Particulate barium fluxes and export production in the northwestern Mediterranean

Biogenic barium, mostly in the barite (BaSO₄) form, has been proposed as a tracer for export production in the ocean. Here we report on biogenic barium (Ba_xs) and particulate organic carbon (POC) fluxes from sediment traps deployed at the DYFAMED site in the Northwestern Mediterranean Sea. Ba_xs fluxes display average values of 37 ± 45 and 50 ± 58 μg/m²/d at 200 and 1000 m respectively, and are linearly correlated to POC fluxes (mean values of 7.9 ± 9.3 and 6.8 ± 6.8 mg C/m²/d at 200 and 1000 m). Export production estimates, calculated using published Ba_xs- or POC-based algorithms, all fall below or close to the lower limit of potential export values proposed in the literature. This work clearly demonstrates the usefulness of Ba_xs as a tracer of oceanic export production in the Northwestern Mediterranean Sea. However, development of a quantitative export production proxy requires a clear understanding of the underlying cause(s) for the observed spatial variations in the relationship between Ba_xs and POC fluxes. The present study confirms that the processes leading to barite formation differ between margin and open-ocean sites and probably account for much of the regional variability in the POC/Ba_xs ratio.     

Dynamics of particle flux and carbon export in the northwestern Mediterranean Sea: A two decade time-series study at the DYFAMED site

The DYFAMED time-series station, located in the open Ligurian Sea, is one of the few pluriannual flux programs in the world and the longest in the Mediterranean Sea. The trap data series is one of only three multi-decadal data sets in existence, and it provides flux information for an environment that is distinct from the other long-term data sets. At DYFAMED, downward fluxes of particles, carbon and other major elements have been regularly measured with sediment traps since 1986 at fixed depths of 200 and 1000 m. An overview is presented of the main trends of particle and carbon fluxes observed during the period 1988–2005, period when the mooring was located on the northern side of the Ligurian Sea. In spite of considerable interannual variability, fluxes displayed a marked seasonal pattern with the highest fluxes occurring during winter and spring and lowest fluxes throughout the stratified season (summer–autumn). Organic carbon fluxes measured at both depths were highly variable over time, ranging from 0.3 to 59.9 (mean 6.8) mg C m⁻² d⁻¹ at 200 m, and from 0.2 to 37.1 (mean 4.3) mg C m⁻² d⁻¹ at 1000 m. Mass fluxes were maximal in winter, whereas carbon fluxes were maximal in late spring. Reasonably good agreement existed between particle fluxes at both depths over the years, indicating a relatively efficient and rapid transport of particles from the upper ocean to the deep sea. However, during certain periods mass flux increased with depth suggesting lateral inputs of particles that by-pass the upper trap. Since 1999, the system has apparently shifted towards an increasing occurrence of extreme flux events in response to more vigorous mixing of the water column during the winter months. Although annual mass fluxes have increased in the last years, mean POC fluxes have not substantially changed over time, due mainly to lower carbon contents of the sinking particles during maxima of mass flux.     

Exploring the connection between 210Po and organic matter in the northwestern Mediterranean

The disequilibrium between ²¹⁰Po and its grandparent ²¹⁰Pb has been proposed as a tracer of the vertical flux of sinking particulate organic matter in the ocean. The mechanism of association between ²¹⁰Po and organic matter is, however, still unclear. To investigate this association we measured trace metals, minerals, organic carbon, nitrogen, and the natural radioisotopes ²³⁴Th, ²²⁸Th, ²¹⁰Po, and ²¹⁰Pb in sinking particles collected in sediment traps at 200 m in the northwestern Mediterranean. Pigments, fatty acids, and amino acids were used to identify the types and sources of particulate organic matter. Multivariate analyses were used to determine which components of sinking particulate matter are traced by ²¹⁰Po and/or by the ²¹⁰Po/²¹⁰Pb ratio. Statistical analysis of the results indicates that the distribution of polonium in sinking marine particles is influenced by fresh phytoplankton-derived, nitrogen-rich organic matter as well as sulfur-containing amino acids. These findings are consistent with previous laboratory observations that the distribution of ²¹⁰Po in biota parallels the distributions of both sulfur and protein, and indicate that these associations persist as material sinks through the water column. While this research generally supports the use of ²¹⁰Po as a specific tracer of the flux of organic matter, the signals traced by ²¹⁰Po/²¹⁰Pb and ²³⁴Th/²³⁸U are not as distinct in the field as in laboratory experiments. Further work is needed to determine more precisely what ²¹⁰Po/²¹⁰Pb traces in order to increase the correspondence of ²¹⁰Po/²¹⁰Pb measurements to biogeochemically important rates and quantities.     

