ALBERT

Description: Highlights: • Comprehensive morphological, seismic, sedimentological, and geotechnical data sets. • Dynamic CPTU provides a powerful, time- and cost-efficient in situ technique. • Development of a regional sub-seafloor strength model offshore Nice airport. • 2D finite element slope stability assessment gives slope failure depth of 〉 50 m. Abstract: In the landslide-prone area near the Nice international airport, southeastern France, an interdisciplinary approach is applied to develop realistic lithological/geometrical profiles and geotechnical/strength sub-seafloor models. Such models are indispensable for slope stability assessments using limit equilibrium or finite element methods. Regression analyses, based on the undrained shear strength (su) of intact gassy sediments are used to generate a sub-seafloor strength model based on 37 short dynamic and eight long static piezocone penetration tests, and laboratory experiments on one Calypso piston and 10 gravity cores. Significant strength variations were detected when comparing measurements from the shelf and the shelf break, with a significant drop in su to 5.5 kPa being interpreted as a weak zone at a depth between 6.5 and 8.5 m below seafloor (mbsf). Here, a 10% reduction of the in situ total unit weight compared to the surrounding sediments is found to coincide with coarse-grained layers that turn into a weak zone and detachment plane for former and present-day gravitational, retrogressive slide events, as seen in 2D chirp profiles. The combination of high-resolution chirp profiles and comprehensive geotechnical information allows us to compute enhanced 2D finite element slope stability analysis with undrained sediment response compared to previous 2D numerical and 3D limit equilibrium assessments. Those models suggest that significant portions (detachment planes at 20 m or even 55 mbsf) of the Quaternary delta and slope apron deposits may be mobilized. Given that factors of safety are equal or less than 1 when further considering the effect of free gas, a high risk for a landslide event of considerable size off Nice international airport is identified.

Description: Background Polychaetes assigned as Scoloplos armiger (Orbiniidae) show a cosmopolitan distribution and have been encountered in all zoogeographic regions. Sibling S. armiger-like species have been revealed by recent studies using RAPDs and AFLP genetic data. We sequenced a ~12 kb fragment of the Scoloplos cf. armiger mitochondrial genome and developed primers for variable regions including the 3' end of the cox3 gene, trnQ, and most of nad6. A phylogenetic analysis of this 528-nucleotide fragment was carried out for S. armiger-like individuals from the Eastern North Atlantic as well as Pacific regions. The aim of this study is to test the cosmopolitan status, as well as to clarify the systematics of this species complex in the Eastern North Atlantic, while using a few specimens from the Pacific Ocean for comparision. Results Phylogenetic analysis of the cox3-trnQ-nad6 data set recovered five different clades of Scoloplos cf. armiger. The fragment of the mitochondrial genome of Scoloplos cf. armiger is 12,042 bp long and contains 13 protein coding genes, 15 of the 22 expected tRNAs, and the large ribosomal subunit (rrnl). Conclusion The sequenced cox3-trnQ-nad6 fragment proved to be very useful in phylogenetic analyses of Scoloplos cf. armiger. Due to its larger sampling scale this study goes beyond previous analyses which used RAPD and AFLP markers. The results of this study clearly supports that Scoloplos armiger represents a species complex and not a cosmopolitan species. We find at least two S. armiger-like species within the Pacific region and three different S. armiger-like species in the North Atlantic. Implications for the taxonomy and the impact on ecological studies are discussed.

