Organic ligand complexation reactions on aluminium-bearing mineral surfaces studied via in-situ multiple internal reflection infrared spectroscopy, adsorption experiments, and surface complexation modelling

Organic ligand complexation reactions at the mineral-water interface play an important role in several environmental and geochemical processes such as adsorption, dissolution, precipitation, pollutant transport, nutrient cycling, and colloidal stability. Although organic ligand surface complexation reactions have been extensively studied, a molecular level understanding regarding the mechanisms underlying the adsorption of such compounds is still limited. The purpose of the current study was to investigate the interactions between some common naturally occurring organic ligands and a common aluminosilicate clay mineral, kaolinite, using a combination of macroscopic and microscopic experimental methods. Molecular level information regarding the structure and binding mode of adsorbed species was obtained using in situ MIR-FTIR spectroscopy. Other experimental techniques including adsorption experiments, surface titrations, and surface complexation modelling were also employed in order to quantify and describe the macroscopic adsorption properties of the organic ligands examined. Three low molecular weight organic acids (oxalic, salicylic, and phthalic acid) and humic acid were chosen as representative organic ligands. Spectroscopic evidence revealed that low molecular weight organic acids are able to form both inner and outer sphere complexes on kaolinite, and the relative concentrations of these surface complexes varies with solution chemistry. Inner sphere coordination modes inferred are a mononuclear bidentate for oxalate (five-membered chelate ring) and phthalate (seven-membered chelate ring); and a mononuclear monodenate (six-membered pseudochelate ring) for salicylic acid. Similar coordination modes were shown to form on simpler mineral (hyrd)oxides. Elucidation of the coordination chemistry of these ligands can provide insights into the dissolution mechanisms of silicate minerals In contrast to low molecular weight organic acids, there was no evidence of inner sphere complexation by humic acid acids on kaolinite or gibbsite. The combined spectroscopic and macroscopic adsorption results suggest that cation bridging and van der Waals interactions are the two most probable mechanisms for the adsorption of humic acid by these mineral substrates. This finding casts doubts over the use of low molecular weight organic acids as humic acid analogs.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Platinum-group element remobilisation and concentration in the Cliff chromitites of the Shetland Ophiolite Complex, Scotland

ABSTRACTThe ~492 Ma Shetland Ophiolite Complex contains an extensive mantle section, within which numerous podiform chromitite bodies formed during melt percolation in a supra-subduction zone setting. One of the Shetland ophiolite chromitite localities has an unusual style of platinum-group element (PGE) mineralization. Specifically, the Cliff chromitite suite has relatively high (&gt;250 ppm) Pt plus Pd, compared to other chromitites in the Shetland Ophiolite Complex. In this study, we apply petrographic observation, mineral chemistry and novel X-ray microtomography data to elucidate the petrogenesis of PGE-bearing phases at Cliff. The combined datasets reveal that the PGE at Cliff have probably been fractionated by an As-rich fluid, concentrating Pt and Ir into visible (0.1–1 µm) platinum-group minerals (PGM) such as sperrylite and irarsite, respectively. The high (&gt;1 ppm) bulk-rock concentrations of the other PGE (e.g. Os) in the Cliff chromitites suggests the presence of abundant fine-grained unidentified PGM in the serpentinized groundmass. The spatial association of arsenide phases and PGM with alteration rims on Cr-spinel grains suggests that the high Pt and Pd abundances at Cliff result from a late-stage low-temperature (e.g. 200–300°C) hydrothermal event. This conclusion highlights the potential effects that secondary alteration processes can have on modifying and upgrading the tenor of PGE deposits.</jats:p

A new Devonian euthycarcinoid reveals the use of different respiratory strategies during the marine-to-terrestrial transition in the myriapod lineage.

