Interactions within natural soils have often been neglected when assessing fate and bioavailability of engineered nanomaterials (ENM) in soils. This review combines patchwise ENM research using natural soils with the much wider literature on ENM performed in standard tests or on the fate of colloids in soils, and an analysis of the diverse ENM characteristics determining availability from the soil organisms’ perspective to assess the main soil characteristics that determine the fate, speciation, and ultimately bioavailability of ENM in natural soils. Predominantly salinity, texture, pH, concentration, and nature of mobile organic compounds and degree of saturation determine ENM bioavailability.

Fate and Bioavailability of Engineered Nanoparticles in Soils: A Review

The most emerging branch of science during the last decade is nanoscience and nanotechnology. Metallic nanoparticles (NPs) have a great role in many scientific fields such as medicine, physics, mechanics, pharmaceutics, and others. In the last few years, scientists found great potential in metal NPs synthesis and applications and even used different spectroscopic or microscopic characterization methods. This book chapter covers the concept behind metal NPs, the advantages and role of metal NPs in pharmaceutical systems, and will focus on the synthetic methods for the production of different metal NPs by using physical, chemical, and biological approaches; allied characterization techniques including spectroscopic, microscopic, and physiochemical techniques; and the applications in medical technology of metal NPs including applications in drug, protein, peptide, and gene delivery; tissue engineering; enzymology; surface coating; biosensing devices; diagnostics and theranostics; in addition to many other applications, concluding with metal NPs’ future potential.

Synthesis, Characterization, and Applications of Metal Nanoparticles

The production and use of nanoparticles (NP) has steadily increased within the last decade; however, knowledge about risks of NP to human health and ecosystems is still scarce. Common knowledge concerning NP effects on freshwater organisms is largely limited to standard short-term (≤48 h) toxicity tests, which lack both NP fate characterization and an understanding of the mechanisms underlying toxicity. Employing slightly longer exposure times (72 to 96 h), we found that suspensions of nanosized (∼100 nm initial mean diameter) titanium dioxide (nTiO2) led to toxicity in Daphnia magna at nominal concentrations of 3.8 (72-h EC50) and 0.73 mg/L (96-h EC50). However, nTiO2 disappeared quickly from the ISO-medium water phase, resulting in toxicity levels as low as 0.24 mg/L (96-h EC50) based on measured concentrations. Moreover, we showed that nTiO2 (∼100 nm) is significantly more toxic than non-nanosized TiO2 (∼200 nm) prepared from the same stock suspension. Most importantly, we hypothesized a mechanistic chain of events for nTiO2 toxicity in D. magna that involves the coating of the organism surface with nTiO2 combined with a molting disruption. Neonate D. magna (≤6 h) exposed to 2 mg/L nTiO2 exhibited a “biological surface coating” that disappeared within 36 h, during which the first molting was successfully managed by 100% of the exposed organisms. Continued exposure up to 96 h led to a renewed formation of the surface coating and significantly reduced the molting rate to 10%, resulting in 90% mortality. Because coating of aquatic organisms by manmade NP might be ubiquitous in nature, this form of physical NP toxicity might result in widespread negative impacts on environmental health.

/pdf/biological-surface-coating-and-molting-inhibition-as-h8a0acf6tr.pdf

Biological surface coating and molting inhibition as mechanisms of TiO2 nanoparticle toxicity in Daphnia magna.

Understanding the fate and biological effects of Ag- and TiO2-nanoparticles in the environment: The quest for advanced analytics and interdisciplinary concepts

Validated and easily applicable analytical tools are required to develop and implement regulatory frameworks and an appropriate risk assessment for engineered nanoparticles (ENPs). Concerning metal-based ENPs, two main aspects are the quantification of the absolute mass concentration and of the “dissolved” fraction in, e.g., (eco)toxicity and environmental studies. To provide information on preparative aspects and on potential uncertainties, preferably simple off-line methods were compared to determine (1) the total concentration of suspensions of five metal-based ENP materials (Ag, TiO2, CeO2, ZnO, and Au; two sizes), and (2) six methods to quantify the “dissolved” fraction of an Ag ENP suspension. Focusing on inductively coupled plasma–mass spectrometry, the total concentration of the ENP suspensions was determined by direct measurement, after acidification and after microwave-assisted digestion. Except for Au 10 nm, the total concentrations determined by direct measurements were clearly lower than those measured after digestion (between 61.1 % for Au 200 nm and 93.7 % for ZnO). In general, acidified suspensions delivered better recoveries from 89.3 % (ZnO) to 99.3 % (Ag). For the quantification of dissolved fractions two filtration methods (ultrafiltration and tangential flow filtration), centrifugation and ion selective electrode were mainly appropriate with certain limitations, while dialysis and cloud point extraction cannot be recommended. With respect to precision, time consumption, applicability, as well as to economic demands, ultrafiltration in combination with microwave digestion was identified as best practice.

/pdf/icp-ms-based-characterization-of-inorganic-nanoparticles-4l0xdkr89v.pdf

ICP-MS-based characterization of inorganic nanoparticles—sample preparation and off-line fractionation strategies

The pore water transport of antimony and titanium, applied as nanoparticles (NPs), was studied by spiking stable suspensions of two different nanomaterials on the surface of an undisturbed floodplain soil. For preparation of stable dispersions, two different strategies were followed. (i) Comparable to those used in industrial applications: titanium dioxide nanoparticles, with an average diameter of 99 nm, were prepared by high-energy ball milling in water, whereas for (ii) antimony trioxide (Sb2O3; average diameter 121 nm) a dispersing agent (sodium salt of poly[(naphthaleneformaldehyde)sulfonate] (pNFS) in water) was used. The upper 17 cm of a floodplain soil (river Rhine, Germany) was sampled using the minimally invasive sediment or fauna incubation experiment (SOFIE® two compartment cell; 3 l volume each), which preserved the pore system of the soil. The cells were equipped with 450 and 100 nm filter probes at different depths providing a non-invasive sampling of the pore water. The pore water was sampled at different times (T = 0, 24, 48, 96 and 196 h) and analysed by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS). Sb and Ti were transported via the pore water of the floodplain soil to a depth of 14 cm, corresponding to the maximum cell depth. The highest Sb concentration in the pore water was detected after 24 h at a depth of 5.5–8 cm. Although the spiked concentration was higher for Ti than for Sb, the total Ti concentration in the pore water of the spiked cell was lower. This indicates a stronger agglomeration of TiO2 NPs or a more intensive interaction of Ti with the solid matrix and a faster transport of Sb towards deeper soil layers. The results show that metal(loid)s from metal oxide NPs are transported in the soil pore water and, hence, have the potential to act as the source of contamination of deeper soil layers after soil surface contamination.

Translocation of Sb and Ti in an undisturbed floodplain soil after application of Sb2O3 and TiO2 nanoparticles to the surface.

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Translocation of Sb and Ti in an undisturbed floodplain soil after application of Sb2O3 and TiO2 nanoparticles to the surface.