Elements of Eoarchean life trapped in mineral inclusions.

Metasedimentary rocks from Isua, West Greenland (over 3,700 million years old) contain 13C-depleted carbonaceous compounds, with isotopic ratios that are compatible with a biogenic origin. Metamorphic garnet crystals in these rocks contain trails of carbonaceous inclusions that are contiguous with carbon-rich sedimentary beds in the host rock, where carbon is fully graphitized. Previous studies have not been able to document other elements of life (mainly hydrogen, oxygen, nitrogen and phosphorus) structurally bound to this carbonaceous material. Here we study carbonaceous inclusions armoured within garnet porphyroblasts, by in situ infrared absorption on approximately 10-21 m3 domains within these inclusions. We show that the absorption spectra are consistent with carbon bonded to nitrogen and oxygen, and probably also to phosphate. The levels of C-H or O-H bonds were found to be low. These results are consistent with biogenic organic material isolated for billions of years and thermally matured at temperatures of around 500 °C. They therefore provide spatial characterization for potentially the oldest biogenic carbon relics in Earth's geological record. The preservation of Eoarchean organic residues within sedimentary material corroborates earlier claims for the biogenic origins of carbon in Isua metasediments.

First-Principles Prediction of Surface Wetting.

We have developed a method for predicting the solvation contribution to solid-liquid interfacial tension (IFT) based on density functional theory and the implicit solvent model COSMO-RS. Our method can be used to predict wetting behavior for a solid surface in contact with two liquids. We benchmarked our method against measurements of contact angle from water-in-oil on silica wafers and a range of self-assembled monolayers (SAMs) with different compositions, ranging from oil-wet to water-wet. We also compared our predictions to literature data for wetting of a polydimethylsilane surface. By explicitly including deprotonation for silica surfaces and carboxylic acid SAMs, very good agreement was obtained with experimental data for nearly all surfaces. Poor agreement was found for amine-terminated SAMs, which could be the result of both method and model insufficiencies and impurities known to be present for such surfaces. Solid-liquid IFT cannot be measured directly, making predictions such as from our method all the more important.

Effect of Divalent Cations on the Interaction of Carboxylate Self-Assembled Monolayers.

Interactions between organic molecules in aqueous environments, whether in the fluid phase or adsorbed on solids, are often affected by the cations present in the solution. We investigated, at nanometer scale, how surface carboxylate interactions are influenced by dissolved divalent cations: Mg2+, Ca2+, Sr2+, and Ba2+. Self-assembled monolayer (SAM) surfaces with exposed terminations of alkyl, -CH3, carboxylate, -COO- , or dicarboxylate, -DiCOO-, were deposited on gold-coated tips and substrates. We used atomic force microscopy (AFM), in chemical force mapping (CFM) mode, to measure adhesion forces between various combinations of SAMs on the tip and substrate, in solutions of 0.5 M NaCl, that contained 0.012 M of one of the divalent cations. The type of cation, the number of carboxyl groups that interact, and their structure on the SAM influenced adhesion between the surfaces. The effect of the reference solution, which only contains Na+ cations, on adhesion force was mainly attributed to van der Waals and hydrophobic forces, explaining the lower force in systems that are more hydrophilic, i.e., -COO--COO-, and higher force for more hydrophobic systems. For charged surfaces, i.e., -COO- and -DiCOO-, in divalent cation solutions results were consistent with ion bridging. The inclusion of a hydrophobic surface, i.e., the -CH3-COO- or -CH3-DiCOO- system, decreased the possibility for strong cation bridging with the charged surface, resulting in lower adhesion. For systems including -COO-, the adhesion force series followed the inverse cation hydrated radius trend (Na+ ≈ Mg2+ < Sr2+ < Ca2+ < Ba2+) whereas -DiCOO- was responsible for lower adhesion force and modified trends, depending on the corresponding surface in the system. Differences in force magnitude between the monolayers were correlated with lower charge availability on the -DiCOO- surface as a result of fewer active sites, probably because of the tendency of exposed malonate surface groups to interact between them, as well as high rigidity, resulting from the molecule structure. The characteristic response of the -DiCOO- surface in solutions of Sr2+ and Ca2+ was correlated with possible malonate complexation modes. Comparison with previous studies suggested that the strong response of a -DiCOO- surface to Sr2+ resulted from bidentate chelation, whereas Ca2+ response was attributed to alpha-mode association to malonate.