Myriapods were, together with arachnids, the earliest animals to occupy terrestrial ecosystems, by at least the Silurian. The origin of myriapods and their land colonization have long remained puzzling until euthycarcinoids, an extinct group of aquatic arthropods considered amphibious, were shown to be stem-group myriapods, extending the lineage to the Cambrian and evidencing a marine-to-terrestrial transition. Although possible respiratory structures comparable to the air-breathing tracheal system of myriapods are visible in several euthycarcinoids, little is known about the mechanism by which they respired. Here, we describe a new euthycarcinoid from Upper Devonian alluvio-lagoonal deposits of Belgium. Synchrotron-based elemental X-ray analyses were used to extract all available information from the only known specimen. Sulfur X-ray fluorescence (XRF) mapping and spectroscopy unveil sulfate evaporation stains, spread over the entire slab, suggestive of a very shallow-water to the terrestrial environment prior to burial consistent with an amphibious lifestyle. Trace metal XRF mapping reveals a pair of ventral spherical cavities or chambers on the second post-abdominal segment that do not compare to any known feature in aquatic arthropods, but might well play a part in air-breathing. Our data provide additional support for amphibious lifestyle in euthycarcinoids and show that different respiratory strategies were used during the marine-to-terrestrial transition in the myriapod lineage

Uranium (VI) Adsorbate Structures on Portlandite [Ca(OH)2] Type Surfaces Determined by Computational Modelling and X-ray Absorption Spectroscopy

Portlandite [Ca(OH)2] is a potentially dominant solid phase in the high pH fluids expected within the cementitious engineered barriers of Geological Disposal Facilities (GDF). This study combined X-ray Absorption Spectroscopy with computational modelling in order to provide atomic-scale data which improves our understanding of how a critically important radionuclide (U) will be adsorbed onto this phase under conditions relevant to a GDF environment. Such data are fundamental for predicting radionuclide mass transfer. Surface coordination chemistry and speciation of uranium with portlandite [Ca(OH)2] under alkaline groundwater conditions (ca. pH 12) were determined by both in situ and ex situ grazing incidence extended X-ray absorption fine structure analysis (EXAFS) and by computational modelling at the atomic level. Free energies of sorption of aqueous uranyl hydroxides, [UO2(OH)n]2–n (n = 0–5) with the (001), (100) and (203) or (101) surfaces of portlandite are predicted from the potential of mean force using classical molecular umbrella sampling simulation methods and the structural interactions are further explored using fully periodic density functional theory computations. Although uranyl is predicted to only weakly adsorb to the (001) and (100) clean surfaces, there should be significantly stronger interactions with the (203/101) surface or at hydroxyl vacancies, both prevalent under groundwater conditions. The uranyl surface complex is typically found to include four equatorially coordinated hydroxyl ligands, forming an inner-sphere sorbate by direct interaction of a uranyl oxygen with surface calcium ions in both the (001) and (203/101) cases. In contrast, on the (100) surface, uranyl is sorbed with its axis more parallel to the surface plane. The EXAFS data are largely consistent with a surface structural layer or film similar to calcium uranate, but also show distinct uranyl characteristics, with the uranyl ion exhibiting the classic dioxygenyl oxygens at 1.8 Å and between four and five equatorial oxygen atoms at distances between 2.28 and 2.35 Å from the central U absorber. These experimental data are wholly consistent with the adsorbate configuration predicted by the computational models. These findings suggest that, under the strongly alkaline conditions of a cementitious backfill engineered barrier, there would be significant uptake of uranyl by portlandite to inhibit the mobility of U(VI) from the near field of a geological disposal facility

Mineral reaction kinetics constrain the length scale of rock matrix diffusion

Mass transport by aqueous fluids is a dynamic process in shallow crustal systems, redistributing nutrients as well as contaminants. Rock matrix diffusion into fractures (void space) within crystalline rock has been postulated to play an important role in the transient storage of solutes. The reacted volume of host rock involved, however, will be controlled by fluid-rock reactions. Here we present the results of a study which focusses on defining the length scale over which rock matrix diffusion operates within crystalline rock over timescales that are relevant to safety assessment of radioactive and other long-lived wastes. Through detailed chemical and structural analysis of natural specimens sampled at depth from an active system (Toki Granite, Japan), we show that, contrary to commonly proposed models, the length scale of rock matrix diffusion may be extremely small, on the order of centimetres, even over timescales of millions of years. This implies that in many cases the importance of rock matrix diffusion will be minimal. Additional analyses of a contrasting crystalline rock system (Carnmenellis Granite, UK) corroborate these results

