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Terrestrial reactive oxygen species (ROS) may have played a central role in the formation of oxic environments and evolution of early life. The abiotic origin of ROS on the Archean Earth has been heavily studied, and ROS are conventionally thought to have originated from H2O/CO2 dissociation. Here, we report experiments that lead to a mineral-based source of oxygen, rather than water alone. The mechanism involves ROS generation at abraded mineral–water interfaces in various geodynamic processes (e.g., water currents and earthquakes) which are active where free electrons are created via open-shell electrons and point defects, high pressure, water/ice interactions, and combinations of these processes. The experiments reported here show that quartz or silicate minerals may produce reactive oxygen-containing sites (≡SiO•, ≡SiOO•) that initially emerge in cleaving Si–O bonds in silicates and generate ROS during contact with water. Experimental isotope-labeling experiments show that the hydroxylation of the peroxy radical (≡SiOO•) is the predominant pathway for H2O2 generation. This heterogeneous ROS production chemistry allows the transfer of oxygen atoms between water and rocks and alters their isotopic compositions. This process may be pervasive in the natural environment, and mineral-based production of H2O2 and accompanying O2 could occur on Earth and potentially on other terrestrial planets, providing initial oxidants and free oxygen, and be a component in the evolution of life and planetary habitability. [ABSTRACT FROM AUTHOR]

Ferric ions can bind strongly with dissolved organic matter (DOM), including humic acids (HA), fulvic acids (FA), and protein-like substances, whereas isolation of Fe-DOM precipitates (Fe-DOMP) and their biochemical characteristics remain unclear. In this work FeCl3 was used to isolate DOM components from various sources, including river, lake, soil, cow dung, and standard tryptophan and tyrosine, through precipitation at pH 7.5–8.5. The Fe-DOMP contribute to total DOM by approximately 38.6–93.8% of FA, 76.2% of HA and 25.0–30.4% of tryptophan and tyrosine, whilst fluorescence spectra allowed to monitor/discriminate the various DOM fractions in the samples. The relative intensity of the main infrared peaks such as 3406‒3383 cm−1 (aromatic OH), 1689‒1635 cm−1 (‒COOH), 1523–1504 cm−1 (amide) and 1176–1033 cm−1 (‒S=O) show either to decline or disappear in Fe‒DOMP. These results suggest the occurrence of Fe bonds with various functional groups of DOM, indicating the formation of π–d electron bonding systems of different strengths in Fe‒DOMP. The novel method used for isolation of Fe-DOMP shows promising in opening a new frontier both at laboratory and industrial purposes. Furthermore, results obtained may provide a better understanding of metal–organic complexes involved in the regulation of the long-term stabilization/sequestration of DOM in soils and waters. [ABSTRACT FROM AUTHOR]

Soil plays an important role in controlling the biogeochemical cycling of nutrients and contaminants in the environment. Reliable analytical techniques are critical to better understand their transformation in soils. Diffusive Gradients in Thin-films technique (DGT) is one of such techniques, which has become increasingly popular in soil research since 1998. Undeniably, DGT attracts increasing attentions from multidisciplinary researchers worldwide. This is mainly due to its inherent merits, including ease of use, in situ measurement, and biomimetic applications. Further, four important aspects of DGT applications in soil research were summarized. They include: 1) chemical speciation, 2) bioavailability measurement, 3) desorption kinetic modeling, and 4) interfacial process mapping of nutrients and contaminants, with main focus on the progresses achieved during the past five years. In short, DGT is effective in studying the biochemical behaviors of nutrients (e.g., phosphate and nitrate), trace elements (e.g., Cd, Ni, Zn, Cu, Pb, and As), and polar organic compounds (e.g., antibiotics, pesticides, and bisphenols) in soils. Toward the end, we proposed several aspects of applying DGT as a versatile tool in soil research. [ABSTRACT FROM AUTHOR]

Since the invention of scanning tunneling microscopy (STM) in 1982 (1), a family of similar techniques known as scanning probe microscopy (SPM) has developed quickly into a powerful tool for […]

Calcite occurs widely as a mineral component in the exoskeletons and tissues of marine and freshwater invertebrates. Matrix macromolecules involved in regulating the biological growth of calcite in these organisms are known to share a carboxylic-rich character that arises from an abundance of the acidic amino acids aspartate (Asp) and glutamate (Glu). This study determines the interactions of Asp with calcite {1014} faces during dissolution using in situ fluid-cell atomic force microscopy (AFM) and macroscopic ex situ optical methods. In control experiments, etch-pit morphologies produced by dissolution in simple undersaturated solutions reflect the inherent symmetry of the {1014} faces with a rhombus form. With the introduction of Asp, surface site reactivities are modified to yield isosceles triangular etch pits and hillocks. With continued exposure to Asp-bearing solutions, these triangular pits coalesce and the surface evolves into a network of interconnected tetrahedral etch hillocks. The component tetrahedral 'sides' have Miller-Bravais indices of (0001), (1101), and (0111). These faces intersect the (1014) face in the [010], [451], and [411] directions to compose the three edges of the triangular etch pits. Structural and stereo-chemical contraints suggest that the (1101) and (0111) faces in the hillock are a combination of corresponding faces from the (1102) and (1100) crystallographic forms. Results of this dissolution study are consistent with previous growth experiments showing that Asp causes preferential development of the {0001} and possibly the {1100} forms of calcite. These observations support mechanisms proposing that the new forms are stabilized by the molecular recognition of Asp functional groups for specific surface sites. Because Asp stabilizes identical faces during growth and dissolution, we suggest that dissolution studies offer an alternative means of determining the crystal forms that develop during biomineralizing processes and a more direct means of identifying those surface sites involved. We demonstrate that the stability of crystallographic directions expressed by step edges is controlled by the relative reactivities of surface sites. Our findings yield new insights into surface structure controls on mineral reactivity.

Succinic acid (SUC) was used to react with calcite to better understand the aspartic (ASP)-calcite interfacial reaction. The results show that the amine group on ASP must be an active participant in surface binding and ASP differs from SUC only in the possession of the [alpha]-N[H.sub.2] group.