Natural frequencies of a vibrating repaired panel in an ocean structure

The present work arose from the need of repairing steel plates badly damaged by corrosion in a portion of the structural element of the naval vehicle. The possibility of removing the portion and replacing it by a patch of a composite material was considered. Its dynamic behavior is altered by the introduction of the patch and the prediction of its new behavior is of great interest in many situations. This condition would appear in other real-life situations like as a localized orthotropic effect caused in the panel by a welding procedure or a metallurgical process. The first four natural frequency coefficients of the composite repaired panel with different types of boundary conditions are determined by means of a variational approach. The displacement function is approximated making use of complete sets of beam functions. The eigenvalues have been computed from (225×225) secular determinants. An independent solution is obtained using the finite element method and a reasonably good agreement with the analytical solution is encountered.     

The morphology and tectonics of the Mark area from Sea Beam and Sea MARC I observations (Mid-Atlantic Ridge 23° N)

High-resolution Sea Beam bathymetry and Sea MARC I side scan sonar data have been obtained in the MARK area, a 100-km-long portion of the Mid-Atlantic Ridge rift valley south of the Kane Fracture Zone. These data reveal a surprisingly complex rift valley structure that is composed of two distinct spreading cells which overlap to create a small, zero-offset transform or discordant zone. The northern spreading cell consists of a magmatically robust, active ridge segment 40–50 km in length that extends from the eastern Kane ridge-transform intersection south to about 23°12′ N. The rift valley in this area is dominated by a large constructional volcanic ridge that creates 200–500 m of relief and is associated with high-temperature hydrothermal activity. The southern spreading cell is characterized by a NNE-trending band of small (50–200 m high), conical volcanos that are built upon relatively old, fissured and sediment-covered lavas, and which in some cases are themselves fissured and faulted. This cell appears to be in a predominantly extensional phase with only small, isolated eruptions. These two spreading cells overlap in an anomalous zone between 23°05′ N and 23°17′ N that lacks a well-developed rift valley or neovolcanic zone, and may represent a slow-spreading ridge analogue to the overlapping spreading centers found at the East Pacific Rise. Despite the complexity of the MARK area, volcanic and tectonic activity appears to be confined to the 10–17 km wide rift valley floor. Block faulting along near-vertical, small-offset normal faults, accompanied by minor amounts of back-tilting (generally less than 5°), begins within a few km of the ridge axis and is largely completed by the time the crust is transported up into the rift valley walls. Features that appear to be constructional volcanic ridges formed in the median valley are preserved largely intact in the rift mountains. Mass-wasting and gullying of scarp faces, and sedimentation which buries low-relief seafloor features, are the major geological processes occurring outside of the rift valley. The morphological and structural heterogeneity within the MARK rift valley and in the flanking rift mountains documented in this study are largely the product of two spreading cells that evolve independently to the interplay between extensional tectonism and episodic variations in magma production rates.     

Mineralogical controls on environmental mobility of arsenic from historic mine processing residues,New Zealand

Processing of arsenopyrite ore took place at Blackwater Au mine, New Zealand, between 1908 and 1951 and no rehabilitation was undertaken after mine closure. High As concentrations in solid processing residues (up to 40 wt% As) are due to secondary As minerals. Site pH regimes vary from 4.1 to circum-neutral. Originally, all processed As was present as arsenolite (arsenic trioxide polymorph, As^III), a by-product of arsenopyrite roasting. Near the roaster, scorodite precipitated as a result of the high dissolved As concentration during arsenolite dissolution. The formation of scorodite has two major consequences. Firstly, the scorodite precipitate cements the ground in the vicinity of the roaster area, thereby creating an impermeable surface crust (up to 30 wt% As) and encapsulating weathered arsenolite grains within the cement. Secondly, formation of scorodite temporarily immobilizes some of the dissolved As that is generated during nearby arsenolite dissolution. Where all the available arsenolite has dissolved, scorodite becomes soluble, and the dissolved As concentrations are controlled by scorodite solubility, which is at least two orders of magnitudes lower than arsenolite solubility. Downstream Eh conditions fall below the As^V/As^III boundary, so that scorodite does not precipitate and dissolved As concentrations are controlled by arsenolite solubility. Dissolved As reaches up to 52 mg/L in places, and exceeds the current WHO drinking water guideline of 0.01 mg/L by 5200 times. This study shows that dissolved As concentrations in discharge waters at historic mine sites are dependent on the processing technology and associated mineralogy.     

