Benthic Fluxes of Dissolved Inorganic Nitrogen in a Coastal Lagoon of the Northern Adriatic Sea: an Interpretation of Spatial Variability Based on Sediment Features and Infauna Activity

Abstract. Dark respiration rates, dissolved inorganic nitrogen (DIN) fluxes and nitrification rates were measured at two sites in the microtidal Sacca di Goro lagoon in September 2000. DIN fluxes correlated with the biomass of the dominant macrofauna species (the amphipod Corophium spp. at station Giralda and the polychaete Neanthes spp. at station Faro). Respiration (> 6 mmol O₂ m⁻²h⁻¹) and ammonium fluxes (> 80μmol N m⁻²h⁻¹) were higher at station Giralda despite the lower organic matter content (4.5 %) and lower macrofauna biomass (4 g AFDW m⁻²). At both sites ammonium fluxes were significantly correlated with the biomass of the benthic infauna, but Corophium stimulated ammonium NH₄⁺ fluxes 3-fold compared to Neanthes. The amphipod also enhanced nitrification rates (> 300 μmol N m⁻²h⁻¹) due to the high density of its burrows, the higher NH₄⁺ regeneration rates and the enhanced oxygen supply to the bacteria.     

Distinct element modelling of the in-plane cyclic response of URM walls subjected to shear-compression

The in-plane capacity of unreinforced masonry (URM) elements may vary considerably depending on several factors, including boundary conditions, aspect ratio, vertical overburden, and masonry texture. Since the overall system resistance mainly relies on the in-plane lateral capacity of URM components when out-of-plane modes are adequately prevented, the structural assessment of URM structures could benefit from advanced numerical approaches able to account for these factors simultaneously. This paper aims at enhancing and optimising the employment of the distinct element method, currently confined to the analysis of local mechanisms of reduced-scale dry-joint blocky assemblies, with a view to simulate the experimentally observed responses of a series of URM full-scale specimens with mortared joints subjected to quasi-static in-plane cyclic loading. To this end, a mesoscale modelling approach is proposed that employs a simplified microscale modelling approach to effectively capture macroscale behaviour. Dynamic relaxation schemes are employed, in combination with time, size, and mass-scaling procedures, to decrease computational demand. A new methodology for numerically describing both unit, mortar and hybrid failure modes, also including masonry crushing due to high-compression stresses, is proposed. Empirical and homogenisation formulae for inferring the elastic properties of interface between elements are also verified, enabling the proposed approach to be applied more broadly. Using this modelling strategy, the interaction between stiffness degradation and energy dissipation rate was accounted for numerically. Although the models marginally underestimate the energy dissipation in the case of slender piers, a good agreement was obtained in terms of lateral strength, hysteretic response, and crack pattern.     

Dissolution and carbonation of a serpentinite: Inferences from acid attack and high P-T experiments performed in aqueous solutions at variable salinity

Dissolution experiments on a serpentinite were performed at 70 °C, 0.1 MPa, in H₂SO₄ solution, in open and closed systems, in order to evaluate the overall dissolution rate of mineral components over different times (4, 9 and 24 h). In addition, the serpentinite powder was reacted with a NaCl-bearing aqueous solution and supercritical CO₂ for 24 h at higher pressures (9-30 MPa) and temperatures (250-300 °C) either in a stirred reactor or in an externally-heated pressure vessel to assess both the dissolution rate of serpentinite minerals and the progress of the carbonation reaction. Results show that, at 0.1 MPa, MgO extraction from serpentinite ranges from 82% to 98% and dissolution rate varies from 8.5 × 10⁻¹⁰ mole m⁻² s⁻¹ to 4.2 × 10⁻⁹ mole m⁻² s⁻¹. Attempts to obtain carbonates from the Mg-rich solutions by increasing their pH failed since Mg- and NH₄- bearing sulfates promptly precipitated. On the other hand, at higher pressures, significant crystallization (5.0-10.4 wt%) of Ca- and Fe-bearing magnesite was accomplished at 30 MPa and 300 °C using 100 g L⁻¹ NaCl aqueous solutions. The corresponding amount of CO₂ sequestered by crystallization of carbonates is 9.4-15.9 mole%. Dissolution rate (from 6.3 × 10⁻¹¹ mole m⁻² s⁻¹ to 1.3 × 10⁻¹⁰ mole m⁻² s⁻¹) is lower than that obtained at 0.1 MPa and 70 °C but it is related to pH values much higher (3.3-4.4) than that (−0.65) calculated for the H₂SO₄ solution.Through a thorough review of previous experimental investigations on the dissolution kinetics of serpentine minerals the authors propose adopting: (i) the log rate [mole m⁻² s⁻¹] value of −12.08 ± 0.16 (1σ), as representative of the neutral dissolution mechanism at 25 °C and (ii) the following relationship for the acidic dissolution mechanism at 25 °C:

log rate=-0.45(±0.09)×pH-10.01(±0.30).     

Retention of biosignatures and mass-independent fractionations in pyrite: Self-diffusion of sulfur

Self-diffusion of sulfur in pyrite (FeS₂) was characterized over the temperature range ∼500-725 °C (∼1 bar pressure) by immersing natural specimens in a bath of molten elemental ³⁴S and characterizing the resulting diffusive-exchange profiles by Rutherford backscattering spectroscopy (RBS). The temperature dependence of the sulfur diffusivity (D_S) conforms to D_S = D_o exp(−E_a/RT), where the pre-exponential constant (D_o) and the activation energy (E_a) are constrained as follows:

     

An ecotoxicological protocol with caged mussels, Mytilus galloprovincialis, for monitoring the impact of an offshore platform in the Adriatic Sea

An ecotoxicological protocol with caged mussels, Mytilus galloprovincialis, was developed to evaluate the potential impact of an offshore gas platform in the central Adriatic Sea. Reference organisms were collected on a seasonal basis from an unpolluted site and transplanted for four weeks in both the sampling area and to the investigated platform. Chemical analyses of trace metals in mussel tissues were integrated with a multi-biomarker approach for the early detection of biological responses at several cellular targets. Induction of metallothioneins, peroxisomal proliferation and activity of acetylcholinesterase were measured as markers for specific classes of chemicals. Special attention was given to oxyradical metabolism and appearance of oxidative-mediated toxicity to reveal a more general onset of cellular disturbance. In addition to individual antioxidants (superoxide dismutase, catalase, glutathione S-transferases, glutathione reductase, Se-dependent and Se-independent glutathione peroxidases, and levels of total glutathione), the total oxyradical scavenging capacity (TOSC) allowed a quantification of the overall capability to neutralize specific forms of intracellular reactive oxygen species (ROS; i.e. peroxyl and hydroxyl radicals). Cellular damages were evaluated as lysosomal destabilization (membrane stability, accumulation of lipofuscin and neutral lipids), lipid peroxidation products (malondialdehyde) and DNA integrity (strand breaks and micronuclei); the air survival test was finally applied to evaluate the overall physiological condition of mussels. Concentration of trace metals (As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Zn) revealed only limited variations in transplanted mussels during various experimental periods and such changes appeared partly related to natural fluctuations. Among biological responses, variations of antioxidants and lysosomal stability were confirmed as sensitive early warning signals for biological disturbance of both natural and anthropogenic origin. The presented protocol with caged mussels allowed marked biological effects caused by the investigated platform to be excluded, and represented a useful approach that is easy to extend for monitoring the impact of offshore activities in the Adriatic sea.     