Specific Ion Effects on the Interaction of Hydrophobic and Hydrophilic Self-Assembled Monolayers.

Interactions between mineral surfaces and organic molecules are fundamental to life processes. The presence of cations in natural environments can change the behavior of organic compounds and thus alter the mineral-organic interfaces. We investigated the influence of Na+, Mg2+, Ca2+, Sr2+, and Ba2+ on the interaction between two models, self-assembled monolayers, that were tailored to have hydrophobic -CH3 or hydrophilic -COO(H) terminations. Atomic force microscopy in chemical force mapping mode, where the tips were functionalized with the same terminations, was used to measure adhesion forces between the tip and substrate surfaces, to gather fundamental information about the role of these cations in the behavior of organic compounds and the surfaces where they adsorb. Adhesion force between hydrophobic surfaces in 0.5 M NaCl solutions that contained 0.012 M divalent cations did not change, regardless of the ionic potential, that is, the charge per unit radius, of the cation. For systems where one or the other surface was functionalized with carboxylate, -COO(H), mostly in its deprotonated form, -COO-, a reproducible change in the adhesion force was observed for each of the ions. The trend of increasing adhesion force followed the pattern: Na+ ≈ Mg2+ < Sr2+ < Ca2+ < Ba2+, suggesting that ionic potential, thus hydrated radius, controls the interaction. The presence of a -CH3 surface in the asymmetric system leads to lower adhesion forces than in the hydrophilic system, whereas the ionic trend remains the same. Although specific ion effects are felt in both systems, the lower adhesion force in the asymmetric system, compared with the hydrophilic system, implies that the -CH3 surface plays an important role.

Specific ion effects on the hydrophobic interaction of benzene self-assembled monolayers.

The interaction of aromatic compounds with various ions in aqueous solutions plays a role in a number of fields, as diverse as protein folding and enhanced oil recovery, among others. Therefore, we have investigated the effect of the four electrolytes, KCl, NaCl, MgCl2 and CaCl2, on the hydrophobic interaction of benzene self-assembled monolayers. Using the jump to contact phenomenon of an atomic force microscope (AFM) tip as an indicator of attractive forces between the surfaces of a sample and the tip, we discovered lower frequencies in the snap in as well as narrower distributions for the snap in distance for the monovalent ions, especially for K(+), compared with the behaviour for the divalent ions. These observations are explained by the accumulation of charge at the surface by cation-π interactions and an influence of the ions on the formation of capillaries that bridge the tip to the surface. Bridging capillaries, i.e. nanometre scale gas bubbles, are some of the factors contributing to the long range hydrophobic interaction. The results demonstrate how ions influence the attraction of hydrophobic entities in aqueous solutions.

Interactions of Na+, K+, Mg2+, and Ca2+ with benzene self-assembled monolayers.

