Daohui Lin

Toxicity of ZnO Nanoparticles to Escherichia coli: Mechanism and the Influence of Medium Components

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 (Zn(3)(PO(4))(2) in PBS) and zinc complexes (of zinc with citrate and amino acids in MD and LB, respectively) dramatically decreased the concentration of Zn(2+) 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.

Interactions of Humic Acid with Nanosized Inorganic Oxides

Adsorption of natural organic matter (NOM) on nanoparticles (NPs) is important for evaluating their transport, transfer, and fate in the environment, which will also affect sorption of hydrophobic organic compounds (HOCs) by NPs and thereby potentially alter the toxicity of NPs and the fate, transport, and bioavailability of HOCs in the environment. Therefore, the adsorption behavior of humic acids (HA) by four types of nano-oxides (i.e., TiO2, SiO2, Al2O3, and ZnO) was examined in this study to explore their interaction mechanisms using techniques including Fourier transform infrared (FTIR) spectroscopy and elemental, zeta potential, and surface area analyses. Adsorption of HA was observed on nanosized TiO2, Al2O3, and ZnO but not on nano-SiO2. Furthermore, HA adsorption was pH-dependent. HA adsorption by nano-oxides was mainly induced by electrostatic attraction and ligand exchange between HA and nano-oxide surfaces. Surface hydrophilicity and negative charges of nano-oxides affected their adsorption of HA. However, the maxima of HA adsorption on nano-oxides were limited by the surface area of nano-oxides. HA phenolic OH and COOH groups were responsible for its ligand exchange with nano-TiO2 and nano-ZnO, respectively, while either HA COOH or HA phenolic/aliphatic OH was responsible for its ligand exchange with nano-Al2O3. HA adsorption decreased the micropore surface area of nano-oxides but not the external surface area because of the micropore blockage. HA adsorption also decreased the zeta potential of nano-oxides, indicating that HA-coated nano-oxides could be more easily dispersed and suspended and more stable in solution than uncoated ones because of their enhanced electrostatic repulsion.

Effects of water chemistry on the dissolution of ZnO nanoparticles and their toxicity to Escherichia coli.

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 Zn(2+) but also the coexisting cations which could reduce the toxicity of Zn(2+). Increasing solution pH, HPO(4)(2), and DOM reduced the concentration of free Zn(2+) released from nano-ZnO, and thus lowered the toxicity of nano-ZnO. In addition, both Ca(2+) and Mg(2+) dramatically reduced the toxicity of Zn(2+) to E. coli. These results highlight the importance of water chemistry on the toxicity evaluation of nano-ZnO in natural waters.

The influence of dissolved and surface-bound humic acid on the toxicity of TiO2 nanoparticles to Chlorella sp.

NOM is likely to coat TiO₂ nanoparticles (nano-TiO₂) discharged into the aquatic environment and influence the nanotoxicity to aquatic organisms, which however has not been well investigated. This study explored the influence of nanoparticle surface-bound humic acid (HA, as a model NOM) as well as dissolved HA on the toxicity of nano-TiO₂ to Chlorella sp., with a specific focus on adhesion of the nanoparticles to the algae. Results showed that nano-TiO₂ and the dissolved HA could inhibit the algal growth with an IC₅₀ of 4.9 and 8.4 mg L⁻¹, respectively, while both dissolved and nanoparticle surface-bound HA could significantly alleviate the algal toxicity of nano-TiO₂. IC₅₀ of nano-TiO₂ increased to 18 mg L⁻¹ in the presence of 5 mg L⁻¹ of the dissolved HA and to 48 mg L⁻¹ as the result of surface-saturation by HA. Co-precipitation experiment and transmission electron microscopy observation revealed that both dissolved and nanoparticle surface-bound HA prevented the adhesion of nano-TiO₂ to the algal cells due to the increased electrosteric repulsion. The generation of intracellular reactive oxygen species (ROS) was significantly limited by the dissolved and nanoparticle surface-bound HA. The prevention of adhesion and inhibition of ROS generation could account for the HA-mitigated nanotoxicity.

Adsorption of Triton X-series surfactants and its role in stabilizing multi-walled carbon nanotube suspensions

Surfactants can enhance the stabilization of carbon nanotubes (CNTs) in water through their adsorption, thus affecting the environmental behavior and application of CNTs. However, the quantitative relationship between adsorption and stabilization and the role of the surfactant structure in the surfactant-CNT interactions are largely unknown. Therefore, Triton X-series surfactants with a same hydrophobic functional group (4-(1,1,3,3-tetramethylbutyl)-phenyl) and different hydrophilic polyethoxyl chain lengths were selected to investigate their adsorption onto CNTs and their ability to stabilize CNT suspensions. Adsorption data were fitted well by Langmuir equation, indicating monolayer coverage on CNTs. Adsorption capacities of the surfactants increased with decreasing hydrophilic chain length: Triton-305<Triton-165<Triton-114<Triton-100. Electrostatic interaction and hydrogen bond could be excluded as the main mechanism because adsorption was not significantly affected by pH change. Hydrophobic and pi-pi interactions between the surfactants and CNTs were the dominant mechanism for their adsorption. CNT suspension data were well fitted to a nonlinear equation with a similar form to the Langmuir equation. Suspended CNT amounts in water were positively related to the adsorption capacities of the surfactants, but negatively with the hydrophilic fraction ratio of the X-series surfactants.

Metal impurities dominate the sorption of a commercially available carbon nanotube for Pb(II) from water.

