The mosaic of habitats of the Seine estuary: Insights from food-web modelling and network analysis

Ecological network analysis was applied in the Seine estuary ecosystem, northern France, integrating ecological data from the years 1996 to 2002. The Ecopath with Ecosim (EwE) approach was used to model the trophic flows in 6 spatial compartments leading to 6 distinct EwE models: the navigation channel and the two channel flanks in the estuary proper, and 3 marine habitats in the eastern Seine Bay. Each model included 12 consumer groups, 2 primary producers, and one detritus group. Ecological network analysis was performed, including a set of indices, keystoneness, and trophic spectrum analysis to describe the contribution of the 6 habitats to the Seine estuary ecosystem functioning. Results showed that the two habitats with a functioning most related to a stressed state were the northern and central navigation channels, where building works and constant maritime traffic are considered major anthropogenic stressors. The strong top-down control highlighted in the other 4 habitats was not present in the central channel, showing instead (i) a change in keystone roles in the ecosystem towards sediment-based, lower trophic levels, and (ii) a higher system omnivory. The southern channel evidenced the highest system activity (total system throughput), the higher trophic specialisation (low system omnivory), and the lowest indication of stress (low cycling and relative redundancy). Marine habitats showed higher fish biomass proportions and higher transfer efficiencies per trophic levels than the estuarine habitats, with a transition area between the two that presented intermediate ecosystem structure. The modelling of separate habitats permitted disclosing each one's response to the different pressures, based on their a priori knowledge. Network indices, although non-monotonously, responded to these differences and seem a promising operational tool to define the ecological status of transitional water ecosystems.

Statistical Analysis of Sea Surface Temperature and Chlorophyll-a Concentration Patterns in the Gulf of Tadjourah (Djibouti)

The sea surface temperature (SST) and chlorophyll-a concentration (CHL-a) were analysed in the Gulf of Tadjourah from two set of 8-day composite satellite data, respectively from 2008 to 2012 and from 2005 to 2011. A singular spectrum analysis (SSA) shows that the annual cycle of SST is strong (74.3% of variance) and consists of warming (April-October) and cooling (November-March) of about 2.5C than the long-term average. The semi-annual cycle captures only 14.6% of temperature variance and emphasises the drop of SST during July-August. Similarly, the annual cycle of CHL-a (29.7% of variance) depicts high CHL-a from June to October and low concentration from November to May. In addition, the first spatial empirical orthogonal function (EOF) of SST (93% of variance) shows that the seasonal warming/cooling is in phase across the whole study area but the southeastern part always remaining warmer or cooler. In contrast to the SST, the first EOF of CHL-a (54.1% of variance) indicates the continental shelf in phase opposition with the offshore area in winter during which the CHL-a remains sequestrated in the coastal area particularly in the south-east and in the Ghoubet Al-Kharab Bay. Inversely during summer, higher CHL-a quantities appear in the offshore waters. In order to investigate processes generating these patterns, a multichannel spectrum analysis was applied to a set of oceanic (SST, CHL-a) and atmospheric parameters (wind speed, air temperature and air specific humidity). This analysis shows that the SST is well correlated to the atmospheric parameters at an annual scale. The windowed cross correlation indicates that this correlation is significant only from October to May. During this period, the warming was related to the solar heating of the surface water when the wind is low (April-May and October) while the cooling (November-March) was linked to the strong and cold North-East winds and to convective mixing. The summer drop in SST followed by a peak of CHL-a, seems strongly correlated to the upwelling. The second EOF modes of SST and CHL-a explain respectively 1.3% and 5% of the variance and show an east-west gradient during winter that is reversed during summer. This work showed that the seasonal signals have a wide spatial influence and dominate the variability of the SST and CHL-a while the east-west gradient are specific for the Gulf of Tadjourah and seem induced by the local wind modulated by the topography.

High resolution mass spectrometry for quantitative analysis and untargeted screening of algal toxins in mussels and passive samplers

Measurement of marine algal toxins has traditionally focussed on shellfish monitoring while, over the last decade, passive sampling has been introduced as a complementary tool for exploratory studies. Since 2011, liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been adopted as the EU reference method (No.15/2011) for detection and quantitation of lipophilic toxins. Traditional LC-MS approaches have been based on low-resolution mass spectrometry (LRMS), however, advances in instrument platforms have led to a heightened interest in the use of high-resolution mass spectrometry (HRMS) for toxin detection. This work describes the use of HRMS in combination with passive sampling as a progressive approach to marine algal toxin surveys. Experiments focused on comparison of LRMS and HRMS for determination of a broad range of toxins in shellfish and passive samplers. Matrix effects are an important issue to address in LC-MS; therefore, this phenomenon was evaluated for mussels (Mytilus galloprovincialis) and passive samplers using LRMS (triple quadrupole) and HRMS (quadrupole time-of-flight and Orbitrap) instruments. Matrix-matched calibration solutions containing okadaic acid and dinophysistoxins, pectenotoxin, azaspiracids, yessotoxins, domoic acid, pinnatoxins, gymnodimine A and 13-desmethyl spirolide C were prepared. Similar matrix effects were observed on all instruments types. Most notably, there was ion enhancement for pectenotoxins, okadaic acid/dinophysistoxins on one hand, and ion suppression for yessotoxins on the other. Interestingly, the ion selected for quantitation of PTX2 also influenced the magnitude of matrix effects, with the sodium adduct typically exhibiting less susceptibility to matrix effects than the ammonium adduct. As expected, mussel as a biological matrix, quantitatively produced significantly more matrix effects than passive sampler extracts, irrespective of toxin. Sample dilution was demonstrated as an effective measure to reduce matrix effects for all compounds, and was found to be particularly useful for the non-targeted approach. Limits of detection and method accuracy were comparable between the systems tested, demonstrating the applicability of HRMS as an effective tool for screening and quantitative analysis. HRMS offers the advantage of untargeted analysis, meaning that datasets can be retrospectively analysed. HRMS (full scan) chromatograms of passive samplers yielded significantly less complex data sets than mussels, and were thus more easily screened for unknowns. Consequently, we recommend the use of HRMS in combination with passive sampling for studies investigating emerging or hitherto uncharacterised toxins.