Ionic liquids for CO_(2) electrochemical reduction

Electrochemical reduction of CO_(2) is a novel research field towards a CO_(2)-neutral global economy and combating fast accelerating and disastrous climate changes while finding new solutions to store renewable energy in value-added chemicals and fuels.Ionic liquids(ILs),as medium and catalysts(or supporting part of catalysts)have been given wide attention in the electrochemical CO_(2) reduction reaction(CO_(2) RR)due to their unique advantages in lowering overpotential and improving the product selectivity,as well as their designable and tunable properties.In this review,we have summarized the recent progress of CO_(2) electro-reduction in IL-based electrolytes to produce higher-value chemicals.We then have highlighted the unique enhancing effect of ILs on CO_(2) RR as templates,precursors,and surface functional moieties of electrocatalytic materials.Finally,computational chemistry tools utilized to understand how the ILs facilitate the CO_(2) RR or to propose the reaction mechanisms,generated intermediates and products have been discussed.

Mineral fibres and environmental monitoring:A comparison of different analytical strategies in New Caledonia

Covered by ultrabasic units for more than a third of its surface,the New Caledonia(South West Pacific)is one of the largest world producers of Ni-ore from lateritic deposits.Almost all outcrops of geological units and open mines contain serpentine and amphibole,also as asbestos varieties.In this geological context,in which weathering processes had a great contribution in the production and dispersion of mineral fibres into the environment,the development of a routinely analytical strategy,able to discriminate an asbestiform fibre from a non-harmful particle,is a pivotal requisite.However,the acquisition of all these parameters is necessary for determining the risk associated to fibres exposition.A multidisciplinary routinely approach,based on the use of complementary simply-to-use but reliable analytical methods is the only possible strategy.In addition,the instrumental apparatus must be easily transportable on the field,directly on the mining site.The employment of specialized tools such as Polarized Light Microscopy associated to Dispersion Staining method(PLM/DS)and portable Raman spectroscopy for identification of environmental asbestos,are proved extremely effective in the improvement of the performance and rapidity of data acquisition and interpretation.Both PLM/DS and handheld Raman devices confirmed to be discriminant in the detection and characterization of asbestos fibres for both serpentine and amphibole.Furthermore,these techniques proved extremely effective even in the presence of strongly fibrous and altered samples.

Organic Carbon (OC) and Organic Matter (OM) in Sediments Collected from Two Wetlands in Central Bida Basin, Nigeria

An improvised auger sediment sampler was used to collect sediments at shallow depths from two wetlands in the Northern Bida Basin for laboratory studies in order to ascertain the impact on the chemical quality of groundwater within these two studied locations. The dissolved organic carbon content of water is an important component of the geochemical cycling of elements capable of affecting groundwater quality. The sediments which serve as a conduit and pathways for the elements’ transport depending on the characteristics of the particle sizes are to be considered in the evaluation of contaminant mobility within the pathways. Representative cored sediment samples were collected and their particle size characterization and chemical analysis for Organic Matter (OM), Organic Carbon (OC) and Moisture Content (MC) were carried out. The hydrometer results show that the sediment particle sizes are in the order of sand > clay > silt in both locations with few exceptions. This represents the geology of the area (sandstone). The Mean values of 1.14% and 1.98% of OC and OM respectively were recorded in the sediment samples collected in parts of Ebgako. In contrast, 1.72% and 2.97% mean values were recorded in sediments collected in part of Bida for OC and OM respectively. The values of the OC and OM in the sediments from the two wetlands are low and may have been dissolved along the groundwater pathways to the aquifer. Other physicochemical parameters analysed in the sediments showed poor correlation. OM and OC were strongly positively correlated and showed an R2 value of 1 and 0.9 respectively for parts of the Bida and Egbako sheets. There is low acidity of the sediments from the two study locations with a mean pH value of 5.64 and 5.13 respectively for Egbako and Bida. The low acidic nature of the sediments and the OM and OC composition have the potential to influence biogeochemical processes in the sediments and can affect the chemical quality of the groundwater in these two study locations.

