Impact of column temperature on triacylglycerol regioisomers separation in silver ion liquid chromatography using heptane-based mobile phases.

This work presents the investigation of the use of heptane as an alternative and less toxic mobile phase to the most used hexane for triacylglycerols (TAGs) analysis in silver ion high-performance liquid chromatography (Ag+-HPLC). The impact of column temperature (in the 5 °C-35 °C range) on the retention and resolution of five pairs of regioisomers relevant for the confectionery industry was investigated using a heptane-based mobile phase modified with acetonitrile (ACN). The retention behaviour was compared for a standard TAG mixture and an interesterified cocoa butter. The temperature effect previously observed with hexane-based mobile phases was confirmed for this new system, and it was also observed that the ACN concentration had an important impact on the strength of the temperature effect, with a higher ACN concentration leading to a lesser impact of temperature on the TAGs' elution behaviour. In general, the study allowed to conclude on the equivalence of hexane and heptane for TAGs regioisomers separation in Ag+-HPLC, independently of the used temperature or the ACN concentration. In addition, the applicability of heptane-based mobile phases for the separation of TAGs regioisomers was demonstrated on three other confectionary fat samples, namely palm olein, interesterified palm olein, and interesterified shea olein.

Antarctic Salt-Cones: An Oasis of Microbial Life? The Example of Boulder Clay Glacier (Northern Victoria Land).

The evaporation of a localized, highly saline water body of the Boulder Clay debris-covered glacier, in the Northern Victoria Land, probably generated the accumulation of mirabilite (Na2SO4 × 10H2O) and thenardite (Na2SO4) in a glacier salt-cone. Such an extremely cold and salty environment resembles the conditions on Mars, so it can be considered a terrestrial analog. The study was aimed at gaining a first glimpse at the prokaryotic community associated with Antarctic mirabilite and thenardite minerals and also to find clues about the origin of the salts. For this purpose, samples were analyzed by a next generation approach to investigate the prokaryotic (Bacteria and Archaea) diversity. Phylogenetic analysis allowed the identification of Bacteroidota, Actinobacteriota, Firmicutes, and Gammaproteobacteria as the main bacterial lineages, in addition to Archaea in the phylum Halobacterota. The genera Arthrobacter, Rhodoglobus, Gillisia, Marinobacter and Psychrobacter were particularly abundant. Interestingly, several bacterial and archaeal sequences were related to halotolerant and halophilic genera, previously reported in a variety of marine environments and saline habitats, also in Antarctica. The analyzed salt community also included members that are believed to play a major role in the sulfur cycle.

Prediction of Trace Metal Distribution in a Tailings Impoundment Using an Integrated Geophysical and Geochemical Approach (Raibl Mine, Pb-Zn Alpine District, Northern Italy).

When mines are decommissioned, tailings piles can act as sources of contamination for decades or even centuries. Tailings, which usually contain high concentrations of metals and trace elements, can be reprocessed for a secondary recovery of valuable elements with an innovative approach to a circular economy. This study offers new results for tailings ponds characterisation and chemical content prediction based on an integrated geophysical-geochemical approach. The study of the Raibl Pb-Zn tailings impoundment was done using bulk chemical analysis on borehole samples, Electrical Resistivity Tomography surveys, and Ground Penetrating Radar measurements. We found valuable and statistically significant correlations between the electrical resistivity of the mining impoundments and the metal distribution, thus providing a practical opportunity to characterise large volumes of metal-bearing tailings. In particular, these results can be useful to aid in the development of environmental monitoring programs for remediation purposes or to implement economic secondary recovery plans.

Water 'on the rocks': a summer drink for thirsty trees?

Drought-induced tree mortality frequently occurs in patches with different spatial and temporal distributions, which is only partly explained by inter- and intraspecific variation in drought tolerance. We investigated whether bedrock properties, with special reference to rock water storage capacity, affects tree water status and drought response in a rock-dominated landscape. We measured primary porosity and available water content of breccia (B) and dolostone (D) rocks. Saplings of Fraxinus ornus were grown in pots filled with soil or soil mixed with B and D rocks, and subjected to an experimental drought. Finally, we measured seasonal changes in water status of trees in field sites overlying B or D bedrock. B rocks were more porous and stored more available water than D rocks. Potted saplings grown with D rocks had less biomass and suffered more severe water stress than those with B rocks. Trees in sites with B bedrock had more favourable water status than those on D bedrock which also suffered drought-induced canopy dieback. Bedrock represents an important water source for plants under drought. Different bedrock features translate into contrasting below-ground water availability, leading to landscape-level heterogeneity of the impact of drought on tree water status and dieback.

Formation of by-products during chemical interesterification of lipids. Detection and characterization of dialkyl ketones by non-aqueous reversed-phase liquid chromatography-high resolution mass spectrometry and gas chromatography-mass spectrometry.

A new class of foreign substances present in the unsaponifiable fraction of vegetable oils undergone to chemical interesterification was systematically investigated. Their chemical structure, corresponding to dialkyl ketones (DAK) molecules, was elucidated both by gas chromatography-mass spectrometry (GC-MS), and liquid chromatography-high resolution mass spectrometry (LC-HRMS). An analytical protocol aimed to qualitative and quantitative detection of DAK molecules in vegetable oils of confectionery industry interest was developed. Being the range of concentration levels to be evaluated dependent on the technological task of interesterification process, the quantitation step was thoroughly examined. All the validation parameters were satisfactory and particularly the concentration determinations were made more reliable by the contemporary use of several quantitation standards. GC-MS and LC-HRMS analytical techniques exhibited comparable performances even if the second one shown better detection sensitivity.

