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The swelling of clay minerals within shale formations during oil and gas exploration, and within compacted bentonite barriers for radioactive waste containment, presents a number of challenges to operators. Whilst much work has been devoted to understanding the interlayer swelling properties of clay mineral crystals, significantly less has been devoted to understanding coupled pore and interlayer swelling in reactive shale/compacted clay minerals. Here we study the swelling of compacted clay mineral tablets on exposure to a range of organic solvents, selected so that the effect of key solvent properties such as dielectric constant, density, octanol-water partition coefficient, viscosity and surface tension can be correlated with the swelling observed. We use a novel non-contact swelling meter to carry out the swelling tests, allowing us to access information on rate of swelling. Short-term swelling rate showed the strongest correlation to the solvent octanol-water partition coefficient. In long term swelling, good correlation was found between total linear swelling and viscosity, and the octanol-water partition coefficient.

The best-known theory accounting for metal-alginate complexation is the so-called "Egg Box"model. In order to gain greater insight into the metal-saccharide interactions that underpin this model, the coordination chemistry of the corresponding monomeric units of alginate, l-guluronate (GulA) and d-mannuronate (ManA) have been studied herein. GulA and ManA were exposed to solutions of different s-block cations and then analysed by 1H and 13C NMR spectroscopy. It was found that the α/β ratio of the pyranose anomeric equilibria of GulA showed large pertubations from the starting value (α/β = 0.21 ± 0.01) upon contact with 1.0 M Ca2+, Sr2+, and Ba2+ (α/β = 1.50 ± 0.03, 1.20 ± 0.02, and 0.58 ± 0.02, respectively) at pD 7.9, but remained almost constant in the presence of Na+, K+, and Mg2+ (α/β = 0.24 ± 0.01, 0.19 ± 0.01, and 0.26 ± 0.01, respectively). By comparison, no significant changes were observed in the α/β ratios of ManA and related mono-uronates d-glucuronate (GlcA) and d-galacturonate (GalA) in the presence of all of the metal ions surveyed. Analysis of the 1H and 13C coordination chemical shift patterns indicate that the affinity of α-GulA for larger divalent cations is a consequence of the unique ax-eq-ax arrangement of hydroxyl groups found for this uronate anomer.

The adsorption and retention of phosphates in soil systems is of wide environmental importance, and understanding the surface chemistry of halloysite (a common soil clay mineral) is also of prime importance in many emerging technological applications of halloysite nanotubes (HNTs). The adsorption of phosphate anions on tubular halloysite (7 Å) has been studied to gain a greater understanding of the mechanism and kinetics of adsorption on the surface of HNTs. Two well-characterized tubular halloysites with differing morphologies have been studied: one polygonal prismatic and one cylindrical, where the cylindrical form has a greater surface area and shorter tube length. Greater phosphate adsorption of up to 42 μmol g–1 is observed on the cylindrical halloysite when compared to the polygonal prismatic sample, where adsorption reached a maximum of just 15 μmol g–1 compared to a value for platy kaolinite (KGa-2) of 8 μmol g–1. Phosphate adsorption shows strong pH dependence, and the differences in phosphate sorption between the prismatic and cylindrical morphologies suggest that phosphate absorption does not occur at the same pH-dependent alumina edge sites and that the lumen may have a greater influence on uptake for the cylindrical form.

Molecular dynamics is a simulation technique used to predict the physical properties of systems based on their chemical structure and evolution of their atomic constituents. For these predictions to be reliable, it is critical that the simulation has reached convergence, whereby representative sampling of the phase space has been gathered. We show that the commonly used root mean square deviation is an unsuitable convergence descriptor for systems featuring surfaces and interfaces. We then present an effective criterion, embodied in the analysis tool DynDen, based on convergence of the linear partial density of all components in the simulation. With a variety of examples we demonstrate the usage of DynDen for the assessment of convergence, as well as for identification of slow dynamical processes, which can be easily missed with conventional analysis. Program summary Program title: DynDen CPC Library link to program files: https://doi.org/10.17632/dfb34rpyw2.1 Developer's repository link: https://github.com/punkpony/DynDen Licensing provisions: GNU General Public License 3 Programming Language: Python 3.X External Routines/Libraries: MDAnalysis, numpy, matplotlib Nature of problem: assessment of convergence in molecular dynamics simulations of interfaces Solution method: reporting on the convergence of correlation of the linear density profiles of each individual system component

Sodium salts of the algal uronic-acids, d-mannuronic acid (HManA) and l-guluronic acid (HGulA) have been isolated and characterised in solution by nuclear magnetic resonance (NMR) spectroscopy. A suite of recently-described NMR experiments (including pure shift and compressive sampling techniques) were used to provide confident assignments of the pyranose forms of the two uronic acids at various pD values (from 7.5 to 1.4). The resulting high resolution spectra were used to determine several previously unknown parameters for the two acids, including their pKa values, the position of their isomeric equilibria, and their propensity to form furanurono-6,3-lactones. For each of the three parameters, comparisons are drawn with the behaviour of the related D-glucuronic (HGlcA) and D-galacturonic acids (HGalA), which have been previously studied extensively. This paper demonstrates how these new NMR spectroscopic techniques can be applied to better understand the properties of polyuronides and uronide-rich macroalgal biomass.

To conserve freshwater resources, domestic and industrial wastewater is recycled. Algal systems have emerged as an efficient, low-cost option for treatment (phycoremediation) of nutrient-rich wastewater and environmental protection. However, industrial wastewater may contain growth inhibitory compounds precluding algal use in phycoremediation. Therefore, extremophyte strains, which thrive in hostile environments, are sought-after. Here, we isolated such an alga - a strain of Synechocystis sp. we found to be capable of switching from commensal exploitation of the nitrogen-fixing Trichormus variabilis, for survival in nitrogen-deficient environments, to free-living growth in nitrate abundance. In nitrogen depletion, the cells are tethered to polysaccharide capsules of T. variabilis using nanotubular structures, presumably for nitrate acquisition. The composite culture failed to establish in industrial/domestic waste effluent. However, gradual exposure to increasing wastewater strength over time untethered Synechocystis cells and killed off T. variabilis. This switched the culture to a stress-acclimated monoculture of Synechocystis sp., which rapidly grew and flourished in wastewater, with ammonium and phosphate removal efficiencies of 99.4% and 97.5%, respectively. Therefore, this strain of Synechocystis sp. shows great promise for use in phycoremediation, with potential to rapidly generate biomass that can find use as a green feedstock for valuable bio-products in industrial applications.

