Fe accumulation based on the average amount of total Mn and Fe content of sediments deposited during the last 100 yr, has been made taking into account diagenetic readjustments. The total Mn and Fe amount stored on the margin during the last century is estimated to be 1.5×10⁶ and 54×10⁶ t, respectively. These values are seven times higher than the total secular external inputs calculated on the basis of present day riverine and atmospheric fluxes. This large discrepancy is mainly explained by the sharp decrease of the Rhone River discharge after dam buildings between 1950 and 1958. A residual discrepancy dating before 1950, is likely to be due to seafloor erosion and gravity induced mechanisms.     

Spatial and vertical distributions of elements in sediments of the Colorado River delta and Upper Gulf of California

The abundance of major components (Fe, Ca, K, and organic carbon) and trace elements was analyzed in surface sediments and core samples from the Colorado River delta (CRD) and the Upper Gulf of California (UGC) using instrumental neutron activation analysis.The spatial distribution patterns of the elements studied are consistent with the model of sedimentary dynamics proposed for this area [Mar. Geol. 158 (1999) 125]: intense tidal resuspension of sediments in the delta with subsequent transport of suspended particulate matter in a southerly direction, followed by sedimentation of fine-grained material in a depocenter near the southwestern margin of the UGC. Concentrations of most of the elements are higher in the surface sediments of this depocenter. The gradual mixing of terrigenous and marine biogenic materials, normally expected for the estuarine sediments, was not detected in the CRD–UGC system because of homogenization of the sediments by tides and wind.Vertical profiles of element contents in samples of the sediment core collected in the depocenter area revealed (i) almost no anthropogenic contamination of the area by environmentally important trace elements such as Cr, Co, Sb, and As; (ii) a twofold decrease of Fe, Sc, Cr, and Co in upper core sediments; and (iii) the enrichment of the sediments at 60–62 cm depth in the core, in calcium carbonate, Ca, Sr, and the Eu_n/Sm_n shale-normalized ratio along with a depletion in this layer of Fe, Sc, Cr, Co, light rare-earth elements (REEs), and some other elements of terrigenous origin, presumably caused by the dilution of fluvial terrigenous material by biogenic carbonates, which were probably introduced at this level in the sediments by the action of a strong episodic winter storm, followed by the advective transport of shell fragments from the coastal clam banks or as a result of strong planktonic bloom.     

Composition and ecological distribution of ichthyoplankton in eastern Beibu Gulf

Surveys were conducted in four seasons in the eastern Beibu Gulf from July 2006 to November 2007,to determine the ichthyoplankton composition,abundance,as well as environmental factors impacted on their spatiotemporal distributions.The fish eggs and larvae were sorted from 303 zooplankton quantitative samples,in which at least 1 order,60 families,31 genera and 61 species of fish eggs and larvae were identified.The species number was highest in summer whereas lowest in winter.With the most abundant fish egg (the average density was 2.41 ind./m 3),spring was the main spawning season,while the greatest mean density of fish larva was 1.35 ind./m 3 in summer.In the whole year around,fish eggs had the trends to aggregate in the nearshore of Guangxi coast,fish larvae were more abundant in the northern water.Relationships between fish eggs and larvae abundance and environmental factors were analyzed by using the Yield-Density model.The spatiotemporal distribution of ichthyoplankton in eastern Beibu Gulf was closely related to the Chl a concentration,and the optimal temperature,salinity and Chl a were 19.4-21.7 C,31.8-33.1 and 1.5-4.8 mg/m 3,respectively.Additionally,the distribution of fish larvae could be effected by ocean currents in summer and autumn.     