Author Correction: Interplay of grounding-line dynamics and sub-shelf melting during retreat of the Bjørnøyrenna Ice Stream.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

Interplay of grounding-line dynamics and sub-shelf melting during retreat of the Bjørnøyrenna Ice Stream.

The Barents Sea Ice Sheet was a marine-based ice sheet, i.e., it rested on the Barents Sea floor during the Last Glacial Maximum (21 ky BP). The Bjørnøyrenna Ice Stream was the largest ice stream draining the Barents Sea Ice Sheet and is regarded as an analogue for contemporary ice streams in West Antarctica. Here, the retreat of the Bjørnøyrenna Ice Stream is simulated by means of two numerical ice sheet models and results assessed against geological data. We investigate the sensitivity of the ice stream to changes in ocean temperature and the impact of grounding-line physics on ice stream retreat. Our results suggest that the role played by sub-shelf melting depends on how the grounding-line physics is represented in the models. When an analytic constraint on the ice flux across the grounding line is applied, the retreat of Bjørnøyrenna Ice Stream is primarily driven by internal ice dynamics rather than by oceanic forcing. This suggests that implementations of grounding-line physics need to be carefully assessed when evaluating and predicting the response of contemporary marine-based ice sheets and individual ice streams to ongoing and future ocean warming.

Discovery of ancient Roman "highway" reveals geomorphic changes in karst environments during historic times.

Sinkholes are a well-known geologic hazard but their past occurrence, useful for subsidence risk prediction, is difficult to define, especially for ancient historic times. Consequently, our knowledge about Holocene carbonate landscapes is often limited. A multidisciplinary study of Trieste Karst (Italy), close to early Roman military fortifications, led to the identification of possible ancient road tracks, cut by at least one sinkhole. Electrical Resistivity Tomography through the sinkhole has suggested the presence of a cave below its bottom, possibly responsible of the sinkhole formation, while Ground Penetrating Radar has detected no tectonic disturbances underneath the tracks. Additionally, archaeological surveys led to the discovery of over 200 Roman shoe hobnails within or close to the investigated route. According to these data, the tracks are interpreted as the remains of a main Roman road, whose itinerary has been reconstructed for more than 4 km together with other elements of ancient landscape. Our results provide the first known evidence of a Roman main road swallowed by sinkholes and suggest that Holocene karst landscapes could be much different from what previously believed. In fact, sinkholes visible nowadays in the investigated region could have been flat areas filled by sediments up to the Roman time.

Characterization and Determination of Interesterification Markers (Triacylglycerol Regioisomers) in Confectionery Oils by Liquid Chromatography-Mass Spectrometry.

Interesterification is an industrial transformation process aiming to change the physico-chemical properties of vegetable oils by redistributing fatty acid position within the original constituent of the triglycerides. In the confectionery industry, controlling formation degree of positional isomers is important in order to obtain fats with the desired properties. Silver ion HPLC (High Performance Liquid Chromatography) is the analytical technique usually adopted to separate triglycerides (TAGs) having different unsaturation degrees. However, separation of TAG positional isomers is a challenge when the number of double bonds is the same and the only difference is in their position within the triglyceride molecule. The TAG positional isomers involved in the present work have a structural specificity that require a separation method tailored to the needs of confectionery industry. The aim of this work was to obtain a chromatographic resolution that might allow reliable qualitative and quantitative evaluation of TAG positional isomers within reasonably rapid retention times and robust in respect of repeatability and reproducibility. The resulting analytical procedure was applied both to confectionery raw materials and final products.

Pressurized brines in continental Antarctica as a possible analogue of Mars.

Interest in brines in extreme and cold environments has recently increased after they have been found on Mars. Those brines can be potential new subsurface habitats for peculiar ecosystems. In the McMurdo Dry Valleys of the Antarctic, the best analogue for Mars conditions, only a few cases of brines have been identified in some perennially frozen lakes and in one case in an underground aquifer. Here, we present the occurrence of pressurized brines in a shallow perennially ice-covered lake south of 70°S in an ice-free area of Victoria Land, Antarctica. For the first time, we also imaged, by means of ground penetrating radar data, the existence of a pingo-like-feature (PLF) formed by the extrusion of brines, which has also been confirmed by borehole evidence. Those brines are fed by an underground talik external to the lake basin, enhancing the possibility of unexploited ecosystems that could find an analogue in Martian environments.

Early Roman military fortifications and the origin of Trieste, Italy.

An interdisciplinary study of the archaeological landscape of the Trieste area (northeastern Italy), mainly based on airborne light detection and ranging (LiDAR), ground penetrating radar (GPR), and archaeological surveys, has led to the discovery of an early Roman fortification system, composed of a big central camp (San Rocco) flanked by two minor forts. The most ancient archaeological findings, including a Greco-Italic amphora rim produced in Latium or Campania, provide a relative chronology for the first installation of the structures between the end of the third century B.C. and the first decades of the second century B.C. whereas other materials, such as Lamboglia 2 amphorae and a military footwear hobnail (type D of Alesia), indicate that they maintained a strategic role at least up to the mid first century B.C. According to archaeological data and literary sources, the sites were probably established in connection with the Roman conquest of the Istria peninsula in 178-177 B.C. They were in use, perhaps not continuously, at least until the foundation of Tergeste, the ancestor of Trieste, in the mid first century B.C. The San Rocco site, with its exceptional size and imposing fortifications, is the main known Roman evidence of the Trieste area during this phase and could correspond to the location of the first settlement of Tergeste preceding the colony foundation. This hypothesis would also be supported by literary sources that describe it as a phrourion (Strabo, V, 1, 9, C 215), a term used by ancient writers to designate the fortifications of the Roman army.