Interactions between cations and organic molecules are found throughout nature, from the functionality and structure of proteins in humans and animals to the exchange of ions in minerals in soil and oil reservoirs with the fluid phases. We have explored the behavior of the s-block elements that are most common in the natural world, namely, Na(+), K(+), Mg(2+), and Ca(2+). Specifically, we investigated how these ions affect the interactions between surfaces covered by self-assembled monolayers (SAMs) terminated with benzene molecules. We used a flat oxidized silicon substrate and an atomic force microscopy (AFM) tip that were both functionalized with 11-phenoxyundecane-1-thiol and measured the adhesion force between them in solutions of each of the four chloride salts. We observed that the adhesion increased in the order of the Hofmeister series: K(+) < Na(+) ≈ Mg(2+) < Ca(2+). Supplementary evidence from X-ray photoelectron spectroscopy (XPS) allowed us to conclude that K(+) binds in the benzene layers, creating a positive surface charge on the benzene-covered surfaces, thus leading to lower adhesion in KCl solutions than in pure water. Evidence suggested that Ca(2+) does not bind to the surfaces but forms bridges between the layers, leading to higher adhesion than in pure water. In Na(+) and Mg(2+) solutions, adhesion is quite similar to that in pure water, indicating a lack of interaction between these two ions and the surfaces, or at least that the interaction is too weak to be detected by our measurements. The results of our studies clearly show that even a nonpolar, hydrophobic molecule, such as benzene, has a role to play in the behavior of aqueous solutions and that it interacts differently depending on which ions are present. Even ions from the same column in the periodic table behave differently.

Adhesion of alkane as a functional group on muscovite and quartz: dependence on pH and contact time.

The interactions between mineral surfaces and organic molecules in water control many processes in nature and in the production of modern materials. To improve the understanding of fluid-surface interactions, we investigated the interface behavior of quartz and muscovite, a model for clay minerals, in aqueous solutions where the pH and composition were controlled. We used atomic force microscopy (AFM) in chemical force mapping (CFM) mode to measure adhesion using tips functionalized with alkyl, -CH3. By combining adhesion forces measured as a function of pH, with data from streaming potential experiments and DLVO calculations, we were able to determine the surface charge density. We observed increased adhesion between the mineral surface and the hydrophobic tips as the contact time increased from 7 ms to ∼2 s. The diffusion of dissolved ions takes time, and density functional theory (DFT) calculations did not indicate a strong hydration of the mineral surfaces. Therefore, we interpret that the loss of ions from the confined space between the tip and sample is a likely explanation of the correlation between the dwell time and adhesion. The maximum adhesion increase with dwell time for muscovite, i.e., 400 ± 77 pN, was considerably larger than for quartz, 84 ± 15 pN, which fits with the different surface structure and composition of the two minerals. We propose two mechanisms to explain these results: (1) cations that are structured in the solution and on the surface remain associated at the tip-sample interface initially but diffuse away during extended contact time and (2) adventitious carbon, the organic material that comes spontaneously from air and solution, can diffuse to the tip-sample interface during contact. This material decreases the surface energy by aggregating near the alkyl tip and increases adhesion between the tip and sample.

Change in organic molecule adhesion on α-alumina (sapphire) with change in NaCl and CaCl2 solution salinity.

We investigated the adhesion of two functional groups to α-alumina as a model for the adsorption of organic molecules on clay minerals. Interactions between organic compounds and clay minerals play an important role in processes such as drinking water treatment, remediation of contaminated soil, oil recovery, and fabricating complicated nanomaterials, and there have been claims that organic compound-clay mineral interaction created the ordering that is necessary for the genesis of life. In many organisms, interaction between organic molecules and biominerals makes it possible to control the growth of bones, teeth, and shells. Adhesion of carboxylic acid, -COO(H), and pyridine, -C5H5N(H(+)), on the {0001} plane of α-alumina wafers has been investigated with atomic force microscopy (AFM) in chemical force mapping (CFM) mode. Both functional groups adhered to α-alumina in deionized water at pH < 5, and adhesion decreased as NaCl or CaCl2 concentration increased. X-ray photoelectron spectroscopy (XPS) showed that Na(+) and Ca(2+) adsorbed to the α-alumina surface at pH < 5, decreasing surface interaction with the carboxylic acid and pyridine groups. We interpret the results as evidence that the tips adhere to alumina through hydrogen bonding when only water is present. In solutions containing NaCl and CaCl2, cations are adsorbed but Cl(-) is not. When NaCl solutions are replaced by CaCl2, Ca(2+) replaces Na(+), but rinsing with ultrapure deionized water (pH 5.6) could not restore the original protonated surface. The results demonstrate that the alumina surface at pH 3 has a higher affinity for inorganic cations than for -COO(H) or -C5H5N(H(+)), in spite of the known positive surface charge of α-alumina {0001} wafers. These results demonstrate that solution salinity plays an important role in surface properties, controlling surface tension (i.e., contact angle) and adsorption affinity on α-alumina and, by analogy, on clay minerals.