Deep sediment transport induced by storms and dense shelf-water cascading in the northwestern Mediterranean basin

Downward particle fluxes and hydrodynamics in the northwestern Mediterranean basin were measured by a sediment trap and a current meter deployed at 2350 m depth, 250 m above bottom, from November 2003 to April 2005. During the winter of 2003–2004 there were high river discharges, two strong E–SE storms and several moderate storms and short periods of moderate dense shelf-water cascading during which dense shelf water did not reach the deep basin. Downward particle fluxes at the basin site were low during most of this winter but increased above one order of magnitude as a consequence of the strong storm and moderate cascading event that occurred in late February 2004. During the winter of 2004–2005, neither important river floods nor strong storms occurred but there were very intense and persistent dense shelf-water cascading events from February to April 2005. Dense shelf water, mixed with offshore convection water, reached the basin site in early March 2005, increasing downward particle fluxes by more than two orders of magnitude for more than 1 month. These observations indicate that events of significant sediment transport to the northwestern Mediterranean basin can be caused by severe winter E–SE storms associated with moderate cascading events or by exceptionally intense and persistent dense shelf-water cascading episodes alone. On the other hand, river floods, severe storms during water column stratification conditions (without cascading) and moderate storms concurrent with moderate dense shelf-water cascading did not generate sediment transport events able to reach the basin.     

Pleistocene progradational growth pattern of the northern Catalonia continental shelf (northwestern Mediterranean)

The Pleistocene sedimentary growth pattern of the northern Catalonia continental shelf is characterized by the vertical stacking of seaward downlapping regressive deposits. These deposits are characterized by a progradational development, with oblique clinoforms of low angle in the middle continental shelf, that become more inclined seaward in the outer continental shelf and shelfbreak. Eustatic sea level fluctuations controlled the development of this sedimentary pattern, whereas sediment supply conditioned the nonuniform progradation along the continental shelf and subsidence due to both sediment loading and tectonics controlled its preservation through and along the continental shelf.     

Vertical distributions of macroplankton and micronekton in the Ligurian and Tyrrhenian seas (northwestern Mediterranean)

Vertical distributions and diel migrations at nineteen stations located in the Ligurian and Tyrrhenian Seas (northwestern Mediterranean) are described in detail and compared for the main species of micronekton and macroplankton. Sampling was performed in April 1994 in the 0–700 m water column in most cases, down to 350, 450 or 550 m for the coastal or relatively shallow sites. Most of the twenty species showed similar distributions throughout the sampled area, either non-diel-migrating distributions such as the euphausiid Stylocheiron longicorne and the fish Cyclothone braueri, or clear diel-migrant behaviour (e.g. the siphonophore Chelophyes appendiculata and the euphausiid Euphausia krohni). Four species, the siphonophore Lensia conoidea, the pteropods Cavolinia inflexa and Clio pyramidata and the salp Salpa fusiformis, showed heterogeneity between distributions, with different preferential daytime depths. For example, moderate or extensive migration and even slight reverse migration were observed in Lensia conoidea, depending on the station sampled. The differences in vertical distributions did not appear to be related to hydrological conditions (temperature, salinity); but rather to chlorophyll content (and ambient light) or bottom depth of the station, or to mating behaviour of the species.     

Increasing imposex in populations of Bolinus brandaris (Gastropoda: Muricidae) in the northwestern Mediterranean.