Formal proposal for the Bathonian GSSP (Middle Jurassic) in the Ravin du Bès Section (Bas-Auran, SE France)

The Bathonian Global Stratotype Section and Point (GSSP) is proposed at the base of limestone bed RB071 (bed 23 in Sturani 1967) in the Ravin du Bès Section (43° 57′ 38′′ N, 6° 18′ 55′′ E), Bas-Auran area, “Alpes de Haute Provence” French department. The Ravin du Bès Section, as formal candidate GSSP for the base of the Bathonian Stage, satisfies most of the requirements recommended by the International Commission on Stratigraphy: 1) The exposure extends over 13 m in thickness. At the Bajocian-Bathonian transition, no vertical (bio-, ichno- or tapho-) facies changes, condensation, stratigraphic gaps or hiatuses have been recorded. Structural complexity, synsedimentary and tectonic disturbances, or important alterations by metamorphism are not relevant constraints. 2) There is a well-preserved, abundant and diverse fossil record across the boundary interval, with key markers (ammonites and nannofossils) for worldwide correlation. The base of the Bathonian Stage and Zigzag Zone in Bas-Auran corresponds to the first occurrence level of Gonolkites convergens Buckman, which coincides with the first occurrence of Morphoceras parvum Wetzel. Calcareous nannofossils, as secondary global marker, are present in all beds and allow characterizing the Bajocian-Bathonian transition. 3) Regional analyses of sequence stratigraphy and manganese chemostratigraphy are available. Spectral gamma-ray data corroborate an Early Bathonian deepening half-cycle of second order. 4) The criteria of accessibility, conservation and protection are assured by the “Réserve Naturelle Géologique de Haute Provence”. The Cabo Mondego Section (Portugal) is suggested as the Bathonian auxiliary section and point (ASSP) within this GSSP proposal.     

Influence of winds and oceanographic conditions on the mucilage aggregation in the Northern Adriatic Sea in 2003–2006

Meteorological and oceanographic conditions in the Northern Adriatic Sea in a year notable for massive mucilage formation (2004) were compared with those in years where this phenomenon did not occur (2003, 2005 and 2006) to suggest possible links. The months preceding the mucilage event in 2004 were considered the ‘incubation period’ and were characterized by a strong freshet in May which increased the water column stability. Winter cooling and scarcity of freshwater inputs from the Po River triggered the dense water formation and intrusion in the northern basin. Weak southeasterly winds and an increase in surface seawater temperatures contributed to maintain and reinforce the water column stability, and at the same time an intense diatom spring bloom created the conditions for accumulation of organic matter. The interplay of climatological forcings and biological processes caused temporal variations of dissolved organic carbon (DOC) and particulate organic carbon (POC) in the basin, with POC playing an important role in the aggregation process, as suggested by its increase relative to DOC before massive mucilage formation. We therefore suggest that high POC/total particulate nitrogen ratios in the suspended particulate organic fraction, a steep increase of POC/Chlorphyll a, and the decreased DOC/POC ratios represent ‘early warning’ signals of the main processes that lead to mucilage events in the Northern Adriatic Sea.     

New chronological and geochemical constraints on the genesis and geological evolution of Ponza and Palmarola Volcanic Islands (Tyrrhenian Sea, Italy)