Tracking single coccolith dissolution with picogram resolution and implications for CO2 sequestration and ocean acidification.

Coccoliths are micrometer scale shields made from 20 to 60 individual calcite (CaCO(3)) crystals that are produced by some species of algae. Currently, coccoliths serve as an important sink in the global carbon cycle, but decreasing ocean pH challenges their stability. Chalk deposits, the fossil remains of ancient algae, have remained remarkably unchanged by diagenesis, the process that converts sediment to rock. Even after 60 million years, the fossil coccolith crystals are still tiny (< 1 µm), compared with inorganically produced calcite, where one day old crystals can be 10 times larger, which raises the question if the biogenic nature of coccolith calcite gives it different properties than inorganic calcite? And if so, can these properties protect coccoliths in CO(2) challenged oceans? Here we describe a new method for tracking dissolution of individual specimens, at picogram (10(-12) g) resolution. The results show that the behavior of modern and fossil coccoliths is similar and both are more stable than inorganic calcite. Organic material associated with the biogenic calcite provides the explanation. However, ancient and modern coccoliths, that resist dissolution in Ca-free artificial seawater at pH > 8, all dissolve when pH is 7.8 or lower. Ocean pH is predicted to fall below 7.8 by the year 2100, in response to rising CO(2) levels. Our results imply that at these conditions the advantages offered by the biogenic nature of calcite will disappear putting coccoliths on algae and in the calcareous bottom sediments at risk.

Characterization of Eyjafjallajokull volcanic ash particles and a protocol for rapid risk assessment.

On April 14, 2010, when meltwaters from the Eyjafjallajökull glacier mixed with hot magma, an explosive eruption sent unusually fine-grained ash into the jet stream. It quickly dispersed over Europe. Previous airplane encounters with ash resulted in sandblasted windows and particles melted inside jet engines, causing them to fail. Therefore, air traffic was grounded for several days. Concerns also arose about health risks from fallout, because ash can transport acids as well as toxic compounds, such as fluoride, aluminum, and arsenic. Studies on ash are usually made on material collected far from the source, where it could have mixed with other atmospheric particles, or after exposure to water as rain or fog, which would alter surface composition. For this study, a unique set of dry ash samples was collected immediately after the explosive event and compared with fresh ash from a later, more typical eruption. Using nanotechniques, custom-designed for studying natural materials, we explored the physical and chemical nature of the ash to determine if fears about health and safety were justified and we developed a protocol that will serve for assessing risks during a future event. On single particles, we identified the composition of nanometer scale salt coatings and measured the mass of adsorbed salts with picogram resolution. The particles of explosive ash that reached Europe in the jet stream were especially sharp and abrasive over their entire size range, from submillimeter to tens of nanometers. Edges remained sharp even after a couple of weeks of abrasion in stirred water suspensions.

Probing the intrinsically oil-wet surfaces of pores in North Sea chalk at subpore resolution.

