Water release patterns of heated speleothem calcite and hydrogen isotope composition of fluid inclusions

Speleothem fluid inclusions are a potential paleo-precipitation proxy to reconstruct past rainwater isotopic composition (δ¹⁸O, δD). To get a better insight in the extraction of inclusion water from heated speleothem calcite, we monitored the water released from crushed and uncrushed speleothem calcite, heated to 900 °C at a rate of 300 °C/h, with a quadrupole mass spectrometer. Crushed calcite released water in three not well individualised peaks between 25 and 360 °C, 360 and 650 °C and between 650 and 800 °C while uncrushed calcite released water in two distinct temperature intervals: between 25 and 550 °C and between 550 and 900 °C.Water from two speleothems from the Han-sur-Lesse cave was recovered using three different techniques: i) the crushing and heating to 360 °C technique, ii) the decrepitation by heating to 550 °C and iii) the decomposition by heating to 900 °C technique. Measurements of the δD of water recovered by the decomposition of Han-sur-Lesse calcite heated to 900 °C did not show a 20 to 30‰ offset as found by previous authors. However a difference of 7‰ was observed between water released before and after decomposition of the calcite. Water recovery from the Han-sur-Lesse samples suggests that a simple heating technique (up to 550 °C) without crushing could both (a) recover water with δD representative of that of the drip water and (b) double the water yield as compared to the crushing and heating method.Our study warns for possible contamination of the recovered inclusion water with hydration water of lime, responsible for the recovery of water with very negative δD values.     

Iron isotope fractionation in subterranean estuaries

Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redox-stratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ⁵⁶Fe values between 0.3 and −1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ⁵⁶Fe values down to −5‰. These low δ⁵⁶Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Fe-oxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ⁵⁶Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ⁵⁶Fe values between −2 and 1.5‰. The relationship between Fe concentration and δ⁵⁶Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ⁵⁶Fe values relative to river values.     

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

How a court, a commissioner and a lobby group brought European transport policy to life in 1985

Until the mid-1980s, transport policy was considered by many as one of the least successful domains of the European integration project. However, from the early 1990s onwards, there are clear signs of a single European transport policy, along with the accompanying implementation of infrastructure projects. What is the explanation for such a change in pace? This paper aims to offer insight in these processes by looking at the mechanisms which form and transform this policy domain. To understand the state of a policy domain and its dynamics over time an institutional approach is taken. Two concepts in political science, ‘policy arrangements’ and ‘supranational governance’ are combined and used as a framework to analyse the European transport policy domain. This analysis describes the development of several elements: organisations, rules, the transnational society, power, resources, and the central transport discourse. It demonstrates that all of these elements have developed from an intergovernmental setting towards a more supranational one. This development was slow in the first decennia when European transport policy was rather passive, but it picked up speed in the 1980s and 1990s. In the pivotal year of 1985, pressure from the transnational society resulted in a rapid change of the rules, the resources and the discourse.     

The Messinian Sicilian stratigraphy revisited: new insights for the Messinian salinity crisis

Controversies around the Messinian salinity crisis (MSC) are because of the difficulties in establishing genetic and stratigraphic relationships between its deep and shallow‐water record. Actually, the Sicilian foreland basin shows both shallow and deep‐water Messinian records, thus offering the chance to reconstruct comprehensive MSC scenarios. The Lower Gypsum of Sicily comprises primary and resedimented evaporites separated in space and time by the intra‐Messinian unconformity. A composite unit including halite, resedimented gypsum and Calcare di Base accumulated between 5.6 and 5.55 Ma in the main depocentres; it records the acme of the Messinian Salinity Crisis during a tectonic phase coupled with sea‐level falls at glacials TG14‐TG12. These deposits fully post‐date primary gypsum, which precipitated in shallow‐water wedge‐top and foreland ramp basins between 5.96 and 5.6 Ma. This new stratigraphic framework results in a three‐stage MSC scenario characterized by different primary evaporite associations: selenite in the first and third stages, carbonate, halite and potash salt in the second one associated with hybrid resedimented evaporites.     

Three-dimensional visualization of mission planning and control forthe NPS autonomous underwater vehicle

The Naval Postgraduate School (NPS) is constructing a small autonomous underwater vehicle (AUV) with an onboard mission control computer. The mission controller software for this vehicle is a knowledge-based artificial intelligence (AI) system requiring thorough analysis and testing before the AUV is operational. The manner in which rapid prototyping of this software has been demonstrated by developing a controller code on a LISP machine and using an Ethernet link with a graphics workstation to simulate the controller's environment is discussed. The development of a testing simulator using a knowledge engineering environment (KEE) expert system shell that examines AUV controller subsystems and vehicle models before integrating them with the full AUV for its test environment missions is discussed. This AUV simulator utilizes an interactive mission planning control console and is fully autonomous once initial parameters are selected     

Analysis, synthesis and modelling of high-resolution observations of salt-marsh eco-geomorphological patterns in the Venice lagoon

