Novel versatile nanomaterials may facilitate strategies for simultaneous soil remediation and agricultural production, but a thorough and mechanistic assessment of efficacy and safety is needed. We ...have established a new soil remediation strategy using nanoscale zero-valent iron (nZVI) coupled with safe rice production in paddy soil contaminated with pentachlorophenol (PCP). In comparison with rice cultivation in contaminated soil with 100 mg PCP per kg soil but without nZVI, the addition of 100 mg nZVI per kg soil increased grain yield by 47.1-55.0%, decreased grain PCP content by 83.6-86.2% and increased the soil PCP removal rate from 49.9 to 83.9-89.0%. The specific role of nZVI-derived root iron plaque formation in the safe production of rice has been elucidated, and the synergistic effect of nZVI treatment and rice cultivation identified in the nZVI-facilitated rhizosphere microbial degradation of PCP. This work opens a new strategy for the application of nanomaterials in soil remediation that could simultaneously enable safe crop production in contaminated lands.
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.
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.
Water chemistry can be a major factor regulating the toxicity mechanism of ZnO nanoparticles (nano-ZnO) in water. The effect of five commonly used aqueous media with various chemical properties on ...the toxicity of nano-ZnO to Escherichia coli O111 (E. coli) was investigated, including ultrapure water, 0.85% NaCl, phosphate-buffered saline (PBS), minimal Davis (MD), and Luria−Bertani (LB). Combined results of physicochemical characterization and antibacterial tests of nano-ZnO in the five media suggest that the toxicity of nano-ZnO is mainly due to the free zinc ions and labile zinc complexes. The toxicity of nano-ZnO in the five media deceased as follows: ultrapure water > NaCl > MD > LB > PBS. The generation of precipitates (Zn3(PO4)2 in PBS) and zinc complexes (of zinc with citrate and amino acids in MD and LB, respectively) dramatically decreased the concentration of Zn2+ ions, resulting in the lower toxicity in these media. Additionally, the isotonic and rich nutrient conditions improved the tolerance of E. coli to toxicants. Considering the dramatic difference of the toxicity of nano-ZnO in various aqueous media, the effect of water chemistry on the physicochemical properties of nanoparticles should be paid more attention in future nanotoxicity evaluations.
Understanding the movement of polycyclic aromatic hydrocarbons (PAHs) from emission sources to sediments is important for achieving long-term pollution control of PAHs in sediments. In this study, by ...exploring the correlation of individual PAHs concentrations (CPAHs) in Taihu Lake sediments reported in the past twenty years with their annual emissions (EPAHs) in the lake region, it was observed that mean concentrations of PAHs with low logKow (i.e., logKow≤4.00) in Taihu Lake sediments were correlated best with their emissions without lagging between the sediment sampling time and the PAHs emitting time. However, for PAHs with middle logKow (i.e., 4.00<logKow≤4.57) or high logKow (i.e., logKow>4.57), their mean concentrations in sediments were correlated best with the emissions of PAHs emitted 1 or 2 years before the sediment sampling time. The longer lagging time of PAHs with middle or high logKow from emission sources to lake sediments could be attributed to their retardation in soils and river sediments around the lake. Moreover, the retardation in soils and river sediments is dependent on PAHs logKow and degradation half-life, indicating the dependence of PAHs concentration in sediments on their environmental behaviors, including sorption and degradation. Kow dependent movement and the time lagging observed in Taihu Lake for PAHs from emission sources to sediments could be valuable for developing measures to control PAHs, especially for congeners with high logKow.
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•Time lagging for PAHs from emission to sediments observed.•Lagging of PAHs attributed to retarding on soils and river sediments.•PAHs retarding on soils and river sediments is dependent on their logKow.•Movement hysteresis of PAHs is valuable for controlling PAHs into sediments.
The increasing application of iron-based nanoparticles (NPs), especially high concentrations of zero-valent iron nanoparticles (nZVI), has raised concerns regarding their environmental behavior and ...potential ecological effects. In the environment, iron-based NPs undergo physical, chemical, and/or biological transformations as influenced by environmental factors such as pH, ions, dissolved oxygen, natural organic matter (NOM), and biotas. This review presents recent research advances on environmental transformations of iron-based NPs, and articulates their relationships with the observed toxicities. The type and extent of physical, chemical, and biological transformations, including aggregation, oxidation, and bio-reduction, depend on the properties of NPs and the receiving environment. Toxicities of iron-based NPs to bacteria, algae, fish, and plants are increasingly observed, which are evaluated with a particular focus on the underlying mechanisms. The toxicity of iron-based NPs is a function of their properties, tolerance of test organisms, and environmental conditions. Oxidative stress induced by reactive oxygen species is considered as the primary toxic mechanism of iron-based NPs. Factors influencing the toxicity of iron-based NPs are addressed and environmental transformations play a significant role, for example, surface oxidation or coating by NOM generally lowers the toxicity of nZVI. Research gaps and future directions are suggested with an aim to boost concerted research efforts on environmental transformations and toxicity of iron-based NPs, e.g., toxicity studies of transformed NPs in field, expansion of toxicity endpoints, and roles of laden contaminants and surface coating. This review will enhance our understanding of potential risks of iron-based NPs and proper uses of environmentally benign NPs.
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•Transformations of iron-based NPs are greatly affected by environmental conditions.•Toxic mechanisms are correlated to transformations of iron-based NPs.•Factors influencing the toxicity and impacts on various organisms are highlighted.•Future directions on transformation and toxicity of iron-based NPs are proposed.
Environmental transformations of iron-based NPs regulate their eco-toxicities.
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.
Plants need to be included to develop a comprehensive toxicity profile for nanoparticles. Effects of five types of nanoparticles (multi-walled carbon nanotube, aluminum, alumina, zinc, and zinc ...oxide) on seed germination and root growth of six higher plant species (radish, rape, ryegrass, lettuce, corn, and cucumber) were investigated. Seed germination was not affected except for the inhibition of nanoscale zinc (nano-Zn) on ryegrass and zinc oxide (nano-ZnO) on corn at 2000
mg/L. Inhibition on root growth varied greatly among nanoparticles and plants. Suspensions of 2000
mg/L nano-Zn or nano-ZnO practically terminated root elongation of the tested plant species. Fifty percent inhibitory concentrations (IC
50) of nano-Zn and nano-ZnO were estimated to be near 50
mg/L for radish, and about 20
mg/L for rape and ryegrass. The inhibition occurred during the seed incubation process rather than seed soaking stage. These results are significant in terms of use and disposal of engineered nanoparticles.
Engineered nanoparticles can inhibit the seed germination and root growth.
► A porous adsorbent, MIL-101, having huge Langmuir surface area of 5870
m
2/g and pore volume of 1.85
cm
3/g, was synthesized. ► We observed that MIL-101 is a potential superior adsorbent for the ...sorptive removal of VOCs. ► Adsorption of VOCs on MIL-101 is captured by a pore filling mechanism, showing the size and shape selectivity of molecules. ► There is a negative linear relationship between the volume adsorption capacity of VOCs and their molecular cross-sectional area. ► The size and shape selectivity of VOC molecules into MIL-101 pores is important in the application of MIL-101 as VOC adsorbent.
Adsorption of gaseous volatile organic compounds (VOCs) on metal–organic frameworks MIL-101, a novel porous adsorbent with extremely large Langmuir surface area of 5870
m
2/g and pore volume of 1.85
cm
3/g, and the influence of VOC molecular size and shape on adsorption were investigated in this study. We observed that MIL-101 is a potential superior adsorbent for the sorptive removal of VOCs including polar acetone and nonpolar benzene, toluene, ethylbeznene, and xylenes. MIL-101 is of higher adsorption capacities for all selected VOCs than zeolite, activated carbon and other reported adsorbents. Adsorption of VOCs on MIL-101 is captured by a pore filling mechanism, showing the size and shape selectivity of VOC molecules. These prove to be a negative linear relationship between the volume adsorption capacities of VOCs and their molecular cross-sectional area values. Most VOC molecules, such as acetone, benzene, toluene, ethylbenzene and p-xylene, enter into MIL-101 pores with the planes having the minimum diameters. However, m-xylene and o-xylene may fill into the pores with the planes having the maximum diameters because of the preferred interaction of MIL-101 with the two methyl groups of adsorbate molecules.
The dissolution of ZnO nanoparticles (nano-ZnO) plays an important role in the toxicity of nano-ZnO to the aquatic organisms. The effects of water chemistry such as pH, ionic components, and ...dissolved organic matter (DOM) on the dissolution of nano-ZnO and its toxicity to Escherichia coli (E. coli) were investigated in synthetic and natural water samples. The results showed that the toxicity of nano-ZnO to E. coli depended on not only free Zn2+ but also the coexisting cations which could reduce the toxicity of Zn2+. Increasing solution pH, HPO42−, and DOM reduced the concentration of free Zn2+ released from nano-ZnO, and thus lowered the toxicity of nano-ZnO. In addition, both Ca2+ and Mg2+ dramatically reduced the toxicity of Zn2+ to E. coli. These results highlight the importance of water chemistry on the toxicity evaluation of nano-ZnO in natural waters.
► The effects of water chemistry on the toxicity of nano-ZnO were investigated. ► Increasing solution pH, HPO42−, and DOM reduced nano-ZnO toxicity to E. coli. ► Ca2+ and Mg2+ could dramatically reduce the toxicity of nano-ZnO to E. coli. ► Free Zn2+ ions and water hardness together controlled nano-ZnO toxicity in waters.
The toxicity of nano-ZnO to E. coli depended on not only free Zn2+ but also Ca2+ and Mg2+ which could reduce the toxicity of Zn2+.