Hydrotalcite, ideally [Mg6Al2(OH)16](CO3)(H2O)4, was studied in samples from Dypingdal, Snarum, Norway (3R and 2H), Zelentsovskaya pit (2H) and Praskovie–Evgenievskaya pit (2H) (both Southern Urals, Russia), Talnakh, Siberia, Russia (3R), Khibiny, Kola, Russia (3R), and St. Lawrence, New York, USA (3R and 2H). Two polytypes, 3R and 2H (both ‘classical’), were confirmed on the basis of single-crystal and powder X-ray diffraction data. Their chemical composition was studied by electron-microprobe analysis, infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The crystal structure of hydrotalcite-3R was solved by direct methods in the space group R$ {\bar 3} $m on three crystals (two data collections at 290 K and one at 120 K). The unit-cell parameters are as follows (290/290/120 K): a = 3.0728(9)/3.0626(3)/3.0617(4), c = 23.326(9)/23.313(3)/23.203(3) Å and V = 190.7(1)/189.37(4)/188.36(4) Å3. The crystal structures were refined on the basis of 304/150/101 reflections to R1 = 0.075/0.041/0.038. Hydrotalcite-2H crystallises in the P63/mmc space group; unit-cell parameters for two crystals are (data collection at 290 K and 93 K): a = 3.046(1)/3.0521(9), c = 15.447(6)/15.439(4) Å, V = 124.39(8)/124.55(8) Å3. The crystal structures were refined on the basis of 160/142 reflections to R1 = 0.077/0.059. This paper reports the first single-crystal structure data on hydrotalcite. Hydrotalcite distribution in Nature, diagnostic features, polytypism, interlayer topology and localisation of M2+–M3+ cations within metal hydroxide layers are discussed.

Alkaline hydrothermal vent environments have gained much attention as potential sites for abiotic synthesis of a range of organic molecules. However the key process of peptide formation has generally been undertaken at lower pH, and using dissolved copper ions to enhance selectivity and reactivity. Here, we explore whether layered precipitate minerals, abundant at alkaline hydrothermal systems, can promote peptide bond formation for surface-bound alanine under cycles of wetting and drying. While we find low level activity in brucite and binary layered double hydroxide carbonate minerals (typically < 0.1% yield), the inclusion of structural copper to form a ternary layered double hydroxide mineral significantly increased the yield to > 7 %. However the performance decreased over successive wetting/drying cycles. Control experiments show that this high degree of dipeptide formation cannot be attributed to leached copper from the mineral structure. While only dipeptides are observed, the yields obtained suggest that such processes, if occurring on the early Earth, could have added to the pool of available biological building units.

Shale oil is currently of interest for unconventional resource exploration and development. Understanding the mechanism of interaction between the complex mixture of organic compounds in shale oil and minerals making up the reservoir rock-oil interface will assist recovery. In this study, molecular dynamics simulation is used to study the adsorption characteristics of a model oil mixture within nanoscale intra-particle pores of kaolinite minerals, which form pore filling structures in shale rock. To better understand the effects of oil composition, temperature and pressure on the adsorption properties of the model oil mixture, a range of temperatures (298 K, 323 K, 348 K and 373 K) and pressures (1 bar, 50 bar, 100 bar and 200 bar) representing up to reservoir conditions were used. This study shows that adsorption and arrangement of oil molecules is dependent on the surface of kaolinite and the distance away from it. The simulations show polar compounds are likely to be adsorbed on aluminol kaolinite basal surfaces, while alkanes preferentially adsorb on silicate surfaces. In addition, the number of oil molecule bound layers, and total adsorption amount on the silicate surface is greater than the aluminol surface. The density of adsorbed oil is reduced with increase in temperature, while the effect of pressure is not as significant. On the basis of performed molecular simulations, we show the adsorption rate of shale oil on the surfaces of kaolinite sheets and assess the removable capacity of the model oil. Keywords: shale oil, molecular dynamics, clay mineral, recovery.

We describe a novel post treatment for layered double hydroxide (LDH) materials using aqueous immiscible (AIM) solvents resulting in improved surface area and powder flow. The effect of solvent functional groups and structure are explored, aided by molecular dynamics simulation of AIM-LDH washing.

Scanning electron microscopy (SEM) is one of the most prevalent methods used to image and quantify the pore size distribution of shale rock, critical in understanding unconventional petroleum systems and production. Generally, digital greyscale SEM images of shale are currently processed for pore quantification either by a manual drawing method, manual threshold method, automatic threshold method, edge detection or watershed methods, all of which have some limitations that impact the quality of pore extraction results. A new, Edge-Threshold Automatic Processing (ETAP) method is reported here to enable robust extraction and quantification of pore data in shale images. Image pre-treatment makes the greyscale of regions brighter than that of kerogen set to the peak value of kerogen greyscale. The pore image is subsequently obtained using an edge detection method. A discriminant function has been designed to determine the best threshold of the greyscale image to obtain the pore image. Finally, combination of both processed pore images gives the final pore image. Our new method overcomes the impact of kerogen, mineral, roughness and artificial debris caused by pre-treatment of samples, which potentially introduce errors using alternative methods. We compare our new method to a systematic manual drawing method. The processing results through ETAP provide reliable results, and gets the highest value of 0.7466 using a discriminant function Qt, compared with the automatic threshold methods, the edge detection method and watershed method. The application of the ETAP method on shale samples of the Longmaxi Formation and Qiongzhusi Formatiosn in Sichuan basin shows that samples from the Longmaxi Formation have more organic pores than that of the Qiongzhusi Formation, however a larger size of inorganic pores develop in the Qiongzhusi shale. This indicates that shale of the Longmaxi Formation has better reservoir properties and reliable preservation conditions.