Holocene climate and environmental history of East Greenland inferred from lake sediments

Prediction of future Arctic climate and environmental changes, as well as associated ice-sheet behavior, requires placing present-day warming and reduced ice extent into a long-term context. Here we present a record of Holocene climate and glacier fluctuations inferred from the paleolimnology of small lakes near Istorvet ice cap in East Greenland. Calibrated radiocarbon dates of organic remains indicate deglaciation of the region before ~10,500 years BP, after which time the ice cap receded rapidly to a position similar to or less extensive than present, and lake sediments shifted from glacio-lacustrine clay to relatively organic-rich gyttja. The lack of glacio-lacustrine sediments throughout most of the record suggests that the ice cap was similar to or smaller than present throughout most of the Holocene. This restricted ice extent suggests that climate was similar to or warmer than present, in keeping with other records from Greenland that indicate a warm early and middle Holocene. Middle Holocene magnetic susceptibility oscillations, with a ~200-year frequency in one of the lakes, may relate to solar influence on local catchment processes. Following thousands of years of restricted extent, Istorvet ice cap advanced to within 365 m of its late Holocene limit at ~AD 1150. Variability in the timing of glacial and climate fluctuations, as well as of sediment organic content changes among East Greenland lacustrine records, may be a consequence of local factors, such as elevation, continentality, water depth, turbidity, and seabirds, and highlights the need for a detailed spatial array of datasets to address questions about Holocene climate change.     

Effects of pH and Ca competition on complexation of cadmium by fulvic acids and by natural organic ligands from a river and a lake

The technique of competitive ligand-exchange/anodic stripping voltammetry (CLE-SV) was used to investigate effects of pH and Ca concentration on cadmium complexation by fulvic acid (FA), as well as Cd speciation in two different freshwaters, a hardwater Lake Greifen and a softwater River Wyre. Binding of Cd to Suwannee river FA (10 mg/l) was determined at different pH (7–8.5) and in the presence of various concentration of Ca²⁺ (0–2 mmol/l). The results from one-ligand discrete models were compared to simulations by the WHAM VI model. In Lake Greifen, the determined dissolved [Cd²⁺] ranged from 10⁻¹³ to 10⁻¹² mol/l, and the conditional stability constant with natural ligands was log K _CdL about 9.5–10.5 (pH 8.6–8.8) with ligand concentrations of 1.2–7.8 × 10⁻⁶ mol/g C. In the softwater River Wyre, dissolved [Cd²⁺] ranged from 4 × 10⁻¹² to 1 × 10⁻¹¹ mol/l, and the ligands were weaker (log K _CdL 8.9–9.8, pH 8.0) with lower ligand concentrations (0.9–2.3 × 10⁻⁶ mol/g C). The titration curves of FA samples were close to the simulated curves by the WHAM VI model at pH 8.0–8.5, but deviated more from the model at lower pH, indicating that the results determined with CLE-SV for Cd-FA complexation are relevant to the data base in the model. Calculation of the Ca competition for Cd binding by FA showed a competition effect of similar strength as the measured one, but indicated a systematic difference between measured and modeled data at pH 7.5. Using the WHAM model for comparison with FA, the complexation of Cd by the River Wyre ligands was close to that of FA, whereas stronger complexation was observed in the Lake Greifen water. These differences may originate from different ligand composition in the lake and the river.     

Age, origin and geodynamic significance of plagiogranites in lherzolites and gabbros of the Piedmont-Ligurian ocean basin

U-Pb zircon dating, Sr-Nd isotope tracing and major/trace/RE element analyses were performed to constrain the age, origin and geodynamic significance of plagiogranites that intrude lherzolites and gabbros in the Ligurian Alps and the Northern Apennines. In addition, a host Fe-diorite was investigated. Samples from the Ligurian Alps were collected from the Voltri Group and the Sestri-Voltaggio Zone, whereas the plagiogranites from the Northern Apennines were taken in the Bracco unit. All these units have been affected by Alpine metamorphism reaching eclogite facies in the Voltri Group, blueschist degree in the Sestri Voltaggio samples, and prehnite-pumpellyite facies in the Bracco Unit, which has additionally been affected by rodingitization.