The muricid gastropod Bolinus brandaris exhibited imposex, a phenomenon linked to the use of organotin biocides. Several stages of imposex development (1-5) could be distinguished and were documented with SEM-photographs for the first time in this species. Additional alterations of the genital tract in females (blocked vulva preventing copulation and deposition of egg capsules) and males (excrecences on the penis and vas deferens) were shown. Imposex intensity on the Catalan coast was very high. The frequency of imposex off Barcelona and Vilanova i la Geltrú was 100%, with all females showing stage 4. Imposex frequency off Sant Carles de la Ràpita was 99.7% and the VDS index scored 3.9. Despite regulations of TBT-containing antifouling paints in Spain since 1990, the present study revealed that frequency and intensity of imposex have increased on the Catalan coast, at least since 1997. However, at present, imposex does not apparently affect the population dynamics of B. brandaris in the studied area, since no serious consequences on female reproduction (only one case of female sterilization) were detected. Gonadal activity and oogenesis were not suppressed or supplanted by spermatogenesis. Sex ratios were not male-biased. Possible sources of organotin biocides are examined.     

Appearance of Chelophyes appendiculata and Abylopsis tetragona (Cnidaria, Siphonophora) in the Bay of Villefranche, northwestern Mediterranean

The vertical and temporal distribution of two calycophoran siphonophores, Chelophyes appendiculata (Eschscholtz, 1829) and Abylopsis tetragona (Otto, 1823) in the Bay of Villefranche (northwestern Mediterranean) was investigated by an analysis of three different planktonic time series. A daily series (1993–1995) showed seasonal peaks of the nectophores of C. appendiculata during spring and particularly in late summer, while the abundance of A. tetragona remained similar throughout the year. A weekly series (1994–1995) showed that C. appendiculata (nectophores and eudoxids) became concentrated above the thermal discontinuity, in the most stratified and warm waters, whereas A. tetragona was collected in large numbers below this discontinuity. A 27-year survey (1966–1993) showed long-term fluctuations of these siphonophore populations, which became abundant in the Bay starting from 1980 and especially after 1984, when the water column grew warm and hypersaline, corresponding to a less rainy period. Temporal (seasonal and long-term) and bathymetric (between 10 and 60 m depth) successions of these two siphonophores were noted in this shallow coastal bay.     

Use of lipids and their degradation products as biomarkers for carbon cycling in the northwestern Mediterranean Sea

Changes in phytoplankton composition and degradation of particulate organic matter (POM) in the northwestern Mediterranean Sea were studied using time-series sediment trap samples collected during the spring of 2003 at the DYFAMED station. Lipid biomarkers (pigments, fatty acids, sterols, acyclic isoprenoids, alkenones and n-alkanols) were used to identify the main contributors to the POM produced during two phytoplankton blooms, while the effects of photooxidation, autoxidation and biodegradation were differentiated using characteristic lipid degradation products. Traps collected material corresponding to pre-bloom, bloom and post-bloom periods. Pigment analyses in the integrated (0-200 m) water column samples indicated that diatoms dominated the initial stages of the bloom event, with smaller amounts of haptophytes and pelagophytes. During the second part of bloom event there was a switch to haptophyte dominance with significant contributions from diatoms and pelagophytes, and an increased contribution from cryptophytes. Fatty acid distributions in the trap samples reflected contributions from marine bacteria, phytoplankton and zooplankton. Photooxidation and autoxidation products of monounsaturated oleic, cis-vaccenic and palmitoleic acids were detected along with photooxidation products from the chlorophyll side-chain. The relatively good correlation between the variation of U₃₇^K′ index and specific phytol autoxidation product percentage allowed us to attribute the alterations of U₃₇^K′ observed during the pre-bloom period and in the deeper traps to the involvement of selective autoxidative degradation processes. A variety of sterol oxidation products formed by biohydrogenation, autoxidation and photooxidation were detected. Sterol degradation products appeared to be less suited than oxidation products of monounsaturated fatty acids for the precise monitoring of the degradation state of POM, but their stable functionalized cyclic structure constitutes a useful tool to estimate the part played by biotic and abiotic processes. In these waters, biotic degradation generally predominates, but abiotic degradation is not negligible and, as expected, the extent of biotic degradation increases with depth. To obtain a more complete picture of POM degradation, the use of a pool of lipid degradation products (i.e. from unsaturated fatty acids, the phytyl side-chain and sterols) should be employed.     