We describe a one-pot synthesis method for carbon filament-supported mixed metal oxide nanoparticles. The thermal intracrystalline reaction of adamantanecarboxylate ions confined inside interlayer galleries of layered double hydroxide materials under a reducing atmosphere (H2) leads to carbon filaments forming in situ within the material. Raman spectroscopy and combined microscopy techniques show the formation of hybrid organic–inorganic carbon filaments with the mixed metal oxide particles interleaved.

International audience; Single phase Casingle bondFe layered double hydroxide (LDH) minerals containing Cl− species in the interlayer was synthesized by coprecipitation with a CaII: FeIII ratio of 2: 1. In both phosphate (PO4) free water and at low aqueous PO4 concentration, the LDH was fully transformed into a mixture of a “ferrihydrite-like” material, calcite and soluble calcium species. Mössbauer spectroscopy and transmission electron microscopy showed that phosphate was removed by the “ferrihydrite like” phase that contained a significant quantity of Ca. At high phosphate concentration the Ca species released from the LDH precipitated to form hydroxyapatite leading to a maximal removal capacity of ~ 130 mg P-PO4 g−1. The Casingle bondFe LDH was deposited onto a pozzolana volcanic rock in order to perform a column experiment under hydrodynamic conditions for 70 days. A high removal capacity was observed, a qB of ~ 4 mg P-PO4 g−1 was measured at the breakthrough of the column, however the pH in the outflow was measured to be higher than 11. Such an increase was due to the very high solubility of the Casingle bondFe LDH.

Layered materials are of interest for use in a wealth of technological applications, many of which require a high surface area for optimal properties and performance. Recently, an industrially scalable method to create high surface area layered double hydroxide (LDH) materials, which may be readily dispersed in non-polar solvents, has been developed. This method involves treatment of LDHs with aqueous miscible organic (AMO) solvents. Here, molecular modeling is exploited to elucidate the AMO solvent-LDH interactions, in order to understand how the dispersion process is facilitated by the AMO treatment. The simulations show how hydrogen-bond networks within the LDH interlayer are disrupted by AMO solvents, leading to delamination.

The chemical profile of biorefined Saccharina latissima, Ascophyllum nodosum and Palmaria palmata after carbohydrate and polyphenol extraction was analysed with the aim to evaluate the nutritional aspects of biorefined seaweeds as a novel animal feed supplement. Optimised enzymatic saccharification has been used to show that the protein concentration in the residue of P. palmata and A. nodosum can be increased by more than 2-fold. Nutritional value of the residue was further enhanced through an increase in total amino acids and fatty acids. As a consequence of removal of inorganic elements such as sodium, potassium and chloride, the total solid and ash content of all three seaweeds was reduced by around 40%. In contrast, divalent metals such as iron and zinc, as well as silicon, accumulated in all three residues. Potentially harmful components such as arsenic and iodine were reduced only in brown biorefined seaweeds, whilst in biorefined P. palmata, iodine increased by 39% compared to a 24% decline of arsenic. Nutritional values such as total fatty acid and total amino acid content increased in all three seaweeds after enzymatic saccharification. Polyphenol removal in all three seaweeds was >80% using aqueous acetonitrile and, in combination with enzymatic saccharification, did not impact on protein recovery in A. nodosum. This highlights the potential of biorefinery concepts to generate multiple products from seaweed such as extracts enriched in polyphenols and carbohydrates and residue with higher protein and lipid content.

In Situ high-temperature powder X-ray diffraction experiments were undertaken for the coarse crystalline natural layered double hydroxides (LDHs) quintinite, hydrotalcite, stichtite, and iowaite in the temperature range 25&ndash, 1000 &deg, C, with thermal analyses of these minerals and their annealed forms carried out in parallel. In the temperature range from 25 &deg, C to 170&ndash, 210 &deg, C quintinite, hydrotalcite, and stichtite (carbonate members of the LDH family) demonstrated contraction of the basal d00n-value of 0.1&ndash, 0.3 &Aring, followed by a sharp contraction of 1.0&ndash, 1.1 &Aring, at T &gt, 170&ndash, C. The high-temperature modified states were stable up to 380&ndash, 420 &deg, C, before decomposing to an amorphous phase. Iowaite (chloride member of the family) was stable up to 320 &deg, C and transformed to an amorphous phase at higher temperature. Iowaite experiences continuous contraction of the d00n-value of up to 0.5 &Aring, in the temperature range 25&ndash, 200 &deg, C, reaching a plateau at a temperature range of 200&ndash, 320 &deg, C. Assessing the reversibility of thermal transformation shows complete reconstruction of the crystal structure of the hydrotalcite and iowaite heated to 300 &deg, C. Solid-state nuclear magnetic resonance analysis shows that some Al changes coordination from 6- to 4-fold, synchronously with quintinite transformation to the amorphous phase. All phases transform to periclase and a spinel-type compound upon further heating. Thermal analysis of samples annealed at 125 &deg, C shows that carbonate members do not have a tendency to form dehydrated phases, whereas for iowaite, a dehydrated phase having 0.9 apfu lesser water content as in the initial sample has been obtained. Thermal evolution of LDHs is found to depend on the nature of the interaction of interlayer species and water molecules to H atoms of the metal-hydroxide layer.

A sustainable route to ketones is described where stearone is produced via ketonic decarboxylation of stearic acid mediated by solid base catalysts in yields of up to 97%, at 250 &deg, C. A range of Mg/Al layered double hydroxide (LDH) and mixed metal oxide (MMO) solid base catalysts were prepared with Mg/Al ratios of between 2 and 6 via two synthetic routes, co-precipitation and co-hydration, with each material tested for their catalytic performance. For a given Mg/Al ratio, the LDH and MMO materials showed similar reactivity, with no correlation to the method of preparation. The presence of co-produced oxide phases in the co-hydration catalysts had negligible impact on reactivity.