Description: Due to their thermodynamically stable low-Mg calcite mineralogy, the shells of brachiopods are often counted among the most reliable archives of the physicochemical conditions that occurred during the Phanerozoic in marine waters. Consequently, traditional and non-traditional isotope and elemental proxy data from brachiopod valves have been analyzed in numerous studies and results obtained have been placed in context with ancient seawater properties. This paper tests the sensitivity of brachiopod shell magnesium isotope (δ26Mg) data to diagenetic alteration. We apply a dual approach by: (i) performing hydrothermal alteration experiments using meteoric, marine, and burial reactive fluids; and (ii) comparing these data to naturally altered, ancient brachiopod shells. The degree of alteration of individual shells is assessed by a combination of fluorescence and cathodoluminescence microscopy. The absence of luminescence might indicate both well-preserved shell material, but also the secondary enrichment of quenching elements such as iron along diagenetic pathways. Complementary oxygen isotope data provide insight into the question of open versus closed system behavior of brachiopod shells. Brachiopod shell magnesium isotope values respond to differential fluid temperature, chemistry, and experiment durations. The patterns observed are complicated by the interplay of kinetic and thermodynamic patterns and the presence of variable amounts of water soluble and water insoluble organic matter within these biominerals. Generally, the range in bulk δ26Mg from experimentally altered (1.52‰) and that of bulk samples from ancient, diagenetically altered brachiopod valves (1.53‰) exceed the geochemical variability of δ26Mgbrachiopod bulk values of most recent specimens (1.26‰) in the lower and upper range. More 26Mg enriched (0.8‰) and more 26Mg depleted (0.7‰) values, respectively, are found in altered shells in comparison to unaltered ones. The data shown here are considered significant for those aiming to reconstruct palaeoenvironmental parameters based on brachiopod archives. Consequently, we propose tentative guidelines for magnesium isotope research applied to ancient carbonates.

Description: With the common goal of more accurately and consistently quantifying ambient concentrations of free metal ions and natural organic ligands in aquatic ecosystems, researchers from 15 laboratories that routinely analyze trace metal speciation participated in an intercomparison of statistical methods used to model their most common type of experimental dataset, the complexometric titration. All were asked to apply statistical techniques that they were familiar with to model synthetic titration data that are typical of those obtained by applying state-of-the-art electrochemical methods - anodic stripping voltammetry (ASV) and competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE-ACSV) - to the analysis of natural waters. Herein, we compare their estimates for parameters describing the natural ligands, examine the accuracy of inferred ambient free metal ion concentrations ([Mf]), and evaluate the influence of the various methods and assumptions used on these results.The ASV-type titrations were designed to test each participant's ability to correctly describe the natural ligands present in a sample when provided with data free of measurement error, i.e., random noise. For the three virtual samples containing just one natural ligand, all participants were able to correctly identify the number of ligand classes present and accurately estimate their parameters. For the four samples containing two or three ligand classes, a few participants detected too few or too many classes and consequently reported inaccurate 'measurements' of ambient [Mf]. Since the problematic results arose from human error rather than any specific method of analyzing the data, we recommend that analysts should make a practice of using one's parameter estimates to generate simulated (back-calculated) titration curves for comparison to the original data. The root-mean-squared relative error between the fitted observations and the simulated curves should be comparable to the expected precision of the analytical method and upon visual inspection the distribution of residuals should not be skewed.Modeling the synthetic, CLE-ACSV-type titration dataset, which comprises 5 titration curves generated at different analytical windows or levels of competing ligand added to the virtual sample, proved to be more challenging due to the random measurement error that was incorporated. Comparison of the submitted results was complicated by the participants' differing interpretations of their task. Most adopted the provided 'true' instrumental sensitivity in modeling the CLE-ACSV curves, but several estimated sensitivities using internal calibration, exactly as is required for actual samples. Since most fitted sensitivities were biased low, systematic error in inferred ambient [Mf] and in estimated weak ligand (L2) concentrations resulted.The main distinction between the mathematical approaches taken by participants lies in the functional form of the speciation model equations, with their implicit definition of independent and dependent or manipulated variables. In 'direct modeling', the dependent variable is the measured [Mf] (or I p) and the total metal concentration ([M]T) is considered independent. In other, much more widely used methods of analyzing titration data - classical linearization, best known as van den Berg/Ružić, and isotherm fitting by nonlinear regression, best known as the Langmuir or Gerringa methods - [Mf] is defined as independent and the dependent variable calculated from both [M]T and [Mf]. Close inspection of the biases and variability in the estimates of ligand parameters and in predictions of ambient [Mf] revealed that the best results were obtained by the direct approach. Linear regression of transformed data yielded the largest bias and greatest variability, while non-linear isotherm fitting generated results with mean bias comparable to direct modeling, but also with greater variability.Participants that performed a unified analysis of ACSV titration curves at multiple detection windows for a sample improved their results regardless of the basic mathematical approach taken. Overall, the three most accurate sets of results were obtained using direct modeling of the unified multiwindow dataset, while the single most accurate set of results also included simultaneous calibration. We therefore recommend that where sample volume and time permit, titration experiments for all natural water samples be designed to include two or more detection windows, especially for coastal and estuarine waters. It is vital that more practical experimental designs for multi-window titrations be developed.Finally, while all mathematical approaches proved to be adequate for some datasets, matrix-based equilibrium models proved to be most naturally suited for the most challenging cases encountered in this work, i.e., experiments where the added ligand in ACSV became titrated. The ProMCC program (Omanović et al., this issue) as well as the Excel Add-in based KINETEQL Multiwindow Solver spreadsheet (Hudson, 2014) have this capability and have been made available for public use as a result of this intercomparison exercise.