A new geochronological and geochemical study of the volcanic rocks of the Ponza and Palmarola Islands, Pontine Archipelago, has been carried out. This archipelago is located along the boundary between the Italian continental shelf and the opening Tyrrhenian basin. It is a key area to study volcanism related to the opening of the Tyrrhenian Sea. Ponza is the oldest felsic magmatic manifestation in the central Tyrrhenian area. Previous studies suggested that Ponza volcanic activity began before 5 Ma. Twenty-five new K–Ar ages constrain the volcanic activity (rhyolitic hyaloclastites and dykes) to the last 4.2 Ma, with two episodes of quiescence between 3.7 and 3.2 Ma and between 2.9 and 1.0 Ma. A new volcanic episode dated at 3.2–2.9 Ma has been identified on the central and southern Ponza, with emplacement of pyroclastic units. At 1.0 Ma, a trachytic episode ended the volcanic activity. The near island of Palmarola exhibits rhyolitic hyaloclastites and domes dated between 1.6 and 1.5 Ma, indicating that the island was entirely built during the Early Pleistocene in a short span of time of ca. 120 ka. Although only 6–8 km apart, the two islands display significantly different geochemical signatures. Ponza rhyolites show major and trace element compositions representative of orogenic magmas of subduction/collision zones: high-K calc-alkaline and metaluminous rhyolites (Agpaitic Index [AI] and Alumina Saturation Index [ASI] <1), high LILE/HFSE (Th/Ta=16–21) and LREE/HFSE ratios (La/Nb>3), and Nb–Ta negative anomalies. In Palmarola, the orogenic character is also present, but much less marked than in Ponza: rhyolites have a peralkaline character (AI>1), lower LILE/HFSE (Th/Ta=11–15), low LREE/HFSE ratios (La/Nb=1–2) close to those of anorogenic lavas, and the Nb–Ta negative anomalies are almost absent. Y/Nb ratios indicate different magmatic sources, one similar to island-arc or active continental margin basalts for Ponza rhyolites, and the others probably involving an OIB type component for Palmarola rhyolites and Ponza trachytes. Palmarola volcanics represent a transitional magmatism: although a preserved collisional geochemical imprint, they show geochemical features approaching those of anorogenic lavas erupted in a within-plate context. The change of magmatism evidenced in this study can be related to the tectonic evolution of the area. Indeed, Hf, Ta and Rb contents suggest that the oldest Pliocene rhyolites of Ponza would emplace in a syn- to late-collisional setting, while the younger Pleistocene rhyolites of Palmarola would be emplaced in a post-collisional setting in which the orogenic character (Th/Ta) decreases and mantle influence (Nb/Ta) increases. Geochemical modeling strongly suggests that the Palmarola rhyolites represent the waning stages of a subduction-related magmatism. The K–Ar datings allow us to estimate precisely the transition of magmatism to last less than 1.3 Ma. The transitional magmas may be the result of the upwelling of asthenospheric mantle inducing melting of a metasomatized lithospheric mantle and the mixing between these two sources. This upwelling could occur during the extension of the Tyrrhenian basin, caused by the slab retreat and steepening, or during a process of slab break-off starting in the Pliocene.     

Compound and hybrid clinothems of the last lowstand Mid-Adriatic Deep: Processes,depositional environments,controls and implications for stratigraphic analysis of prograding systems

Clinoforms with a range of scales are essential elements of prograding continental margins. Different types of clinoforms develop during margin growth, depending on combined changes in relative sea level, sediment supply and oceanographic processes. In studies of continental margin stratigraphy, trajectories of clinoform ‘rollover’ points are often used as proxies for relative sea-level variation and as predictors of the character of deposits beyond the shelf-break. The analysis of clinoform dynamics and rollover trajectory often suffers from the low resolution of geophysical data, the small scale of outcrops with respect to the dimensions of clinoform packages and low chronostratigraphic resolution. Here, through high-resolution seismic reflection data and sediment cores, we show how compound clinoforms were the most common architectural style of margin progradation of the late Pleistocene lowstand in the Adriatic Sea. During compound clinoform development, the shoreline was located landward of the shelf-break. It comprised a wave-dominated delta to the west and a barrier and back-barrier depositional system in the central and eastern area. Storm-enhanced hyperpycnal flows were responsible for the deposition of a sandy lobe in the river mouth, whereas a heterolithic succession formed elsewhere on the shelf. The storm-enhanced hyperpycnal flows built an apron of sand on the slope that interrupted an otherwise homogeneous progradational mudbelt. Locally, the late lowstand compound clinoforms have a flat to falling shelf-break trajectory. However, the main phase of shelf-break bypass and basin deposition coincides with a younger steeply rising shelf-break trajectory. We interpret divergence from standard models, linking shelf-break trajectory to deep-sea sand deposition, as resulting from a great efficiency of oceanographic processes in reworking sediment in the shelf, and from a high sediment supply. The slope foresets had a large progradational attitude during the late lowstand sea-level rise, showing that oceanographic processes can inhibit coastal systems to reach the shelf-edge. In general, our study suggests that where the shoreline does not coincide with the shelf-break, trajectory analysis can lead to inaccurate reconstruction of the depositional history of a margin.