U-Pb zircon ages of 150 ± 1, 153 ± 1 and ≈ 156 Ma were obtained, respectively, for two plagiogranites and the host Fe-diorite in the Ligurian Alps, and an age of 153 ± 1 Ma was determined for the plagiogranite in Northern Apennines. Inherited components in zircon and initial Pb in plagioclase indicate mixing of variously differentiated basaltic magmas with small amounts of roughly 1.7–2.1 Ga old continental crust material. REE patterns in both the plagiogranites and the host diorite are characterized by high REE abundance, and moderate LREE enrichment. Nd isotopic compositions lie in the range of N-MORB sources, yielding initial epsilon Nd values between + 8.8 and + 9.7, whereas Sr is isotopically heterogeneous. The geochemical pattern of the plagiogranites and the host Fe-diorite requires melting of a MORB-type mantle source that experienced LREE enrichment shortly before melting. The most likely explanation for such enrichment is the injection of melts derived by small degrees of melting from an adjacent mantle region. The basaltic, LREE-enriched parent magmas generated from this enriched domain have probably undergone up to about 72% of low-pressure fractional crystallization prior to their emplacement into the gabbro-peridotite complex.

The 156–150 Ma magmatism occurred in close relation to normal faulting, sedimentation of breccias, and detachment of the mantle complex from its overlying continental crust, followed by exposure on the ocean floor. This tectono-magmatic event in the Ligurian Alps and the Northern Apennines reflects rifting of the Adriatic-Iberian continental plate segment, preceding wider opening of the Piedmont-Ligurian ocean basin and pillow basalt deposition.     

Impact of ancient metal smelting on arsenic pollution in the Pecora River Valley,Southern Tuscany,Italy

A significant As anomaly has been reported in the literature for stream sediments and unlithified Quaternary deposits of the Pecora River valley in Southern Tuscany, extending from the “Colline Metallifere” pyrite-base metals district to the Tyrrhenian Sea. The As anomaly spreads over several square kilometers around a core that exceeds 500 ppm. Several source contributions (from natural to anthropogenic) have been invoked to explain the observed As distribution in the Pecora Valley, including the metal-working industry which was active in this area, particularly in Etrusco-Roman times and in the Middle Ages. In order to evaluate the contribution of ancient mining and metallurgical activities in the Pecora Valley to elevated As concentrations in the environment, a detailed mineralogical and geochemical survey of metallurgical slags and smelted ore minerals was undertaken from six different sites through the Pecora Valley: Poggio Butelli (Etrusco-Roman iron slags); Sata Creek, Arialla, Marsiliana, Forra and Cascata sites (all Medieval base metals slags). The As content of Etrusco-Roman slags is relatively low (few tens of ppm), whereas Medieval slags show variable, but higher amounts of base metals (±Ag) (ranging from tens to tens of thousands ppm) and As (up to 267 ppm, with average contents of about 40 ppm). Arsenic is mostly partitioned in sulfides disseminated through the glassy groundmass rather than in solid solution with the glassy matrix. Remnants of the ore used for base metal and Ag smelting during the Middle Ages had the highest As contents (up to about 1000 ppm).     

Provenance, environmental and paleogeographic controls on sandstone composition in an incised-valley system: the Eocene La Meseta Formation, Seymour Island, Antarctica