Rock–water–carbon interactions germane to serpentinization in hydrothermal vents have occurred for over 4 billion years, ever since there was liquid water on Earth. Serpentinization converts iron(II) containing minerals and water to magnetite (Fe3O4) plus H2. The hydrogen can generate native metals such as awaruite (Ni3Fe), a common serpentinization product. Awaruite catalyzes the synthesis of methane from H2 and CO2 under hydrothermal conditions. Native iron and nickel catalyze the synthesis of formate, methanol, acetate, and pyruvate—intermediates of the acetyl-CoA pathway, the most ancient pathway of CO2 fixation. Carbon monoxide dehydrogenase (CODH) is central to the pathway and employs Ni0 in its catalytic mechanism. CODH has been conserved during 4 billion years of evolution as a relic of the natural CO2-reducing catalyst at the onset of biochemistry. The carbide-containing active site of nitrogenase—the only enzyme on Earth that reduces N2—is probably also a relic, a biological reconstruction of the naturally occurring inorganic catalyst that generated primordial organic nitrogen. Serpentinization generates Fe3O4 and H2, the catalyst and reductant for industrial CO2 hydrogenation and for N2 reduction via the Haber–Bosch process. In both industrial processes, an Fe3O4 catalyst is matured via H2-dependent reduction to generate Fe5C2 and Fe2N respectively. Whether serpentinization entails similar catalyst maturation is not known. We suggest that at the onset of life, essential reactions leading to reduced carbon and reduced nitrogen occurred with catalysts that were synthesized during the serpentinization process, connecting the chemistry of life and Earth to industrial chemistry in unexpected ways.

The role of mineral surfaces in concentrating and facilitating the polymerisation of simple protobiomolecules during the Hadean and Archean has been the subject of much research in order to constrain the conditions that may have led to the origin of life on early Earth. Here we examine the adsorption of the amino acid aspartate on layered double hydroxide minerals, and use a combined computer simulation – experimental spectroscopy approach to gain insight into the resulting structures of the host-aspartate material. We show that the uptake of aspartate occurs in alkaline solution by anion exchange of the dianion form of aspartate, rather than by surface adsorption. Anion exchange only occurs at values of pH where a significant population of aspartate has the amino group deprotonated, and is then highly efficient up to the mineral anion exchange capacity.

Organic dyes such as methylene blue (MB) are often used in the characterization of clays and related minerals, but details of the adsorption mechanisms of such dyes are only partially understood from spectroscopic data, which indicate the presence of monomers, dimers, and higher aggregates for varying mineral surfaces. A combination of quantum (density functional theory) and classical molecular simulation methods was used to provide molecular detail of such adsorption processes, specifically the adsorption of MB onto kaolinite basal surfaces. Slab models with vacuum-terminated surfaces were used to obtain detailed structural properties and binding energies at both levels of theory, while classical molecular dynamics simulations of aqueous pores were used to characterize MB adsorption at infinite dilution and at higher concentration in which MB dimers and one-dimensional chains formed. Results for the neutral MB molecules are compared with those for the corresponding cation. Simulations of the aqueous pore indicate preferred adsorption on the hydrophobic siloxane surface, while charge-balancing chloride ions adsorb at the aluminol surface. At infinite dilution and in the gas-phase models, MB adsorbs with its primary molecular plane parallel to the siloxane surface to enhance hydrophobic interactions. Sandwiched dimers and chains are oriented perpendicular to the surface to facilitate the strong hydrophobic intermolecular interactions. Compared with quantum results, the hybrid force field predicts a weaker MB adsorption energy but a stronger dimerization energy. The structure and energetics of adsorbed MB at infinite dilution are consistent with the gas-phase binding results, which indicate that monomer adsorption is driven by strong interfacial forces rather than by the hydration properties of the dye. These results inform spectroscopic studies of MB adsorption on mineral surfaces while also revealing critical areas for development of improved hybrid force fields.

Clay–polymer nanocomposite materials have gained much attention owing to their low weight ratio of filler to reinforcement properties, delivering lightweight yet resilient materials with excellent barrier properties to gas diffusion. An important process in their production is clay exfoliation, as maximum reinforcement and improvement of barrier properties occur when the clay mineral platelets are fully separated and dispersed through the polymer matrix with a preferred orientation. In this study we examine clay swelling—the first step leading to exfoliation—using molecular dynamics to generate solvation energetics, swelling curves, and atomic density profiles of three types of clay minerals—montmorillonite, vermiculite, and hectorite—with interlayer Na+ cations and/or three quaternary ammonium surfactants in water and ethanol. Analysis based on the provided simulations can help to distinguish between favorable and unfavorable swelling profiles of mineral/surfactant/solvent systems and therefore guide fur...

Hybrid organic-inorganic layered double hydroxide materials have been prepared with an ultra-high aspect ratio via an environmentally friendly co-hydration approach where metal hydroxides and adamantane-carboxylic acid were used as the reagents. The method avoids use of either acidic or basic precipitation methods, or using a large excess of anion. The effect of organic anion, metal cation and synthesis method on developing ultra-high aspect ratio crystallites was studied.

In this study, classical molecular dynamic simulations have been used to examine the molecular properties of the water-alkane interface at various NaCl salt concentrations (up to 3.0 mol/kg). A variety of different force field combinations have been compared against experimental surface/interfacial tension values for the water-vapour, decane-vapour and water-decane interfaces. Six different force fields for water (SPC, SPC/E, TIP3P, TIP3Pcharmm, TIP4P & TIP4P2005), and three further force fields for alkane (TraPPE-UA, CGenFF & OPLS) have been compared to experimental data. CGenFF, OPLS-AA and TraPPE-UA all accurately reproduce the interfacial properties of decane. The TIP4P2005 (four-point) water model is shown to be the most accurate water model for predicting the interfacial properties of water. The SPC/E water model is the best three-point parameterisation of water for this purpose. The CGenFF and TraPPE parameterisations of oil accurately reproduce the interfacial tension with water using either the TIP4P2005 or SPC/E water model. The salinity dependence on surface/interfacial tension is accurately captured using the Smith & Dang parameterisation of NaCl. We observe that the Smith & Dang model slightly overestimates the surface/interfacial tensions at higher salinities (>1.5 mol/kg). This is ascribed to an overestimation of the ion exclusion at the interface.

