Analysis and characterization of naturally occurring and engineered nanomaterials in the environment are critical for understanding their environmental behaviors and defining real exposure scenarios for environmental risk assessment. However, this is challenging primarily due to the low concentration, structural heterogeneity, and dynamic transformation of nanomaterials in complex environmental matrices. In this critical review, we first summarize sample pretreatment methods developed for separation and preconcentration of nanomaterials from environmental samples, including natural waters, wastewater, soils, sediments, and biological media. Then, we review the state-of-the-art microscopic, spectroscopic, mass spectrometric, electrochemical, and size-fractionation methods for determination of mass and number abundance, as well as the morphological, compositional, and structural properties of nanomaterials, with discussion on their advantages and limitations. Despite recent advances in detecting and characterizing nanomaterials in the environment, challenges remain to improve the analytical sensitivity and resolution and to expand the method applications. It is important to develop methods for simultaneous determination of multifaceted nanomaterial properties for in situ analysis and characterization of nanomaterials under dynamic environmental conditions and for detection of nanoscale contaminants of emerging concern (e.g., nanoplastics and biological nanoparticles), which will greatly facilitate the standardization of nanomaterial analysis and characterization methods for environmental samples.

Iron sulfide nanoparticles (nano-FeS) have shown great potential for in situ remediation of Cr(VI) pollution by reducing Cr(VI) to the less soluble and toxic Cr(III). However, material oxidation that inevitably occurs during storage and application alters its reactivity. Herein, we show that partial oxidation of nanoparticulate mackinawite (FeS) significantly enhances its capability in sequestering Cr(VI). Oxidation of nano-FeS increases its binding affinity to Cr(VI), likely due to preferential inner-sphere complexation of Cr(VI) oxyanions to ferric over ferrous iron in mackinawite/lepidocrocite (FeS/γ-FeOOH) nanocomposites. A trade-off is that oxidation mitigates Cr(VI) reduction by lowering the electron-donating potential of the material and the electron transfer at a solution−material interface and consequently hinders the transformation of adsorbed Cr(VI) to Cr(III). Notably, the rate-limiting step of Cr(VI) sequestration transitions from adsorption to reduction during oxidation, as demonstrated with batch experiments coupled with kinetic modeling. Thus, an optimum oxidation degree exists, wherein the gain in the overall performance from enhanced adsorption overcompensates the loss from inhibited reduction, resulting in maximum sequestration of aqueous Cr(VI) as solid-phase Cr(III). Our findings inform better assessment and design of nanomaterials for Cr(VI) remediation and may be extended to interactions of other oxyanions with natural and engineered nanoparticles during oxidative aging.

No abstract

Nanoplastics are an increasing environmental concern. In aquatic environments, nanoplastics will acquire an eco-corona by interacting with macromolecules (e.g., humic substances and extracellular polymeric substances (EPS)). Here, we show that the properties of the eco-corona and, consequently, its ability to enhance the transport of nanoplastics vary significantly with the surface functionality of nanoplastics and sources of macromolecules. The eco-corona derived from the EPS of Gram-negative Escherichia coli MG1655 enhances the transport of polystyrene (PS) nanospheres in saturated porous media to a much greater extent than the eco-corona derived from soil humic acid and fulvic acid. In comparison, the eco-corona from all three sources significantly enhance the transport of carboxylated PS (HOOC-PS). We show that the eco-corona inhibits the deposition of the two types of nanoplastics to the porous media mainly via steric repulsion. Accordingly, an eco-corona consisting of a higher mass of larger-sized macromolecules is generally more effective in enhancing transport. Notably, HOOC-PS tends to acquire macromolecules of lower hydrophobicity than PS. The more disordered and flexible structures of such macromolecules may result in greater elastic repulsion between the nanoplastics and sand grains and, consequently, greater transport enhancement. The findings of this study highlight the critical role of eco-corona formation in regulating the mobility of nanoplastics, as well as the complexity of this process.

Due to the extremely low solubility, mercury sulfide minerals, as the major environmental mercury sinks, are generally considered to be inert mercury species with minimal bioavailability. Here, we demonstrate that...