Modelling the habitat suitability of cetaceans: Example of the sperm whale in the northwestern Mediterranean Sea

Cetaceans are mobile and spend long periods underwater. Because of this, modelling their habitat could be subject to a serious problem of false absence. Furthermore, extensive surveys at sea are time and money consuming, and presence–absence data are difficult to apply. This study compares the ability of two presence–absence and two presence-only habitat modelling methods and uses the example of the sperm whale (Physeter macrocephalus) in the northwestern Mediterranean Sea. The data consist of summer visual and acoustical detections of sperm whales, compiled between 1998 and 2005. Habitat maps were computed using topographical and hydrological eco-geographical variables. Four methods were compared: principal component analysis (PCA), ecological niche factor analysis (ENFA), generalized linear model (GLM) and multivariate adaptive regression splines (MARS). The evaluation of the models was achieved by calculating the receiver operating characteristic (ROC) of the models and their respective area under the curve (AUC). Presence–absence methods (GLM, AUC=0.70, and MARS, AUC=0.79) presented better AUC than presence-only methods (PCA, AUC=0.58, and ENFA, AUC=0.66), but this difference was not statistically significant, except between the MARS and the PCA models. The four models showed an influence of both topographical and hydrological factors, but the resulting habitat suitability maps differed. The core habitat on the continental slope was well highlighted by the four models, while GLM and MARS maps also showed a suitable habitat in the offshore waters. Presence–absence methods are therefore recommended for modelling the habitat suitability of cetaceans, as they seem more accurate to highlight complex habitat. However, the use of presence-only techniques, in particular ENFA, could be very useful for a first model of the habitat range or when important surveys at sea are not possible.     

Hawaiian submarine terraces,canyons, and Quaternary history evaluated by seismic-reflection profiling

The numerous submarine and elevated terraces that fringe shorelines of the Hawaiian Islands have been used as classic examples of mid-ocean Quaternary eustatic terraces. Submarine canyons are important geomorphic features of island slopes. Later reef growth often partly masks both the terraces and canyons. Although difficult to match from one side of an island to the other, some of the terraces have been correlated to successions of higher and lower Quaternary sea levels determined elsewhere in the world. Subbottom seismic reflection profiling now permits a new view of the problem, especially as related to the most recent marine history of Oahu. The geophysical work allows a partial deciphering of former terraces, now buried by younger reefs and sand, and at the same time shows that the heads of submarine canyons do connect with subaerial valleys beneath the succession of Quaternary nearshore deposits. However, the work has disclosed so many additional buried terraces as to raise serious doubts whether it will be possible, without improved techniques of dating the deposits themselves, to unravel the history of Quaternary sea-level changes in Hawaii, much less to correlate them with events recorded elsewhere.     

Dry atmospheric deposition and diazotrophy as sources of new nitrogen to northwestern Mediterranean oligotrophic surface waters