Enhanced oil recovery is becoming commonplace in order to maximize recovery from oil fields. One of these methods, low-salinity enhanced oil recovery (EOR), has shown promise; however, the fundamental underlying chemistry requires elucidating. Here, three mechanisms proposed to account for low-salinity enhanced oil recovery in sandstone reservoirs are investigated using molecular dynamic simulations. The mechanisms probed are electric double layer expansion, multicomponent ionic exchange, and pH effects arising at clay mineral surfaces. Simulations of smectite basal planes interacting with uncharged nonpolar decane, uncharged polar decanoic acid, and charged Na decanoate model compounds are used to this end. Various salt concentrations of NaCl are modeled: 0‰, 1‰, 5‰, and 35‰ to determine the role of salinity upon the three separate mechanisms. Furthermore, the initial oil/water-wetness of the clay surface is modeled. Results show that electric double layer expansion is not able to fully explain the effects of low-salinity enhanced oil recovery. The pH surrounding a clay’s basal plane, and hence the protonation and charge of acid molecules, is determined to be one of the dominant effects driving low-salinity EOR. Further, results indicate that the presence of calcium cations can drastically alter the oil wettability of a clay mineral surface. Replacing all divalent cations with monovalent cations through multicomponent cation exchange dramatically increases the water wettability of a clay surface and will increase EOR.

Nitrogen stable isotope ratios (δ15N) in macroalgae are often used to identify sources of nitrogenous pollution in fluvial and estuarine settings. This approach assumes that the macroalgal δ15N is representative of the sources of the pollution averaged over a timespan in the order of days to weeks, but the preferential uptake of a particular nitrogen compound or potential for fractionation in the water column or during uptake and assimilation by the macroalgae could make this assumption invalid. Laboratory studies were therefore performed to investigate the uptake and assimilation of both nitrate and ammonium at a variety of concentrations using the vegetative (non-fertile) tips of the brown macroalgae, Fucus vesiculosus. Nitrate appeared to fractionate at high concentrations, and was found to be taken up more rapidly than ammonia; within 13 days, the macroalgae tips were in isotopic equilibrium with the nitrate solution at 500 μM. These experiments were complemented by an investigation involving the translocation of macroalgae collected from a site enriched in 15N relative to natural levels (Staithes, UK), to the River Tees, Middlesbrough (UK), a site depleted in 15N relative to natural levels. The nitrogen isotope signature shifted 50% within 7 days, with samples deployed nearer the surface subject to greater change. These findings suggest that the translocation of macroalgae with isotopically distinct signatures can be used as a rapid, cost-efficient method for nitrogen biomonitoring in estuarine environments.

Clay swelling experiments frequently involve monitoring the one-dimensional displacement with time of an initially dry clay plug as it imbibes water from a supply at its base. This article presents a new analytical solution for interpreting such experiments based on Richards' equation for flow in a partially saturated porous medium combined with a linear empirical function relating moisture ratio with void ratio. The analytical solution is described by just two parameter groups. The first parameter group describes the swelling potential of the clay. The second parameter group describes the rate at which the swelling plug reaches equilibrium, which is controlled by permeability and capillary pressure. Application of the analytical solution is demonstrated by calibration to one-dimensional displacement data from clay swelling experiments for an illite and bentonite clay.

A problem in the use of macroalgae for biofuel is that harvesting of seaweed is generally seasonal, and there is a need to preserve and store seaweed to supply year-round production processes. Ensiling is a widely used preservation method in agriculture, but there is little research on ensiling seaweed. The changes in ash content, higher heating value (HHV) and dry matter (DM%) of algal biomass together with mass loss (ML) during ensilage for a year was studied for two species of seaweed, Laminaria digitata (LD) and Palmaria palmata (PP), with and without the addition of Lactobacillus plantarum. The mean ash content of the two species was significantly different (LD 24.3 % and PP 18.0 %) and remained constant after 90 days ensiling. The mean HHV before ensiling for PP was higher, 14.2 kJ g−1, compared to LD, 11.9 kJ g−1. Both the species (P < 0.05) and ensilage period (P < 0.05) had a significant effect on HHV. The overall DM% of the ensiled LD (22.4 %) and PP (22.0 %) were similar with a gradual increase in the DM% after 90 days ensiled. There was no effect of the ensiling with or without L. plantarum on DM%. There was a continuous wet matter loss during ensilage, and although the HHV of the ensiled wet biomass increased as the macroalgae became drier over time, the energy available from each kilogramme of wet macroalgae ensiled declined over the year to 78 % in LD and 59 % in PP.

Berea sandstone has been used by the petroleum industry as a representative model siliciclastic rock for a number of years. However, only incomplete data has been reported in the literature regarding its petrographic, geochemical, and petrophysical properties. In particular knowledge of the mineral distribution along the pore walls is particularly scarce, despite the fact that mineral exposed in the pore space will be crucial in determining the rock-fluid interactions that occur during core-flooding experiments. In this paper, four Berea sandstone samples (with 4 different permeability ranges from

We present the results of large-scale molecular simulations, run over several tens of nanoseconds, of 25-mer sequences of single-stranded ribonucleic acid (RNA) in bulk water and at the surface of three hydrated positively charged MgAl layered double hydroxide (LDH) minerals. The three LDHs differ in surface charge density, through varying the number of isomorphic Al substitutions. Over the course of the simulations, RNA adsorbs tightly to the LDH surface through electrostatic interactions between the charged RNA phosphate groups and the alumina charge sites present in the LDH sheet. The RNA strands arrange parallel to the surface with the base groups aligning normal to the surface and exposed to the bulk aqueous region. This templating effect makes LDH a candidate for amplifying the population of a known RNA sequence from a small number of RNAs. The structure and interactions of RNA at a positively charged, hydroxylated LDH surface were compared with those of RNA at a positively charged calcium montmorillonite surface, allowing us to establish the comparative effect of complexation and water structure at hydroxide and silicate surfaces. The systems were studied by computing radial distribution functions, atom density plots, and radii of gyration, as well as visualization. An observation pertinent to the role of these minerals in prebiotic chemistry is that, for a given charge density on the mineral surface, different genetic sequences of RNA adopt different configurations.