The Stava Valley Tailings Dams Disaster:A Reference Point for the Prevention of Severe Mine Incidents

On July 19,1985,at Stava near Tesero(Italian Alps),two reservoirs collapsed,causing the death of 268 people and the destruction of many buildings.The two adjacent basins were constructed for the decantation and storage of fine-grained waste material,which was pumped from a nearby fluorite mine.The consequence of the failure was a vast flowslide that found its way downstream along the Stava valley destroying many houses in the village of Stava,eventually reaching Tesero,where more property was wrecked or severely damaged.The Stava valley disaster was one of the most tragic of its kind.This paper aims to give a contribution on the technical aspects related to the causes of this catastrophic event.It also describes alternative technical solutions for the proper management of mining waste disposal and environmental protection proposed by the Stava 1985 Foundation for disseminating knowledge and awareness on how to make these geotechnical structures safer and more profitable and avoid other similar disasters that still keep occurring every year around the world.

Automated Image Analysis of Mud and Mudrock Microstructure and Characteristics of Hemipelagic Sediments: IODP Expedition 339

The microstructural analysis of muds and mudrocks requires very high-resolution measurement. Recent advances in electron microscopy have contributed significantly to the improved characterisation of mudrock microstructures and their consequent petrophysical properties. However, imaging through electron microscopy is limited to small areas of coverage such that upscaling of these properties is a great challenge. In this paper, we develop a new methodology for multiple large-area imaging using scanning electron microscopy through automated acquisition and stitching from polished thin-sections and ion-milled samples. The process is fast, efficient and minimises user-input and bias. It can provide reliable, quantifiable data on sediment grain size, grain orientation, pore size and porosity. Limitations include the time involved for individual runs and manual segmentation, the large amount of computer memory required, and instrument resolution at the nano-scale. This method is applied to selected samples of Quaternary muddy sediments from the Iberian margin at IODP Site 1385. The section comprises finegrained(very fine clayey silts), mixed-composition, biogenic-terrigenous hemipelagites, with a pronounced but non-regular colour cyclicity. There is a multi-tiered and diverse trace fossil assemblage of the deep-water Zoophycos ichnofacies. The sediment microstructures show small-scale heterogeneity in all properties, and an overall random fabric with secondary preferred grain-alignment. These results on the fabric differ, in part, from previous studies of hemipelagic muds. Further work is underway on their comparison with other deep-water sediment facies.

Characterization and catalytic activity of soft-templated Ni0-CeO_(2) mixed oxides for CO and CO_(2) co-methanation

Nanosized NiO,CeO_(2) and NiO-CeO_(2) mixed oxides with different Ni/Ce molar ratios were prepared by the soft template method.All the samples were characterized by different techniques as to their chemical composition,structure,morphology and texture.On the catalysts submitted to the same reduction pretreatment adopted for the activity tests the surface basic properties and specific metal surface area were also determined.NiO and CeO_(2) nanocrystals of about 4 nm in size were obtained,regardless of the Ni/Ce molar ratio.The Raman and X-ray photoelectron spectroscopy results proved the formation of defective sites at the NiO-CeO_(2) interface,where Ni species are in strong interaction with the support.The microcalorimetric and Fourier transform infrared analyses of the reduced samples highlighted that,unlike metallic nickel,CeO_(2) is able to effectively adsorb CO_(2),forming carbonates and hydrogen carbonates.After reduction in H2 at 400°C for 1 h,the catalytic performance was studied in the CO and CO_(2) co-methanation reaction.Catalytic tests were performed at atmospheric pressure and 300°C,using CO/CO_(2)/H_(2) molar compositions of 1/1/7 or 1/1/5,and space velocities equal to 72000 or 450000 cm^(3)∙h^(-1)∙gcat^(-1).Whereas CO was almost completely hydrogenated in any investigated experimental conditions,CO_(2) conversion was strongly affected by both the CO/CO_(2)/H_(2) ratio and the space velocity.The faster and definitely preferred CO hydrogenation was explained in the light of the different mechanisms of CO and CO_(2) methanation.On a selected sample,the influence of the reaction temperature and of a higher number of space velocity values,as well as the stability,were also studied.Provided that the Ni content is optimized,the NiCe system investigated was very promising,being highly active for the CO_(x) co-methanation reaction in a wide range of operating conditions and stable(up to 50 h)also when submitted to thermal stress.