Description: Nitrous oxide (N2O) is a climate-relevant atmospheric trace gas. It is produced as an intermediate of the nitrogen cycle. The open and coastal oceans are major sources of atmospheric N2O. However, its oceanic distribution is still largely unknown. Here we present the first measurements of the water column distribution of N2O in the Gulf of Aqaba and the Red Sea. Samples for N2O depth profiles were collected at the time-series site Station A in the northern Gulf of Aqaba (June and September 2003, and February 2004) and at several stations in the central Red Sea (October 2014, January and August 2016). Additionally, we measured N2O concentrations in brine pool samples collected in the northern and central Red Sea (January 2005 and August 2016). In the Gulf of Aqaba, N2O surface concentrations ranged from 6 to 8 nmol L−1 (97–111% saturation) and were close to the equilibrium with the overlying atmosphere. A pronounced temporal variability of the N2O water column distribution was observed. We suggest that this variability is a reflection of the interplay between N2O production by nitrification and its consumption by N2 fixation in the layers below 150 m during summer. N2O surface concentrations and saturations in the central Red Sea basin ranged from 2 to 9 nmol L−1 (43–155% saturation). A pronounced temporal variability with significant supersaturation in October 2014 and undersaturation in January and August 2016 was observed in the surface layer. In October 2014, N2O in the water column seemed to result from production via nitrification. Low N2O water column concentrations in January and August 2016 indicated a significant removal of N2O. We speculate that either in-situ consumption or remote loss processes of N2O such as denitrification in coastal regions were responsible for this difference. Strong meso- and submesoscale processes might have transported the coastal signals into the central Red Sea. In addition, enhanced N2O concentrations of up to 39 nmol L−1 were found at the seawater-brine pool interfaces which point to an N2O production via nitrification and/or denitrification at low O2 concentrations. Our results indicate that the Red Sea and the Gulf of Aqaba are unique natural laboratories for the study of N2O production and consumption pathways under extreme conditions in one of the warmest and most saline regions of the global ocean.