Numerous studies suggested carbon nanotubes (CNTs) as a type of promising sorbent for heavy metals from water and explained the sorption mechanism mainly by oxygen-containing functional groups on CNT surfaces but neglected the potential role of metal catalyst residues in CNTs. This is a first study showing that metal impurities could dominate the sorption of one type of commercially available CNTs (P-CNTs) for Pb(II) from water, which will help to understand and guide environmental applications of CNTs as a sorbent. Sorption capacity of P-CNTs (27.3 mg g(-1)) for Pb(II) was much higher than that of the water-washed P-CNTs (W-CNTs, 4.7 mg g(-1)). SEM-EDS and ICP-MS analyses showed that both P-CNTs and W-CNTs contained metal impurities (mainly Co and Mo) which released into the solutions during the sorption, especially P-CNTs. XAFS examination and precipitation experiments demonstrated that PbMoO(4) formation between Pb(II) and CNT-released MoO(4)(2-) and subsequent precipitation in the sorptive solutions was the dominant mechanism for the apparent sorption of Pb(II) by P-CNTs.

Different stabilities of multiwalled carbon nanotubes in fresh surface water samples.

The stability of multiwalled carbon nanotubes (MWNTs) in particulate aggregates and surfactant-facilitated suspensions after being mixed into eight types of fresh surface water samples was investigated. MWNTs in particulate aggregates could not be stabilized in any of the water samples except for the one having relatively high content of dissolved organic matter with the aid of sonication. Sodium dodecyl benzenesulfonate (SDBS), polyethylene glycol octylphenyl ether (TX100) and cetyltrimethyl ammonium bromide (CTAB) were used to prepare MWNT suspensions. SDBS- and TX100-stabilized MWNTs could partly remain suspending after being mixed into the water samples, whereas CTAB-stabilized MWNTs readily sedimentated due to the surface charge neutralization by the surface water contained negatively-charged anions and colloids. This is a first systematic study examining the stability of carbon nanotubes in natural surface waters, the results from which will be useful for understanding the transport, fate and ecological effect of carbon nanotubes in the aqueous environment.

Surface-bound humic acid increased Pb2+ sorption on carbon nanotubes

Solid humic acid (HA) particles were dissolved and subsequently coated on a type of multiwalled carbon nanotubes (MWCNTs). Pb(2+) sorption from water by the solid HA, the MWCNTs and the obtained HA-MWCNT complexes was compared. The underlying mechanism of the difference in the sorption was discussed with the data at different pHs, results of desorption in the presence and absence of Ca(2+) and the characterizations using inductively coupled plasma mass spectrometry, X-ray energy dispersion spectroscopy and X-ray absorption fine structure spectroscopy. The effect of MWCNT-contained impurities on the sorption was also examined. It was shown that the surface-bound HA introduced oxygen-containing functional groups and negative charges on the MWCNTs, thus greatly increasing Pb(2+) sorption on the MWCNTs. Pb(2+) could be electrostatically attracted into outer-sphere of the electric double layer of the HA-MWCNT complexes, a fraction of which would form coordination complexes with carboxyl groups in the inner- and/or outer-sphere.

The relationship between humic acid (HA) adsorption on and stabilizing multiwalled carbon nanotubes (MWNTs) in water: effects of HA, MWNT and solution properties.

This study was aimed to explore the relationship between humic acid (HA, as a model NOM) adsorption on and stabilizing multiwalled carbon nanotubes (MWNTs) in water with a focus on the effects of HA, MWNT and solution properties. It was found that MWNT-surface area-normalized adsorption of HAs (Q(SA)) increased with increasing outer-diameter of the MWNTs and decreasing polarity of the HAs. However, at low pH values (ca. <4) or high ionic strengths (ca. >1mmolL(-1) Ca(2+)), the HA adsorption decreased with decreasing polarity of the HAs. The MWNT stabilization increased with increasing Q(SA), but the increase leveled off when Q(SA) exceeded a threshold value markedly lower than the maximum Q(SA), especially for the MWNTs with relative large outer-diameters. On the whole, the Q(SA)-normalized MWNT stabilization, presenting the capability of the MWNT-adsorbed HAs for the MWNT stabilization, increased with increasing HA polarity and solution pH, but with decreasing Ca(2+) concentration. However, the stabilized MWNTs by the HAs with greater polarity could be more subject to destabilization by Ca(2+). The results of this study are believed to shed light on predictive understanding the interaction between MWNTs and NOM and the environmental behavior of MWNTs.

Effect of humic acids on physicochemical property and Cd(II) sorption of multiwalled carbon nanotubes

Carbon nanotubes (CNTs), as a type of superior adsorbents for both organic and inorganic contaminants, are increasingly introduced into the environment. Ubiquitous natural organic matter (NOM) would coat on the released CNTs and change their physicochemical properties and sorption of contaminants. The effects of four sequentially extracted humic acids (HAs, as a model NOM) from a peat soil on the physicochemical properties and Cd(II) sorption of three multiwalled CNTs (MWNTs) with different surface areas were investigated. The MWNTs as purchased with very few oxygen-containing functional groups had relatively low sorption capacities (0.93-1.49 mg g(-1)) for Cd(II) and the sorption capacity increased with increasing surface area of the MWNTs. Surface-coating with the HAs lowered surface areas of the MWNTs but greatly increased their sorption capacities (5.42-18.4 mg g(-1)). The MWNT-bound HAs introduced oxygen-containing functional groups and negative charges to the MWNT surfaces, which could thus increase the apparent sorption of Cd(II) through chemical complexation and electrostatic attraction, respectively. The later-extracted HAs with lower polarity were more favorable for the surface-coating but increased less Cd(II) sorption by the MWNTs. The results are expected to shed light on understanding the underlying mechanism of the effect of NOM on the sorption of heavy metal ions by CNTs.