Atmospheric dry deposition of nitrogen (N) and dinitrogen (N₂) fixation rates were assessed in 2004 at the time-series DYFAMED station (northwestern Mediterranean, 43°25′N, 7°52′E). The atmospheric input was monitored over the whole year. Dinitrogen fixation was measured during different seasonal trophic states (from mesotrophy to oligotrophy) sampled during nine cruises. The bioavailability of atmospherically deposited nutrients was estimated by apparent solubility after 96 h. The solubility of dry atmospheric N deposition was highly variable (from ∼18% to more than 96% of total N). New N supplied to surface waters by the dry atmospheric deposition was mainly nitrate (NO₃⁻) (∼57% of total N, compared to ∼6% released as ammonium (NH₄⁺)). The mean bioavailable dry flux of total N was estimated to be ∼112 μmol m⁻² d⁻¹ over the whole year. The NO₃⁻ contribution (70 μmol NO₃⁻ m⁻² d⁻¹) was much higher than the NH₄⁺ contribution (1.2 μmol NH₄⁺ m⁻² d⁻¹). The N:P ratios in the bioavailable fraction of atmospheric inputs (122.5–1340) were always much higher than the Redfield N:P ratio (16). Insoluble N in atmospheric dry deposition (referred to as “organic” and believed to be strongly related to anthropogenic emissions) was ∼40 μmol m⁻² d⁻¹. N₂ fixation rates ranged from 2 to 7.5 nmol L⁻¹ d⁻¹. The highest values were found in August, during the oligotrophic period (7.5 nmol L⁻¹ at 10 m depth), and in April, during the productive period (4 nmol L⁻¹ d⁻¹ at 10 m depth). Daily integrated values of N₂ fixation ranged from 22 to 100 μmol N m⁻² d⁻¹, with a maximum of 245 μmol N m⁻² d⁻¹ in August. No relationship was found between the availability of phosphorus or iron and the observed temporal variability of N₂ fixation rates. The atmospheric dry deposition and N₂ fixation represented 0.5–6% and 1–20% of the total biological nitrogen demand, respectively. Their contribution to new production was more significant: 1–28% and 2–55% for atmospheric dry deposition and N₂ fixation, respectively. The dry atmospheric input was particularly significant in conditions of water column stratification (16–28% of new production), while N₂ fixation reached its highest values in June (46% of new production) and in August (55%).     

Sedimentation rates in Funka Bay,HokkaidÔ

Undisturbed sediment cores were collected by a modified gravity corer from Funka Bay. The sedimentation rate is determined by both²¹⁰Pb and pumice chronological methods. The sedimentation rates by²¹⁰Pb method are concordant with those by pumice methods. The derived rate varies from 0.06 to 0.22 g cm^–2 y^–1, and an average is 0.09 g cm^–2 y^–1.     

Seasonal and depth-related dynamics of prokaryotes and viruses in surface and deep waters of the northwestern Mediterranean Sea

The study site located in the northwestern Mediterranean Sea was visited nine times in 2005–2006 to collect water samples from the epi- (5 m), meso- (200, 600 m), and bathypelagic (1000, 2000 m) zone. Total abundance of prokaryotes and viruses was determined by flow cytometry (FCM). Prokaryotic abundance in the epi-, meso-, and bathypelagic varied between 0.9 and 15.9×10⁵, 0.6 and 2.1×10⁵, and 0.3 and 1.3×10⁵ ml⁻¹, respectively. Variation of viral abundance in the epi-, meso-, and bathypelagic was between 1.2 and 57.5×10⁶, 0.5 and 3.5×10⁶, and 0.4 and 1.3×10⁶ ml⁻¹, respectively. The fraction of low (LNA) and high (HNA) nucleic acid prokaryotes averaged 42.9% and 57.1% throughout the water column and did not differ between depth layers. Throughout the water column the fraction of low, medium, and high fluorescent viruses (Vir-LF, Vir-MF, Vir-HF) averaged 66.3%, 30.2%, and 3.5%. Vir-LF and Vir-MF did not differ between depth layers; however, Vir-HF showed a preference for surface waters. The fraction of LNA cells decreased in the epi- and increased in the bathypelagic with decreasing stratification. The fraction of Vir-LF viruses increased in the epipelagic and decreased in the bathypelagic with increasing prokaryotic abundance. Also, the relationship between viral abundance and the bacterial community was different in surface and deep waters. The data suggest that different mechanisms of interaction between viruses and their prokaryotic hosts prevail at the surface and in deep waters.     