Biostratigraphy and palaeoenvironment of deposition of Nsukka Formation,Anambra Basin,southeastern Nigeria

Biostratigraphy investigation of Nsukka Formation was carried out by subjecting weLt cutting samples obtained from Nzam-1 weLL to patynotogicat studies with the view towards determining the relative geologic age and pataeoenvironment of deposition of the sediments. SampLes were treated in the Laboratory through digestion with hydrofluoric acid, sieving with 5 μm, oxidation with Nitric acid and mounting of the sLides into sections with DPX mountant. A fairLy high abundance and diversity of miospores were recovered, white the interval （847-1372 m） contains distinctive and diagnostic patynomorphs which are stratigraphicatty important. A Spinizonocolpites baculatus assemblage zone was established based on the basal occurrence of S. baculatus, Spinizonocolpites echinatus, Constructipollenites ineffectus, Periretisyncolpites sp. Periretisyncolpites giganteus, Monocolpites sp 1, Foveotriletes margaritae, Syncolporites marginatus, and Longapertites marginatus. The upper part of the intervat is marked by association of Anacolosidites luidonisis （at top）, Mauritiidites crassibaculatus, Retistephanocolpites williamsi, Proteacidites dehaani, Echitriporites trianguliformis, Proxapertites cursus, Retidiporites magdalenensis, S. baculatus, Retitricolpites gigeonetti, F. margaritae and Araucariadtes sp. The Nsukka Formation is dated as Late Maastrichtian based on the cooccurrence of recovered index fossits. Importantly, Cretaceous-Tertiary （K/T） boundary is marked by high fossil content in the Maastrichtian sediments compared to paucity in patynomorph that characterises the overtying Pateocene facies. Pataeoenvironment of the anatyzed section varies atternatety from marginaL marine to continental setting based on the presence of land-derived miospores and dinoflagettates.

Zooming in REE and Other Trace Elements on Conodonts:Does Taxonomy Guide Diagenesis?

Conodont elements are calcium phosphate(apatite structure)mineralized remains of the cephalic feeding apparatus of an extinct marine organism.Due to the high affinity of apatite for rare earth elements(REE)and other high field strength elements(HFSE),conodont elements were frequently assumed to be a reliable archive of sea-water composition and changes that had occurred during diagenesis.Likewise,the crystallinity index of bioapatite,i.e.,the rate of crystallinity of biologically mediated apatite,should be generally linearly dependent on diagenetic alteration as the greater(and longer)the pressure and temperature to which a crystal is exposed,the greater the resulting crystallinity.In this study,we detected the uptake of HFSE in conodont elements recovered from a single stratigraphic horizon in the Upper Ordovician of Normandy(France).Assuming therefore that all the specimens have undergone an identical diagenetic history,we have assessed whether conodont taxonomy(and morphology)impacts HFSE uptake and crystallinity index.We found that all conodont elements are characterized by a clear diagenetic signature,with minor but significant differences among taxa.These distinctions are evidenced also by the crystallinity index values which show positive correlations with some elements and,accordingly,with diagenesis;however,correlations with the crystallinity index strongly depend on the method adopted for its calculation.

A multidisciplinary approach in recognizing seep-carbonates:A case study from the Loiano Formation(late Eocene)in the northern Apennines(Italy)

Carbonate deposits related to active seeps are documented along most continental margins and are characterized by peculiar seep-related facies and by chemical(isotope signature),paleontological and mineralogical markers.Their fossil analogues are recognized all over the world by the same features and occurred since the beginning of Phanerozoic.In this paper,we present a new seep outcrop(Castagneto village,Reggio Emilia,northern Italy)belonging to the late Eocene Loiano Formation which,to our knowledge,is in Italy the most ancient seep deposit with not-reworked chemosymbiotic fauna.The outcrop can be roughly divided into two portions,a northern part showing abundant presence of macrofossils in silty carbonate matrix and subhorizontal subdivisions,and a southern part,where macrofossils are almost absent,characterized by sub-vertical internal subdivisions and a clear vertical structure consisting of the rhythmic alternation of light and dark mineralization.Detailed analysis of samples from the southern portion showed the occurrence of authigenic calcite and pyrite,the latter with a peculiar framboidal texture.This feature,together with the occurrence of chemosymbiotic species and~(13)C isotope depletion,suggests possible hydrocarbon-rich fluid-related genesis and provides useful criteria for identifying hydrocarbon-rich fluid-related deposits in geologic units.