Pore surface properties control oil recovery. This is especially true for chalk reservoirs, where pores are particularly small. Wettability, the tendency for a surface to cover itself with fluid, is traditionally defined by the angle a droplet makes with a surface, but this macroscopic definition is meaningless when the particles are smaller than even the smallest droplet. Understanding surface wetting, at the pore scale, will provide clues for more effective oil recovery. We used a special mode of atomic force microscopy and a hydrophobic tip to collect matrices of 10,000 force curves over 5- x 5-mum(2) areas on internal pore surfaces and constructed maps of topography, adhesion, and elasticity. We investigated chalk samples from a water-bearing formation in the Danish North Sea oil fields that had never seen oil. Wettability and elasticity were inhomogeneous over scales of 10s of nanometers, smaller than individual chalk particles. Some areas were soft and hydrophobic, whereas others showed no correlation between hardness and adhesion. We conclude that the macroscopic parameter, "wetting," averages the nanoscopic behavior along fluid pathways, and "mixed-wet" samples have patches with vastly different properties. Development of reservoir hydrophobicity has been attributed to infiltrating oil, but these new results prove that wettability and elasticity are inherent properties of chalk. Their variability, even on single particles, must result from material originally present during sedimentation or material sorbed from the pore fluid some time later.

Binding of ethanol on calcite: the role of the OH bond and its relevance to biomineralization.

The interaction of OH-containing compounds with calcite, CaCO(3), such as is required for the processes that control biomineralization, has been investigated in a low-water solution. We used ethanol (EtOH) as a simple, model, OH-containing organic compound, and observed the strength of its adsorption on calcite relative to OH from water and the consequences of the differences in interaction on crystal growth and dissolution. A combination of atomic force microscopy (AFM) and molecular dynamics (MD) simulations showed that EtOH attachment on calcite is stronger than HOH binding and that the first adsorbed layer of ethanol is highly ordered. The strong ordering of the ethanol molecules has important implications for mineral growth and dissolution because it produces a hydrophobic layer. Ethanol ordering is disturbed along steps and at defect sites, providing a bridge from the bulk solution to the surface. The strong influence of calcite in structuring ethanol extends further into the liquid than expected from electrical double-layer theory. This suggests that in fluids where water activity is low, such as in biological systems optimized for biomineralization, organic molecules can control ion transport to and from the mineral surface, confining it to specific locations, thus providing the organism with control for biomineral morphology.

3.7 billion year old biogenic remains.

3.7 Billion year old inclusions inside garnet crystals contain 13C depleted carbonaceous material consistent with biogenic origin. Additional evidence in the form of the other elements of life mainly O, N and P were found to be structural bound to this material by using a new technique, AFM-IR. Here we show additional evidence that support our claim. By overlaying maps generated by the AFM-IR we show how the location of 100's of nm sized contiguous domains of nitrile and possibly phosphonate overlap inside the inclusion. This shows that O, N and P are not only co-localized to the same inclusion but they are co-localized to the same patch of carbonaceous material inside the inclusion. They therefore provide spatial characterization for potentially the oldest biogenic remains in Earth's geological record and corroborates earlier claims2 for the biogenic origins of carbon in Isua metasediments.

Organic-Silica Interactions in Saline: Elucidating the Structural Influence of Calcium in Low-Salinity Enhanced Oil Recovery.

Enhanced oil recovery using low-salinity solutions to sweep sandstone reservoirs is a widely-practiced strategy. The mechanisms governing this remain unresolved. Here, we elucidate the role of Ca2+ by combining chemical force microscopy (CFM) and molecular dynamics (MD) simulations. We probe the influence of electrolyte composition and concentration on the adsorption of a representative molecule, positively-charged alkylammonium, at the aqueous electrolyte/silica interface, for four electrolytes: NaCl, KCl, MgCl2, and CaCl2. CFM reveals stronger adhesion on silica in CaCl2 compared with the other electrolytes, and shows a concentration-dependent adhesion not observed for the other electrolytes. Using MD simulations, we model the electrolytes at a negatively-charged amorphous silica substrate and predict the adsorption of methylammonium. Our simulations reveal four classes of surface adsorption site, where the prevalence of these sites depends only on CaCl2 concentration. The sites relevant to strong adhesion feature the O- silica site and Ca2+ in the presence of associated Cl-, which gain prevalence at higher CaCl2 concentration. Our simulations also predict the adhesion force profile to be distinct for CaCl2 compared with the other electrolytes. Together, these analyses explain our experimental data. Our findings indicate in general how silica wettability may be manipulated by electrolyte concentration.