Many important properties of clay minerals are defined by the species of charge-balancing cation. Phenomena such as clay swelling and cation exchange depend on the cation species present, and understanding how the cations bind with the mineral surface at a fundamental level is important. In the present study the binding affinities of several different charge-balancing cations with the basal surface of the smectite mineral, montmorillonite, have been calculated using molecular dynamics in conjunction with the well-tempered metadynamics algorithm. The results follow a Hofmeister series of preferred ion adsorption to the smectite basal surfaces of the form: K+ > Na+ > Ca2+ > Cs+ > Ba2+ The results also revealed the energetically favorable position of the ions above the clay basal surfaces. Key features of the free-energy profiles are illustrated by Boltzmann population inversions and analyses of the water structures surrounding the ion and clay surface. The results show that weakly hydrated cations (K+ and Cs+) preferentially form inner-sphere surface complexes (ISSC) above the ditrigonal siloxane cavities of the clay, while the more strongly hydrated cations (Na+) are able to form ISSCs above the basal O atoms of the clay surface. The strongly hydrated cations (Na+, Ca2+, and Ba2+), however, preferentially form outer-sphere surface complexes. The results provide insight into the adsorption mechanisms of several ionic species on montmorillonite and are relevant to many phenomena thought to be affected by cation exchange, such as nuclear waste disposal, herbicide/pesticide-soil interactions, and enhanced oil recovery.

In this study, classical molecular dynamics simulations have been used to understand the key interactions and surface structure of a set of organic molecules at the hydrated surfaces of the 1:1 clay mineral kaolinite. Decane, decanoic acid, and decanamine have been modeled at both the hydroxylated and silicate surfaces of kaolinite. Additionally, the effect of pH is observed via looking at the protonated decanamine and decanoate anion forms. The key results show that relative affinity of the organic molecules to the kaolinite surface may be readily switched between the hydroxylated and the silicate surfaces according to the pH and the nature of the organic head functional group. Decane molecules readily form droplets atop the silicate surface and do not adsorb to the hydroxyl surface, as do protonated decanoic acids. In stark contrast, decanoate anions do not adsorb to the silicate surface, yet adsorb to the hydroxyl surface through an anion exchange mechanism. Decanamine readily adsorbs to both silicate and hydroxyl surfaces, though the hydroxyl–amine interactions are mediated through water bridges. Once charged, the decanamine remains adsorbed to both surfaces, however, both interactions are ionically mediated, rather than through van der Waals and hydrogen bonds. Furthermore, protonated decanamine is observed to adsorb to the hydroxyl surface via anion bridges, a phenomenon that is typically associated with positively charged layered double hydroxides rather than negatively charged clay minerals.

In this study we investigate the fundamentals of a problem pertinent to the cement and concrete manufacturing industries, where clay minerals are pollutants of sands due to their capacity to adsorb additives designed to improve concrete workability. In this density functional theory (DFT) investigation we examine the adsorption of a selection of organic monomers, (e.g., CH3CH2CHOHCH3 and (CH3)3N+CH2CHOHCH2CH3,Cl–) on kaolinite (Al2Si2O5(OH)4) to determine the nature of the basal surface/monomer interactions and, also, to determine whether the presence of an additional clay layer and separately water changes the nature of these interactions. We gauge these effects by examining their formation energies, structural configurations post relaxation, Mulliken charges, and molecular orbitals occupancies. The results show that interactions are predominantly electrostatic for charged monomers and H-bonding for noncharged and also that increasing the complexity of these systems does not change the nature of these in...

Recent work suggests a link between chiral asymmetry in the amino acid iso-valine extracted from the Murchison meteorite and the extent of hydrous alteration. We present the results of neutron scattering experiments on an exchanged, 1-dimensionally ordered n-propyl ammonium vermiculite clay. The vermiculite gel has a (001) d-spacing of order 5nm at the temperature and concentration of the experiments and the d-spacing responds sensitively to changes in concentration, temperature and electronic environment. The data show that isothermal addition of D-histidine or L-histidine solutions produces shifts in the d-spacing that are different for each enantiomer. This chiral specificity is of interest for the question of whether clays could have played an important role in the origin of biohomochirality., 10 Pages, 5 Figures

International audience; A mechanistic model of microalgae is used to explore the implications of modifying microalgal chlorophyll content and photosynthetic efficiency with an aim to optimizing commercial biomass production. The models show the potential for a ten-fold increase in microalgae productivity in genetically modified versus unmodified configurations, while also enabling the use of bioreactors of greater optical depth operating at lower dilution rates. Analysis suggests that natural selection of a trait benefiting the individual (high Chl:C; i.e. high antennae size) conflicts with artificial selection of a trait (low Chl:C) of most benefit to production at the population level. The implication is that GM strains rather than strains selected from nature will be most beneficial for commercial algal biofuels production. Further, escaped GM algae populations may, depending on the specific nature of the modification, be quickly out-competed by the natural forms because individually a high Chl:C is beneficial in low light environments. However, it remains possible that changes in biochemical composition associated with genetic modification of photosystem competence, or with other selection processes to enhance commercial gain, may adversely affect the value of such organisms as prey for zooplankton, leading to the unwanted generation of future harmful algae.

