Isotopic and geochemical characterization of salinization in the shallow aquifers of a reclaimed subsiding zone: The southern Venice Lagoon coastland

The coastal plain bordering the southern Venice Lagoon is a reclaimed lowland characterized by high subsidence rate, and ground level and water-table depth below sea level. In this agricultural region, where the surface hydrologic network is entirely artificially controlled by irrigation/drainage canals, salinization problems have long been encountered in soils and groundwaters. Here we use isotopic and geochemical tracers to improve our understanding of the origin of salinization and mineralization of the semi-confined aquifer (0–40 m), and the freshwater inputs to this hydrological system. Water samples have been collected at different seasons in the coastal Adriatic Sea, lagoon, rivers and irrigation canals, as well as in the semi-confined aquifer at depths between 12 and 35 m (14 boreholes), and in the first confined aquifer (three boreholes drilled between 40 and 80 m depth). Stable isotopes (δ¹⁸O and δD) and conductivity profiles show that direct saline intrusion from the sea or the lagoon is observed only in a restricted coastal strip, while brackish groundwaters are found over the entire topographic and piezometric depression in the centre of the study area. Fresh groundwaters are found only in the most western zone. The sharp isotopic contrast between the western and central regions suggests disconnected hydrological circulations between these two parts of the shallow aquifer. The border between these two regions also corresponds to the limits of the most strongly subsiding zone.Our results can be interpreted in terms of a four end-member mixing scheme, involving (1) marine water from the lagoon or the open sea, (2) alpine and pre-alpine regional recharge waters carried either by the main rivers Adige, Bacchiglione and Brenta (irrigation waters) or by the regional groundwater circulation, (3) local precipitation, and (4) evaporated waters infiltrated from the surface. Infiltration from the surface is also revealed by the stratification of the electrical conductivity profiles, showing that the brackish groundwaters are overlain by a shallow layer of less saline water all over the central depression. In the first confined aquifer, the groundwaters have isotopic compositions similar to the deep groundwaters of the Venetian confined aquifers (40–400 m depth). The isotopic data and the Br/Cl ratio show that the origin of the salinization of the phreatic aquifer can be ascribed to seawater intrusion alone, with no indication of the involvement of deep brines (identified at 450 m depth) in the process.The chemical composition of the saline and brackish groundwaters is characterized by an excess of sodium and a deficit of calcium compared to conservative mixing between fresh groundwaters and seawater. This suggests that the phreatic aquifer is progressively freshening, as a consequence of the beneficial influence of the extensive irrigation/drainage network, including raised canals acting as a hydraulic barrier along the coast. This freshening tendency may have been lasting since the reclamation in the mid-twentieth century, and has probably been accelerated by the ban on groundwater abstraction since the 1970s.     

Intentional contamination of water distribution networks: developing indicators for sensitivity and vulnerability assessments

Performing a comprehensive risk analysis is primordial to ensure a reliable and sustainable water supply. Though the general framework of risk analysis is well established, specific adaptation seems needed for systems such as water distribution networks (WDN). Understanding of vulnerabilities of WDN against deliberate contamination and consumers’ sensitivity against contaminated water use is very vital to inform decision-maker. This paper presents an innovative step-by-step methodology for developing comprehensive indicators to perform sensitivity, vulnerability and criticality analyses in case of absence of early warning system (EWS). The assessment and the aggregation of these indicators with specific fuzzy operators allow identifying the most critical points in a WDN. Intentional intrusion of contaminants at these points can potentially harm both the consumers as well as water infrastructure. The implementation of the developed methodology has been demonstrated through a case study of a French WDN unequipped with sensors.     

Asymptotic Analysis and Layer Decomposition for the Couplex Exercise

This document explores the possibilities of multiscale expansions and domain decomposition to solve part of the Couplex 1 exercise. We concentrate on the hydrostatic pressure and show that the slenderness of the domain and the large variations of the Darcy constants allows an analytical approximation which our test reveals to be true to relative errors smaller than 10^–3. The numerical tests are done in 2D with freefem+ and in 3D with freefem3D. Some considerations are also given for Iodine transport.     

Water sorption on martian regolith analogs: Thermodynamics and near-infrared reflectance spectroscopy

The near-infrared reflectance spectra of the martian surface present strong absorption features attributed to hydration water present in the regolith. In order to characterize the relationships between this water and atmospheric vapor and decipher the physical state of water molecules in martian regolith analogs, we designed and built an experimental setup to measure near-IR reflectance spectra under martian atmospheric conditions. Six samples were studied that cover part of the diversity of Mars surface mineralogy: a hydrated ferric oxide (ferrihydrite), two igneous samples (volcanic tuff, and dunite sand), and three potential water rich soil materials (Mg-sulfate, smectite powder and a palagonitic soil, the JSC Mars-1 regolith stimulant). Sorption and desorption isotherms were measured at 243 K for water vapor pressure varying from 10⁻⁵ to ∼0.3 mbar (relative humidity: 10⁻⁴ to 75%). These measurements reveal a large diversity of behavior among the sample suite in terms of absolute amount of water adsorbed, shape of the isotherm and hysteresis between the adsorption and desorption branches. Simultaneous in situ spectroscopic observations permit a detailed analysis of the spectral signature of adsorbed water and also point to clear differences between the samples. Ferric (oxy)hydroxides like ferrihydrite or other phases present in palagonitic soils are very strong water adsorbent and may play an important role in the current martian water cycle by allowing large exchange of water between dust-covered regions and atmosphere at diurnal and seasonal scales.     