The present paper describes observations, analyses and models of salt-marsh channel network and vegetation patterns with the aim of contributing to the development of predictive models of ecological and morphological co-evolution. Existing and new observations are described, with particular emphasis on remote sensing and ancillary field surveys, which are shown to allow reliable, accurate and repeatable quantitative characterizations of landform and vegetation properties over the spatial scales of interest. The observed channel network morphological characters are then used as the basis and validation of models describing the emergence of channel network and vegetation spatial patterns. In particular, with reference to observations performed in the Venice Lagoon, the note describes: (i) new, 2-cm resolution, characterizations of channel network geometry obtained from “proximal sensing” photographic observations; (ii) the reliable quantitative maps of salt-marsh vegetation which may be retrieved from hyperspectral remote sensing data and field ancillary observations; (iii) a synthesis of recent and new analyses of the statistical properties of vegetation and landform spatial organization, that may be inferred from the maps so derived; (iv) recent and new conceptual and quantitative ecological and geomorphic models developed and validated by remote-sensing and field observations. A coherent observational and theoretical eco-morphodynamic framework is then proposed.     

The Vema Transverse Ridge (Central Atlantic)

Transverse ridges are elongate reliefs running parallel and adjacent to transform/fracture zones offsetting mid-ocean ridges. A major transverse ridge runs adjacent to the Vema transform (Central Atlantic), that offsets the Mid-Atlantic Ridge by 320 km. Multibeam morphobathymetric coverage of the entire Vema Transverse ridge shows it is an elongated (300 km), narrow (<30 km at the base) relief that constitutes a topographic anomaly rising up to 4 km above the predicted thermal contraction level. Morphology and lithology suggest that the Vema Transverse ridge is an uplifted sliver of oceanic lithosphere. Topographic and lithological asymmetry indicate that the transverse ridge was formed by flexure of a lithospheric sliver, uncoupled on its northern side by the transform fault. The transverse ridge can be subdivided in segments bound by topographic discontinuities that are probably fault-controlled, suggesting some differential uplift and/or tilting of the different segments. Two of the segments are capped by shallow water carbonate platforms, that formed about 3–4 m.y. ago, at which time the crust of the transverse ridge was close to sea level. Sampling by submersible and dredging indicates that a relatively undisturbed section of oceanic lithosphere is exposed on the northern slope of the transverse ridge. Preliminary studies of mantle-derived ultramafic rocks from this section suggest temporal variations in mantle composition. An inactive fracture zone scarp (Lema fracture zone) was mapped south of the Vema Transverse ridge. Based on morphology, a fossil RTI was identified about 80 km west of the presently active RTI, suggesting that a ridge jump might have occurred about 2.2 m.a. Most probable causes for the formation of the Vema Transverse ridge are vertical motions of lithospheric slivers due to small changes in the direction of spreading of the plates bordering the Vema Fracture Zone.     

Input of atmospheric lead to marine sediments in a south-east Pacific coastal area (approximately 36 degrees S)

Atmospheric input of Pb to coastal sediments in the south-east Pacific (approximately 36 degrees S) was estimated using: (1) a salt marsh (non-local emission sources) as a natural collector of atmospheric fluxes and (2) Pb concentrations in rain and air samples, both considered to be representative of the atmospheric input in the study area. A radioisotopic geochronology technique ((210)Pb) was used to estimate the total Pb atmospheric supply to the sediments. The results show that atmospheric input to Concepción Bay accounts for 13-68% of Pb in near shore sediments, evaluated through salt marsh and rain, both showing comparable results. Consequently, there are other relevant Pb sources to explain the higher concentrations in this area. Sediments in the shelf are subject to important influence of upwelling waters, estimated by Salamanca [Sources and sinks of (210)Pb in Concepción Bay, Chile (1993) PhD thesis, Marine Science Research Center, State University of New York at Stony Brook, USA] using (210)Pb. The atmospheric input, however, is mainly responsible for the total Pb input, since the salt marsh (natural atmospheric collector) shows similar Pb(xs) inventories than the shelf, corresponding to a regional-scale Pb emissions.     

Toward a generic method for studying water renewal, with application to the epilimnion of Lake Tanganyika

We present a method, based on the concept of age and residence time, to study the water renewal in a semi-enclosed domain. We split the water of this domain into different water types. The initial water is the water initially present in the semi-enclosed domain. The renewing water is defined as the water entering the domain of interest. Several renewing water types may be considered depending on their origin. We present the equations for computing the age and the residence time of a certain water type. These timescales are of use to understand the rate at which the water renewal takes place. Computing these timescales can be achieved at an acceptable extra computer cost.The above-mentioned method is applied to study the renewal of epilimnion (i.e. the surface layer) water in Lake Tanganyika. We have built a finite element reduced-gravity model modified to take into account the water exchange between the epilimnion and the hypolimnion (i.e. the bottom layer), the water supply from precipitation and incoming rivers, and the water loss from evaporation and the only outgoing river. With our water renewal diagnoses, we show that the only significant process in the renewal of epilimnion water in Lake Tanganyika is the water exchange between the epilimnion and the hypolimnion, other phenomena being negligible.