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The adsorption of dissolved organic matter (DOM) to metal (oxy)hydroxide mineral surfaces is a critical step for C sequestration in soils. Although equilibrium studies have described some of the factors controlling this process, the molecular-scale description of the adsorption process has been more limited. Chemical force spectroscopy revealed differing adhesion strengths of DOM extracted from three soils and a reference peat soil material to an iron (oxy)hydroxide mineral surface. The DOM was characterized using ultrahigh-resolution negative ion mode electrospray ionization Fourier Transform ion cyclotron resonance mass spectrometry. The results indicate that carboxyl-rich aromatic and N-containing aliphatic molecules of DOM are correlated with high adhesion forces. Increasing molecular mass was shown to decrease the adhesion force between the mineral surface and the DOM. Kendrick mass defect analysis suggests that mechanisms involving two carboxyl groups result in the most stable bond to the mineral surface. We conceptualize these results using a layer-by-layer "onion" model of organic matter stabilization on soil mineral surfaces.

Abstract: In this paper, a detailed study of the nucleation and growth of plasma assisted oxide coatings on model graphitic substrates has been performed. The surface chemistry and morphology of these films (as they grow on graphite) have been monitored using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). It is shown that oxide coatings start as islands having average height of 3–5 nm. The density and lateral size of these islands grow to form complete layers. Therefore complete and smooth coverage can be obtained with a film thickness in the range of a few nanometers (3–5 nm). The coating chemical composition is identical to SiO2. Detailed XPS analysis during overlayer growth reveals the presence of strong –Si–C– bonds at the graphite–coating interface. This is an important finding that can help to predict the mechanical, thermal and other functional properties of the interface. The durability of this coating at high operating temperatures has been investigated, and it is found to withstand up to 1000 °C heat treatments in argon environment. [Copyright &y& Elsevier]

Abstract: Plasma-assisted functional films have significant potential in various engineering applications. They can be tailored to impart desired properties by bonding specific molecular groups to the substrate surface. The aim of this investigation was to develop a fundamental understanding of the atomic level growth, coverage and functional effectiveness of plasma nano-films on flat surfaces and to explore their application-potential for complex and uneven shaped nano-materials. In this paper, results on plasma-assisted nano-scale fluorocarbon films, which are known for imparting inertness or hydrophobicity to the surface, will be discussed. The film deposition was studied as a function of time on flat single crystal surfaces of silicon, sapphire and graphite, using microwave plasma. X-ray photoelectron spectroscopy (XPS) was used for detailed study of composition and chemistry of the substrate and coating atoms, at all stages of deposition. Atomic force microscopy (AFM) was performed in parallel to study the coverage and growth morphology of these films at each stage. Combined XPS and AFM results indicated complete coverage of all the substrates at the nanometer scale. It was also shown that these films grew in a layer-by-layer fashion. The nano-films were also applied to complex and uneven shaped nano-structured and porous materials, such as microcellular porous foam and nano fibers. It was seen that these nano-films can be a viable approach for effective surface modification of complex or uneven shaped nano-materials. [Copyright &y& Elsevier]

Abstract: Cleaved surfaces of dolomite were studied using ex-situ X-ray photoelectron spectroscopy (XPS) following exposure of the surfaces to various experimental conditions. Dolomite samples exposed to air, to a highly undersaturated solution (0.1M NaCl, pH=9), and to solution with a supersaturation (−Δμ/kT) of 5.5 (pH=9) were investigated with semiquantitative methods of analysis to ascertain the degree of non-stoichiometry resulting at the dolomite surface from reactive conditions. It was found that the dolomite cleavage surface in undersaturated solution was not altered significantly from the stoichiometric surface termination. The composition of the cleaved surface after exposure to supersaturated solution, a surface known to have self-limiting growth characteristics under similar conditions, was found to be Ca2+ rich (Ca x Mg2− x (CO3)2, 1.7> x >1.3). The observations, while underscoring differences in hydration/dehydration kinetics of the two alkaline earth cations, suggest that achievement of equilibrium at dolomite–water interfaces may be subject to significant barriers from both undersaturated and supersaturated solutions. [Copyright &y& Elsevier]