Anthropogenic vs. lithogenic origins of trace elements (As, Cd, Pb, Rb, Sb, Sc, Sn, Zn) in water column particles: northwestern Mediterranean Sea

The distribution of heavy metal was analyzed in water column particles collected in autumn (October 1985) and spring (March 1986) by two series of sediment traps from a mooring located in the northeastern Mediterranean Sea continental slope. Four traps were set, at 50, 100, 300, 600 m depths on the mooring in 645 m deep water in the Lacaze-Duthier canyon. The total metal concentrations were determined by ICP-MS. Results show that Rb and Sc contents display typical shale values. As, Cd, Pb, Sb, Zn (normalized to Sc) display high enrichment factors (up to 50) over shale compositions. Distinctive temporal variability as well as the respective contributions of local (Têt, Aude) and remote (Rhône) rivers and Sahara-derived aerosols have been identified. Fluxes of most elements observed in the upper 100 m can be attributed to atmospheric fluxes. In the deepest traps (300 and 600 m) these fluxes are, however, mostly dominated by riverine particles advected from the continental shelf. Most of the trace-element enrichments are more likely to be related to the anthropogenic input rather than to biological cycling. Isotopic composition of lead determined by ICP-MS enabled to evaluate that the proportion of anthropogenic lead derived from European gasoline consumption ranged between 50 and 100%.     

The Var turbidite system (Ligurian Sea, northwestern Mediterranean)—morphology, sediment supply, construction of turbidite levee and sediment waves: implications for hydrocarbon reservoirs

The Var turbidite system is a small sandy system located in the Ligurian Basin. It was deposited during the Pliocene-Quaternary in a flat-floored basin formed during the Messinian salinity crisis. The system was fed through time by the Var and Paillon canyons that connect directly to the Var and Paillon rivers. It is still active during the present sea-level highstand. Two main mechanisms are responsible for gravity-flow triggering in the Var turbidite system: (1) mass-wasting events affect mainly the upper part of the continental slope, in areas where volumes of fresh sediment delivered by rivers are highest, and result from the under-consolidation state of slope sediments and earthquakes, and (2) high-magnitude river floods resulting from melting of snow and convective rainfall during fall and spring seasons, and generating hyperpycnal turbidity currents at river mouths when the density of freshwater transporting suspended particles exceeds that of ambient seawater. Failure- and flood-induced gravity flows are involved through time in the construction of the Var Sedimentary Ridge, the prominent right-hand levee of the Var system, and sediment waves. Processes of construction of both the Var Ridge and sediment waves are closely connected. Sandy deposits are thick and abundant in the eastern (downchannel) part of the ridge. Their distribution is highly constrained by the strong difference of depositional processes across the sediment waves, potentially resulting through time in the individualization of large and interconnected sand bodies.     

Atmospheric input of dissolved inorganic phosphorus and silicon to the coastal northwestern Mediterranean Sea: Fluxes,variability and possible impact on phytoplankton dynamics

One hundred twelve rainwater samples collected from 1986 to 2003 at the signal station of Cap Ferrat (France, NW Mediterranean coast) were analysed for phosphate and silicate contents. This sampling site is affected by a European urban-dominated background material, with episodic Saharan dust inputs. The input of dissolved inorganic phosphorus (DIP) and dissolved inorganic silicon (DISi) was calculated. The most significant loadings of DIP and DISi were selected in order to assess their potential impact on phytoplankton dynamics, particularly in oligotrophic conditions, when surface waters are nutrient-depleted. The theoretical new production triggered by DIP and DISi inputs (NP_atmo) was estimated through Redfield calculations. The maximum theoretical DIP-triggered NP_atmo was up to 670 mg C m⁻² in October, at the end of the oligotrophic period (135 mg C m⁻³ in the 5 m-thick surface layer). During the same period, the daily integrated primary production measured at the DYFAMED site (NW Mediterranean Sea) was on average 219 mg C m⁻² d⁻¹ within the 0–100 m depth water column, while the mean daily primary production in the 5 m-thick surface layer was 1.6 mg C m⁻³ d⁻¹. However, high NP_atmo due to high DIP inputs might be episodically limited by lower DISi inputs, which may consequently lead to episodic preferential growth of non-siliceous phytoplanktonic species.