Frasnian rugose and tabulate corals from the eastern Taurus (Kozan region,Turkey)

A section near the Kilgen Lake (Adana Province) has yielded a fauna of rugose and tabulate corals including Disphyllum cf. rugosum (Wedekind, 1922), D. cf. curtum Hill, 1954, Wapitiphyllum sp., Thamnopora sp., and Alveolites sp. This coral assemblage is consistent with the previous Frasnian age assigned to the limestones of the Gümü?ali Formation. The rather well-preserved material provides new data on the structure and microstructure of Disphyllum and allows to describe in Thamnopora unusual calicinal morphology (septal ridges, median teeth, and pseudopercula) as well as new structures linked to the lateral increase (basal low wall, apical cul-de-sac).     

Paléoenvironnements et caractérisation des roches mères pétrolières des séries pré-salifères du bassin intérieur du Gabon

The Interior Basin of Gabon, created during the break-up between South America and Africa, displays thick Neoproterozoic to Aptian p.p. fluvio-lacustrine deposits overlain by Aptian to Albian marine facies. Rock–Eval analyses from outcrop and drillhole samples show high content in organic matter (up to 25%) related to types I and II. These intervals are encountered within Permian, Neocomian–Barremian as well as Aptian siliciclastic succession. They constitute fairly good to excellent potential petroleum source rocks, which are most probably at the origin of oil indices recognized both in drillholes and in surface.     

Trace element geochemistry of CR chondrite metal

We report trace element analyses by laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) of metal grains from nine different CR chondrites, distinguishing grains from chondrule interior (“interior grains”), chondrule surficial shells (“margin grains”), and the matrix (“isolated grains”). Save for a few anomalous grains, Ni‐normalized trace element patterns are similar for all three petrographic settings, with largely unfractionated refractory siderophile elements and depleted volatile Au, Cu, Ag, S. All three types of grains are interpreted to derive from a common precursor approximated by the least‐melted, fine‐grained objects in CR chondrites. This also excludes recondensation of metal vapor as the origin of the bulk of margin grains. The metal precursors were presumably formed by incomplete condensation, with evidence for high‐temperature isolation of refractory platinum‐group‐element (PGE)‐rich condensates before mixing with lower temperature PGE‐depleted condensates. The rounded shape of the Ni‐rich, interior grains shows that they were molten and that they equilibrated with silicates upon slow cooling (1–100 K h^?1), largely by oxidation/evaporation of Fe, hence their high Pd content, for example. We propose that Ni‐poorer, amoeboid margin grains, often included in the pyroxene‐rich periphery common to type I chondrules, result from less intense processing of a rim accreted onto the chondrule subsequent to the melting event recorded by the interior grains. This means either that there were two separate heating events, which formed olivine/interior grains and pyroxene/margin grains, respectively, between which dust was accreted around the chondrule, or that there was a single high‐temperature event, of which the chondrule margin records a late “quenching phase,” in which case dust accreted onto chondrules while they were molten. In the latter case, high dust concentrations in the chondrule‐forming region (at least three orders of magnitude above minimum mass solar nebula models) are indicated.     

Zircon geochronology and geochemistry to constrain the youngest eruption events and magma evolution of the Mid-Miocene ignimbrite flare-up in the Pannonian Basin,eastern central Europe

A silicic ignimbrite flare-up episode occurred in the Pannonian Basin during the Miocene, coeval with the syn-extensional period in the region. It produced important correlation horizons in the regional stratigraphy; however, they lacked precise and accurate geochronology. Here, we used U–Pb (LA-ICP-MS and ID-TIMS) and (U–Th)/He dating of zircons to determine the eruption ages of the youngest stage of this volcanic activity and constrain the longevity of the magma storage in crustal reservoirs. Reliability of the U–Pb data is supported by (U–Th)/He zircon dating and magnetostratigraphic constraints. We distinguish four eruptive phases from 15.9 ± 0.3 to 14.1 ± 0.3 Ma, each of which possibly includes multiple eruptive events. Among these, at least two large volume eruptions (>10 km³) occurred at 14.8 ± 0.3 Ma (Demjén ignimbrite) and 14.1 ± 0.3 Ma (Harsány ignimbrite). The in situ U–Pb zircon dating shows wide age ranges (up to 700 kyr) in most of the crystal-poor pyroclastic units, containing few to no xenocrysts, which implies efficient recycling of antecrysts. We propose that long-lived silicic magma reservoirs, mostly kept as high-crystallinity mushes, have existed in the Pannonian Basin during the 16–14 Ma period. Small but significant differences in zircon, bulk rock and glass shard composition among units suggest the presence of spatially separated reservoirs, sometimes existing contemporaneously. Our results also better constrain the time frame of the main tectonic events that occurred in the Northern Pannonian Basin: We refined the upper temporal boundary (15 Ma) of the youngest counterclockwise block rotation and the beginning of a new deformation phase, which structurally characterized the onset of the youngest volcanic and sedimentary phase.     

Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.