Two synthetic goethites of varying crystal size distributions were analyzed by BET, conventional TEM, cryo-TEM, atomic resolution STEM and HRTEM, and electron tomography in order to determine the effects of crystal size, shape, and atomic scale surface roughness on their adsorption capacities. The two samples were determined by BET to have very different site densities based on CrVI adsorption experiments. Model specific surface areas generated from TEM observations showed that, based on size and shape, there should be little difference in their adsorption capacities. Electron tomography revealed that both samples crystallized with an asymmetric {101} tablet habit. STEM and HRTEM images showed a significant increase in atomic-scale surface roughness of the larger goethite. This difference in roughness was quantified based on measurements of relative abundances of crystal faces {101} and {201} for the two goethites, and a reactive surface site density was calculated for each goethite. Singly coordinated sites on face {210} are 2.5 more dense than on face {101}, and the larger goethite showed an average total of 36% {210} as compared to 14% for the smaller goethite. This difference explains the considerably larger adsorption capacitiy of the larger goethite vs the smaller sample and points toward the necessity of knowing the atomic scale surface structure in predicting mineral adsorption processes.

Crystal surfaces provide physical interfaces between the geosphere and biosphere. It follows that the arrangement of atoms at the surfaces of crystals profoundly influences biological components at many levels, from cells through biopolymers to single organic molecules. Many studies have focused on the crystal–molecule interface in water using large, flat single crystals. However, little is known about atomic-scale surface structures of the nanometer- to micrometer-sized crystals of simple metal oxides typically used in batch adsorption experiments under conditions relevant to biogeochemistry and the origins of life. Here, we present atomic-resolution microscopy data with unprecedented detail of the circumferences of nanosized rutile (α-TiO2) crystals previously used in studies of the adsorption of protons, cations, and amino acids. The data suggest that one-third of the {110} faces, the largest faces on individual crystals, consist of steps at the atomic scale. The steps have the orientation to provide undercoordinated Ti atoms of the type and abundance for adsorption of amino acids as inferred from previous surface complexation modeling of batch adsorption data. A remarkably uniform pattern of step proportions emerges: the step proportions are independent of surface roughness and reflect their relative surface energies. Consequently, the external morphology of rutile nanometer- to micrometer-sized crystals imaged at the coarse scale of scanning electron microscope images is not an accurate indicator of the atomic smoothness or of the proportions of the steps present. Overall, our data strongly suggest that amino acids attach at these steps on the {110} surfaces of rutile.

Manganese (Mn) oxides are among the strongest mineral oxidants in the environment and impose significant influence on mobility and bioavailability of redox-active substances, such as arsenic, chromium, and pharmaceutical products, through oxidation processes. Oxidizing potentials of Mn oxides are determined by Mn valence states (2+, 3+, 4+). In this study, the effects of beam damage during electron energy-loss spectroscopy (EELS) in the transmission electron microscope have been investigated to determine the “safe dose” of electrons. Time series analyses determined the safe dose fluence (electrons/nm2) for todorokite (106 e/nm2), acid birnessite (105), triclinic birnessite (104), randomly stacked birnessite (103), and δ-MnO2 (<103) at 200 kV. The results show that meaningful estimates of the mean Mn valence can be acquired by EELS if proper care is taken.

The nature of Ni-hydroxide precipitates on pyrophyllite were re-examined by analytical electron microscopy (AEM), high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), powder X-ray diffraction (PXRD), and extended X-ray absorption fine structure (EXAFS) spectroscopy. Chemical analysis of precipitates showed that the precipitate contains about 20% Al. HRTEM imaging showed that the precipitate was amorphous and PXRD failed to find any crystalline peaks associated with crystalline Ni−Al layered double-hydroxide (LDH) or α-Ni(OH)2. These results confirmed the conclusion from EXAFS spectroscopic data that Al coprecipitated with Ni on Al-rich substrates to form Ni−Al LDH surface precipitates. However, the HRTEM data clarifies that although the bonding environment of the precipitate is like that of Ni−Al LDH, no long-range ordering of the structure exists. The study illustrates the need for TEM observations to complement EXAFS data and the potential importance of amorphous materials in environmental settings.

Increasing evidence suggests that the physicochemical properties of inhaled nanoparticles influence the resulting toxicokinetics and toxicodynamics. This report presents a method using scanning transmission electron microscopy (STEM) to measure the Mn content throughout the primary particle size distribution of welding fume particle samples collected on filters for application in exposure assessment and health research. Dark field images were collected to assess the primary particle size distribution and energy-dispersive X-ray and electron energy loss spectroscopy were performed for measurement of Mn composition as a function of primary particle size. A manual method incorporating imaging software was used to measure the primary particle diameter and to select an integration region for compositional analysis within primary particles throughout the size range. To explore the variation in the developed metric, the method was applied to 10 gas metal arc welding (GMAW) fume particle samples of mild steel that were collected under a variety of conditions. The range of Mn composition by particle size was −0.10 to 0.19%/nm, where a positive estimate indicates greater relative abundance of Mn increasing with primary particle size and a negative estimate conversely indicates decreasing Mn content with size. However, the estimate was only statistically significant (p<0.05) in half of the samples (n=5), which all had a positive estimate. In the remaining samples, no significant trend was measured. Our findings indicate that the method is reproducible and that differences in the abundance of Mn by primary particle size among welding fume samples can be detected.Highlights► First quantitative method for measuring Mn composition by primary particle size in welding fume. ► The primary particle count median diameter ranged between 3.2 and 9.8 nm in welding fume samples. ► Five of ten welding fume samples had a positive trend of Mn composition by primary particle size.