The surge of interest in and scientific publications on the structure and properties of nanocomposites has made it rather difficult for the novice to comprehend the physical structure of these new materials and the relationship between their properties and those of the conventional range of composite materials. Some of the questions that arise are: How should the reinforcement volume fraction be calculated? How can the clay gallery contents be assessed? How can the ratio of intercalate to exfoliate be found? Does polymerization occur in the clay galleries? How is the crystallinity of semi-crystalline polymers affected by intercalation? What role do the mobilities of adsorbed molecules and clay platelets have? How much information can conventional X-ray diffraction offer? What is the thermodynamic driving force for intercalation and exfoliation? What is the elastic modulus of clay platelets? The growth of computer simulation techniques applied to clay materials has been rapid, with insight gained into the structure, dynamics and reactivity of polymer-clay systems. However these techniques operate on the basis of approximations, which may not be clear to the non-specialist. This critical review attempts to assess these issues from the viewpoint of traditional composites thereby embedding these new materials in a wider context to which conventional composite theory can be applied. (210 references).

The Holywell Shale is part of the Carboniferous Bowland Shale Formation, identified as the main potential shale gas system in the UK. Here, we report geochemical and petrographic data from five outcrops of the Lower and Upper Holywell Shale across northeast Wales. At outcrop, the Holywell Shale is immature to early oil mature and has total organic carbon (TOC) values ranging between 0.1 and 10.3 wt %, with a mean of 1.9 wt %. Carbon isotope data clearly differentiate terrestrial and marine organic matter and show that both occur throughout the Holywell, with terrestrial sources (Type III/IV) dominating the Upper Holywell and marine sources dominating the Lower Holywell (Type II/III). Trace element data indicate that bottom waters were oxygenated, resulting in poorly preserved organic matter, supported by C/N and HI data. A range of silt- and clay-rich lithofacies occur, which show no relationship to either the amount or type of organic matter. We interpret the data in terms of a mixed supply of terrestrial and marine organic matter to marine depositional environments in which there was sufficient hydrodynamic energy to transport fine-grained sediment as bed load. The resulting mudstones exhibit a range of sedimentary textures with millimetre- to centimetre-scale silt–clay bed forms which show almost no relationship to organic matter type and amount. The small-scale variability and heterogeneity of both organofacies and lithofacies means that the reservoir quality of the Holywell Shale is inherently difficult to predict.

Layer double hydroxides (LDHs) based on the hydrotalcite structure (Mg6Al2(OH)16CO3·4H2O) have been synthesized by coprecipitation, sol–gel and urea hydrolysis methods and with Mg:Al ratios of 2:1 and 5:1. Scanning electron microscopy shows the coprecipitated phases present the smallest individual crystallite sizes (ca. 150 nm) with the largest crystallites (2–4 μm) for urea hydrolysis. Sol–gel samples show crystallites (150–450 nm) fused together into much larger particles. The samples have been calcined at 723 K in flowing air to produce metal oxide phases which have then been rehydrated in the presence of hydroxide ions to produce meixnerite-like LDH phases (Mg6Al2(OH)20·4H2O). The base catalytic activity of these rehydrated samples has been measured by GC for the aldol self-condensation of acetone. Activity data has been correlated with sample characteristics to gain insight into the active sites and mode of action of these catalysts.

We present a joint experimental and theoretical investigation into the adsorption of polycationic quaternary ammonium polymers on the clay mineral kaolinite. Within the cement and concrete manufacturing industries such polymers are used to improve the final product by inerting the adsorption capacity of the clay minerals for more expensive additives. The adsorption of the presently used polymer (FL22) was compared with both a similar variant, but without a hydroxyl group (Fl22mod) and uncharged polyvinyl alcohol (PVA). Experimental results show that adsorption of FL22 is higher than that of FL22mod at both pH 6 and at pH > 10 and that the adsorption of PVA is the highest. Theoretical density functional theory (DFT) results and simplified models consisting of the basal surfaces of kaolinite, with monomers of FL22, FL22mod and PVA gave monomer coverage per unit surface area of kaolinite, a comparison of the configurations of the relaxed models, formation energies and Mulliken charges. These results show that the polycationic polymers interact with the basal surfaces of kaolinite electrostatically, explaining the high affinity of these polymers for kaolinite surfaces in the experimental results. The hydroxyl groups of FL22 and PVA form hydrogen bonds with the basal surfaces of kaolinite in conditions of pH 6. The joint experimental and theoretical results suggest that, due to the presence of the hydroxyl group, the conformation of FL22 changes under pH, where at neutral pH it lies relatively flat to the kaolinite surfaces, but at higher pH, conformational changes of the polymer occur, thereby increasing the adsorbed quantity of FL22.

Rock-Eval pyrolysis analysis of unconventional mudstone reservoirs use the S1 peak (kg free liquid per tonne of rock) to determine the volume of oil that can be potentially produced by hydraulic fracking. The data presented in this paper were obtained from a study of the unconventional oil potential of the marine late Jurassic Kimmeridge Clay Formation of the southern Viking Graben area of the UK and Norwegian sectors of the North Sea. Typical marine silty mudstones with >2%TOC contains

A significant proportion of renewable feedstocks research has been devoted to the production of bio-fuels and bio-chemicals from biomass, primarily via thermochemical conversion processes. This chapter presents an overview of alternative pyrolysis methodologies, which can convert biomass directly into solid (char), liquid (bio-oil), and gaseous products. In this report, the influence of the pyrolysis conditions employed, the design of reactor, and the nature of the biomass feedstock used upon the chemical composition of the product fractions are surveyed. A summary of the mechanisms by which the pyrolysis of the principle biomass constituents occurs is given. This is accompanied by an indication of the complications that arise as a result of the complex and heterogeneous nature of biomass, including the potential roles of the various salts and minerals naturally present in such feeds. From a commercial standpoint, the multi-component nature, different forms and structures of biomass, all pose significant challenges for the utilization of biomass in the manufacture of fuels and chemicals. Consequently, the in and ex situ use of a host of additives and catalysts (including molecular sieves, metal oxides, and transition metal-modified oxides) is reviewed, which have been incorporated in order to provide selectivity in pyrolytic biomass upgrading.