Scleractinian cold-water corals in the Gulf of Cádiz—First clues about their spatial and temporal distribution

This paper presents the first compilation of information on the spatial distribution of scleractinian cold-water corals in the Gulf of Cádiz based on literature research and own observations (video footage, sediment samples). Scleractinian cold-water corals are widely distributed along the Spanish and Moroccan margins in the Gulf of Cádiz, where they are mainly associated with mud volcanoes, diapiric ridges, steep fault escarpments, and coral mounds. Dendrophyllia cornigera, Dendrophyllia alternata, Eguchipsammia cornucopia, Madrepora oculata and Lophelia pertusa are the most abundant reef-forming species. Today, they are almost solely present as isolated patches of fossil coral and coral rubble. The absence of living scleractinian corals is likely related to a reduced food supply caused by low productivity and diminished tidal effects. In contrast, during the past 48 kyr scleractinian corals were abundant in the Gulf of Cádiz, although their occurrence demonstrates no relationship with main climatic or oceanographic changes. Nevertheless, there exists a conspicuous relationship when the main species are considered separately. Dendrophylliids are associated with periods of relatively stable and warm conditions. The occurrence of L. pertusa mainly clusters within the last glacial when bottom current strength in the Gulf of Cádiz was enhanced and long-term stable conditions existed in terms of temperature. Madrepora oculata shows a higher tolerance to abrupt environmental changes.     

The relationship between chromophoric dissolved organic matter and dissolved organic carbon in the European Atlantic coastal area and in the West Mediterranean Sea (Gulf of Lions)

The absorption coefficient of chromophoric dissolved organic matter (aCDOM) has been found to be correlated with fluorescence emission (excitation at 355 nm). In the coastal European Atlantic area and in the Western Mediterranean Sea (Gulf of Lions), a significant statistical dependence has been found between aCDOM and fluorescence with dissolved organic carbon (DOC) concentration. The relationship shows that, in the river plume areas (Rhine in the North Sea and Rhône in the Gulf of Lions), a consistent fraction of DOC (from 40% to 60% of the average of the DOC measured) is non-absorbing in visible light range, where the dissolved organic matter (DOM) is typically absorbent. In comparison, in the open sea, apparently not affected by the continental inputs, the entire DOC belongs to the chromophoric DOM whose specific absorption is lower (5 to 10 times) than that found in the river plume areas.     

Seagrass distribution and abundance in Eastern Gulf of Mexico coastal waters

The marine angiosperms Thalassia testudinum, Syringodium filiforme, and Halodule wrightii form two of the largest reported seagrass beds along the northwest and southern coasts of Florida where they cover about 3000 square km in the Big Bend area and about 5500 square km in Florida Bay, respectively. Most of the leaf biomass in the Big Bend area and outer Florida Bay was composed of Thalassia testudinum and Syringodium filiforme which were distributed throughout the beds but which were more abundant in shallow depths. A short-leaved form of Halodule wrightii grew in monotypic stands in shallow water near the inner edges of the beds, while Halophila decipiens and a longer-leaved variety of H. wrightii grew scattered throughout the beds, in monotypic stands near the outer edges of the beds, and in deeper water outside the beds. Halophila engelmanni was observed scattered at various depths throughout the seagrass beds and in monospecific patches in deep water outside the northern bed. Ruppia maritima grew primarily in brackish water around river mouths. The cross-shelf limits of the two major seagrass beds are controlled nearshore by increased water turbidity and lower salinity around river mouths and off-shore by light penetration to depths which receive 10% or more of sea surface photosynthetically active radiation. Seagrasses form large beds only along low energy reaches of the coast. The Florida Bay seagrass bed contained about twice the short-shoot density of both Thalassia testudinum and Syringodium filiforme, for data averaged over all depths, and about four times the average short-shoot density of both species in shallow water compared with the Big Bend seagrass bed. The differences in average seagrass abundance between Florida Bay and the Big Bend area may be a consequence of the effects of greater seasonal solar radiation and water temperature fluctuations experienced by plants in the northern bed, which lies at the northern distribution limit for American Tropical seagrasses.     