In Situ EXAFS Study of Sr Adsorption on TiO2(110) under High Ionic Strength Wastewater Conditions

In order to provide important details concerning the adsorption reactions of Sr, batch reactions and a set of both ex situ and in situ Grazing Incidence X-ray Absorption Fine Structure (GIXAFS) adsorption experiments were completed on powdered TiO2 and on rutile(110), both reacted with either SrCl2 or SrCO3 solutions. TiO2 sorption capacity for strontium (Sr) ranges from 550 ppm (SrCl2 solutions, second order kinetics) to 1400 ppm (SrCO3 solutions, first order kinetics), respectively, and is rapid. Sr adsorption decreased as a function of chloride concentration but significantly increased as carbonate concentrations increased. In the presence of carbonate, the ability of TiO2 to remove Sr from the solution increases by a factor of ~4 due to rapid epitaxial surface precipitation of an SrCO3 thin film, which registers itself on the rutile(110) surface as a strontianite-like phase (d-spacing 2.8 &Aring;). Extended X-ray Absorption Fine Structure (EXAFS) results suggest the initial attachment is via tetradental inner-sphere Sr adsorption. Moreover, adsorbates from concentrated SrCl2 solutions contain carbonate and hydroxyl species, which results in both inner- and outer-sphere adsorbates and explains the reduced Sr adsorption in these systems. These results not only provide new insights into Sr kinetics and adsorption on TiO2 but also provide valuable information concerning potential improvements in effluent water treatment models and are pertinent in developing treatment methods for rutile-coated structural materials within nuclear power plants

Geochemical evidence of the seasonality, affinity and pigmenation of Solenopora jurassica

Solenopora jurassica is a fossil calcareous alga that functioned as an important reef-building organism during the Palaeozoic. It is of significant palaeobiological interest due to its distinctive but poorly understood pink and white banding. Though widely accepted as an alga there is still debate over its taxonomic affinity, with recent work arguing that it should be reclassified as a chaetetid sponge. The banding is thought to be seasonal, but there is no conclusive evidence for this. Other recent work has, however demonstrated the presence of a unique organic boron-containing pink/red pigment in the pink bands of S. jurassica. We present new geochemical evidence concerning the seasonality and pigmentation of S. jurassica. Seasonal growth cycles are demonstrated by X-ray radiography, which shows differences in calcite density, and by varying δ13C composition of the bands. Temperature variation in the bands is difficult to constrain accurately due to conflicting patterns arising from Mg/Ca molar ratios and δ18O data. Fluctuating chlorine levels indicate increased salinity in the white bands, when combined with the isotope data this suggests more suggestive of marine conditions during formation of the white band and a greater freshwater component (lower chlorinity) during pink band precipitation (δ18O). Increased photosynthesis is inferred within the pink bands in comparison to the white, based on δ13C. Pyrolysis Gas Chromatography Mass Spectrometry (Py-GCMS) and Fourier Transform Infrared Spectroscopy (FTIR) show the presence of tetramethyl pyrrole, protein moieties and carboxylic acid groups, suggestive of the presence of the red algal pigment phycoerythrin. This is consistent with the pink colour of S. jurassica. As phycoerythrin is only known to occur in algae and cyanobacteria, and no biomarker evidence of bacteria or sponges was detected we conclude S. jurassica is most likely an alga. Pigment analysis may be a reliable classification method for fossil algae

Impact of the Diamond Light Source on research in Earth and environmental sciences: current work and future perspectives.

Diamond Light Source Ltd celebrated its 10th anniversary as a company in December 2012 and has now accepted user experiments for over 5 years. This paper describes the current facilities available at Diamond and future developments that enhance its capacities with respect to the Earth and environmental sciences. A review of relevant research conducted at Diamond thus far is provided. This highlights how synchrotron-based studies have brought about important advances in our understanding of the fundamental parameters controlling highly complex mineral–fluid–microbe interface reactions in the natural environment. This new knowledge not only enhances our understanding of global biogeochemical processes, but also provides the opportunity for interventions to be designed for environmental remediation and beneficial use

Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy

Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms