Root Uptake and Phytotoxicity of ZnO Nanoparticles

Increasing application of nanotechnology highlights the need to clarify nanotoxicity. However, few researches have focused on phytotoxicity of nanomaterials; it is unknown whether plants can uptake and transport nanoparticles. This study was to examine cell internalization and upward translocation of ZnO nanoparticles by Lolium perenne (ryegrass). The dissolution of ZnO nanoparticles and its contribution to the toxicity on ryegrass were also investigated. Zn2+ ions were used to compare and verify the root uptake and phytotoxicity of ZnO nanoparticles in a hydroponic culture system. The root uptake and phytotoxicity were visualized by light, scanning electron, and transmission electron microscopies. In the presence of ZnO nanoparticles, ryegrass biomass significantly reduced, root tips shrank, and root epidermal and cortical cells highly vacuolated or collapsed. Zn2+ ion concentrations in bulk nutrient solutions with ZnO nanoparticles were lower than the toxicity threshold of Zn2+ to the ryegrass; shoot Zn contents under ZnO nanoparticle treatments were much lower than that under Zn2+ treatments. Therefore, the phytotoxicity of ZnO nanoparticles was not directly from their limited dissolution in the bulk nutrient solution or rhizosphere. ZnO nanoparticles greatly adhered onto the root surface. Individual ZnO nanoparticles were observed present in apoplast and protoplast of the root endodermis and stele. However, translocation factors of Zn from root to shoot remained very low under ZnO nanoparticle treatments, and were much lower than that under Zn2+ treatments, implying that little (if any) ZnO nanoparticles could translocate up in the ryegrass in this study

Adsorption Mechanisms of Organic Chemicals on Carbon Nanotubes

Carbon nanotubes (CNTs) have drawn special research attention because of their unique properties and potential applications. This review summarizes the research progress of organic chemical adsorption on CNTs, and will provide useful information for CNT application and risk assessment. Adsorption heterogeneity and hysteresis are two widely recognized features of organic chemical−CNT interactions. However, because different mechanisms may act simultaneously, mainly hydrophobic interactions, π−π bonds, electrostatic interactions, and hydrogen bonds, the prediction of organic chemical adsorption on CNTs is not straightforward. The dominant adsorption mechanism is different for different types of organic chemicals (such as polar and nonpolar), thus different models may be needed to predict organic chemical−CNT interaction. Adsorption mechanisms will be better understood by investigating the effects of properties of both CNTs and organic chemicals along with environmental conditions. Another major factor affecting adsorption by CNTs is their suspendability, which also strongly affects their mobility, exposure, and risk in the environment. Therefore, organic chemical−CNT interactions as affected by CNT dispersion and suspending merit further experimental research. In addition, CNTs have potential applications in water treatment due to their adsorption characteristics. Thus column and pilot studies are needed to evaluate their performance and operational cost

Adsorption of Phenolic Compounds by Carbon Nanotubes: Role of Aromaticity and Substitution of Hydroxyl Groups

With increasing production and application of carbon nanotubes (CNTs), it becomes necessary to understand the interaction between CNTs and aromatic compounds, an important group of organic contaminants and structural components of large organic molecules in biological systems. However, so far few experimental studies have been conducted to systematically investigate the sorption mechanism of polar aromatics to CNTs. Therefore, cyclohexanol, phenol, catechol, pyrogallol, 2-phenylphenol, 1-naphthol, and naphthalene were selected to investigate the role of aromatic structure and -OH substitution in the polar aromatics-CNTs system. Sorption affinity of these compounds by CNTs increased with increasing number of aromatic rings, with an order of cyclohexanol < phenol <2-phenylphenol <1-naphthol, and was greatly enhanced by -OH substitution, with an order of phenol (1 -OH) < catechol (2 -OH) < pyrogallol (3 -OH). Four possible solute-sorbent interactions, i.e., hydrophobic effect, electrostatic interaction, hydrogen bonding, and π-π bonds, were discussed to address the underlying mechanism of the enhanced sorption affinity by -OH substitution. It was evident that electron-donating substitution on the aromatic rings strengthened the π-π interaction between the aromatics and CNTs and thus the adsorption affinity. These results will advance the understanding of the sorption behavior of CNTs in the environmental systems

Sorption of Organic Contaminants by Biopolymer-Derived Chars

Sorption of phenanthrene and naphthalene by chitin and cellulose, as well as these biopolymer-derived chars, was examined. Carbon contents were much higher in the chars than their respective biopolymers, and nitrogen was dramatically accumulated in the chitin-derived chars. After charring, sorption of these two compounds was greatly increased, which was attributed to the newly created surface area, porosity, and aromatic components. The aromatic carbon content of the biopolymer chars increased with an increase in the charring temperature. Sorption of phenanthrene and naphthalene to chitin and cellulose was dominated by partitioning. However, after charring, sorption of these two compounds became much more of an adsorption process, because of the newly created surfaces and micropores. The maximum mass sorption capacity of phenanthrene and naphthalene by the original biopolymers and their chars was positively correlated with their surface areas, suggesting that active sorption sites were largely on the surfaces of chars. At low solute concentrations, sorption of phenanthrene and naphthalene by biopolymer chars was dominated by the micropore-filling mechanism; with an increase in the solute concentration, sorption of these two compounds by biopolymer chars shifted to a surface-sorption-dominant process. The maximum mass sorption capacity and Kow-normalized sorption amount of phenanthrene were lower than those of naphthalene by the biopolymers and their chars, showing the influence of molecular dimension on sorption. This study demonstrates the significantly enhanced sorption of hydrophobic organic compounds by highly polar biopolymers through charring and the joint roles of surface area, porosity, and surface functionalities of biopolymer-derived chars in governing sorption

Importance of Structural Makeup of Biopolymers for Organic Contaminant Sorption

Sorption of pyrene, phenanthrene, naphthalene, and 1-naphthol by original (lignin, chitin, and cellulose) and coated biopolymers was examined. Organic carbon normalized distribution coefficients (Koc) of all compounds by the original biopolymers followed the order lignin > chitin > cellulose, in line with the order of their hydrophobicity. Hydrophobicity of structurally similar organic compounds is the main factor determining their ability to occupy sorption sites in biopolymers. Specific interactions (e.g., H-bonding) between 1-naphthol and chitin or cellulose increased its ability to occupy sorption sites. Lignin coating resulted in an increased Koc for phenanthrene (13.6 times for chitin and 6.9 times for cellulose) and 1-naphthol (6.0 times for chitin and 3.7 times for cellulose) relative to the acetone-treated chitin and cellulose. Also, these coated biopolymers had increased isotherm nonlinearity, due to the newly formed condensed domains. An increase in phenanthrene and 1-naphthol sorption by lignin-coated biopolymers as compared to chitin and cellulose was contributed by the newly created high-energy sites in condensed domains and coated lignin. Results of this study highlight the importance of the structural makeup of biopolymers in controlling the sorption of hydrophobic organic compounds

Humic Acid Fractionation upon Sequential Adsorption onto Goethite

Mineral−humic complexes are commonly distributed in natural environments and are important in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study investigated the structural and conformational changes of humic acid (HA) and mineral−HA complexes after sequential HA adsorption by goethite, using UV−visible spectroscopy, high performance size exclusion chromatography (HPSEC), Fourier transform infrared (FT-IR) spectroscopy, and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The HA remaining in the solution after adsorption showed low polarity index values ((N + O)/C), which indicates that polar functional moieties are likely to adsorb on the goethite surface. In addition, we observed decreased E4/E6 and E2/E3 ratios of unbound HA with increasing number of coatings, implying that aliphatic rich HA fractions with polar functional moieties readily adsorb to the goethite surface. According to IR spectra, carbohydrate carbon would be the important fractions associated with goethite. NMR spectra provided evidence for HA fractionation during adsorption onto the mineral surface; that is, aliphatic fractions were preferentially adsorbed by goethite while aromatic fractions were left in solution. Relatively small molecular weight (MW) HA fractions had a greater affinity for the goethite surface based on analyses of the HPSEC chromatograms, which differs from the results reported in the literature. Finally, our results suggest that the polar aliphatic fractions of HA were mainly adsorbed to goethite via electrostatic attraction and/or ligand exchange reactions

Sorption of Phenanthrene by Humic Acid-Coated Nanosized TiO₂ and ZnO

Phenanthrene sorption by nano-TiO2 and nano-ZnO particles was enhanced significantly by coated humic acids (HAs), implying that additional toxicity can be potentially given to these nano-oxides by adsorbed HOCs once released to the environment. Phenanthrene isotherms of adsorbed HA on nano-TiO2 and nano-ZnO were more nonlinear than that of their respective bulk HA. Both HA conformation changes and fractionation were observed upon HA adsorption on nano-TiO2 and nano-ZnO, which further affected phenanthrene sorption. Nano-TiO2 and nano-ZnO interacted with different functional groups of HA (i.e., phenolic OH with nano-TiO2, while COOH with nano-ZnO), leading to different conformations of adsorbed HA. Interaction of HA phenolic OH with nano-TiO2 increased the π-polarity/polarizability of adsorbed HA and, consequently, its phenanthrene adsorption affinity and isotherm nonlinearity. Interactions of COOH groups on HA aromatic rings with nano-ZnO would also increase the π-polarity/polarizability of adsorbed HA and its phenanthrene adsorption affinity, whereas interactions of COOH groups on HA aliphatic chains with nano-ZnO would make the adsorbed HA be in a more condensed state with lower partitioning affinity. Increase in adsorption and decrease in partitioning were responsible for the more nonlinear phenanthrene isotherms of adsorbed HA than bulk HA

Sorption and Conformational Characteristics of Reconstituted Plant Cuticular Waxes on Montmorillonite

Plant cuticular waxes are essential barriers that regulate the transport of water and organic molecules to intact cuticular membranes. They also compose a significant fraction of the recalcitrant aliphatic components of soil organic matter (SOM). In this study, we examined the sorption and desorption of three polycyclic aromatic hydrocarbons (PAHs), naphthalene (NAPH), phenanthrene (PHEN), and pyrene (PYR), by cuticular waxes of green pepper (Capsicum annuum) that had been reconstituted by loading them onto montmorillonite (at four different loadings). The reconstituted wax samples, with and without sorbed PAHs, were characterized by solid-state 13C NMR to supply the evidence of melting transition. The sorption isotherms fit well to a Freundlich equation. Sorption isotherms were practically linear except for that of PYR sorption to the low-load wax−montmorillonite sample. The organic-carbon-normalized sorption coefficients (Koc) depended on PAH's lipophilicity (e.g., octanol−water partition coefficient) and increased with increasing wax-load on clay. Desorption was dependent on PAH's molecular sizes and sorbed amounts and on the wax load of the clay. Desorption hysteresis was observed only at high loads of NAPH and PHEN, and it decreased with both increasing wax load and molecular size (i.e. NAPH > PHEN >> PYR). Contributing to hysteresis, the melting transition of the reconstituted waxes after sorbing the PAHs was confirmed by solid-state 13C NMR data. Upon adsorption, the intensity of the NMR peak at 29 ppm (attributed to mobile amorphous paraffinic domains) increased, and a peak at 167 ppm (−COOH) appeared, reflecting the transition of solid amorphous to mobile amorphous domains in the reconstituted waxes. The intensity of melting induced by PAH adsorption decreased with increasing PAH molecular size

Tannic Acid Adsorption and Its Role for Stabilizing Carbon Nanotube Suspensions

Dissolved organic matter (DOM) has been reported to stabilize carbon nanotube (CNT) suspensions, which increases concern over the subsequent transport and behavior of CNTs. However, it is unknown exactly which compounds or functional groups cause the stabilization of CNTs in natural environments. Naturally occurring tannic acid (TA), which has a large number of aromatic functional groups, was used as a surrogate of DOM to investigate its interaction with CNTs. CNT suspendability in TA solution increased with increasing CNT diameter without the aid of sonication. Sorption affinity of CNTs for TA increased with decreasing CNT diameter, positively related to their surface area. A two-stage sorption model was proposed to illustrate the interaction between CNTs and TA. TA molecules may be adsorbed first onto CNTs with aromatic rings binding to the surface carbon rings via π−π interactions, until forming a monolayer; the TA monolayer then further sorbed the dissolved TA by hydrogen bonds and other polar interactions. The sorbed TA increased the steric repulsion between individual CNTs, which might disperse the relatively loose CNT aggregates and result in the stabilization of large-diameter CNTs in TA solution. The sorption and suspending process were also examined by transmission electron microscopy, providing further evidence for the above proposed CNT−TA interactions. This study implies that widely distributed TA may promote the mobility and transport of CNTs in natural aqueous environments

Competitive and Complementary Adsorption of Bisphenol A and 17α-Ethinyl Estradiol on Carbon Nanomaterials

Competitive adsorption between organic chemicals is an important process affecting their environmental behavior and risk. Overlapping of adsorption sites between solutes was often emphasized in the literature. However, chemicals with different properties may complementarily occupy different sorption sites. The objective of this study was to test this hypothesis by collecting detailed information on competitive and accumulative adsorption of different chemicals on carbon nanomaterials (CNMs). Bisphenol A (BPA) and 17α-ethinyl estradiol (EE2) are different with regard to their hydrophobicity and molecular structures, and they were selected as model chemicals. The cumulative adsorption of both BPA and EE2 in bisolute adsorption experiments resulted in much higher total adsorption than in single-solute adsorption experiments. A new competitive−complementary adsorption concept was proposed. This information indicates that the modeling concept of competitive adsorption should be improved to better understand the fate and risk of both CNMs and organic chemicals