Geochemical constraints on the distribution of gas hydrates in the Gulf of Mexico

Gas hydrates are common within near-seafloor sediments immediately surrounding fluid and gas venting sites on the continental slope of the northern Gulf of Mexico. However, the distribution of gas hydrates within sediments away from the vents is poorly documented, yet critical for gas hydrate assessments. Porewater chloride and sulfate concentrations, hydrocarbon gas compositions, and geothermal gradients obtained during a porewater geochemical survey of the northern Gulf of Mexico suggest that the lack of bottom simulating reflectors in gas-rich areas of the gulf may be the consequence of elevated porewater salinity, geothermal gradients, and microbial gas compositions in sediments away from fault conduits.     

Clay mineral distribution in sediments of the Gulf of Thailand and the South China Sea

The 25 sediment samples collected from the Gulf of Thailand and the South China Sea were analyzed for clay mineral investigation. Results showed the presence of 35% montmorillonite, 13% chlorite, 30% illite, and 22% kaolinite in sediments of the Gulf and also 16% montmorillonite, 21% chlorite, 41% illite, and 22% kaolinite in sediments of the South China Sea. The relatively high concentration of montmorillonite in sediments of the Gulf as compared with that in sediments of the South China Sea may suggest that montmorillonite in these area has been largely derived from soil formation of the bordering land areas of the Gulf, particularly from the northern part of Malay Peninsula. On the contrary, the content of illite in sediments of the South China Sea is higher than that in the Gulf. This mineral appears to have been supplied from Borneo as well as the Mekong Delta. However, chlorite which shows a similar distribution to that of illite in sediments of the Gulf and the South China Sea has not indicated Borneo Isl. as a principal source area for chlorite. Greater resemblance in amount of kaolinite in both sediments of the Gulf and the South China Sea is due to the prevailing distribution of kaolinite as low latitude clay mineral on the bordering land areas. The distribution of clay minerals in sediments of the study area appears to be closely related to the soil formation and geology of the adjacent land areas.This work was carried out at Geological and Mineralogical Institute, Tokyo University of Education.     

Holocene climate in the Persian Gulf as deduced from grain-size and pteropod distribution

Detailed coarse-fraction analyses have been made of twelve sediment cores from the Persian Gulf (40–100 m water depth) in order to detect Holocene climatic changes.The only indication of such a change was provided by the terrigenous material (i.e., the < 63 μ fraction) carried into the Gulf by rivers. All cores show characteristic variations in the quantity of terrigenous material and alternating fine- and coarse-grained layers.There was no other parameter which could point to variations in climate. This might be due to the fact that the sediments are sorted as a result of reworking by tidal currents (velocities 25–50 cm/sec): fine and light particles are removed. Any climatically-produced variations in amount or size of benthonic and planktonic organisms have probably been obliterated by tidal currents. The importance of this factor varied with time: during increased terrigenous supply, tidal currents modified the sediment surface for only short periods and a fine-grained layer was, therefore, deposited. A lesser supply of terrigenous material, on the other hand, resulted in the deposition of a coarse-grained layer.Contemporaneous sedimentation of layers with much terrigenous material (fine-grained layer) and with little terrigenous material (coarse-grained layer) is suggested. Observed petrographic variations are presumably due to large-scale changes of climate and not to local sedimentary variations (including shifts of river-mouth processes).Accordingly, the cores were correlated by examining the percentage of coarse fraction and the median diameter of the sand fraction. The assumption is that the higher the percentage of coarsegrained material, the lower the amount of terrigenous material transported into the Persian Gulf.In support of this correlation, another parameter - varying independently from grain size within one core - was examined: the species composition of pteropod shells. These quantitative changes could also be correlated, because there were different core sections with different species compositions.Correlation of the cores by grain size and by pteropod species provides the same results.Four different climatic zones could be distinguished between the lower and the upper part of the Holocene: a relatively arid period at about 9000 years B.P. was succeeded by a more humid period; this then was followed by a period of less rainfall and finally a period during the Late Holocene when rainfall increased again. This sequence is comparable to the established European climate chronology.