The Eocene La Meseta Formation is the youngest exposed unit of the back-arc James Ross Basin, Antarctic Peninsula, cropping out in Seymour (Marambio) Island. The formation comprises 720 m of clastic sedimentary rocks of deltaic, estuarine and shallow marine origin. It was subdivided into six unconformity-based units (Valle de Las Focas, Acantilados, Campamento, Cucullaea I, Cucullaea II and Submeseta Allomembers) grouped into three main facies associations. Facies association I represents valley-confined deposition in a progradational/aggradational tide-dominated and wave-influenced delta front/delta plain environment. Facies association II includes tidal channels, mixed tidal flats, tidal inlets and deltas, washover and beach environments. Facies association III represents nonconfined tide- and storm-influenced nearshore environments. La Meseta Formation sandstones are quartzofeldspathic with some hybrid arenites (glauconite and carbonate bioclasts-rich). Sandstone detrital modes are subdivided into two distinctive petrofacies: the low quartz petrofacies (petrofacies I, Q<55% and L>12%), interpreted to retain the original provenance signal, and the high quartz petrofacies (petrofacies II, Q>55% and L<12%), representing the reworking product of the former after selective elimination of the more labile components. Petrofacies I sandstone framework grains were mainly derived from a dissected magmatic arc and an associated metamorphic belt. Textural evidence for recycling of some grains (e.g. garnet) from older sedimentary units during valley incision is not conclusive. Changes in the relative participation of source areas during the evolution of the incised-valley system are evaluated from the relative proportions of lithic fragments and monomineralic clasts derived from each rock type. Two lithic assemblages were recognized. The mixed lithic assemblage (Rv/Rm+Rp<1.4) shows participation of all rock types; it represented valley-confined environments, either during the initial stage of valley development, or after main episodes of incision. The volcanic lithic assemblage (Rv/Rm+Rp>1.4) is clearly dominated by volcanic-derived clasts; it developed at times of high sea level and/or during later stages of the valley fill, when an “energy fence” at the shoreline prevented delivery of sediment from the Antarctic Peninsula, thus enhancing the relative participation of local volcanic sources.     

A curious case of agreement between conventional thermobarometry and phase equilibria modelling in granulites: New constraints on P–T estimates in the Antarctica segment of the Musgrave–Albany–Fraser–Wilkes Orogen

The Windmill Islands region in Wilkes Land, east Antarctica, preserves granulite facies metamorphic mineral assemblages that yield seemingly comparable P–T estimates from conventional thermobarometry and mineral equilibria modelling. This is uncommon in granulite facies terranes, where conventional thermobarometry and phase equilibria modelling generally produce conflicting P–T estimates because peak mineral compositions tend to be modified by retrograde diffusion processes. In situ U–Pb monazite geochronology and calculated metamorphic phase diagrams show that the Windmill Islands experienced two phases of high thermal gradient metamorphism during the Mesoproterozoic. The first phase of metamorphism is recorded by monazite ages in two widely separated samples and occurred at c. 1,305 Ma. This event was regional in extent, involved crustally derived magmatism and reached conditions of ~3.2–5 kbar and 690–770°C corresponding to very high thermal gradients of >150°C/kbar. The elevated thermal regime is interpreted to reflect a period of extension or increased extension in a back‐arc setting that existed prior to c. 1,330 Ma. The first metamorphic event was overprinted by granulite facies metamorphism at c. 1,180 Ma that was coeval with the intrusion of charnockite. This event involved peak temperatures of ~840–850°C and pressures of ~4–5 kbar. A phase of granitic magmatism at c. 1,250–1,210 Ma, prior to the intrusion of the charnockite, is interpreted to reflect a phase of compression within an overall back‐arc setting. Existing conventional thermobarometry suggests conditions of ~4 kbar and 750°C for M₁ and 4–7 kbar and 750–900°C for M₂. The apparent similarities between the phase equilibria modelling and existing conventional thermobarometry may suggest either that the terrane cooled relatively quickly, or that the P–T ranges obtained from conventional thermobarometry are sufficiently imprecise that they cover the range of P–T conditions obtained in this study. However, without phase equilibria modelling, the veracity of existing conventional P–T estimates cannot be evaluated. The calculated phase diagrams from this study allow the direct comparison of P–T conditions in the Windmill Islands with phase equilibria models from other regions in the Musgrave–Albany–Fraser–Wilkes Orogen. This shows that the metamorphic evolution of the Wilkes Land region is very similar to that of the eastern Albany–Fraser Orogen and Musgrave Province in Australia, and further demonstrates the remarkable consistency in the timing of metamorphism and the thermal gradients along the ~5,000 km strike length of this system.