Thematic Articles

Biogenic uraninite is of interest to geoscientists for its importance to bioremediation strategies, remarkably small particle size, and biological origin. Recent studies have begun to illuminate the chemical/structural complexities of this important natural nanomaterial. Intriguingly, in spite of its incredibly diminutive size, the molecular-scale structure, energetics, and surfacearea-normalized dissolution rates of hydrated biogenic uraninite appear to be similar to those of coarser-particle, abiotic, stoichiometric UO2. These findings have important implications for the role of size as a moderator of nanoparticle aqueous reactivity and for the bioremediation of subsurface U (VI) contamination.

Topsoils are often contaminated by trace metals, and it is important to understand how different processes govern the transport of such metals to fresh and marine waters. This paper presents measurements of natural nanoparticles and colloidal organic matter in soil and river samples from Germany and Sweden. In our analytical approach, a nanoparticle separation technique is combined with multielement detection and applied to soil and river samples to link the macroscale field observations with detailed molecular studies in the laboratory. It was determined that lead is associated with iron oxide colloids, which are ubiquitous nanoparticles that can be efficiently transported. Eventually both iron oxides and lead are removed by flocculation under conditions of estuarine mixing. Iron-rich nanoparticles compete efficiently with natural organic matter (NOM) complexation for lead binding in both the soil and river systems studied.

Soils contain many kinds of inorganic and organic particles with at least one dimension in the nanoscale or colloidal range (<100 nm). Well-known examples are clay minerals, metal (hydr)oxides, and humic substances, while allophane and imogolite are abundant in volcanic soils. Apparently, only a small proportion of nanoparticles in soil occur as discrete entities. Organic colloids in soil, for example, are largely associated with their inorganic counterparts or form coatings over mineral surfaces. For this reason, individual nanoparticles are difficult to separate and collect from the bulk soil, and extraction yields are generally low. By the same token, the characterization of soil nanoparticles often requires advanced analytical and spectroscopic techniques. Because of their large surface area and the presence of surface defects and dislocations, nanoparticles in soil are very reactive towards external solute molecules. The focus of research in recent years has been on the interactions of nanoparticles with environmental pollutants and on their impact on the movement, fate, and bioavailability of contaminants.><100 nm). Well-known examples are clay minerals, metal (hydr) oxides, and humic substances, while allophane and imogolite are abundant in volcanic soils. Apparently, only a small proportion of nanoparticles in soil occur as discrete entities. Organic colloids in soil, for example, are largely associated with their inorganic counterparts or form coatings over mineral surfaces. For this reason, individual nanoparticles are difficult to separate and collect from the bulk soil, and extraction yields are generally low. By the same token, the characterization of soil nanoparticles often requires advanced analytical and spectroscopic techniques. Because of their large surface area and the presence of surface defects and dislocations, nanoparticles in soil are very reactive towards external solute molecules. The focus of research in recent years has been on the interactions of nanoparticles with environmental pollutants and on their impact on the movement, fate, and bioavailability of contaminants.

The most continuous and intimate contact the average person has with nanoparticles is almost surely through the air, which is replete with them. Nanoparticles are being generated continuously and in large numbers by vehicles and industries in urban areas and by vegetation and sea spray in rural areas. Volcanoes are sporadic sources of huge numbers. Nanoparticles have large surface area to volume ratios and react rapidly in the atmosphere, commonly growing into particles large enough to interact with radiation and to have serious consequences for visibility and local, regional, and global climate. They also have potentially significant health effects.

Nanoparticle properties can show marked departures from their bulk analog materials, including large differences in chemical reactivity, molecular and electronic structure, and mechanical behavior. The greatest changes are expected at the smallest sizes, e.g. 10 nanometers and less, where surface effects are likely to dominate bonding, shape, and energy considerations. The precise chemistry at nanoparticle interfaces can have a profound effect on structure, phase transformations, strain, and reactivity. Certain phases may exist only as nanoparticles, requiring transformations in chemistry, stoichiometry, and structure with evolution to larger sizes. In general, mineral nanoparticles have been little studied.

At first glance, nano and Earth seem about as far apart as one can imagine. Nanogeoscience seems to be a word connecting opposites. But to a growing number of Earth scientists, this term makes sense. Although relatively difficult to detect and study, natural nanomaterials are ubiquitous in nature. Their properties are often different (sometimes dramatically different) from those of the same material at a larger size. In many cases, larger equivalents do not even exist. By understanding natural nanomaterials, we can acquire another perspective from which to view Earth’s chemical and physical properties. Important insights into local, regional, and even global phenomena await our understanding of processes that are relevant at the smallest scales of Earth science research.