Description: Highlights • Cu speciation was investigated for the first time in the South-East Atlantic using CLE-AdCSV. • [Cu2+] were mostly below the putative biolimiting threshold of various marine microorganisms. • Cu speciation parameters showed a poor correlation with assessed biogeochemical parameters. • Spatial differences in Cu speciation parameters suggest that biogeochemical processes and sources strongly influence Cu speciation. Organic ligands play a key role in the marine biogeochemical cycle of copper (Cu), a bio-essential element, regulating its solubility and bioavailability. However, the sources, abundance, and distribution of these ligands are still poorly understood. In this study, we examined vertical Cu speciation profiles from the South-East Atlantic (GEOTRACES section GA08). Profiles were collected from a range of ocean conditions, including the Benguela upwelling region, the oligotrophic South Atlantic Gyre, and the Congo River outflow. In general, the lack of a significant correlation between most of the parameters assessed here with Cu speciation data obscures the provenance of Cu-binding ligands, suggesting that Cu speciation in the South-East Atlantic is influenced by a complex interplay between biotic and abiotic processes. Nevertheless, the total dissolved Cu (CuT) illustrated an allochthonous origin in the working area, while Cu-binding ligands showed both an allochthonous and a biogenic, autochthonous origin. Pigment concentrations showed that the phylogeography of different microorganisms influenced the spatial features of the Cu-binding ligand pool in the South-East Atlantic. Allochthonous Cu-binding ligand sources in the upper water column are likely associated with dissolved organic matter which originated from the Congo River and the Benguela upwelling system. Deep water ligand sources could include refractory dissolved organic carbon (DOC), resuspended benthic inputs, and lateral advected inputs from the shelf margin. The degradation of L1-type ligands and/or siderophores in low oxygen conditions may also be a source of L2-type ligands in the deep. Free Cu ion levels (1.7 to 156 fM), the biologically available form of CuT, were below the putative biolimiting threshold of many marine organisms. Two classes of ligands were found in this study with total ligand concentrations ([LT]) ranging from 2.5 to 283.0 nM and conditional stability constants (logKCuL, Cu2+cond) ranging from 10.7 to 14.6. The Cu speciation values were spatially variable across the three subregions, suggesting that biogeochemical processes and sources strongly influence Cu speciation. Highlights • Cu speciation was investigated for the first time in the South-East Atlantic using CLE-AdCSV. • [Cu2+] were mostly below the putative biolimiting threshold of various marine microorganisms. • Cu speciation parameters showed a poor correlation with assessed biogeochemical parameters. • Spatial differences in Cu speciation parameters suggest that biogeochemical processes and sources strongly influence Cu speciation.

Description: Highlights • Dissolved iron limits primary production in offshore South Pacific surface waters. • Phytoplankton is elevated in high-iron filaments in mesoscale eddies east of New Zealand. • Iron in these eddies is due to entrainment of high-iron coastal water into offshore water. • The resultant eddy-driven flux of iron supports production in the Subtropical Front. Abstract Subtropical and subantarctic waters either side of the southern hemisphere Subtropical Front are considered iron-limited, suggesting production within the front is dependent on a supply of iron from atmospheric deposition, zonal advection of coastal water, or upwelling. We present the results from a one-day biogeochemical survey in Subtropical Water east of the North Island, New Zealand, in a region where mesoscale cyclonic and anticyclonic eddies entrain chlorophyll in filaments around the eddies. There was no significant relationship between upper mixed layer chlorophyll and any physical or macronutrient quantity. However, chlorophyll was significantly positively correlated with dissolved iron. A simple model suggests that while vertical entrainment of iron into the upper mixed layer occurred, most of the dissolved iron in the eddy was due to entrainment of high-iron coastal water into low-iron offshore Subtropical Water, and that this iron supports primary production in otherwise iron-deficient water. We suggest that a significant component of the total primary production within the Subtropical Front may be determined by mesoscale eddy induced lateral advection of iron.

Description: Highlights • Investigation on PFAS in seafood was conducted for the first time in North Africa. • Long-chain PFAS were predominant in seafood from the study area. • Among seafood, crustaceans exhibited the highest concentrations of PFAS. • PFOS was the predominant PFAS compound in most marine species. • Human health risks for PFAS exposure via seafood consumption was minimal. Abstract Despite the ubiquity of per- and polyfluorinated alkyl substances (PFAS) in all environmental compartments, little is known about the pollution they cause on the African continent, neither on levels, nor effects. Here we examined the occurrence and levels of 21 legacy and emerging PFAS in 9 marine species (3 fish, 2 crustaceans and 4 mollusks) collected from Bizerte lagoon, Northern Tunisia. Furthermore, assessment of potential human health risks through consumption of contaminated seafood was examined. This is the first study assessing PFAS in Mediterranean coastal areas of North Africa. Twelve out of the 21 targeted PFAS were detected, evidencing the occurrence of PFAS in seafood from North Africa, albeit at low levels. The Ʃ21PFAS concentrations in all seafood samples ranged from 0.202 ng g−1 dry weight (dw) to 2.89 ng g−1 dw, with a mean value of 1.10 ± 0.89 ng g−1 dw. The profiles of PFAS varied significantly among different species, which might be related to their different trophic level, protein content, feeding behaviour and metabolism. Generally, current exposure to PFAS through seafood consumption indicates that it should not be of concern to the local consumers, at least for those PFAS for which information is available.