Prebiotic RNA polymerisation: energetics of nucleotide adsorption and polymerisation on clay mineral surfaces.

We measured the binding energy and bonding parameters between model nucleotide functional groups and model clay mineral surfaces in solutions of acidic pH. We demonstrate that basal surfaces of clay minerals interact most strongly with nucleobases and show that the adsorption of the phosphate group to clay edges could facilitate polymerisation. Our results suggest that Al- and Fe-rich edge sites behave similarly in nucleotide polymerisation through change of the phosphodiester bond strength. We present an internally consistent set of thermodynamic parameters that represent the nucleotide-clay mineral system.

The effect of ionic strength on oil adhesion in sandstone--the search for the low salinity mechanism.

Core flood and field tests have demonstrated that decreasing injection water salinity increases oil recovery from sandstone reservoirs. However, the microscopic mechanism behind the effect is still under debate. One hypothesis is that as salinity decreases, expansion of the electrical double layer decreases attraction between organic molecules and pore surfaces. We have developed a method that uses atomic force microscopy (AFM) in chemical force mapping (CFM) mode to explore the relationship between wettability and salinity. We functionalised AFM tips with alkanes and used them to represent tiny nonpolar oil droplets. In repeated measurements, we brought our "oil" close to the surface of sand grains taken from core plugs and we measured the adhesion between the tip and sample. Adhesion was constant in high salinity solutions but below a threshold of 5,000 to 8,000 ppm, adhesion decreased as salinity decreased, rendering the surface less oil wet. The effect was consistent, reproducible and reversible. The threshold for the onset of low salinity response fits remarkably well with observations from core plug experiments and field tests. The results demonstrate that the electric double layer force always contributes at least in part to the low salinity effect, decreasing oil wettability when salinity is low.

Langmuir and Langmuir-Blodgett films of amphiphilic hexa-peri-hexabenzocoronene: new phase transitions and electronic properties controlled by pressure.

We present the synthesis as well as the structural and electronic properties of an amphiphilic derivative of hexaalkylhexa-peri-hexabenzocoronene (HBC), which contains one alkyl substituent that is terminated with a carboxylic acid group. The molecules form well-defined Langmuir films when spread from a solution at the air-water interface. Grazing-incidence X-ray diffraction (GIXD) and X-ray reflectivity studies of the Langmuir monolayer reveal two crystallographic phases at room temperature which depend on the surface pressure applied to the film. Scattering from very well-ordered (zeta = 200-400 A) pi-stacked lamellae of HBC molecules tilted approximately 45 degrees relative to the surface normal is observed in the low-pressure phase. In this phase, the HBC molecules pack in a rectangular two-dimensional unit cell with a = 22.95 A and b = 4.94 A. In the high-pressure phase, coherence from the pi stack is lost. This is a consequence of stress induced by the crystallization of the substituent alkyl chains into a hexagonal lattice, which has a trimerized superstructure in one direction: a = 3 x b = 15.78 A, b = 5.26 A, gamma = 120 degrees, A = 71.9 A2 = 3 x 23.9 A2. Thin monolayer films can be transferred to solid supports by the Langmuir-Blodgett (LB) technique. Atomic force microscopy (AFM) with atomic resolution reveals the crystalline packing of alkyl chains in the high-pressure phase. Kelvin force microscopy (KFM) shows a clear potential difference between the high- and low-pressure phases. This is discussed in terms of orbital delocalization (band formation) in the highly coherent low-pressure phase, which is in contrast to the localized molecular orbitals present in the high-pressure phase. The highly coherent pi stack is expected to sustain a very high charge-carrier mobility.