Origins of life studies represent an exciting and highly multidisciplinary research field. In this review we focus on the contributions made by theory, modelling and simulation to addressing fundamental issues in the domain and the advances these approaches have helped to make in the field. Theoretical approaches will continue to make a major impact at the “systems chemistry” level based on the analysis of the remarkable properties of nonlinear catalytic chemical reaction networks, which arise due to the auto-catalytic and cross-catalytic nature of so many of the putative processes associated with self-replication and self-reproduction. In this way, we describe inter alia nonlinear kinetic models of RNA replication within a primordial Darwinian soup, the origins of homochirality and homochiral polymerization. We then discuss state-of-the-art computationally-based molecular modelling techniques that are currently being deployed to investigate various scenarios relevant to the origins of life.

Because of the importance of mineral catalyzed decarboxylation reactions in both crude oil formation and, increasingly, biofuel production, we present a model study into the decarboxylation of the shortest fatty acid, propionic acid C(2)H(5)COOH, into an alkane and CO(2) catalyzed by a pyrophillite-like, phyllosilicate clay. To identify the decarboxylation pathway, we searched for a transition state between the reactant, comprised of the clay plus interlayer fatty acid, and the product, comprised of the clay plus interlayer alkane and carbon dioxide. Using linear and quadratic synchronous transit mechanisms we searched for a transition state followed by vibrational analysis to verify the intermediate found as a transition state. We employed a periodic cell, planewave, ab initio density functional theory computation to examine total energy differences, Mulliken charges, vibrational frequencies, and the frontier orbitals of the reactants, intermediates, and products. The results show that interpretation of vibrational data, Mulliken charges and Fermi-level orbital occupancies is necessary for the classification of a transition state in this type of mixed bulk surface plus interlayer species, clay-organic system.

Since a mineral-mediated origin of life was first hypothesized over 60 years ago, clays have played a significant role in origins of life studies. Such studies have hitherto rarely used computer simulation to understand the possible chemical pathways to the formation of biomolecules. We use molecular dynamics techniques, performed on supercomputing grids, to carry out large-scale simulations of various 25-mer sequences of ribonucleic acid (RNA), in bulk water and with aqueous montmorillonite clay over many tens of nanoseconds. Hitherto, there has only been limited experimental data reported for these systems. Our simulations are found to be in agreement with various experimental observations pertaining to the relative adsorption of RNA on montmorillonite in the presence of charge balancing cations. Over time scales of only a few nanoseconds, specific RNA sequences fold to characteristic secondary structural motifs, which do not form in the corresponding bulk water simulations. Our simulations also show that, in aqueous Ca(2+) environments, RNA can tether to the clay surface through a nucleotide base, leaving the 3'-end of the strand exposed, providing a mechanism for the regiospecific adsorption and elongation of RNA oligomers on clay surfaces.

Layered double hydroxides (LDHs) have been shown to form staged intermediate structures in experimental studies of intercalation. However, the mechanism by which staged structures are produced remains undetermined. Using molecular dynamics simulations, we show that LDHs are flexible enough to deform around bulky intercalants such as deoxyribonucleic acid (DNA). The flexibility of layered materials has previously been shown to affect the pathway by which staging occurs. We explore three possible intermediate structures which may form during intercalation of DNA into Mg2Al LDHs and study how the models differ energetically. When DNA strands are stacked directly on top of each other, the LDH system has a higher potential energy than when they are stacked in a staggered or interstratified structure. It is generally thought that staged intercalation occurs through a Daumas-Herold or a Rudorff model. We find, on average, greater diffusion coefficients for DNA strands in a Daumas-Herold configuration compared to a Rudorff model and a stage-1 structure. Our simulations provide evidence for the presence of peristaltic modes of motion within Daumas-Herold configurations. This is confirmed by spectral analysis of the thickness variation of the basal spacing. Peristaltic modes are more prominent in the Daumas-Herold structure compared to the Rudorff and stage-1 structures and support a mechanism by means of which bulky intercalated molecules such as DNA rapidly diffuse within an LDH interlayer.

Origins of life studies represent an exciting and highly multidisciplinary research field. In this review we focus on the contributions made by theory, modelling and simulation to addressing fundamental issues in the domain and the advances these approaches have helped to make in the field. Theoretical approaches will continue to make a major impact at the "systems chemistry" level based on the analysis of the remarkable properties of nonlinear catalytic chemical reaction networks, which arise due to the auto-catalytic and cross-catalytic nature of so many of the putative processes associated with self-replication and self-reproduction. In this way, we describe inter alia nonlinear kinetic models of RNA replication within a primordial Darwinian soup, the origins of homochirality and homochiral polymerization. We then discuss state-of-the-art computationally-based molecular modelling techniques that are currently being deployed to investigate various scenarios relevant to the origins of life.

A layered double hydroxide (LDH) mineral filler particle has been designed and employed in rubber vulcanization to prepare a more environmentally friendly rubber composite. The LDH delivers zinc ions in the vulcanization process as accelerators, stearate anions as activators and simultaneously the mineral sheets act as a nanofiller to reinforce the rubber matrix whilst totally replacing the separate zinc oxide (ZnO) and stearic acid conventionally used in the formulation of rubber. This method leads to a significant reduction (nearly 10 times) of the zinc level and yields excellent transparent properties in the final rubber product. The morphological characterization, rheometric curing behaviour, mechanical properties and uniaxial multi-hysteresis behaviours of the resultant rubber/LDH nanocomposite are studied in this paper.

Layered double hydroxides (LDHs) intercalated with terephthalate anions represent one of the most studied organo-LDH systems. We have prepared MgAl terephthalate-LDHs using an efficient hydrothermal approach from the respective metal hydroxide precursors. In contrast to terephthalate LDHs prepared by other methods, and as a result of the absence of competing anions, a large excess of terephthalate acid was not required, thereby allowing for an environmentally attractive synthetic route. The LDHs were prepared from starting reactant Mg/Al ratios of 2, 3, 4 and 5 and were found to exhibit unusually high degrees of order as evidenced from X-ray diffraction studies, especially at the Mg/Al ratio of 2. Further analysis of the X-ray diffraction data showed that, as in previous studies, three distinct interlayer arrangements could be identified. Scanning electron microscopy was used to compare and contrast the morphology of crystals formed with those prepared by other methods of LDH synthesis and confirms the high degree of structural integrity achieved by the synthetic method.